Shadpour Mallakpour

Chaudhery Mustansar Hussain

Handbook of
Consumer
Nanoproducts
Handbook of Consumer Nanoproducts
Shadpour Mallakpour •
Chaudhery Mustansar Hussain

Handbook of Consumer
Nanoproducts

With 359 Figures and 92 Tables

Shadpour Mallakpour Chaudhery Mustansar Hussain
Chemistry Chemistry and Environmental Science
Isfahan University of Technology New Jersey Institute of Technology
Isfahan, Iran Newark, NJ, USA

ISBN 978-981-16-8697-9 ISBN 978-981-16-8698-6 (eBook)

ISBN 978-981-16-8699-3 (print and electronic bundle)
https://doi.org/10.1007/978-981-16-8698-6
© Springer Nature Singapore Pte Ltd. 2022
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Dedication by C. M. Hussain
I would like to dedicate this handbook to
My beloved GOD
“Meray Pyarey Allah (SWT)”

Dedication by S. Mallakpour
I would like to dedicate this handbook to
My wife MINA
My son IMAN
My Daughters Adeleh and Fereshteh
My Granddaughter TERMEH
Preface

Recently, nanotechnology-based consumer products have generated a fast-growing

buyer market. The majority of nanoproducts are usually used in healthcare and
fitness, home and garden, appliances, coatings, electronics, foods and beverages,
sporting goods, clothing, bikes, touch screens, and automobiles. Additionally, apart
from their antimicrobial and antibacterial properties, nanoparticles have been heavily
used in a wide range of medical supplies and household products, such as food
packing and storage utensils, cleaning agents, textiles, water filters, humidifiers, and
sprays. The production, transportation, daily use, and disposal of nanoproducts have
already influenced the environment and human health, although these effects are still
not well understood quantitatively. In the natural environment, nanoparticles
undergo further transformations: being released as ions, aggregated and agglomer-
ated, surface modified, or embedded into natural matrices. This handbook offers a
comprehensive understanding about nanoproducts manufacturing, utilization, and
impact on the environment. In general, this handbook summarizes recent progresses
and developments in nanotechnology-based consumer products at both experimental
and theoretical models scales.
To capture the comprehensive impression of consumer nanoproducts and to offer
reader a logical and eloquent design of the topic and concentrated up-to-date
reference, the handbook is divided into several parts, where each part comprises
several chapters. It starts with an introduction where modern research perspective of
consumer nanoproducts is explored. Part 2 discusses design and engineering tech-
nology for consumer nanoproducts. Part 3 defines various consumer nanoproducts
based on polymer films and bio-hybrid polymer nanofiber. Part 4 talks about
consumer nanoproducts based on polymer nanocomposites matrices. Part 5 details
consumer nanoproducts based on composites based on shape-memory alloys. Part
6 is dedicated to consumer nanoproducts based on bio-nanoceramics and
bio-nanocomposites, and Part 7 debates consumer nanoproducts based on biocom-
patible nanopolymers. Part 8 describes consumer nanoproducts based on graphene
and graphene nanocomposite. Then Part 9 to 14 are devoted to consumer nano-
products for biomedical, food, textile and packaging, cosmetics & environment,
advanced consumer nanoproducts (waterborne paints, adhesives, coatings, and
dispersible lattices) applications. In Part 15, safety risk, ELSI & economics of
consumer nanoproducts are detailed. Part 16, clarified role of consumer

vii
viii Preface

nanoproducts for green and sustainable future. Then Last part 17 of conclusion
having discussion on consumer nanoproducts in antimicrobial application.
The aim of this handbook is to deliver the recent advancements in
nanotechnology-based consumer products arena. This handbook is intended for a
very wide-ranging audience working in the fields of advanced materials science,
chemistry, chemical engineering and technology, physics, and sustainability. This
handbook will be an invaluable reference source for the libraries in universities and
industrial institutions, government and independent institutes, individual research
groups, and scientists working in the field of nanoproducts. Overall, this handbook is
planned to be a useful handbook for advanced undergraduate, graduate students,
researchers, and scientists who are searching for new advanced nanoproducts for
modern research demands. The editors and contributors of all chapters are famous
researchers, scientists, and experts from academia and industry. On behalf of
Springer, we thank contributors of all chapters for their exceptional and whole-
hearted efforts in making of this handbook. Special thanks to Swati Meherishi
(Editorial Director, Springer Nature), Niraja Deshmukh (Project Coordinator,
Springer Nature), and the entire Major Reference Works team at Springer Nature
for their wholehearted support and help during this project. In the end, all appreci-
ation to Springer for publishing this handbook.

Isfahan, Iran Shadpour Mallakpour

Newark, USA Chaudhery Mustansar Hussain
March 2022
Acknowledgments

We would like to acknowledge Chaudhery Ghazanfar Hussain for his dedicated

support during compilation of this handbook. We also would like to thank Dr. Vajiha
Behranvand, Dr. Farbod Tabesh, Miss Fariba Sirous, and Elham Azadi for their
special support during the making this handbook.

ix
Contents

Volume 1

Part I Introduction: Consumer Nanoproducts ................. 1

1 Consumer Nanoproducts: A Brief Introduction . . . . . . . . . . . . . . . 3

Gaurav Yadav and Md. Ahmaruzzaman

2 Green Nanoproducts: A Far-Reaching Review . . . . . . . . . . . . . . . 17

Sukanchan Palit and Chaudhery Mustansar Hussain

3 New Consumer Nanoproducts: Modern Perspective . . . . . . . . . . . 35

Deepankara V. Shastri and Kantha D. Arunachalam

4 Consumer Nanoproducts: A New Viewpoint . . . . . . . . . . . . . . . . . 59

Sherly Antony, Prasanth Rathinam, R. Reshmy, Raveendran Sindhu,
Parameswaran Binod, and Ashok Pandey

Part II Design and Engineering Technology for Consumer

Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

5 Effect of Mechanical Alloying in Polymer/Ceramic

Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
M. V. Khumalo and M. C. Khoathane

6 Identification and Quantification of Nanomaterials in

Consumer Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Pratap Kumar Deheri and Biswabandita Kar

Part III Consumer Nanoproducts Based on Polymer Films

and Bio-hybrid Polymer Nanofiber . . . . . . . . . . . . . . . . . . . . . . . . . . 141

7 Polymer-Hybrid Nanocomposites Films and Fiber-Based

Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Kamlesh Kumar and Sunita Mishra
xi
xii Contents

Part IV Consumer Nanoproducts Based on Polymer

Nanocomposites Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

8 Consumer Nanoproducts Based on Polymer Nanocomposites

Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
María Paula Guarás and Vera A. Alvarez

9 Polymer Nanocomposites for Futuristic Energy Storage

Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
A. K. Nath and J. M. Kalita

10 Metal Organic Framework Nanoparticles-Based Polymeric

Membrane for Industrial Mixture Separation . . . . . . . . . . . . . . . . 227
Dipeshkumar D. Kachhadiya and Z. V. P. Murthy

Part V Consumer Nanoproducts Based on Composites

Based on Shape Memory Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241

11 Polymer Nanocomposite Matrix-Based Nanoproducts . . . . . . . . . . 243

Ihsan Flayyih Hasan AI-Jawhari

12 Polycarbonate Nanocomposites for High Impact Applications ... 257

Vishwanath Dagaji Jadhav, Akhil Jayawant Patil, and
Balasubramanian Kandasubramanian

Part VI Consumer Nanoproducts Based on Bionanoceramics

and Bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
13 Nanoproducts Based on Shape Memory Materials ............ 285
Ali Nabipourchakoli and Baode Zhang

Part VII Consumer Nanoproducts Based on Biocompatible

Nanopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335

14 Bionanoceramic and Bionanocomposite-Based Nanoproducts:

Concepts, Processing, and Applications . . . . . . . . . . . . . . . . . . . . . 337
Tanvir Arfin

Part VIII Consumer Nanoproducts Based on Graphene and

Graphene Nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355

15 Graphene Nanocomposite-Based Nanoproducts for

Renewable Energy Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Seyyed Mojtaba Mousavi, Seyyed Alireza Hashemi, Chin Wei Lai,
and Gity Behbudi
Contents xiii

16 Graphene Nanocomposite-Based Nanoproducts . . . . . . . . . . . . . . . 373

Susanta Bera, Atanu Naskar, Hasmat Khan, and Sunirmal Jana

17 Novel Graphene-Based Nanocomposites-Based Nanoproducts ... 401

Srinivasarao Yaragalla, Bhavitha K. B., and Sabu Thomas

18 Graphene-Based Nanoproducts: Applications and the Vast

Vision for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Sukanchan Palit and Chaudhery Mustansar Hussain

19 Consumer Nanoproducts Based on Graphene and Graphene

Nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
Tanvir Arfin

20 Performance of Graphene: A Brief Literature Review on

Technologies for Composite Manufacturing . . . . . . . . . . . . . . . . . . 453
R. Sundarakannan, V. Arumugaprabu, S. Vigneshwaran,
P. Sivaranjana, and R. Deepak Joel Johnson

21 Consumer Applications of Graphene and Its Composites . . . . . . . 471

Ramesh K. Guduru and Anurag Ateet Gupta

22 Applications of Graphene and Graphene-Based Nanocomposite

for Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
Jnyanashree Darabdhara and Md. Ahmaruzzaman

Part IX Consumer Nanoproducts for Biomedical Applications . . . 523

23 Nanotechnology Applied to Personalized 3D Dressings for

Diabetic Feet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
Guillermo Tejada Jacob, Guillermo R. Castro, and Vera A. Alvarez

24 Consumer Nanoproducts for Biomedical Applications . . . . . . . . . 549

Deepa Thomas, R. Reshmy, Eapen Philip, Aravind Madhavan,
Raveendran Sindhu, Parameswaran Binod, and Ashok Pandey

25 “Nanosilver”: A Versatile and New-Generation Nanoproduct

in Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
Shikha Gulati, Sanjay Kumar, Anchita Diwan, Parinita Singh, and
Ayush Mongia

26 Synthesis of Biocompatible Chitosan Nanoparticles by

Some Greener Methods for Drug Encapsulations . . . . . . . . . . . . . 595
Srijita Basumallick

27 Application of Nanoparticles in Medicine . . . . . . . . . . . . . . . . . . . . 611

May M. Eid
xiv Contents

28 Characterization of Nanoparticles by FTIR and

FTIR-Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
May M. Eid
29 Biomedical Applications of Nanozymes: Disease Diagnosis
and Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
Venkata Krishna Bayineni, Venkateswara R. Naira, and Ravi-Kumar
Kadeppagari
30 Plant-Based Consumer Health Gold Nanoproducts:
Benign Nanoformulations for Wound Healing and Treatment
of Infections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
Shikha Gulati, Sanjay Kumar, Nandini Sharma, Prishita Sharma, and
Kanchan Batra
Volume 2

Part X Consumer Nanoproducts for Food . . . . . . . . . . . . . . . . . . . . 715

31 Consumer Nanoproducts for Food . . . . . . . . . . . . . . . . . . . . . . . . . 717

Prasanth Rathinam, Sherly Antony, R. Reshmy, Raveendran Sindhu,
Parameswaran Binod, and Ashok Pandey

32 Zein-Based Nanoproducts in Nutrition and Food Sectors . . . . . . . 735

Soumitra Banerjee, Patel Chandra Prakash, and
Ravi-Kumar Kadeppagari

33 Nanotechnology: A Revolutionary Approach Toward Food

Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
Mansi Rastogi, C. V. Bhavana, and Ravi-Kumar Kadeppagari

34 Application of Nanotechnology for Encapsulation of

Micronutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Chandan Kumar Sahu, Shelke Dhanashri Sanjay, and
Ravi-Kumar Kadeppagari

35 Nanosensors: Consumer Nanoproducts for the Detection of

Adulterants and Toxicants in Food . . . . . . . . . . . . . . . . . . . . . . . . . 773
Shikha Gulati, Sanjay Kumar, Anantpreet Kaur Sood, and
Vaidehi Sharma

36 Plant-Based Nanomaterials: Novel and Highly Effectual

Preservatives for Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
Shikha Gulati, Sanjay Kumar, Kartika Goyal, and Ambika Singh
Contents xv

Part XI Consumer Nanoproducts for Textile and Packaging . . . . . 825

37 The Design, Synthesis, and Characterization of Iron

Oxide-Based Coating-Based Nanoproducts . . . . . . . . . . . . . . . . . . 827
Fatma Kubra Ata, Seda Yalçınkaya, and Serap Yalcin
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal
Wound Dressing Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
Sneha Paul and Changam Sheela Sasikumar
39 Starch Based Bio-nanocomposites : Modern and Benign
Materials in Food Packaging Industry . . . . . . . . . . . . . . . . . . . . . . 881
Shikha Gulati, Sanjay Kumar, Parul Chandra, Atishay Jain,
Lavanya Ahuja, Kanchan Batra, and Nandini Sharma
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern
Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
Shikha Gulati, Sanjay Kumar, Sanah Kumar, Vidhi Wadhawan, and
Kanchan Batra

Part XII Consumer Nanoproducts for Cosmetics .............. 929

41 Consumer Nanoproducts for Cosmetics . . . . . . . . . . . . . . . . . . . . . 931

Reshu Virmani and Kamla Pathak
42 Nanocosmetics: Opportunities and Risks . . . . . . . . . . . . . . . . . . . . 963
Ambika and Pradeep Pratap Singh
43 Role of Nanotechnology in Cosmeceuticals . . . . . . . . . . . . . . . . . . . 985
Mahtabin Rodela Rozbu, Samiha Nuzhat, and Paulraj Mosae
Selvakumar
44 Nanobiotechnology-Based Anti-aging Products . . . . . . . . . . . . . . . 1005
Rex Jeya Rajkumar Samdavid Thanapaul, Mosae Selvakumar Paulraj,
and Daniel S. Roh
45 Nanocosmeceuticals: Novel and Advanced Self-Care
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1031
Shikha Gulati, Sanjay Kumar, Rachit Wadhwa, Shweta Lamba, and
Kanchan Batra
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1057
Ravi Chauhan, Amit Kumar, Ramna Tripathi, and Akhilesh Kumar
47 Utilization of Consumer Nanoproducts for Cosmetics
and Their Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1073
Shashi Chawla, Divyanshi Thakkar, and Prateek Rai
xvi Contents

Part XIII Consumer Nanoproducts for Environment ........... 1095

48 Nanoproducts: Biomedical, Environmental, and Energy

Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1097
Shikha Kaushik
49 Composite Nanocoatings for Environmental Remediation . . . . . . . 1123
A. Joseph Nathanael and Palaniswamy Suresh Kumar
50 Biomass-Based Carbon Materials for Heavy Metal Removal . . . . 1139
Sathya Moorthy Ponnuraj and Palaniswamy Suresh Kumar
51 Environmental and Occupational Health Hazards of
Nanomaterials in Construction Sites . . . . . . . . . . . . . . . . . . . . . . . . 1157
S. Ajith and V. Arumugaprabu
52 Consumer Nanoproducts for Environment . . . . . . . . . . . . . . . . . . 1169
Anika Tasnim Chowdhury, Nazifa Rafa, Ahmedul Kabir, and
Paulraj Mosae Selvakumar
53 Bio-nanocomposites for Modern Agricultural Applications . . . . . . 1201
Matias Menossi, Claudia Casalongué, and Vera A. Alvarez
54 Consumer Nanoproducts and Environmental Engineering
Science: Critical Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1239
Sukanchan Palit and Chaudhery Mustansar Hussain
55 Toxicological Perspectives and Environmental Risks of
Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1253
Shikha Gulati, Sanjay Kumar, Shradha Jain, Radhika,
Nandini Sharma, and Kanchan Batra
56 Consumer Nanoproducts Based on Polymer Nanocomposites
for Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1277
Caren Rosales, Magdalena L. Iglesias-Montes, and Vera A. Alvarez
57 Consumer Nanocomposites for Environmental Pollution
Control: A Far-Reaching Review . . . . . . . . . . . . . . . . . . . . . . . . . . 1301
Sukanchan Palit and Chaudhery Mustansar Hussain
58 Environmental Aspect on Nanoproducts . . . . . . . . . . . . . . . . . . . . 1321
Saptarshi Roy and Md. Ahmaruzzaman

Part XIV Advanced Consumer Nanoproducts (Waterborne

Paints, Adhesives, Coatings, and Dispersible Lattices) . . . . . . . . . . . 1343

59 Silver-Nanoparticle-Embedded Antimicrobial Paints . . . . . . . . . . . 1345

Murodjon Abdukhakimov, Renat Khaydarov, Praveen Thaggikuppe
Krishnamurthy, and Svetlana Evgrafova
Contents xvii

60 Eco-friendly Nanostructured Materials for Arsenic

Removal from Aqueous Basins . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1355
Estefanía Baigorria, Romina P. Ollier Primiano, and Vera A. Alvarez

Part XV Safety Risk, ELSI, and Economics of Consumer

Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379

61 Nanoproducts and Legal Aspects of Consumer Protections:

An Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1381
Mohammad Ershadul Karim

Part XVI Green and Sustainable Future with Consumer

Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1407

62 Sustainable Future with Nanoproducts . . . . . . . . . . . . . . . . . . . . . 1409

Sukanchan Palit, Chaudhery Mustansar Hussain, and
Shadpour Mallakpour
63 Green and Sustainable Approaches of Nanoparticles . . . . . . . . . . 1433
A. Ravikumar and K. S. Prakash
64 Green and Sustainable Future with Consumer Nanoproducts . . . . 1455
Saruchi, Vaneet Kumar, Harsh Kumar, and Diksha Bhatt
65 Nanocarriers for Antioxidant Cosmetic Products . . . . . . . . . . . . . 1473
Jimena S. Gonzalez, Romina P. Ollier Primiano, and Vera A. Alvarez

Part XVII Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1497

66 Consumer Nanoproducts in Antimicrobial Application . . . . . . . . . 1499

Sujith Ravi and Ishwarya R. Kishore
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1515
About the Authors

Professor Shadpour Mallakpour, organic polymer

chemist, graduated from the Department of Chemistry,
University of Florida (UF), Gainesville, Florida, USA,
in 1984. He spent 2 years as postdoc at UF. He joined
the Department of Chemistry, Isfahan University of
Technology (IUT), Iran, in 1986. Professor Mallakpour
held several positions such as chairman of the Depart-
ment of Chemistry and deputy of research of the Depart-
ment of Chemistry at IUT. From 1994 to 1995, he
worked as visiting professor, University of Mainz, Ger-
many, and from 2003 to 2004 as visiting professor,
Virginia Tech, Blacksburg, USA. Now he has published
more than 890 journal papers and book chapters and
more than 440 conference papers and has received more
than 40 awards. The most important award to him was
given for the selection of first laureate on fundamental
research, at 21st Khwarizmi International award in
2008. He has been listed as the Top 1% Scientists in
Chemistry in ISI Essential Science Indicators since
2003. He was selected as academic guest of the 59th
Meeting of Nobel Prize Winners in Chemistry, 2009, at
Lindau, Germany. He has presented many lectures as
invited or keynote speaker in different national and
international conferences and universities. He was mem-
ber of organizing and scientific committees for several
national and international conferences. He was also the
chairperson of many national and international meet-
ings. In recent years, he has focused on the preparation
and characterization of polymers containing chiral
amino acid moieties under green conditions using ionic
liquids and microwave irradiation as new technology,

xix
xx About the Authors

and on introducing these aspects in nanotechnology for

the preparation of novel chiral bionanocomposite poly-
mers as well as polymer nanocomposities for hazardous-
materials-removal technologies.

Chaudhery Mustansar Hussain, PhD, is an adjunct

professor and director of laboratories in the Department
of Chemistry and Environmental Science at the New
Jersey Institute of Technology (NJIT), Newark, New
Jersey, USA. His research is focused on the applications
of nanotechnology and advanced materials, environ-
mental management, analytical chemistry, smart mate-
rials and technologies, and other various industries.
Dr. Hussain is the author of numerous papers in peer-
reviewed journals as well as a prolific author and editor
of approximately hundred books, including scientific
monographs and handbooks in his research areas. He
has published with Elsevier, American Chemical Soci-
ety, Royal Society of Chemistry, Springer, John Wiley &
Sons, and CRC Press.
Contributors

Murodjon Abdukhakimov Institute of Nuclear Physics, Academy of Sciences of

Uzbekistan, Tashkent, Uzbekistan
Md. Ahmaruzzaman Department of Chemistry, National Institute of Technology,
Silchar, Assam, India
Lavanya Ahuja Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Ihsan Flayyih Hasan AI-Jawhari Department of Biology, Faculty of Education
for Pure Sciences, University of Thiqar, AL-Nasiriya, Iraq
S. Ajith Department of Civil Engineering, Kalasalingam Academy of Research and
Education, Krishnankoil, Tamil Nadu, India
Vera A. Alvarez Thermoplastic Composite Materials, Institute of Research in
Materials Science and Technology (INTEMA), CONICET –Mar del Plata National
University, Mar del Plata, Argentina
Ambika Department of Chemistry, Hansraj College, University of Delhi, Delhi,
India
Sherly Antony Department of Microbiology, Pushpagiri Institute of Medical Sci-
ences and In-charge of Microbial Technology and Infectious Diseases Laboratory,
Pushpagiri Research Centre, Thiruvalla, Kerala, India
Tanvir Arfin Environmental Materials Division, CSIR-National Environmental
Engineering Research Institute (CSIR-NEERI), Nagpur, India
Hyderabad Zonal Centre, CSIR-National Environmental Engineering Research
Institute (CSIR-NEERI), Hyderabad, Telangana, India
V. Arumugaprabu Department of Mechanical Engineering, School of Automotive
and Mechanical Engineering, Kalasalingam Academy of Research and Education,
Krishnankovil, Tamil Nadu, India
Kantha D. Arunachalam Centre for Environmental Nuclear Research, SRM Insti-
tute of Science and Technology, Chennai, India

xxi
xxii Contributors

Fatma Kubra Ata Department of Genetics and Bioengineering, Kirsehir Ahi

Evran University, Kirsehir, Turkey
Estefanía Baigorria Thermoplastic Composite Materials, Institute of Research in
Materials Science and Technology (INTEMA), CONICET –Mar del Plata National
University, Mar del Plata, Argentina
Institute of Science and Technology, São Paulo State University (UNESP), Soro-
caba, Brazil
Soumitra Banerjee Centre for Incubation, Innovation, Research and Consultancy
(CIIRC), Department of Food Technology, Jyothy Institute of Technology, Benga-
luru, Karnataka, India
Srijita Basumallick Department of Chemistry, Asutosh College under Calcutta
University, Kolkata, India
Kanchan Batra Department of Zoology, Kalindi College, University of Delhi,
New Delhi, Delhi, India
Gity Behbudi Department of Chemical Engineering, University of Mohaghegh
Ardabili, Ardabil, Iran
Susanta Bera Specialty Glass Technology Division, CSIR-Central Glass and
Ceramic Research Institute, Kolkata, West Bengal, India
Diksha Bhatt Department of Biotechnology, CT Group of Institutions Jalandhar,
Jalandhar, Punjab, India
C. V. Bhavana Centre for Incubation, Innovation, Research and Consultancy
(CIIRC), Department of Food Technology, Jyothy Institute of Technology, Benga-
luru, Karnataka, India
Parameswaran Binod Microbial Processes and Technology Division, CSIR-
National Institute for Interdisciplinary, Science and Technology (CSIR-NIIST),
Thiruvananthapuram, Kerala, India
Claudia Casalongué Grupo de Fisiología del Estrés en Plantas, Instituto de
Investigaciones Biológicas (IIB), Facultad de Ciencias Exactas y Naturales,
Universidad Nacional de Mar del Plata (UNMdP) y Consejo Nacional de
Investigaciones Científicas y Técnicas (CONICET), Buenos Aires, Argentina
Guillermo R. Castro Laboratorio de Nanobiomateriales, CINDEFI, Departamento
de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata
(UNLP) -CONICET (CCT La Plata), Buenos Aires, Argentina
Parul Chandra Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Ravi Chauhan THDC Institute of Hydropower Engineering and Technology,
Tehri, India
Contributors xxiii

Shashi Chawla Department of Chemistry, Amity Institute of Applied Sciences,

Amity University Uttar Pradesh, Noida, India
Anika Tasnim Chowdhury Science and Math Program, Asian University for
Women, Chittagong, Bangladesh

Jnyanashree Darabdhara Department of Chemistry, National Institute of Tech-

nology, Silchar, Assam, India

Pratap Kumar Deheri Kalinga Institute of Industrial Technology (KIIT), Bhuba-

neswar, Odisha, India
Shelke Dhanashri Sanjay Centre for Incubation, Innovation, Research and Con-
sultancy (CIIRC), Department of Food Technology, Jyothy Institute of Technology,
Bengaluru, Karnataka, India
Anchita Diwan Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India

May M. Eid Spectroscopy Department, National Research Center (NRC),

ElDokki, Cairo, Egypt
Svetlana Evgrafova Sukachev institute of forest of the Siberian Division of the
Russian Academy of Sciences, Krasnoyarsk, Russian Federation
Institute of Fundamental Biology and Biotechnology, Siberian Federal University,
Krasnoyarsk, Russian Federation

Jimena S. Gonzalez Materiales Compuestos Termoplásticos (CoMP), Instituto de

Investigaciones en Ciencia y Tecnología de Materiales (INTEMA), Universidad
Nacional de Mar del Plata (UNMdP) – Consejo Nacional de Investigaciones
Científicas y Técnicas (CONICET), Mar del Plata, Argentina
Kartika Goyal Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India
María Paula Guarás Grupo de Materiales Compuestos Termoplásticos (CoMP),
Instituto de Investigaciones en Ciencia y Tecnología de Materiales (INTEMA),
Facultad de Ingeniería, Universidad Nacional de Mar del Plata (UNMdP) y Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET), Mar del Plata,
Argentina
Ramesh K. Guduru Pandit Deendayal Petroleum University, Gandhinagar, Guja-
rat, India

Shikha Gulati Department of Chemistry, Sri Venkateswara College, University of

Delhi, New Delhi, Delhi, India

Anurag Ateet Gupta Pandit Deendayal Petroleum University, Gandhinagar, Guja-

rat, India
xxiv Contributors

Seyyed Alireza Hashemi Nanomaterials and Polymer Nanocomposites Labora-

tory, School of Engineering, University of British Columbia, Kelowna, Canada
Chaudhery Mustansar Hussain Chemistry and Environmental Science, New
Jersey Institute of Technology, Newark, NJ, USA
Magdalena L. Iglesias-Montes Grupo de Ecomateriales, Instituto de
Investigaciones de Ciencia y Tecnología de Materiales (INTEMA), CONICET-
UNMdP, Mar del Plata, Argentina
Vishwanath Dagaji Jadhav Plastic and Polymer Engineering Department, Maha-
rashtra Institute of Technology, Aurangabad, Maharashtra, India
Atishay Jain Department of Biological Sciences, Sri Venkateswara College, Uni-
versity of Delhi, New Delhi, Delhi, India
Shradha Jain Department of Biological Sciences, Sri Venkateswara College, Uni-
versity of Delhi, New Delhi, Delhi, India
Sunirmal Jana Specialty Glass Technology Division, CSIR-Central Glass and
Ceramic Research Institute, Kolkata, West Bengal, India
R. Deepak Joel Johnson Department of Mechanical Engineering, Saveetha School
of Engineering, Saveetha School of Medical and Technical Sciences, Thandalam,
Chennai, Tamil Nadu, India
Bhavitha K. B. International and Inter-University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
Department of Physics, St Teresas’s College, Ernakulam, Kerala, India
Ahmedul Kabir Science and Math Program, Asian University for Women, Chit-
tagong, Bangladesh
Dipeshkumar D. Kachhadiya Department of Chemical Engineering, Sardar
Vallabhbhai National Institute of Technology, Surat, Gujarat, India
Ravi-Kumar Kadeppagari Centre for Incubation, Innovation, Research and Con-
sultancy (CIIRC), Department of Food Technology, Jyothy Institute of Technology,
Bengaluru, Karnataka, India
J. M. Kalita Department of Physics, Cotton University, Guwahati, India
Balasubramanian Kandasubramanian Polymer Processing Laboratory, Depart-
ment of Metallurgical and Materials Engineering, Defence Institute of Advanced
Technology (DU), Ministry of Defence, Pune, Maharashtra, India
Biswabandita Kar Kalinga Institute of Industrial Technology (KIIT), Bhubanes-
war, Odisha, India
Mohammad Ershadul Karim Faculty of Law, University of Malaya, Kuala
Lumpur, Malaysia
Bangladesh Supreme Court, Dhaka, Bangladesh
Contributors xxv

Shikha Kaushik Department of Chemistry, Rajdhani College, University of Delhi,

New Delhi, India
Hasmat Khan Specialty Glass Technology Division, CSIR-Central Glass and
Ceramic Research Institute, Kolkata, West Bengal, India
Renat Khaydarov Institute of Nuclear Physics, Academy of Sciences of Uzbeki-
stan, Tashkent, Uzbekistan
M. C. Khoathane Department of Chemical, Metallurgical and Materials Engineer-
ing, Polymer Technology Division, Tshwane University of Technology, Pretoria,
South Africa
M. V. Khumalo Department of Chemical, Metallurgical and Materials Engineer-
ing, Polymer Technology Division, Tshwane University of Technology, Pretoria,
South Africa
Ishwarya R. Kishore Faculty of Medicine and Health Sciences, Department of
Microbiology, SRM Medical College Hospital and Research Centre, SRM Institute
of Science and Technology, Chengalpet, Tamilnadu, India
Venkata Krishna Bayineni Department of Biology, Prayoga Institute of Education
Research, Bengaluru, Karnataka, India
Praveen Thaggikuppe Krishnamurthy JSS College of Pharmacy, Ootacamund,
Tamil Nadu, India
Akhilesh Kumar Department of Physics, Govt. Girls P. G. College, Rajajipuram,
Lucknow, India
Amit Kumar THDC Institute of Hydropower Engineering and Technology, Tehri,
India
Harsh Kumar Department of Chemistry, Dr B R Ambedkar National Institute of
Technology Jalandhar, Jalandhar, Punjab, India
Kamlesh Kumar CSIR-Central Scientific Instruments Organisation, Sector-30,
Chandigarh, India
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India
Sanah Kumar Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Sanjay Kumar Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India
Palaniswamy Suresh Kumar Environmental and Water Technology, Centre of
Innovation (EWTCOI), Ngee Ann Polytechnic, Singapore, Singapore
Vaneet Kumar Department of Applied Sciences, CT Group of Institutions Jalan-
dhar, Jalandhar, Punjab, India
xxvi Contributors

Chandan Kumar Sahu Centre for Incubation, Innovation, Research and Consul-
tancy (CIIRC), Department of Food Technology, Jyothy Institute of Technology,
Bengaluru, Karnataka, India
Chin Wei Lai Nanotechnology and Catalysis Research Center, University of
Malaya, Kuala Lumpur, Malaysia
Shweta Lamba Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India
Aravind Madhavan Rajiv Gandhi Center for Biotechnology, Thiruvanan-
thapuram, India
Shadpour Mallakpour Chemistry, Isfahan University of Technology, Isfahan, Iran
Matias Menossi Grupo de Materiales Compuestos Termoplásticos (CoMP),
Instituto de Investigaciones en Ciencia y Tecnología de Materiales (INTEMA),
Facultad de Ingeniería, Universidad Nacional de Mar del Plata (UNMdP) y Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET), Buenos Aires,
Argentina
Sunita Mishra CSIR-Central Scientific Instruments Organisation, Sector-30,
Chandigarh, India
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India
Ayush Mongia Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India
Seyyed Mojtaba Mousavi Department of Chemical Engineering, National Taiwan
University of Science and Technology, Taipei, Taiwan
Z. V. P. Murthy Department of Chemical Engineering, Sardar Vallabhbhai
National Institute of Technology, Surat, Gujarat, India
Ali Nabipourchakoli Nuclear Science and Technology Research Institute, Tehran,
Iran
Venkateswara R. Naira Department of Biology, Prayoga Institute of Education
Research, Bengaluru, Karnataka, India
Atanu Naskar Specialty Glass Technology Division, CSIR-Central Glass and
Ceramic Research Institute, Kolkata, West Bengal, India
A. K. Nath Department of Physics, Cotton University, Guwahati, India
A. Joseph Nathanael Centre for Biomaterials, Cellular and Molecular
Theranostics (CBCMT), Vellore Institute of Technology (VIT), Vellore, TN, India
Samiha Nuzhat Science and Math Program, Asian University for Women, Chitta-
gong, Bangladesh
Contributors xxvii

Romina P. Ollier Primiano Thermoplastic Composite Materials, Institute of

Research in Materials Science and Technology (INTEMA), CONICET –Mar del
Plata National University, Mar del Plata, Argentina
Sukanchan Palit Department of Chemical Engineering, University of Petroleum
and Energy Studies, Energy Acres, Post-Office-Bidholi via Premnagar, Dehradun,
Uttarakhand, India
Ashok Pandey Centre for Innovation and Translational Research, CSIR- Indian
Institute for Toxicology Research (CSIR-IITR), Lucknow, India
Kamla Pathak Faculty of Pharmacy, Uttar Pradesh University of Medical Sci-
ences, Etawah, Uttar Pradesh, India
Akhil Jayawant Patil Department of Mechanical Engineering, Birla Institute of
Technology and Science, Pilani, Goa, India
Sneha Paul Medical division, Scope eknowledge, A Straive company, Chennai,
India
Mosae Selvakumar Paulraj Science and Math Program, Asian University for
Women, Chittagong, Bangladesh
Panaiyaanmai - Centre for Self reliance and Sustainable Development, Munnetram
Green Industry, Kadayam, Tenkasi, Tamil Nadu, India
Eapen Philip Post Graduate and Research Department of Chemistry, Bishop
Moore College, Mavelikara, Kerala, India
Sathya Moorthy Ponnuraj Department of Nano Science and Technology, Tamil
Nadu Agricultural University, Coimbatore, Tamil Nadu, India
K. S. Prakash Department of Chemistry, Bharathidasan Government College for
Women (Autonomous) (Affiliated to Pondicherry University, Pondicherry),
Puducherry, India
Patel Chandra Prakash Centre for Incubation, Innovation, Research and Consul-
tancy (CIIRC), Department of Food Technology, Jyothy Institute of Technology,
Bengaluru, Karnataka, India
Pradeep Pratap Singh Department of Chemistry, Swami Shraddhanand College,
University of Delhi, Delhi, India
Radhika Department of Biological Sciences, Sri Venkateswara College, University
of Delhi, New Delhi, Delhi, India
Nazifa Rafa Science and Math Program, Asian University for Women, Chittagong,
Bangladesh
Prateek Rai Department of Chemistry, Amity Institute of Applied Sciences, Amity
University Uttar Pradesh, Noida, India
xxviii Contributors

Mansi Rastogi Department of Environment Sciences, Maharshi Dayanand Univer-

sity, Rohtak, Haryana, India
Prasanth Rathinam Department of Biochemistry, Pushpagiri Institute of Medical
Sciences and In-charge of Biochemistry Laboratory and Medical Biotechnology
Laboratory, Pushpagiri Research Centre, Thriuvalla, Kerala, India
Sujith Ravi Faculty of Medicine and Health Sciences, Department of Microbiol-
ogy, SRM Medical College Hospital and Research Centre, SRM Institute of Science
and Technology, Chengalpet, Tamilnadu, India
A. Ravikumar Department of Chemistry, SRM Institute of Science and Technol-
ogy, Kattankulathur, Tamil Nadu, India
R. Reshmy Post Graduate and Research Department of Chemistry, Bishop Moore
College, Mavelikara, Kerala, India
Daniel S. Roh Division of Plastic and Reconstructive Surgery, Department of
Surgery, Boston University School of Medicine, Boston, Massachusetts, USA
Caren Rosales Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto
de Investigaciones de Ciencia y Tecnología de Materiales (INTEMA), CONICET-
UNMdP, Mar del Plata, Argentina
Saptarshi Roy Department of Chemistry, National Institute of Technology, Silchar,
Assam, India
Mahtabin Rodela Rozbu Science and Math Program, Asian University for
Women, Chittagong, Bangladesh
Rex Jeya Rajkumar Samdavid Thanapaul Division of Plastic and Reconstruc-
tive Surgery, Department of Surgery, Boston University School of Medicine, Bos-
ton, Massachusetts, USA
Saruchi Department of Biotechnology, CT Group of Institutions Jalandhar, Jalan-
dhar, Punjab, India
Changam Sheela Sasikumar Clinical research, S.S healthcare; Clinical Research,
Hycare Super specialty, Seed Fund Technical sub committee; Golden Jubilee
Women Biotech Park; Department of Biochemistry, Saveetha Dental College,
Chennai, India
Paulraj Mosae Selvakumar Science and Math Program, Asian University for
Women, Chittagong, Bangladesh
Nandini Sharma Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Prishita Sharma Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Contributors xxix

Vaidehi Sharma Department of Biological Sciences, Sri Venkateswara College,

University of Delhi, New Delhi, Delhi, India
Raveendran Sindhu Microbial Processes and Technology Division, CSIR-
National Institute for Interdisciplinary, Science and Technology (CSIR-NIIST),
Thiruvananthapuram, Kerala, India
Ambika Singh Department of Biological Sciences, Sri Venkateswara College,
University of Delhi, New Delhi, Delhi, India
Parinita Singh Department of Chemistry, Sri Venkateswara College, University of
Delhi, New Delhi, Delhi, India
P. Sivaranjana School of Automotive and Mechanical Engineering, Kalasalingam
Academy of Research and Education, Krishnankovil, Tamil Nadu, India
Anantpreet Kaur Sood Department of Biological Sciences, Sri Venkateswara
College, University of Delhi, New Delhi, Delhi, India
R. Sundarakannan School of Automotive and Mechanical Engineering,
Kalasalingam Academy of Research and Education, Krishnankovil, Tamil Nadu,
India
Guillermo Tejada Jacob Grupo de Materiales Compuestos Termoplásticos
(CoMP), Instituto de Investigaciones en Ciencia y Tecnología de Materiales
(INTEMA), Facultad de Ingeniería, Universidad Nacional de Mar del Plata
(UNMdP) y Consejo Nacional de Investigaciones Científicas y Técnicas
(CONICET), Mar del Plata, Argentina
Divyanshi Thakkar Department of Chemistry, Amity Institute of Applied Sci-
ences, Amity University Uttar Pradesh, Noida, India
Deepa Thomas Post Graduate and Research Department of Chemistry, Bishop
Moore College, Mavelikara, Kerala, India
Sabu Thomas International and Inter-University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
Ramna Tripathi THDC Institute of Hydropower Engineering and Technology,
Tehri, India
Deepankara V. Shastri Centre for Environmental Nuclear Research, SRM Insti-
tute of Science and Technology, Chennai, India
S. Vigneshwaran Department of Mechanical Engineering, Saveetha School of
Engineering, Saveetha School of Medical and Technical Sciences, Thandalam,
Chennai, Tamil Nadu, India
Reshu Virmani School of Pharmaceutical Sciences, MVN University, Palwal,
Haryana, India
xxx Contributors

Vidhi Wadhawan Department of Biological Sciences, Sri Venkateswara College,

University of Delhi, New Delhi, Delhi, India
Rachit Wadhwa Department of Chemistry, Sri Venkateswara College, University
of Delhi, New Delhi, Delhi, India
Gaurav Yadav Department of Chemistry, National Institute of Technology,
Silchar, Assam, India
Serap Yalcin Department of Molecular Biology and Genetics, Kirsehir Ahi Evran
University, Kirsehir, Turkey
Seda Yalçınkaya Department of Food Engineering, Süleyman Demirel University,
Isparta, Turkey
Srinivasarao Yaragalla Istituto Italiano di Tecnologia, Smart Materials Group,
Genova, Italy
Baode Zhang Liaoning Shihua University, Fushun, Liaoning, China
 Part I
Introduction: Consumer Nanoproducts
Consumer Nanoproducts: A Brief
Introduction 1
Gaurav Yadav and Md. Ahmaruzzaman

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Composition of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Nanomaterial Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
CPI Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Some Key Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Natural Source of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Types of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Inorganic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Metallic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Polymer-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Lipid-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Abstract
Nanotechnology is an advanced technology widely used for the manufacture of
scratchless eyeglasses, ceramic coating in the solar cells, transparent sunscreens,
crack-resistant paints, and many more. Nanotechnology provides the lighter,
stronger, smarter, and cleaner surfaces. Properties of a particle in nanoscale
change in uncertain ways. Nanotechnology can increase performance and new
functionalities as well as decrease the use of chemical hazardous substance.
Nanomaterials have a wide range of novel applications creating a new revolution
for industries, e.g., nanoparticles of TiO2 used in sunscreens.
In our daily life, a lot of products that we use have a significant role of
nanotechnology, from tennis rackets to clothing. Most of these products are
made with the help of nanotechnology and also contain nanomaterials. With the
help of nanotechnology, more than 380 products are available for the consumers.

G. Yadav · M. Ahmaruzzaman (*)

Department of Chemistry, National Institute of Technology, Silchar, Assam, India

© Springer Nature Singapore Pte Ltd. 2022 3

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_85
4 G. Yadav and M. Ahmaruzzaman

In the automobile sector, there are many safety factors related to nanotechnology.
In tires, nanomaterials improve the adhesive property so that in the wet condition,
a vehicle can stop. The rigidity of a car can be increased with the help of
nanoparticles.
Nanotechnology can also be applied for the processing, safety, packaging, and
production of food. A nanocoating process should enhance food packaging by
taking antimicrobial agents right on the coated film surface.
Nanomaterials are widely being used in medicine and biology in various ways
and encompass the direct application of products into patients. Aerogel that acts
as an excellent insulator is a nanomaterial.
The consumption of nanoparticles in developed countries is found to be more
than 1012 particles/day consisting of mixed silicates and TiO2. In nanofood
products, engineered nanomaterials fall into three categories: surface
functionalized materials, inorganic, and organic. In this chapter, we read the
various uses of nanotechnology in various fields. In this context, we will discuss
the most representative use of the nanoproducts and their activities as well as
advantages of nanotechnology with a brief overview.

Keywords
Nanotechnology · Consumer nanoproducts · Consumer product inventory (CPI) ·
Applications · Natural sources

Introduction

Nanotechnology has various potentials for the development of new applications and
products in many consumer and industry sectors. This is because nanotechnology
can offer better functionalities and performance as well as decrease the use of unsafe
chemical substances, generate less waste, and consume materials and energy, thus
increasing effectiveness. A wide range of novel applications leads to nanotechnology
as a hotbed of the industrial revolution [1]. Many nanotechnology products belong to
fitness, and the health sector includes cosmetic products on the Woodrow Wilson
Database [2]. This is followed by other applications like electronics, paints, food,
and much more. The database leads to suffering from insufficient information. CPI
(consumer product inventory) in 2010 listed 1012 products from 24 countries. After
CPI, nanotechnology-related inventory has expanded over the globe. A German
company launches a nanotechnology-related product database in 2006 [3]. In May
2014, nearly 586 products are listed in this database. In 2009, two European
organizations BEUC (European consumer organization) and ANEC (European
consumer voice in standardization) made a joint effort to develop “consumer nano-
products with nano-claims” available in Europe for consumers [4]. In 2011 and
2012, a new version focused on products containing silver nanoparticles, and it
contains 141 silver nanoproducts. Ecological council, Danish consumer council, and
the Technical University of Denmark launched “The Nanodatabase” in 2012 that
1 Consumer Nanoproducts: A Brief Introduction 5

contains nanoproducts available for purchase and available in the European market
[5]. This inventory currently contains 1423 products and is continually updated.
CPI database provides relevant and useful information to stakeholders who are
involved in (a) developing tools and strategies that ensure safe and responsible use of
the nanoproducts and (b) understanding which products include nanotechnology. In
the USA, nanotechnology is regulated without any provisions as hazardous chemical
substances and pesticides. When nanomaterials are used as drugs, cosmetics, and
food additives, these are regulated under the FFDCA (Federal Food, Drug, and
Cosmetic Act).
In European Union, nanoproducts are regulated under registration, evaluation,
and authorization regulations and the CLP (classification, labeling, and packaging)
regulation when classified as hazardous chemical substances [6]. European Com-
mission also regulated the nanoproducts that contain cosmetics and titanium dioxide
but not zinc oxide [7]. European Union brings many advantages like a lower cost for
industries, and thus an inventory would benefit for companies, consumers, and
government [8] (Fig. 1).

Fig. 1 Nanotechnology from lab to consumer products

6 G. Yadav and M. Ahmaruzzaman

Table 1 Various uses of nanoproducts and nanomaterials

Science or
industry Application Additional feature of nanoproducts
Medicine Bandages, plasters, dressing on Due to continue release of Ag
wound with disinfecting layer of nanoparticles, antibacterial effect may last
Ag NPs for a week
Curtains, clothing, screens Helps to limit the infections in hospital;
Nanotubes covering implants having biocidal property
Increases surface for consistency
Cosmetology Ag nanoparticles-enriched soap Bacteria elimination
Facial cream enriched with Greater efficiency due to active substances
copper, silver, platinum, and gold
Construction Ag NPs containing antibacterial Protect the wall to retard the growth of
industry paint microorganisms
Self-cleansing or fog-free For fireplaces
property of glass
Textile Antistatic membrane formed by Waterproof that allows only steam
industry nanoparticles Prevent from unpleasant odors
Socks made of fibers
Food Nanosilver deposition into AC Air purification to prevent contaminations
industry working in nonvegetarian plants Extends the storage life and assure the
Packaging of food products safety of the product. Ag nanoparticles
prevent it from mold, fungi, and bacterial
flora
Electronic Graphene battery is used in Consider the natural conductor of
electrical resistant coating electricity which is most effective
Motor Durable and lightweight Modern construction solutions
industry materials Shine and dirt resistant for a long time
Car care products

The innovation in nanoproducts gives much more benefit and opportunity in

many branches of the market. One of the necessary features is to make certain the
safety of life and protect the environment. This results in the safe use of the
nanoproducts. With the help of innovation, nanoscale began to form products with
new applications and properties given in the Table 1 (Source: Own research by: Pulit
et al., 2012; Nowacka & Niemczuk, 2012; Szymański, 2012; Sokół 2012;
Szewczyk, 2011; Schlecht & Schroeder, 2010).

Composition of Nanoproducts

In recent years, nanotechnology-based products are growing fast for consumer. Of

the 1817 materials listed in CPI, approximately 39 various types of nanomaterials are
found in these products that are formed from metal like Ti, Zn, Au, and Ag; metal
oxide like ZnO, TiO2, and Fe2O3; and carbonaceous (CNTs, graphene, fullerenes,
carbon) and silica. Metals and metal oxides comprise one of the largest nanoproduct
compositions that is almost 37% of the product. Metal oxides like TiO2, SiO2, and
1 Consumer Nanoproducts: A Brief Introduction 7

ZnO are the most used nanomaterial in products worldwide. Ag nanoparticle is the
most important for the production of various nanoproducts; it is used in 207 products
(14.5%) [5]. Due to its antimicrobial property [9], it is present in 438 (24%) products
listed in CPI. Of carbonaceous materials (89), the majority of them contain single- or
multiwalled CNTs (38 products) and carbon nanoparticles (39) or carbon black.
Nanomaterial components listed in CPI are given below:

Aluminum oxide, boron, calcium, carbon, carbon nanotube, ceramics, carnauba wax, cerium
oxide, chromium, cobalt, clay, copper, fullerene, gold, graphite, graphene, iodine, iridium, iron,
lead, liposome, lithium, manganese, magnesium, nanomicelles, nanocellulose, nickel, organics,
palladium, polymer, platinum, retinol, silver, silicon, titanium, tungsten disulfide, zinc oxide,
zeolite, and zirconia

Some of the nanoproducts contain more than one component, like TiO2 and Ag
that are combined with each other in ten products (electronics and cosmetics). Zinc
oxide and titanium dioxide are paired in 10 products (cosmetics, paints, and sun-
screens). Silver and nano-ceramics are used in combination for cosmetics, water
filtration products, and humidifiers. These result in the use of nanohybrids [10] in
consumer products (Fig. 2).

Fig. 2 Nanoproduct growth during the period from 2005 to 2010

8 G. Yadav and M. Ahmaruzzaman

Nanomaterial Function

Nanoproducts give unexpected benefits by adding nanomaterials into products. Nano-

materials like silicon dioxide and titanium dioxide are used for protective coatings and
environmental treatment (treat air and water in the home to protect products). Silver,
gold, titanium dioxide, and others are used for cosmetic products. A wide variety of
nanoproducts related to health (dietary supplements) contains silver, gold, calcium,
magnesium, ceramics, silicon dioxide, etc. Silver has a wide range of applications. It is
mostly used in household products, medical supplies, food packaging, textiles, cleans-
ing agents, water filters, and sprays. Apart from Ag, ZnO and TiO2 are also used in food
packaging to maintain colors and prevent them from spoiling. CNTs are widely used in
industries and products like clothing, bike, touch screens, and sporting goods for their
excellent strength and superior thermal and electrical conductivity.
Gold NPs are good for biological and chemical imaging. Gold NPs are also
important for diagnosis of cancer and cancer therapy, catalysis, and sensing. Silver
NPs are mostly used for their anti-inflammatory and antimicrobial properties. They
are most extensively used for catalytic, optical, and sensing for detecting various
monitoring biotransformation [11] and biomolecules. CNTs have cytoprotective
effect [12] and antioxidant potential. This helps in detection of chronic skin diseases,
infections, and early-stage skin cancer. It is also applied in cosmetic products such as
makeup, moisturizers, and sunscreens [12] (Fig. 3).

CPI Growth

In 2011, CPI mentioned 1314 products: from then, 489 products are not available
containing nanoparticles, and 500 products are added. In 2015, the total number of
products available is 1814. CPI is the most extensive inventory of nanotechnology
consumer products available based on the review. Among 62 countries, products
come from 622 companies. The products listed in CPI have the following criteria:
(1) they are happily acquired by consumers, (2) they contain nanoparticles by
manufacturer, and (3) their claim appears in CPI staff for containing nanoparticles.
There is continuous growth of products containing nanotechnology; not all
products are available in the market. In 2011, the nanoproduct market value was
about 4.18 billion dollars, and by the end of 2014, the total cost of manufacture of
nanoproduct crosses should be 2.6 trillion dollars by lux research. And it was
estimated that in 2025 its value would be 100 billion dollars. Various numbers of
nanoproducts from various countries are listed in the table (source: file:///C:/Users/
DELL/Downloads/Beilstein_J_Nanotechnol-06-1769-s001.pdf).

Serial number Country Companies Products

1 USA 290 773
2 Korea 64 132
3 Germany 63 338
4 UK 35 104
5 Japan 32 56
(continued)
1 Consumer Nanoproducts: A Brief Introduction 9

Serial number Country Companies Products

6 China 24 57
7 Denmark 12 47
8 France 10 34
9 Taiwan 10 28
10 Australia 10 21
11 Canada 9 17
12 Switzerland 7 44
13 Italy 7 14
14 Israel 6 10
15 Poland 4 17
16 Austria 4 11
17 Thailand 4 4
18 Singapore 3 24
19 Malaysia 3 4
20 Finland 3 3
Others 22 86
Total 622 1814

267

738 182
143
119

43 33

personal clothing cosmetics sporting filtration sunscreen

care goods

209

126
105
59 44 30
ss

en

es

ge

rs

n
nc

re
te
ne

i
rd

ra
ov

ld
ia
pu
ga

ve
fit

hi
om

pl
m

rc
be
d

ap
d

co
an

t
an

au

fo
d

d
an
th

s
e

an

od
m
al

od
he

ho

go
cs
fo

ni
ro
ct
e
el

Fig. 3 Various benefits of nanomaterial additives into consumer product

10 G. Yadav and M. Ahmaruzzaman

Some Key Concepts

Nanoparticle term is simply referred as a nanomaterial in general. Nanoparticles are

solid, and three-dimensional sizes range from 1 to 1000 nm with many functionalities.
They can interact with many cells in the human body. Nanoparticles can improve the
stability and solubility of the active compound. Drug’s efficiency can be enhanced
with the help of nanotechnology and also protect the drug for degradation.
Food packaging is done with nanomaterials to enhance its aging process and
increase its life or avoid spoilage. Food supplement such as dietary plays an influen-
tial role in the medical field. Food supplements can be used in cardiovascular disease,
neurological, diabetes, and cancer. Nanoparticle possesses various characteristics,
some of which are used in cosmetic and dermatological. Engineered NPs are used for
better skin permeation. CNTs are used in chronic skin disease diagnosis and infec-
tions. It is also used in moisturizers, sunscreens, makeup, and rejuvenating products.

Natural Source of Nanoproducts

In recent years, plants and their part play an exciting role in the cosmetic, pharma-
ceutical, and food industries. Plant-based products provide a significant role in the
treatment of some diseases and are of low cost. Nanotechnology used for medical
purposes is termed nanomedicine. With the help of nanoscale, we can control and
manipulate matter by new systems [13, 14]. Nanotechnology helps to integrate
molecules, due to this show less toxicity, greater efficiency, and multiple mecha-
nisms of action. Much biological activity in humans occurs at the nanoscale, making
nanomedicine cross barriers and interact with the tissues [15]. Numerous reactive
nanomaterials are able to absorb the biomolecules. Nanomedicine could provide
cost-effective and improved healthcare; for example, silver nanoparticle obtained
from Ananas comosus is an antioxidant. Fullerene is used as an antiaging obtained
from plant extract name Camellia sinensis [16]. Lipid nanoparticles are used as an
antioxidant [17], UV protector, and hydratation [18]. Polymeric NPs obtained from
aloe vera should be used to treat burn wounds [19].

Plant extract Name of NPs Applications References

Aloe vera Polymeric NPs Burn wound treatment [19]
Iresine herbstii Silver NPs Antimicrobial and eczema [20]
Pistacia integerrima Gold NPs Psoriasis and anti-inflammatory [21]
Plectranthus amboinicus ZnO NPs Antifungal [22]

Types of Nanoparticles

Nanoparticles are of different types. Nanoparticles are categorized into two parts:
inorganic and organic. Inorganic NPs contain metallic NPs, silica NPs, and ceramic
NPs, and organic NPs contain lipid NPs and polymeric NPs (Fig. 4).
1 Consumer Nanoproducts: A Brief Introduction 11

Fig. 4 Nanotechnology in health products

12 G. Yadav and M. Ahmaruzzaman

Inorganic Nanoparticles

Inorganic nanoparticle size ranges from 2 to 100 nm. Inorganic nanoparticles

contain Ag, Au, SiO2, TiO2, etc. Inorganic nanoparticles are biocompatible,
nontoxic, hydrophilic, and stable as compared to organic nanoparticles. Inorganic
nanoparticles are made up of inorganic elements like Ag, Au, Si, Ti, etc., and
organic nanoparticles are formed from polymers. In sunscreens, TiO2 is the most
widely used nanoparticle because it has a high sun protection factor. It acts as a
UV filter in sunscreens [23]. Inorganic nanoparticles gained intense attention in
oncology due to a wide range of applications like tumor drug delivery, imaging,
and enhancement of radiotherapy. Iron oxide is widely used in MRI for hyper-
thermia. Metallic nanoparticles are heavily used in engineering and biomedical
science. Gold nanoparticles are used to enhance the capacity of drugs so they can
easily reach the targeted site. Silver NPs are widely used in medical field due to
antifungal, antibacterial, antiviral, anti-inflammatory, and osteoinductive effect
[24–26]. Because of this, it is used for the treatment of cancer including breast
cancer cells [27]. Silica nanoparticles are used in various fields such as photo-
dynamic therapy, gene delivery, drug delivery, protein delivery, and for diagnosis
of DNA. Carbon nanotubes have various properties like ultralightweight, high
thermal conductivity, electronic property, and high aspect ratio. Single-walled
CNTs have additional property called photoluminescence which is applied in
diagnosis. CNTs have various advantages over others like nonbiodegradable,
non-immunogenic nature, biocompatible, elastic nature, and having minimum
cytotoxicity.

Metallic Nanoparticles

Many metals form the nanostructure. These nanoparticles have a sizeable area-
volume ratio and surface area and have unique physical and optical properties that
are easy to prepare [14, 28, 29]. The particle’s surface can be functionalized and
modified due to the surface chemistry [14, 28]. These characteristics of metallic NPs
are essential for cancer treatment. These are also helpful in analytical processes,
sensing, and imaging.
Silver and gold nanoparticles have various types of catalytic and optical properties.
With the help of gold NPs, the drug delivery system can be studied [29]. Gold NPs are
also used for immune labeling of samples. Iron oxide is the most widely used nano-
particle. They have paramagnetic properties; along with that, they show chemical
stability, highly magnetic, and low toxicity under physiological condition [26], so
they can be used for tracking of stem cells [29]. It is also used in electronics and
functional coatings of the material to protect. Besides these, they are easy to recycle.
Metallic nanoparticles have gained intense attention in the market in various products
like clothing, footwear, creams, and plastic containers. Some other applications of
metallic nanoparticle are given below [30].
1 Consumer Nanoproducts: A Brief Introduction 13

Metals Applications
Aluminum Explosive, fuel additives, coating additive
Iron Environment remediation, magnetic imaging
Gold Photodynamic therapy, cellular imaging
Silver Batteries, photography, electrical, antimicrobial
Silica Drugs carrier, adsorbent, gene delivery, thermal and electric insulator, filter
Copper materials
Manganese Antibiotic treatment, antimicrobial (antibacterial, antiviral, antifouling, etc.),
Cerium catalyst, lubricants, nanocomposite coating, inks, filters
Nickel Catalyst, batteries
Titanium Computer chip, fuel additive
dioxide Conduction, magnetic property, printing ink, catalyst
Zinc Sterilization, antibacterial coating, cosmetics, photocatalyst, sunscreens
Sunscreen, skin protection

Polymer-Based Nanoparticles

Polymer NPs are submicron-sized reliable drug carriers that may or may not be
degradable. Polymeric NPs have a large surface-to-volume ratio, so they have the
ability to change the bioactivity of drugs [31]. They can be easily synthesized and
has wide applications in all fields [32]. They allow specific targeting, controlled
release of drugs, and stability.
Natural polymers like dextran, proteins like albumin and gelatin, alginate,
chitosan, and a synthetic polymer such as PLA (polylactic acid), copolymers of
glycolic and lactic acid, and PCL (poly-Ɛ-caprolactone) are used to prepare poly-
meric NPs [14, 28, 33–35]. Sometimes synthetic polymers are also used. For NP
production, natural hydrophilic polymers are efficient due to better biocompatibility,
drug-loading capacity, and less opsonization [36].
Polymeric NPs contain protein nanoparticles having many advantages. Proteins
like gelatin and albumin show properties like biocompatibility and are easy to
prepare. Protein NPs have the ability to bind the drugs in a nonspecific manner.
They can interact with the solvent [37] also. Albumin is a highly effective drug
carrier [38]. It is refer for albumin effective found in blood plasma and act as a
protein carrier for drugs.
Type of Bioactive/type
polymer of drug Application purpose References
PLGA/PLA/ Coumarin-6 Bioimaging, theranostics, and drug delivery [39]
PCL (C-6)
PLGA Rapamycin Anti-glioma activity [40]
AcDex Hyperforin Anti-inflammatory activity [41]
Biopolymer of Amphotericin B Antifungal [42]
PCL Amp-B
PCL/PGLA Ciprofloxacin Accelerated healing, tissue regeneration, [43]
anti-inflammatory
(continued)
14 G. Yadav and M. Ahmaruzzaman

Type of Bioactive/type
polymer of drug Application purpose References
PEG Pegademase Immunodeficiency disease [44, 45]
bovine
PLGA-PEG Paclitaxel Brain cancer, pancreatic andovarian [46]
(PTX)
PGLA Curcumin Pancreatic cancer, antibacterial [44, 47]
Activity
PLGA Fenofibrate Diabetic retinopathy [48]

Lipid-Based Nanoparticles

Lipid NPs contain phytosomes, ethosomes, liposomes, and matrix-based nano-

structures like NLCs (nanostructured lipid carriers), LDCs (lipid-drug conjugates),
SLNs (solid-lipid nanoparticles), etc. [28]. Lipid NPs allow drug targeting and
poorly water-soluble molecule [49].
Liposome having sizes that range from 50 to 1000 nm is an ideal drug delivery
due to their morphology. Their structure entrapped the drugs having high molecular
weight. Gene therapy and anticancer delivery are the prime focus of liposome
formulations [14]. Liposome protects, stores, and transfers a considerable amount
of drugs. The lipid protects the drugs from chemical inactivation and enzymatic
degradation. It is also possible to form cationic and anionic liposomes with enhanced
efficiency.
SNLs composed of lipid solids are colloidal particles at both body and room
temperature. SNLs are biodegradable and biocompatible, lack organic solvent,
provide drug stability, and are easy to scale up [38, 50]. Many classes of SNLs are
used for drug delivery, such as antioxidant, antibacterial, genetic material, and
therapeutic use [28, 51]. Drug targeting, gene delivery, and vaccine delivery are
also successfully used [28]. NLCs provide stability during storage, better drug
loading, and drug release modulation [28, 52].

Conclusion

The use of nanotechnology-based products is increasing continuously and gains

attention. Nanotechnology is used to overcome issue like low water solubility, low
permeability, and low in vivo stability. This chapter tells us about the capability of
nanoparticles and the use of nanomaterials in daily lives. In the future, there will be a
need of more products, and we need to increase the knowledge of consumers about
nanoproducts. The positive attitude of the respondents helps in growing the use of
nanoproducts. The financial condition of consumers like adjusting the price helps a
lot to grow the use of nanoproducts.
1 Consumer Nanoproducts: A Brief Introduction 15

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https://pubs.rsc.org/en/content/articlehtml/2016/en/c5en00182j
https://ec.europa.eu/health/scientific_committees/opinions_layman/en/nanotechnologies/l-3/5-
nanoparticles-consumer-products.htm
https://backend.orbit.dtu.dk/ws/portalfiles/portal/118574286/AbstractBook_2015_SNO_SUN.pdf
https://www.beilstein-journals.org/bjnano/articles/6/181
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Green Nanoproducts: A Far-Reaching
Review 2
Sukanchan Palit and Chaudhery Mustansar Hussain

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
The Aim and Objective of This Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
The Vast Scientific Doctrine of Nanomaterials and Engineered Nanomaterials . . . . . . . . . . . . . . . . 20
Green Nanoproducts and the Vast World of Science and Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Desalination, Membrane Science, and the Future of Global Water Shortage . . . . . . . . . . . . . . . . . . . 21
Application of Nanotechnology in Groundwater Remediation and Drinking Water
Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Environmental and Energy Sustainability and the Vast Vision for the Future . . . . . . . . . . . . . . . . . . 22
Green Nanotechnology, Green Sustainability, and the Visionary Future . . . . . . . . . . . . . . . . . . . . . . . . 23
Recent Scientific Advancements in the Field of Green Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Recent Scientific Advances in the Field of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Recent Scientific Advancements in the Field of Green Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . 28
The Vast Scientific Sagacity and Scientific Profundity in the Field of Application of Green
Nanomaterials in Environmental Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Arsenic and Heavy Metal Groundwater Remediation and the Application
of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Future Scientific Directions and Futuristic Recommendations of This Study . . . . . . . . . . . . . . . . . . 31
Conclusion, Summary, and Vast Scientific Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

S. Palit
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Post-Office-Bidholi via Premnagar, Dehradun, Uttarakhand, India
e-mail: [email protected]
C. M. Hussain (*)
Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, USA
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 17

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_1
18 S. Palit and C. M. Hussain

Abstract
The world of science of nanotechnology, nanomaterials, and engineered nano-
materials today stands in the middle deep scientific introspection and vision.
Green nanoproducts in the similar vein has immense applications in environmen-
tal protection and are in the path of newer rejuvenation. Nanotechnology has been
defined as research and development at the atomic, molecular, or macromolecular
scales. Rapid industrialization, burgeoning human population, loss of natural
resources, and degradation of ecological biodiversity have urged scientists and
engineers globally to delve deep into the area of nanotechnology and nano-
materials. Nanoproducts and nanomaterials have today tremendous applications
in diverse areas of science and engineering. Green nanotechnology and its
immense scientific prowess will veritably one day open new doors of scientific
innovation and scientific instinct in the field of nanomaterials and engineered
nanomaterials. In this treatise, the authors deeply elucidate on the vast application
areas of nanomaterials and nanoproducts in environmental protection and vast
and varied areas of science and technology. The areas of green chemistry, green
engineering, and green sustainability are dealt with immense scientific vision and
scientific profundity in this chapter. Green nanotechnology is a marvel of science
and technology today. Environmental degradation and destruction of biodiversity
are challenges of science and civilization today. This chapter will surely unfold
newer futuristic thoughts and newer futuristic recommendations in the field of
green nanoproducts applications in environmental remediation and the vast world
of environmental engineering science. A new dawn in the field of global science
and engineering will surely evolve if scientists and engineers move towards
positive research directions in green nanotechnology, green chemistry, and
green engineering.

Keywords
Green · Nanoproducts · Nanotechnology · Nanomaterials · Water · Environment ·
Pollution · Arsenic

Introduction

Mankind and science today are in the middle of deep scientific vision and scientific
far-sightedness. The challenges and scientific intricacies of human civilization and
environmental protection are today vast and versatile. Environmental engineering,
chemical engineering, and nanotechnology are vast areas of scientific endeavor.
Immense challenges, immense vision, and the targets of scientific research pursuit
are the veritable forerunners towards a new scientific world of nanotechnology and
nanomaterials/nanoparticles. Vast industrialization, loss of natural resources, and the
needs of science and technology in human advancements are the true pallbearers
towards a new domain of nanomaterials and green nanoproducts. Conventional and
nonconventional environmental engineering tools are the true research areas of
2 Green Nanoproducts: A Far-Reaching Review 19

environmental protection science today. There are lot of limitations and challenges in
the path towards scientific triumph in application of environmental engineering
tools. Nanotechnology, nanoparticles, and nanomaterials are the boons of human
civilization today and thus the need of a detailed scientific investigation. Engineered
nanomaterials and green chemistry are the other areas of deep scientific investigation
today. The world today is moving from one crisis over another. Technology and
engineering science has practically no answers to the burgeoning crisis of heavy
metal and arsenic groundwater and drinking water contamination. Thus the need of a
concerted effort in research pursuit in green nanotechnology, nanomaterials, and
green nanoproducts. The upshot of this treatise is vast and replete with scientific
imagination and scientific ingenuity. Nanomaterials and engineered nanomaterials
applications in science and human society will all be the forerunners towards a new
era in green nanotechnology, green chemistry, and green engineering. Thus a new
world order in nanotechnology and material science will gear forward towards a
newer scientific landscape in diverse areas of science and engineering which
includes applied sciences. Biological sciences and the world of biotechnology and
bioremediation are the needs and marvels of science and technology. Human
scientific perseverance and deep futuristic scientific thoughts will veritable open a
new door of scientific knowledge and scientific discernment.

The Aim and Objective of This Study

The aim and objective of this study is to elucidate on the scientific success and the
scientific excellence in the areas of nanotechnology applications in environmental
protection and green sustainability. Environmental or green sustainability will on the
long run be the upshot of civilization’s scientific prowess. Energy and environmental
sustainability and its application areas in human society are the requirements of
civilization’s progress. Sustainable development whether it is energy, environmental,
social, or economic are the immediate needs of the hour. The authors tread upon the
field of green or environmental sustainability. Green nanotechnology and nano-
biotechnology are the marvels of scientific research pursuit globally today. In the
similar vein, green chemistry and green engineering are moving from one visionary
phase to another. The primary aim and objective of this treatise is to elucidate upon
the success and vision in green nanotechnology and nanoproducts applications in
human society. The main advantages and disadvantages in the application of green
nanotechnology in human society are the other main pillars of this chapter. Health
effects and public health engineering issues are the major concerns of application of
nanomaterials in environmental remediation. These are the other focal points of this
chapter. A deep investigation in environmental and green sustainability also is one of
the pivots of this chapter. In engineering and technological sense, global stance in
environmental or green sustainability is not that developed. The visionary words of
Mrs. Gro Harlem Brundtland, former Prime Minister of Norway, on the “science of
sustainability” needs to be reenvisioned and revitalized with the progress of scien-
tific rigor and civilization. This treatise vastly redefines the needs of environmental
20 S. Palit and C. M. Hussain

sustainability in the march of human civilization. The other areas of deep scientific
introspection are the domains of green engineering, conventional and non-
conventional environmental engineering techniques. United Nations Sustainable
Development Goals will surely embolden the challenges, the needs of human
society, and the scientific marvels and ingenuity in the fields of sustainability,
environmental protection, nanotechnology, and chemical engineering. Today, chem-
ical engineering is aligned with diverse areas of scientific vision. A newer beginning
and a newer futuristic thought in the field of integrated water resource management,
wastewater management, and urban water quality management will veritably open
new windows of scientific innovation and scientific instinct in decades to come.
These scientific and engineering issues are deeply delved with scientific conscience
in this chapter. The major research thrust area today are the fields of sustainable
resource management, waste minimization, zero-waste concepts, and circular econ-
omy. A deep scientific introspection and a vastly scientific reinventing in the field of
circular economy and waste reduction will surely open new windows of scientific
imagination, scientific prowess, and deep scientific provenance. Zero-waste tools
and its vast fundamental concepts are the scientific imperatives and scientific
adjudication of human scientific progress. In this treatise, the authors deeply pro-
nounce and reiterate the immediate needs of circular economy and blue economy in
the true emancipation of environmental protection and its scientific integrity.

The Vast Scientific Doctrine of Nanomaterials and Engineered

Nanomaterials

The vast and varied scientific doctrine of nanomaterials and engineered nano-
materials are veritably changing the face of human civilization today. Engineered
nanomaterials and its applications in diverse areas of science and engineering are the
wonders of science, civilization, and mankind today. The application of green
nanotechnology and green nanoproducts will surely widen the scientific thoughts
and scientific ingenuity globally today. The scientific doctrine and the scientific
imagination in the field of nanomaterials, nanoproducts, and nanocrystals needs to
be advanced and reenvisioned with the progress of science, technology, and civili-
zation. Green nanotechnology and application of green chemistry and green engi-
neering in human advancements and scientific rigor will surely go a long and
visionary way in true realization of the science of environmental protection. The
scientific world and humankind are today in a state of disaster as sustainability
whether it is energy, environmental, or social are in the process of new rejuvenation.
In this entire treatise, the authors stress on the scientific success, the scientific needs,
and the profundity of engineering science in the avenues of determination and
scientific grit. Integrated water resource management and wastewater management
are in a state of disaster in many developing nations around the world. Drinking
water is scarce in many nations around the globe. Thus the need of Sustainable
Development Goals in the true realization of water remediation and environmental
protection.
2 Green Nanoproducts: A Far-Reaching Review 21

Green Nanoproducts and the Vast World of Science

and Engineering

Green nanoproducts and green nanotechnology are today visionary areas of scien-
tific research pursuit. Humankind’s immense scientific and engineering vision, and
the global challenges of water science and technology are the torchbearers towards a
new genre and a deep scientific and engineering ingenuity. Arsenic and heavy metal
groundwater poisoning are the disasters and catastrophes in many developing and
developed nations around the world. South Asia particularly Bangladesh and India
are in the throes of world’s largest environmental disasters that is arsenic ground-
water and drinking water poisoning and thus the immediate need of the science of
green nanoproducts, green nanotechnology, and green nanoproducts. Human man-
kind’s research and development areas in green nanoproducts will surely one day
unveil the scientific intricacies, and the scientific challenges and barriers in the field
of both green nanotechnology, green engineering, and environmental pollution
control. In this treatise, the authors deeply elucidate the applications of green
nanoproducts and green nanotechnology in the true realization and the true
upbraiding of the science of environmental protection and global industrial pollution
control. A newer remarkable area in the field of environmental engineering science is
slowly emerging as science, technology, and human scientific progress moves
forward. The vast world of science and engineering of environmental integrity and
security will surely ensue in the wide path towards scientific forbearance and deep
scientific articulation. In the near future, green nanotechnology will revolutionize the
vistas of learning outcomes, deep scientific intellect, and the redemption of science
and engineering.

Desalination, Membrane Science, and the Future of Global Water

Shortage

Desalination and membrane science are the veritable inventions and scientific vision
of tomorrow. Water stressed countries around the world today stands in the midst of
deep scientific difficulties, provenance, and barriers. The frontiers of the science of
desalination and membrane science are today surpassing vast and varied visionary
boundaries. Desalination and membrane science are today opposite sides of the
visionary coin. The future of global water shortage and lack of clean drinking
water are the true burdens of human civilization today. In many South Asian
countries around the world, arsenic groundwater poisoning is challenging the
human progress and the scientific determination. Mankind’s immense scientific
grit and alacrity will surely open new vistas of learning outcomes and environmental
engineering curriculum in developing and developed nations around the world.
Membrane separation processes are today linked with integrated water resource
management and integrated urban water quality management. Water resource engi-
neering, public health engineering, and environmental engineering science are today
linked with each other. Management of people, planet, and human habitat are the
22 S. Palit and C. M. Hussain

utmost needs of the hour. The United Nations Sustainable Development clearly
states the need of energy, environmental, social, and economic sustainability as
moments of scientific truth and scientific vision. Today, sustainable resource man-
agement and circular economy are the scientific truth and the scientific judgement of
global environmental engineering crisis. Human successive generations in arsenic
infected regions around the globe particularly India and Bangladesh are in an
unusual health-related burden and technologies should be readdressed and
reinvented in the global mitigation of this monstrous crisis. Thus the future of global
water shortage will surely enhance the needs of scientific understanding and scien-
tific divination in human civilization in days to come.

Application of Nanotechnology in Groundwater Remediation

and Drinking Water Treatment

Groundwater and drinking water contamination in developing and developed nations

around the world are today veritably challenging the global scientific fabric. The
scientific redeeming, deep scientific ardor, and the world of scientific challenges in
the field of groundwater remediation will eventually usher in a new age in the field of
nanotechnology and green nanotechnology. Application of nanotechnology in ground-
water remediation is a novel area of engineering science. Technologies and innova-
tions in the field of water and wastewater treatment will truly unravel the scientific
travails and scientific barriers of chemical engineering separation processes. The true
concepts of chemical process engineering such as unit operations of chemical engi-
neering, mass transfer operations, heat transfer, chemical reaction engineering, and
process integration will today unveil the vast domains of environmental protection and
water remediation integrity. Graphenes, fullerenes, and carbon nanotubes are today
intensely used in diverse areas of engineering research endeavor. Due to their remark-
able physicochemical properties, nanomaterials applications are changing the vast
scientific frontiers. Also conventional and nonconventional environmental engineer-
ing tools in water and wastewater treatment are the other areas of deep scientific
comprehension. Soon a new age of desalination and membrane separation processes
will lead to a visionary as well as an effective are of engineering and science.

Environmental and Energy Sustainability and the Vast Vision

for the Future

The global scientific stance and ingenuity in environmental and energy sustainability
are bright and groundbreaking. Today, frequent environmental disasters, loss of
ecological biodiversity, and environmental degradation are challenging and deeply
confronting the vast scientific firmament. The vast vision for the future in the field of
environmental sustainability, water purification science, and industrial wastewater
treatment needs to be reorganized as science and engineering moves forward
towards one paradigm over another. The visionary words on the science of “sustain-
ability” by Dr. Gro Harlem Brundtland, former Prime Minister of Norward, need to
2 Green Nanoproducts: A Far-Reaching Review 23

be rethought and revisited with the progress of civilization and science. United
Nations Sustainable Development Goals also need to be strictly addressed across
all developing and developed nations around the world. Lack of clean drinking
water, improper sanitation, education, human habitat, and housing are the pillars of
United Nations Sustainable Development Goals. Circular economy and sustainable
resource management are the needs of today’s human progress and human scientific
rigor. Sustainability can never be ignored if civilization is in the process of mitigation
of climate change, global warming, and scarcity of pure drinking water. In water
stressed countries around the globe, desalination techniques and membrane science
assume immense importance. The authors in this treatise deeply and profoundly
address these scientific and engineering issues.

Green Nanotechnology, Green Sustainability, and the Visionary

Future

Green nanotechnology and environmental or green sustainability will surely unfold

newer visionary areas in the vast domains of environmental protection, water and
wastewater treatment. The science of sustainability today stands in the middle of
vision, transcendence, and immense scientific determination. The visionary future in
environmental engineering, chemical process engineering, and membrane science are
the absolute needs of the hour. The world today is moving towards rapid industrial-
ization and immense economic growth. Nanotechnology with green chemistry and
green engineering are thus the utmost imperatives of science and civilization. Green
sustainability or environmental sustainability are today the visionary areas of scientific
research pursuit. Environmental sustainability and water and wastewater treatment are
two opposite sides of the visionary coin. Human civilization’s immense scientific
stance and scientific forbearance needs to be readdressed and restructured with the
march of science and engineering. Nanotechnology and nanoengineering are today
integrated with diverse areas of science and engineering such as environmental
engineering, chemical engineering, biological sciences, biotechnology, biomedical
engineering, and applied sciences. Today, humankind’s immense scientific prowess
and engineering vision in the field of environmental protection lies in the hands of the
domain of green nanotechnology and nanobiotechnology. Nanobiotechnology is a
novel area of science and engineering today. A deep introspection in the domain of
green nanotechnology, nanobiotechnology, and water resource management are the
needs of human advancements today. The authors deeply investigate these issues
along with the interfaces of environmental protection with nanotechnology.

Recent Scientific Advancements in the Field of Green

Nanoproducts

Technology and engineering science of nanoproducts and green nanotechnology are

today in the avenues of deep scientific revelation and scientific fortitude. Human race
is in the midst of immense scientific and engineering turmoil. Global environmental
24 S. Palit and C. M. Hussain

disasters are veritably in the process of human civilization’s catastrophe. Here comes
the scientific and engineering applications of green nanotechnology and green
nanoproducts. In this section, the authors deeply delve into the scientific difficulties
and scientific barriers in nanotechnology applications and the issues of public health
engineering.
Verma et al. (2019) [1] deeply discussed with cogent insight green nanotechnol-
ogy and advancements in phytoformulation research. The ultimate goal of any
scientific development is to increase human well-being and human health. A
newer dawn in the field of green nanotechnology is ushering in immense scientific
might and determination [1]. Novel strategies are highly required for the achieve-
ment of safe and therapeutic treatments beyond the conventional ones. Green
nanotechnology is a branch of technology that utilizes the fundamental concepts
of green chemistry and green engineering. Green nanotechnology is a branch of
nanotechnology which can be applied in phytoformulations, and it significantly
contributes to environmental sustainability through the production of nanomaterials
and nanoproducts [1]. The vast scientific rationale behind the use of plants in
nanoparticle formulations is that they are easily available and vastly possesses a
wide variety of metabolites, such as vitamins, antioxidants, and nucleotides. Inter-
national laws and regulations, domestic laws, government and private party pro-
grams and regulations, and the vast gamut of policies are being carefully reviewed
and readdressed to increase their utility and nurture and enhance these nanomaterials
applications in human society [1]. The authors deeply discussed in details the herbal
approach for developing nanoparticles, nanoparticles synthesized from plant
extracts, and the green synthesis of metal nanoparticles [1]. Risk aspect and risk
assessment of green nanotechnology will surely lead a long and visionary towards a
sustainable global order. Risk management and risk communication are the other
areas of scientific introspection. Today, green nanoproducts have immense scientific
potential and are moving towards commercialization. Thus a new world of scientific
regeneration is evolving in the vast scientific landscape [1].
Dhingra et al. (2010) [2] deeply discussed in minute details the sustainable
nanotechnology through green methods and life cycle thinking. Life cycle thinking
is a major area of human scientific and engineering rigor. Deeply citing the myriad
applications of nanotechnology, this paper vastly emphasizes the need to conduct
“life cycle” based assessments as early in the product development process [2]. This
is for better understanding of the potential environmental and the health conse-
quences of nanomaterials over the entire life cycle of a nano-enabled product
[2]. Incorporating life cycle thinking for making largely informed decisions at the
product design stage, combining life cycle and risk analysis, using sustainable
manufacturing practices and implementing green chemistry solutions and alterna-
tives are seen as plausible solutions. The scientific vision of sustainability nanotech-
nology solutions are the coinwords of today’s endeavor of science and engineering.
The authors deeply discussed nanomanufacturing methods and environmental con-
cerns, industrial ecology and life cycle analysis, and energy intensity of carbon
nanofibers and nanoparticles. Combination of life cycle analysis and risk assessment
are the other pillars of this research pursuit [2].
2 Green Nanoproducts: A Far-Reaching Review 25

OECD Science, Technology and Industry Policy Papers, No.5 (2013) [3] deeply
discussed with scientific insight and scientific forbearance nanotechnology for green
innovation. This paper brings together information collected through discussions
and projects undertaken by OECD working party on nanotechnology (WPN).
Sustainable and diverse scientific solutions are the needs of the hour in global
scientific landscape [3]. This report discusses (1) introduction to green nanotechnol-
ogy, (2) strategies for green innovation, and (3) the impact of green nanotechnology.
The need for development of affordable ways of addressing global challenges in
areas such as energy, environment, and health has never been so intriguing. Human
habitat and scientific ardor are today in the process of newer regeneration. Nano-
technology for green innovation or green nanotechnology aims for products and
processes that are highly safe, energy efficient, reduce wastes, and lessen greenhouse
gas emissions [3]. This report deeply elucidates the policy environment for green
nanotechnology, the potential impact of nanotechnology for green innovation, and
green innovation through nanotechnology. Nanotechnology for sustainable devel-
opment of tires and nanotechnology for efficiency of electronic and optical compo-
nents are the other cornerstones of this research pursuit. Human sufferings are
immense today due to global water shortage and global warming. In less developed
countries around the world, it is a terrible and gruesome condition [3]. Thus strat-
egies for green innovation through technology are the utmost needs of the hour.
Fostering nanotechnology research from laboratory to commercialization will go a
long and visionary way in the proper implementation of nanotechnology to human
society. This report widely discusses these scientific and engineering issues behind
green nanotechnology applications [3].
A new beginning in the field of green nanotechnology and green nanoproducts
will surely usher in futuristic vision and futuristic recommendations. Environmental
engineering curriculum and its learning outcomes globally needs to be revamped. In
this entire treatise, the authors deeply reiterate these scientific and engineering
issues.

Recent Scientific Advances in the Field of Nanomaterials

Nanocrystals and nanomaterials are the veritable coinwords of scientific emancipa-

tion globally. Scientific humanism and the world of engineering and science are
today in the crossroads of an immense environmental disaster and thus the need of
the truth and revelation of science and technology. In this section, the authors deeply
discuss with scientific and engineering insight the recent advances in the field of
nanocrystals and nanomaterials with special importance on green nanotechnology.
Werkneh et al. (2019) [4] discussed with immense scientific insight applications
of nanotechnology and biotechnology for sustainable water and wastewater treat-
ment. Water pollution and freshwater scarcity have become a serious problem and a
burning issue throughout the world. It has concerns to both public health, environ-
mental engineering, and human health [4]. To reduce these challenges, various
treatment techniques have been adopted. Civilization’s scientific and engineering
26 S. Palit and C. M. Hussain

prowess are in a state of immense disaster as civilization confronts climate change

and global warming. Among the various technologies, nanotechnology and sustain-
able biotechnology-based treatment tools are usually applied separately for water
and wastewater treatment [4]. Green sustainability stands in the middle of introspec-
tion and scientific and engineering ardor [4]. The ardor and the difficulties in
nanotechnology applications in environmental remediation are discussed with
lucid insight in this paper. Heavy metal groundwater and drinking water contam-
ination are veritable burden to science and civilization. The authors pointedly
focus on the various tools of environmental remediation and nanotechnology
applications [4]. A new direction in the field of nanomaterials and engineered
nanomaterials will surely evolve as science, technology, and mankind moves
ahead. Improved water supply and proper sanitation are the areas of high concern
in many developing and developed nations around the world. Environmental
biotechnology and nanotechnology will surely usher in a new era in human
mankind. From the industrial sectors and due to lack of improved water supply
and sanitation systems, high quantities of pollutants are discharged and thrown into
the surrounding environment every day. Increasing concentrations of toxic pollut-
ants including heavy metals, organic and inorganic pollutants, and other complex
compounds are being discharged in huge volumes in domestic and industrial
wastewaters [4]. Therefore, there is an urgent need to remove these pollutants
from wastewater before the final discharge of the treated water into the natural
environment and the surrounding ecosystem. Mankind’s immense scientific prow-
ess and ardor in the field of water purification, water and wastewater treatment thus
needs to be reenvisioned as science and engineering surges ahead [4]. Firstly, there
is an immediate need of deliberations in conventional and nonconventional envi-
ronmental engineering techniques. The conventional water treatment technologies
used for remediation of water pollutants are the activated carbon-based adsorption,
membrane filtration, ion exchange, coagulation and flocculation, reverse osmosis,
flotation and extraction, electrochemical treatment, advanced oxidation processes
and biosorption that are being used in several industrial and commercial scenarios.
Nanomaterials are very small in size, i.e., approximately 1–100 nm and shows
unique characteristics that enables them to be used in water and wastewater
applications [4]. They exhibit high surface area to volume ratio, which is very
significant to produce high surface area than the bulk counterparts. Nano-oxides
(silver, gold, iron, and titanium) are common nanomaterials which have been
employed for the remediation of pollutants in contaminated water and soil envi-
ronment scenarios. The vast and ever-growing field of environmental biotechnol-
ogy offers to solve complex environmental remediation problems. The
International Society of Environmental Biotechnology defines environmental bio-
technology as an “environment that helps to promote the development, use, and
regulation of biological systems for the remediation of contaminated land, air and
water environments that works in an efficient manner to sustain a vastly environ-
ment friendly society” [4]. Nanotechnology offers immense advantages such as
unique physicochemical characteristics such as the large specific surface area,
higher reactivity, and small size. Nanotechnology offers several advantages
2 Green Nanoproducts: A Far-Reaching Review 27

because of their unique physicochemical characteristics such as large surface area,

higher reactivity, and small size. Environmental biotechnology addresses veritably
sustainability issues such as environmental friendliness and low cost for large-
scale industrial operations [4]. Today in the scientific arena, vision and ingenuity
are the needs of civilization’s progress. Sustainability whether it is environmental
or energy are the utmost needs of civilization’s progress. In this treatise, the
technological advancements of nano and biotechnologies for the sustainable and
effective treatment of water and wastewater treatment are veritably addressed
[1]. The applications of various nanomaterials for disinfection and microbial
control, adsorption and catalytic oxidation, and sensing and environmental mon-
itoring issues have also been elucidated in details in this treatise [1]. With vast
respect to microbial technology, their advantages and disadvantages in bioreme-
diation and biotransformation of contaminants as well as toxicological aspects are
deeply explained [4].
Biswas et al. (2005) [5] deeply discussed with vision and scientific
far-sightedness nanoparticles and the environment. Nanoparticles are a class of
materials with properties distinctively different from their bulk and large scale. A
critical review of the very broad topic of environmental nanoparticles is deeply
presented in this paper [5]. Engineering vision, technological transcendence, and the
truth of science are the needs of human mankind and its progress. Nanocrystals and
nanoparticles applications are the next generation science and engineering. Because
of the vast nature of the topic, this review endeavor is focused on gas-borne
nanoparticles. Nanoparticle sources, anthropogenic emissions from industrial and
occupational settings, and conversion and formation in the atmosphere are discussed
in minute details in this paper [5]. Nanotechnology has been deeply defined as
research and development initiative at the atomic, molecular, or macromolecular
scales. Today, nanoparticles are highly considered to be the building blocks for the
science of nanotechnology and are referred to particles with at least one dimension of
less than 100 nm [2]. Nanoscale materials find extensive use in a variety of different
areas such as electronic, magnetic, and optoelectronic, biomedical, pharmaceutical,
cosmetic, energy, environmental, catalytic, and material science applications. Today,
there is a growing concern that nanoparticles could be highly detrimental to the
environment and the human health. Thus a newer area of scientific introspection in
the field of environmental health is slowly emerging. Environmental and sustainable
energy technology are the other areas of scientific research pursuit in this chapter. The
field of nanoscience and nanotechnology today has tremendous promise and vast
applicability in a variety of different sectors. Human civilization’s scientific advance-
ments in the field of nanotechnology today are in the midst of scientific forbearance
and deep scientific thoughts and ingenuity [5]. Today, detailed understanding of
process parameters, process design, and mechanistic pathways of nanoparticle
formation needs to be addressed and developed. These are the areas of future
recommendations of this study [5].
Nanomaterials and the areas of applied sciences such as physics, chemistry,
biological sciences, and biotechnology are today integrated with each other. In the
similar vein, environmental engineering science and chemical process engineering
28 S. Palit and C. M. Hussain

are also integrated with the science of nanotechnology. In this entire treatise, the
authors deeply stress on the scientific needs and the vast scientific profundity in the
application of nanomaterials in human scientific advancements.

Recent Scientific Advancements in the Field of Green

Nanotechnology

Green nanotechnology, green chemistry, and green engineering are today in the
avenues of newer regeneration. Environmental degradation and disasters are urging
scientists, engineers, and governments globally to delve deep into green technology
and green engineering research. In this section, the authors deeply elucidate the
success of engineering and science in proper implementation of green nanotechnol-
ogy in the global scenario. In today’s scientific world, one needs to be aware of the
limitations and possible threats of application of nanomaterials and nanotechnology
in environmental remediation. These areas need to be covered with lucidity and
insight as science and civilization moves forward.
Nath et al. (2013) [6] deeply discussed with scientific vision and scientific
determination green nanotechnology as a new hope for medical biology. The
development of eco-friendly technologies in material synthesis is of considerable
importance in order to expand their biological applications. The science of nano-
technology and green nanotechnology are today opposite sides of the visionary coin.
This review highlights the classification of nanoparticles giving special emphasis on
biosynthesis of metal nanoparticle by viable and important organisms [6]. This
treatise also focuses on the applications of these biosynthesized nanoparticles in a
wide area such as catalysis, targeted drug delivery, cancer treatment, antibacterial
agent, and the important domain of biosensors. Humankind today stands in the
middle of deep scientific vision and scientific redeeming. The proliferation of
science and engineering in the global scenario needs to be reenvisioned as civiliza-
tion treads forward [6]. Nanomaterials, with its characteristic dimension at the range
of 1–100 nm, are at the leading edge and promising area of science and engineering
today. In recent decades, nanomaterials, specifically metal nanoparticles, have
received immense interest in diverse areas of applied science ranging from nano-
technology to biological sciences. Although widespread interest and vision in
nanomaterials is recent, the concept was actually introduced over 40 years back
[6]. Due to extremely small size and high surface volume ratio of nanoparticles, the
physicochemical properties of nanoparticles-containing materials are quite different
from bulk materials. The authors discussed in details classification of nanoparticles,
superparamagnetic particles, liposomes, fullerenes, buckyballs, and carbon nano-
tubes [6]. The areas of dendrimer, quantum dots, and liquid crystals are the other
areas of scientific introspection in this treatise [6]. Nanomaterials and engineered
nanomaterials are today in the path of newer scientific and engineering rejuvenation
and vision. A new dawn in the field of green nanotechnology is slowly emerging
today. Metal nanoparticles and characterization methods and synthesis of metal
nanoparticles by traditional chemical and physical methods are the other
2 Green Nanoproducts: A Far-Reaching Review 29

cornerstones of this article [6]. Laser ablation, inert gas condensation, sol-gel
method, and hydrothermal and solvothermal synthesis are also discussed in minute
details. Bioinspired green material synthesis and its scientific and engineering vision
are also dealt in minute details in this paper. Applications of metal nanoparticles in
medical biology are also dealt with lucid and cogent insight in this paper [6]. In this
review, the authors provided an account of the biological methods for metal nano-
particles(green nano) synthesis, as well as its applications in biomedical devices and
environmental remediation. Metal nanoparticle biosynthesis is discussed in minute
details in this paper. Today, very less research and development forays are found in
the science of sustainability and nanotechnology. Thus, this is the immediate need of
the hour. The transformation towards sustainable development is veritably an impor-
tant economic opportunity. What is needed today is the areas of redevelopment – a
groundbreaking shift in the field of medical sciences and human advancements.
Today, an important area of human progress is the field of medical science. The
authors deeply discuss these scientific, engineering, and sustainability issues [6].
Goel et al. (2014) [7] discussed with scientific and engineering vision green
nanotechnology. Green nanotechnology is application of nanotechnology in the
vast domain of sustainable development. This domain targets and envisions sustain-
ability whether environmental or energy [7]. Green nanotechnology is the result of
the world’s vast and large fascination with tiny molecules and the scientific potential
involved in it [7]. Green nanotechnology is highly supporting the development of
sustainable solutions to address various global issues. The greatness and the scien-
tific ingenuity in the field of green technology and nanotechnology are today
ushering in a new epoch in the field of global science and engineering initiatives.
Green nanotechnology uses green chemistry, green engineering, and industrial
ecology to discover the magical world of nanomaterials and nano-products
[7]. Thus green nanotechnology and green chemistry needs to be revamped as
science, engineering, and humankind moves forward. The authors discussed in
details the goals and aspects of nanotechnology, innovations in green nanotechnol-
ogy, and concerns relating to innovations of green nanotechnology. The main goals
and the vision of green nanotechnology is to produce nanomaterials and engineered
nanomaterials that do not harm the environment and ecology and are eco-friendly
also to derive specific nanoproducts from these nanomaterials and using them in
welfare of human society [7]. Today, green nanotechnology and green nanomaterials
are in the path of newer vision and newer scientific imagination [7]. Green nano-
technology works on the principle of green chemistry and green engineering. This
area of research pursuit targets conservation of natural resources without harming the
environment and ecological biodiversity. Civilization, humankind, science, and
engineering today stands in the midst of scientific vision and vast scientific under-
standing. The authors discussed in minute details the green nanotechnology appli-
cations such as (1) nanotechnology for greener cars, (2) micro- and nanofibrillar
cellulose, (3) efficiency in electronic components, and (4) carbon nanotubes for
green innovation [7]. The authors also discussed in minute details the environmental
sustainability issues behind green nanotechnology applications in human society.
The main concern of green nanotechnology applications are the upstream processing
30 S. Palit and C. M. Hussain

of these green nanoproducts. Surely, the world of science and engineering will
witness a new beginning if research and development initiatives in nanomaterials
and engineered nanomaterials moves towards right directions of scientific
ingenuity [7].
Nanoscience and nanoengineering today stands in the middle of deep scientific
introspection and vision. This entire treatise targets the interface of green chemistry
and green engineering with nanotechnology. A new dawn in the field of green
nanotechnology will surely evolve if humankind pursues science and engineering
in the right directions.

The Vast Scientific Sagacity and Scientific Profundity in the Field

of Application of Green Nanomaterials in Environmental
Protection

Green nanomaterials and green nanocrystals are today in the wide path of scientific
divination. Technological and engineering challenges are immense in the applica-
tion of nanocrystals and green nanotechnology in human society. Application of
nanomaterials and engineered nanomaterials in environmental remediation are the
new avenues of science and engineering today. The authors in this treatise deeply
trudges into the field of nanocrystals applications, green nanomaterials applica-
tions, and green nanotechnology applications. A new day in the field of engineer-
ing science will evolve as mankind and science confronts the numerous
environmental issues, loss of natural resources, and environmental degradation.
In today’s global scientific scenario, green nanomaterials and green nanotechnol-
ogy are at the forefront of research and development initiatives. The sagacity and
profundity of science of green nanotechnology needs to be reenvisioned and
restructured with the march of science and civilization. Rapid industrial growth,
mass manufacturing, and rampant industrialization are at the forefront of a global
disaster that is loss of ecological biodiversity and environmental degradation. In
this entire treatise, the authors deeply target the need of green nanotechnology and
green engineering in the research pursuit of humankind. The status of global
environment is extremely grave and thought-provoking due to rapid degradation
of environment and global ecology. The immediate need of global research and
development initiative in the field of green nanomaterials is to target areas of
applications of nanotechnology in environmental engineering, chemical process
engineering, petroleum engineering, and applied sciences. Provision of clean
drinking water, proper sanitation, housing, shelter, and the success of the science
of environmental and energy sustainability are all the utmost needs of human
civilization today. In this treatise, the authors deeply discussed the need of nano-
crystals in the pursuit of the science of environmental protection and water
remediation. A new era in the field of environmental engineering science will
surely emerge if science and civilization move in the right direction with immense
scientific might, forbearance, and scientific grit.
2 Green Nanoproducts: A Far-Reaching Review 31

Arsenic and Heavy Metal Groundwater Remediation

and the Application of Nanotechnology

Arsenic and heavy metal groundwater remediation are veritable disasters of human
civilization today. In South Asia such as Bangladesh and India, this is an ever-
growing disaster. Application of innovative technologies such as nanomaterials and
nanotechnology are visionary areas of scientific research pursuit. The world of
challenges, the immense difficulties and barriers in scientific pursuit in groundwater
remediation will truly be the forerunners of futuristic thoughts and futuristic vision.
Groundwater remediation and the vast world of environmental engineering are today
aligned with the science and engineering of nanotechnology. In many countries of
South Asia, arsenic groundwater contamination has taken monstrous proportions.
Technology development and technology management are today the needs of global
science and engineering in every fields. In water and wastewater treatment, technol-
ogy development is the need of the hour. Nanomaterials and nanocrystals research
areas are surging ahead as mankind and science confronts with the devastating
challenges of water and wastewater contamination. The crux of this treatise is
multifaceted with a deep and sound vision towards green nanotechnology. Scientific
and technological advancements and engineering vision are the need of human
civilization today and its progress. Water and industrial wastewater treatment are
the primordial issues of science and technology today. South Asia is in the middle of
a greater devastation that is arsenic and heavy metal groundwater contamination.
This is the largest engineering and scientific disaster in the global scenario. Appli-
cation of nanotechnology and nanomaterials in water treatment and environmental
remediation are new avenues of science and engineering. A deep introspection in the
application of nanotechnology in arsenic groundwater remediation and its scientific
truth and scientific greatness will surely open new domains of research pursuit in
years to come [8–21].

Future Scientific Directions and Futuristic Recommendations

of This Study

Science, technology, and mankind are today in the path of newer scientific divina-
tion. Future scientific directions and future recommendations of this study needs to
be envisioned as regards application of green nanotechnology in human progress and
scientific advancements. The world of science and engineering today stands befallen
and transfixed as human scientific endeavor surges forward. Nanotechnology, nano-
materials, and green engineering are today’s targeted areas of scientific vision and
profundity. The world of science and technology stands immensely shocked today as
degradation of environment, loss of ecological biodiversity, and depletion of natural
resources devastates the scientific fabric globally [20], [21]. The futuristic targets of
environmental protection and nanotechnology can be summarized as:
32 S. Palit and C. M. Hussain

• A greater scientific emancipation in the field of nanoscience and nanoengineering.

• Sustainable water resources need to be reorganized and revitalized as civilization
moves forward.
• Environmental, energy, social, and economic sustainability need to be envisioned
as global environment needs to be protected.
• Sustainable development as regards environmental remediation needs to be
burgeoned with the progress of science [17–19].

In this chapter, the author deeply targets the need of nanotechnology and nano-
engineering in green chemistry and green engineering. A newer visionary era in
nanocrystals, nanoparticles, and green nanotechnology will surely evolve if a larger
vision in the field of scientific validation is replete with scientific ingenuity and
scientific truth. Governments around the world should be able to stand forward with
immense vision if futuristic targets in environmental remediation are met. The
overarching goal of this treatise is to target the futuristic needs of nanotechnology
in environmental protection and a greater emancipation of green nanotechnology.
Nanoscience and nanoengineering are the wonders of global science and engineering
and the scientific truth of present-day human civilization. Future directions in
research pursuit should be targeted towards a greater scientific and engineering
emancipation of green chemistry, green engineering, and green nanotechnology.
Today, human scientific and engineering vision in the field of green nanotechnology
and environmental nanotechnology are in a state of immense introspection and
vision. A deep scientific understanding and knowledge prowess are the utmost
needs of the hour. A new visionary epoch will surely emerge if scientists, engineers,
researchers, governments, and the human society takes a rigid step towards success-
ful implementation of green engineering, green chemistry, and green nanotechnol-
ogy. The future of environmental protection and nanotechnology lies in the hands of
these scientific and engineering issues [17–19].

Conclusion, Summary, and Vast Scientific Perspectives

Science, technology, and engineering are moving fast in this present-day human
civilization. Green nanoproducts and nanomaterials are the marvels and the need of
human civilization today. Technological and scientific prowess and validation are
needed as there are health issues in the application of nanotechnology in human
society. Nanocrystals applications in diverse areas of science and engineering are the
immediate needs of the hour as civilization and science stands in the middle of
environmental degradation. Ever-growing population, rapid industrialization, and
the new vision of science and engineering are the veritable forerunners towards a
newer visionary era in the field of environmental protection, chemical process
engineering, and the vast world of nanoscience and nanoengineering. Successive
human generations need to be envisioned as regards protection of environment.
Green nanoproducts or nanomaterials are today latent areas of engineering science
yet highly developed. The ingenuity and the profundity of heavy metal groundwater
2 Green Nanoproducts: A Far-Reaching Review 33

remediation needs to be envisioned in the crucial juncture of introspection and

vision. The vision of mankind needs to be reorganized as regards application of
green nanotechnology. In this chapter, the authors deeply target the need of both
nanoscience and green nanotechnology in the advancement of science and human
society. Green nanotechnology is the alignment of green chemistry, green engineer-
ing, and nanotechnology. Scientific truth, the vast scientific knowledge and under-
standing, and the world of challenges in the field of nanotechnology and
nanoengineering will surely open up new areas of scientific research pursuit in
environmental protection and green chemistry. The scientific perspectives in envi-
ronmental protection and application of nanomaterials will widen knowledge and
prowess in human scientific pursuit in decades to come. Mankind will one day truly
usher in a new era and a newer thought process in environmental and water and
wastewater remediation if concerted efforts from scientists, engineers, and govern-
ments move in the right direction. Climate change is another area of research pursuit
today. This area is aligned with nanotechnology and nano-remediation. Scientific
perspectives and deep scientific prowess will immensely be a boon of human
civilization if environmental protection and environmental engineering are deeply
envisioned.

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http://www.insituarsenic.org
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New Consumer Nanoproducts: Modern
Perspective 3
Deepankara V. Shastri and Kantha D. Arunachalam

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Innovations and Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Nanotechnology: Materials Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Consumer Nanoindustry from Molecular Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Applications of Nanoproducts (Nps) in the Consumer Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Silica (SiO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Silver (Ag) Nanoparticles in the Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Titanium Dioxide (TiO2) in the Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Zinc Oxide (ZnO) in the Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Textile Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Consumer Electronics Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Nanotechnology and Its Implications to Electronics Innovation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Applications of Nanoelectronics R&D stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Nanoproducts in Cosmeceutical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Moisturizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Sunscreens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Anti-Aging Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Hair Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Skin Cleaning Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Lip and Nail Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Exposure and Penetration of Nanoparticles to Skin and Body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Innovations in Nanoconsumer Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Easy-to-Clean Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Anti-Graffiti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Antimicrobial Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

D. V. Shastri · K. D. Arunachalam (*)

Centre for Environmental Nuclear Research, SRM Institute of Science and Technology, Chennai,
India
e-mail: [email protected]; [email protected]

© Springer Nature Singapore Pte Ltd. 2022 35

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_2
36 D. V. Shastri and K. D. Arunachalam

Anti-Fingerprint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Antifog . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Corrosion Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Wear and Tear Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Scratch Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Tensile Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Photocatalytic Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Antireflective Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Nanophotonics and Consumer Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Advantages and Disadvantages of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Potential Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Potential Drawbacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

Abstract
Nanotechnology is invariably becoming a modern science of the promising future
because of its key aspects in various aspects in various aspects like electronics,
medicine, and many engineering features. Due to its interdisciplinary nature
ranging from modern medicine, food, microelectronics, pharmaceuticals, and
cosmetics. During initial days, it was limited to elite engineering perspectives,
but at present it is booming into consumer product industries at a brisker pace.
Even though the production of nanoparticles remains quite a complex and costly
process, the distinct advantages are far more than its drawbacks. A considerable
majority of consumer products that use nanotechnology exploit interface effects.
By clever manipulation of one interface just by making it rougher, smoother, or
increasing the density of particles we can change many properties like surface
area, volume, etc. Another major effect used in consumer nanoproducts is a
quantum mechanical effect where we can make products unique by manipulating
optical, electronic, and magnetic properties. But what bothers is the application of
nanotechnology in fields like pharmaceuticals; cosmetics needs to be studied
further for its complications for health. Perhaps familiar consumer products like
mobile phones and modern computers have mostly used nanotechnology for
production to date, economic drive, and rise of technology, making way to fit
more and more components in small areas of electronic products, which is
possible only by nanotechnology. As device sizes shrink it’s becoming more
portable, economical, and energy efficient. In this chapter, there is various
innovation to nanotechnology and modern perspectives of effects on the con-
sumer market are explored.

Keywords
Nanoconsumer products · Interface effects · Consumer market · Innovations in
nanoproducts · Nanoelectronics · Nanophotonics consumer market ·
Cosmeceutical
3 New Consumer Nanoproducts: Modern Perspective 37

Introduction

The most punctual precise statement of nanotechnology is given in a discourse

delivered by Richard Feynman (American physicist, 1918–1988) in 1959, famously
known as “there’s plenty of room at the bottom.” In this intellectual discourse,
Feynman examined the significance of manipulating things from a more minor
and deep perspective and it could reveal to us quite a bit of incredible effects
regarding bizarre wonders that happen in complex circumstances. He portrayed
how material wonders alter their appearance relying upon the size and presented
two difficulties: formation of a nanomotor and the downsizing of letters to the
magnitude that would allow the entire encyclopedia Britannica to fit on the header
of a pin.
There’s an extraordinary interdisciplinary combination of researchers committed
to the extensive investigation of a world so little, researchers could not perceive it –
even with a microscope that we can call it as nanotechnology, the area of atoms and
nanostructures. Nanotechnology is so new, nobody is certain what will happen to
it. So as to instantly comprehend the uncommon universe of nanotechnology, we
undoubtedly have to get a thought of the units of measurements included. A
nanometer (nm) is one-billionth of a meter, more shorter compared to visible light.
As little as a nanometer may be, it’s still extensively contrasted with the nuclear
range. A particle has a distance across of about 0.1 nm. A molecule’s core is a lot
smaller – about less than 1 nm. You and everything around you is made of
molecules. Nature has idealized the study of assembling everything around us
according to molecular designs. For example, our bodies are amassed in a particular
way from many living cells. Cells can be correlated with natural nanomachines. At
the nuclear range, components are at their most essential level. On the nanoscale, we
can possibly manipulate these particles to make nearly any structures as per our
needs.
A famous talk named “little wonders: the world of nanoscience,” nobel prize
winner Dr. Horst störmer explained nanoscale is extra appealing than the nuclear
scale on the grounds that the nanoscale remains the primary thing where we can
collect things – it’s not until we begin assembling particles that we can make
anything valuable.
Specialists at times typically differ about what sufficiently establishes the nano-
scale, yet as a standard rule, you can typically consider nanotechnology managing
anything estimating somewhere in the effective range of 1 and 100 nm greater than
microscale, and less than that is the nuclear range.
Nanotechnology is swiftly turning into a multidisciplinary domain. Scholars,
scientific experts, physicists, and specialists are completely engaged with the inves-
tigation of material properties at the nanoscale. Many scientists trust that the various
controls build up a typical language and speak with each other. At exactly that key
point, Dr. Horst störmer says, “can we instruct nanoscience since you can’t compre-
hend the universe of nanotechnology without a firm base in various modern
sciences?”
38 D. V. Shastri and K. D. Arunachalam

As of now, researchers discover two nano-sized structures specifically notewor-

thy: nanowires and carbon nanotubes. Nanowires can be remarkably small in the size
of 1–100 nm, once in a while as little as 1 nanometer. Researchers would like to
utilize them to fabricate small transistors for PC chips and other electronic gadgets.
Over the most recent few years, carbon nanotubes have eclipsed nanowires. We’re
despite everything finding out regarding these structures however, what we’ve
discovered this far is intriguing.
Carbon nanotube is a chamber of carbon molecules in the nanolevel. Envision a
layer of carbon particles which would resemble a layer of hexagons. In the event that
you fold that layer into a cylinder, you’d have a carbon nanotube. Carbon nanotube
characteristics rely upon techniques of rolling the layer. As such, despite the
accomplished fact that all carbon nanotubes are typically made of carbon, they can
be altogether various from each other typically depending on how you adjust the
specific molecules.
With the precise organization of atoms, you can make a carbon nanotube that is
many times greater strength than steel, yet multiple times lightweight. Leading
specialists undoubtedly intend to make construction materials out of carbon nano-
tubes, especially for possible things like modern vehicles and planes. More light-
weight means of transport would mean better eco-friendliness, and the additional
quality means expanded traveler security.
Carbon nanotubes can likewise be potent semiconductors with the appropriate
strategy of particles. Researchers are as yet taking a shot at discovering approaches
to produce carbon nanotubes, a sensible choice for transistors in microchips, and
different hardware.

Innovations and Impacts

By far most nanotech everyday consumer items available currently take utilize of
interface impacts. The interface is a 2D surface that denotes the link between two
materials. At the point when an interface is made smoother or rougher, we can
manipulate surface area. To increase the surface to volume ratio we can downsize the
particle size. A material comprising nanoscopic building squares displays a very
huge surface region to volume proportion. This impacts for instance the reactant
movement of nanoparticles. The reverse, a nanoporous framework, can be utilized as
a layer infiltration form or as a protective material. This impact can likewise be
abused when property of a provided substance is applied to a surface. In numerous
cases, a little, practically undetectable covering of the material will at present give
the wanted physical property. Additional sorts of impacts that are starting to be fused
on nanotech items are quantum mechanical impacts, yet to a much smaller degree
than interface impacts. Quantum mechanics can bring about exceptional optical,
electrical, as well as attractive engineering properties of nanomaterials. This impact
was taken advantage of as right on time as medieval occasions when gold nano-
particles were utilized to enrich church windows with a ruddy shading. A cutting-
edge audio player or smartphone stores information instantly in memory utilizing the
3 New Consumer Nanoproducts: Modern Perspective 39

quantum mechanical tunnel impact. At long last, despite the fact that it’s anything
but a normal physical impact as on account of interface and quantum impacts,
multifaceted nature is another significant factor promoting inclusion in nanotech
consumer items. The customer profits by the accession of smaller and compact
gadgets have been most obviously outlined by the microelectronics industry. There
gives off an impression of being no end as far as anyone can tell to the consistent
advancement of processor speed and memory size by utilizing scaling down to make
progressively complex hardware. A few item developments depend either on the
utilization of nanoparticles or alleged nanotubes. Numerous different items manage
improved water repellency. Thus these three issues are quickly presented under-
neath. This is followed by a far-reaching rundown of impacts and advancements.
Many book chapters are available regarding nanomaterials [1–3].

Nanotechnology: Materials Perspective

The absolute most encouraging nanomaterials are formations where carbon mole-
cules led by basically in hexagons, comprising football similar structures familiar as
fullerenes, chambers familiar as carbon nanotubes, and sheets known as graphene. In
1990, scientists at the Max Planck Institute for Atomic Physics and at the University
of Arizona found a technique for synthesizing fullerenes in bigger amounts. This
development prompted extensive fullerene-related protecting movement by sub-
stances that presently observed financially feasible chances, including scholarly
professionals furthermore, organizations. Fullerenes have been utilized commer-
cially to upgrade items, for example, badminton rackets furthermore, cosmetic
agents; however, their majority encouraging applications are in natural hardware
and biological sciences. The development of mono-walled carbon nanotubes –
chambers with dividers produced using a solitary walled layer of carbon – was at
the same time detailed in 1993 by analysts of NEC Corporation in Japan and by
scientists at IBM in California [4]. Considering at that point, the investigation into
carbon nanotubes has withdrawn; for instance, at the US National Science Founda-
tion, nanotubes were the second most intensely subsidized nanotechnology point in
the range of 2001 and 2010. Likewise with fullerenes, a range of business items as of
now utilize carbon nanotubes, including thin films. Nonetheless, the considerable
guarantee applications – those that take favorable positions of the electrical proper-
ties of carbon nanotubes – remain apparent to be numerous from the business
stage [5].
Graphene, the most up-to-date carbon-based nanomaterial of intrigue, was at that
point depicted hypothetically in 1947, in any case, its physical segregation didn’t
happen till 2004, when Andre Geim, Konstantin Novoselov, and partners at the
University of Manchester indicated that they could utilize adhesive tape to split
separate graphene sheets from graphite sources. In 2010, Geim and Novoselov won
the Nobel Prize for their graphene work. Their rational advancement incited impres-
sive graphene-related protection, however with barely any business items up until
this point. Graphene has applications extending gadgets to biosensing, yet huge
40 D. V. Shastri and K. D. Arunachalam

obstacles to execute remains. With regard to incorporating graphene into solar cells
applications and batteries maintain a guarantee for enhanced energy change and
capacity, yet similar advancement requires enhancements in large-scale assembling
and transportation operation.
A few wonders become articulated as the magnitude of the framework size
diminishes. These comprise measurable mechanical impacts, just as quantum
mechanical impacts, for instance, the “quantum size impact” where the electronic
characteristics of solids are changed with an incredible decrease in molecule size.
This impact doesn’t become an integral factor by going from full-scale to small-scale
measurements. Nonetheless, quantum impacts can become huge when the nanome-
ter size extent is achieved, normally at separations of below 100 nm, the alleged
quantum domain. Furthermore, various physical properties change when contrasted
with perceptible frameworks. One model is the expansion in the surface area to
volume proportion adjusting mechanical, thermal, and reactant characteristics of
materials. Dissemination and responses at the nanoscale, nanostructures materials,
and nanodevices from quick particle transport are for the most part said to be
nanoionics. Mechanical characteristics of nanosystems are of enthusiasm for the
nanomechanics study. The reactant action of nanomaterials likewise starts possible
dangers in their communication with biological materials. Many books cover nano-
materials and the techniques that can play vital roles in many industrial procedures,
such as increasing sensitivity, magnifying precision, and improving production
limits and also environmental effects of nanomaterials [6–8].
Materials diminished to the nano-measure can show various characteristics
contrasted with what they display on a macroscale, empowering special uses. A
material, for example, gold, which is artificially idle at ordinary scales, can fill in as
an intense substance impetus at nanoscales. A great part of the interest with nano-
technology originates upon these quantum and surface marvels that issue displays in
the nanorange [9].

Consumer Nanoindustry from Molecular Perspective

Current engineered science has arrived at where we can manipulate smaller mole-
cules to whatsoever desired shape. These techniques are utilized currently to fabri-
cate a broad range of valuable synthetic compounds in the field of pharmaceuticals or
consumer polymers. This capacity brings up the issue of stretching out this sort of
control to the following bigger level, looking for techniques to gather these single
particles into supramolecular assembly consisting of numerous atoms organized in
an all-around characterized way.
These methodologies use the ideas of self-assembly additional supramolecular
science to consequently organize themselves into several valuable compliances
through a bottom-up approach. The idea of molecular recognition is particularly
significant: Particles can be structured with the goal that a particular setup or course
of action is supported due to noncovalent intermolecular forces. The Watson–Crick
base-pairing requirements are a straightforward consequence of this, as is the
3 New Consumer Nanoproducts: Modern Perspective 41

particularity of an enzyme being specific to a single substrate, or the precise folding

of the protein itself. In this manner, at least two segments can be intended to be
reciprocal and commonly appealing with the goal that they make an increasingly
unpredictable and helpful aggregate.
Such bottom-up approaches ought to be equipped for creating gadgets to resem-
ble and be a lot less expensive than top-down strategies, however might be over-
powered as the scale and unpredictability of the ideal assembly increments. Majority
helpful structures demand complex and thermodynamically improbable game plans
of particles. Incidentally, there are numerous instances of self-assembly dependent
on molecular recognition in science, most prominently Watson–Crick base pairing
and chemical substrate communications. The test for nanotechnology is whether
these standards can be utilized to design the latest builds notwithstanding
characteristic ones.

Applications of Nanoproducts (Nps) in the Consumer Industry

The recognition, the estimation, and the evaluation of NPs contained in shopper
items, for example, food, food bundling, beauty care products, and individual
consideration items are especially in research and development stages. Matrix,
where the NPs are scattered, addresses the exploratory plan important to quantify
the arrangement of physicochemical boundaries needed, a decision distinctive one
case at a time case. A total nanoproducts portrayal probably won’t be attainable in
all circumstances, however the consolidated utilization of various strategies.

Food Industry

The innovative work of nanotechnologies in the food area is dynamic and extraor-
dinary in all means, from food handling to the packing and transportation. Some
food items presently advanced by NPs enhance the supplement and bioactive
transportation frameworks, surface and flavor illustration, and microbiological con-
trol. In the domain of food handling and bundling, NPs are utilized either as
antimicrobial and to construct profoundly touchy biosensors for identifying patho-
gens, allergens, and contaminants that can influence food quality and security
[10]. The consequence of these uses is that numerous food items, expended now
and again from hundreds of years and containing normally happening NPs, are
currently enhanced by purposefully included or defiling NPs, and the defilement
could have its underlying foundations additionally in the farming, where nano-
formulations are utilized to support the agriculture [11].
In the food industry, the portrayal of nanoparticles ought to incorporate five
phases: as fabricated, as conveyed for use in food/feed items, as present in the
food/feed grid, as utilized in contamination testing, and as present in biological
fluids and tissues, this in light of the fact that the equivalent physicochemical
boundary may change in the various situations. The assurance of the
42 D. V. Shastri and K. D. Arunachalam

physicochemical qualities of nanoparticles is significant in all phases since, for

instance, as fabricated include the laborers’ introduction, in situ (in the food/feed
lattice) is pertinent for the poisonousness testing and in natural liquids and tissues are
significant for the “absorption, distribution, metabolism, and excretion.”
Upon the record of representative produced nanomaterial detailed in [12], the
most explored NPs in the food area are SiO2, TiO2, ZnO, and Ag since they are those
straightforwardly included or in a roundabout way consolidated in food by means of
ecological pollution or movement from food connection materials [13, 14].

Silica (SiO2)

There are different types of synthetic silica (SiO2) for food uses. Silica colloidal are
settled scatterings of nonagglomerated, for the most part round SiO2, particles
utilized in the food business as a guide for explaining wine, lager, organic product
juices, and so on. Precipitated silica is comprised of essential particles in the
extended scope of between 5 and 100 nm, collected and clustered in the last item;
it is utilized as anti-caking substance in food powders, in medicinal services items,
for example, toothpaste, cleansers, and beautifiers. Pyrogenic silica comprises of
agglomerated and totaled essential particles of the size normally from 5–100 nm; it is
utilized in beautifiers and toothpaste as an antistatic operator in creature feed and
hygroscopic powders, as a bearer for dynamic fixings, and as an antifoaming
specialist in the production of decaffeinated espresso and tea, broiler, and fish
handling working paper [15]. Powdery items like dry milk, instant soups, ketchup
preparing blends, cake blends, espresso flavors, and nutrients are without a doubt the
items where the presence of SiO2 as E551 is increasingly plausible as a result of its
anti-caking properties.

Silver (Ag) Nanoparticles in the Food Industry

Silver is an additive (E174) confirmed by the European Commission approved to be

utilized quantum satis as a silver-dyed crush or as a minuscule sheet to shading the
outside covering of ice cream parlor, for the beautification of chocolates, and in
alcohols. Due to its antibacterial activity, silver is additionally permitted in the
handling, the preservation, and the utilization of food, e.g., as an antibacterial
covering of food readiness equipment, stockpiling compartments, bundling mate-
rials, and internal surfaces of ice chests and dishwashers, just as being consolidated
into plastic food holders [16].
Nanosilver isn’t in this way thought to be a food additive, regardless of whether it
may be ingested as dietary enhancements; however, it may be found in food items as
a contaminant, as lingering of pesticide medicines in farming or relocating from
compartments, realizing that bundling materials including AgNPs have been indus-
trially accessible outside the European Union (EU) since numerous time [17]. Silver
3 New Consumer Nanoproducts: Modern Perspective 43

is typically looked as AgNPs, i.e., in its particulate structure considering it must

remain unblemished as molecule after processing using the gastrointestinal tract
[18]. In any case, silver nanoparticles are hard to be identified considering they will
in general break down in particles or potentially total/agglomerate.

Titanium Dioxide (TiO2) in the Food Industry

Food-class TiO2 is in the EU as E171 and its determination for food utilizes is in
Commission Directive, which updates the Commission Directive 95/45/EC. In
Europe, its utilization in nourishments is allowed by and large, with some pre-
determined exemptions, at quantum satis levels (i.e., as a great part of the substance
that is required for the ideal impact, yet not more), whereas in the USA, the
utilization of TiO2 as a human food–added substance should not surpass 1% by
weight.
TiO2 is utilized as an additive for color (splendid white, shading record CI 77891,
pigment white 6) in human food items in view of its brilliance, refractive index 2.4,
and as a surface changer in a wide assortment of sweet nourishments, toothpaste, and
another eatable items. TiO2 is every now and again announced as a “natural color
agent” and is thus all around acknowledged by customers. TiO2 is likewise utilized
in oral pharmaceutical details, and the Pharmaceutical Excipients Handbook [19]
considers nano-sized TiO2 a nonaggravation and nontoxic binding material.
Data about the physicochemical characteristics of nanosized TiO2 for food
applications is constrained despite the fact that the quantity of items containing it
is extensive and expanding; no data is generally provided regarding the amount,
molecule size, and molecule structure in any event, when the item is marked as
including E171.

Zinc Oxide (ZnO) in the Food Industry

ZnO is recorded as “usually accepted as harmless” (GRAS) by the US FDA

(21CFR182.8991). As a food added substance, it is the most regularly utilized
zinc supplement in the stronghold of oat-based nourishments. ZnO has been addi-
tionally joined into the linings of food jars in bundles for meat, fish, corn, and peas to
save colors and to forestall decay. The flow look function for finding successful
biocidal specialists, option in contrast to the highly expensive gold and silver, is
concentrating on metal oxides and ZnO, in its nanoparticulate structure, and is a
decent possibility for the advancement of different food bundling items as a result of
its antimicrobic and ultraviolet-permeable properties [20–22].
The physicochemical portrayal of ZnO NPs for food applications is still scant,
just scarcely any investigations have concentrated on the movement of ZnO nano-
particles to food and the toxicant effect of ZnO NPs should, in any case, be assessed
to decide the positive or negative impacts on sanitation [23].
44 D. V. Shastri and K. D. Arunachalam

Textile Industry

The major drawback of fabrics is getting simply soiled. Fabrics created of cotton are
lean to absorb fluids. This disadvantage can be defeated by expanding the water
repellency with fluorinated carbon chains making the material more hydrophobic.
A notable hydrophobic material is polytetrafluoroethylene (PTFE) or teflon. This
material has been utilized to create waterproof garments, for example, Gore-Tex,
which comprises a few covered layers encompassing a slender teflon film (Fig. 1).
Nanoparticles, for example, SiO2, increase the washing perpetual quality of the fabric
finish. Dendrimers have been accounted for to upgrade the water repellency by
expanding the fluorine content in the outermost layer of texture. A few material items
from connections to whole outfits have been associated with the “nano” term up until
now. Anyway, the innovation is for the most part dependent on the old-style fluorinated
carbon. The space of “functional materials” has developed altogether. What’s more, one
potential new usefulness is the chambering of electronic gadgets into clothes, familiar as
“wearable gadgets”; these may discover applications in athletic sports, medication, and
well-being. Silver-containing textures have been effectively researched for rewarding
neurodermatitis. Silver-containing socks have been accounted for in the forestalling foot
bad odor. The notable UV-defensive property of titanium dioxide has likewise been
added to material filaments. Addition of TiO2 particles to the polymer soften brings
about a manufactured fiber with inserted UV assurance. This item has been effectively
used to produce material with a light assurance constituent of up to 80.

Fig. 1 Schematic representation of layers corresponding to teflon/Gore-Tex. (Source-Wikimedia

Commons, the free media repository)
3 New Consumer Nanoproducts: Modern Perspective 45

Consumer Electronics Industry

The term nanoelectronics alludes to the utilization of nanotechnology in electronic

segments. These segments are frequently just a couple of nanometers in size. Be that
as it may, the smaller electronic segments become, the harder they are to produce.
Nanoelectronics covers a differing set of gadgets and materials, with the basic
trademark that they are little to such an extent that physical impacts modify the
properties of the materials on a nanoscale – between atomic collaborations and
quantum mechanical properties assume a critical job in the activities of these
gadgets. At the nanoscale, new marvels overshadow those that hold influence in
the full-scale world.
The principal transistors worked in 1947 were more than 1 centimeter in size; the
littlest working transistor today is 7 nanometers in length – over 1.4 multiple times
littler (1 cm rises to ten million nanometers). The consequence of these endeavors are
billion-transistor processors where, when industry grasps 7 nm assembling methods,
20 billion transistor-based circuits are incorporated into a solitary chip. Nanoscale
junctions are in still research stage for various applications in consumer electronic
industry[47, 48].
In modern electronics, the trendy expression “nano” has gotten focus recently
because of nano-sized transistors and nano-displays with exceptional color con-
trast. Be that as it may, there are various areas where nanotechnology could have
played a job, for example, display screens, memory, and battery. Late advance-
ments have offered to ascend to a mammoth jump in the size of memory and
processors.

Nanotechnology and Its Implications to Electronics Innovation

• By lessening the size of transistors utilized in incorporated circuits.

• Specialists are building up to memory chips with an expected thickness of 1 TB
(terabytes) of memory for every square inch and this expands the thickness of
memory chips.
• By improving showcase screens/display on hardware gadgets, this lessens power
utilization and furthermore the weight and thickness of the screens.
• By customary scaling limits in standard complementary metal oxide semicon-
ductor (CMOS) innovation. This improvement of nanoelectronic parts are called
as “Past CMOS” area of advancement.

Applications of Nanoelectronics R&D stage

• Cadmium selenide nanocrystals stored on plastic sheets are to shape adaptable

electronic circuits. The point of researchers is for low-force prerequisites, basic
manufacture procedure, and mix of adaptability.
• Incorporating silicon nanophotonics parts into complementary metal-oxide-semi-
conductor (CMOS) coordinated circuits. This optical strategy is planned to give
46 D. V. Shastri and K. D. Arunachalam

faster information communication between incorporated circuits than is conceiv-

able with signs.
• Building up a lead-free bind solid sufficient for space missions and other high-
pressure situations utilizing copper nanoparticles.
• Working with incorporated circuits utilizing carbon nanotubes has been created
by researchers at Stanford University. They had likewise evolved techniques to
expel metallic nanotubes, a calculation to manage skewed nanotubes.
• A laser that utilizes a nano-designed silicon surface helps generate the light with a
lot more tight recurrence control created by researchers at Caltech.
• Nanowires that would empower level board showcases to be adaptably produced
using anodes.
• Transistors worked in single-atom-thick graphene film to empower exceptionally
rapid transistors.
• Analysts have built up an intriguing strategy for framing PN intersections, a key
segment of transistors, in graphene.
• Combination gold nanoparticles with natural atoms to make a transistor familiar
as a NOMFET (nanoparticle organic memory field-effect transistor).
• Causing coordinated circuits with highlights that can be estimated in
nanometers (nm).
• Utilizing carbon nanotubes to guide electrons to enlighten pixels, bringing about
a lightweight, millimeter-thick “nano-emissive” show board.
• Utilizing nanosized attractive rings to make magnetoresistive random access
memory (MRAM).
• Scientists have created less power, higher thickness techniques utilizing nano-
scale magnets called magnetoelectric irregular access memory (MeRAM), and
furthermore created atomic-estimated transistors which increment transistor
thickness in coordinated circuits.
• Utilizing self-adjusting nanostructures to fabricate nanoscale coordinated circuits.

Nanoproducts in Cosmeceutical

The word “cosmeceutical” is used to define a product that fits the niche between a
drug and cosmetics. Cosmeceuticals are the quickest developing section of the
consumer industry, and various skin cosmeceutical medicines for conditions, for
example, photoaging, melanin-related Suntan, wrinkles, and hair harm have come
into far-reaching use. In the cosmeceutical field, nanotechnology has assumed a
significant job. Utilizing new strategies to control subjects at a nanolevel, they have
been at the base of various advancements, start up new viewpoints for the eventual
fate of the cosmeceutical sector. Nanotechnology-supported cosmeceuticals provide
the upside of assorted variety in items, and expanded bioavailability of dynamic
fixings and increment the tasteful intrigue of cosmeceutical items with delayed
impacts. Anyway, expanded utilization of nanotechnology in cosmeceuticals has
elevated worry regarding the conceivable infiltration of nanoparticles through the
skin and expected dangers to people’s well-being. Among the innovations utilized to
3 New Consumer Nanoproducts: Modern Perspective 47

create exquisite and powerful cosmeceuticals, nanotechnology discovers uncommon

spots. In the restorative field, it is accepted that the smaller particles are promptly
assimilated into the skin and fix harm effectively and all the more productively [24].
Integration of nanotechnology and cosmeceuticals is planned for making infuriate
scents last more, sunscreens to protect the skin, antiaging creams to retaliate the years,
and lotions to keep up the hydration of the skin. A portion of the nanotechnology-
supported developments are nanoemulsions, nanocapsules, nanopigments, liposome
plans, nanocrystals, strong lipid nanoparticles, carbon nanotubes, fullerenes, and
dendrimers. The essential favorable circumstances of utilizing nanoparticles in
cosmeceuticals remember progress for the dependability of corrective fixings by
epitomizing inside the nanoparticles; proficient security of the skin from destructive
bright (UV) beams; tastefully satisfying items focusing of dynamic fixing to the ideal
site; and controlled arrival of dynamic elements for delayed impact [25, 26].

Moisturizers

Stratum corneum is the essential barrier between the body and the external environ-
ment. Water from the layer corneum gets dissipated rapidly prompting parchedness.
This lack of hydration of skin can be deflected by utilizing lotions that give
adaptability to the skin. At the point when lotions are applied to the skin, a thin
film of humectant is shaped which holds dampness and provides a superior look to
the skin. Liposomes, nanoemulsions, and solid lipid nanoparticles are broadly
utilized saturating plans on account of their drawn-out impacts. These are viewed
as the most helpful item for the administration of different skin conditions.

Sunscreens

Sunscreens are applied to protect the skin from harmful sunlight. Zinc oxide (ZnO)
and titanium dioxide (TiO2) are the best affirmed mineral-based fixing that shields
the skin from sun harm. This mineral structures a materialistic boundary on the skin
that reflects UVA and UVB beams from infiltrating bottom to the more deeper layers
of skin and is less bothering [27]. The principal disadvantage of sunscreens is it
leaves white powdery substance on the skin [28]. This is the place nanoparticles take
into play. Enhanced sunscreens are only one of the numerous imaginative employ-
ments of nanotechnology. Sunscreen items utilizing nanoparticles of ZnO or TiO2
are straightforward, less oily, and less rank and have expanded stylish intrigue.

Anti-Aging Products

Chemical items, contamination, stress, harmful sun rays, and scraped areas are
engaged with skin maturing. Collagen assumes a significant job in skin restoration
and wrinkles inversion impact. The amount of collagen in the skin diminishes
48 D. V. Shastri and K. D. Arunachalam

alongside age. The maturing of the skin shows itself from multiple points of view:
drying out, loss of versatility and surface, diminishing, harmed obstruction work, the
appearance of spots, alteration of surface line isotropy, and, at long last, wrinkles.
The greater part of the cosmeceuticals have been created with cases of anti-wrinkle
and firming, saturating and lifting, and skin conditioning and brightening action.
Anti-aging items are the fundamental cosmeceuticals in marketing as of now being
made utilizing nanotechnology. L’Oreal has utilized nanotechnology in items, for
example, Revitalift anti-wrinkle cream which contains nanosomes of Pro-Retinol
An, and claims that it immediately retains the skin and decreases the presence of
wrinkles. The use of retinol can increment epidermic water content, epidermal
hyperplasia, and cell restoration while improving the collagen union [29]. Retinol
additionally meddles with melanogenesis and represses lattice metalloproteinases,
which are engaged with collagen breakdown. The medical advantages remember a
decrease in the presence of barely recognizable differences and wrinkles and helping
of lentigines [30]. Lancôme acquaints Hydra Zen Cream with recharge the skin’s
solid look which comprises nano-encapsulated tri-ceramide [31].

Hair Care

Hair care is one more encouraging domain for nanotechnology. Industries are
utilizing nanotechnology in hair care items and exploration is continuous to find
the methods of how nanoparticles can be utilized to forestall going bald and preserve
glow, and well-being of hairs. Not at all like normal hair fixing items, nanoemulsion
in hair makeup doesn’t obliterate the external structure of the hair filaments, called
fingernail skin, to infiltrate into the hair strands. Sericin made out of cationic sericin
nanoparticles is a functioning territory of hair cosmeceuticals. Research has demon-
strated that sericin nanoparticles in hair cosmeceuticals effectively cling to the
outside of the hair seal and handle the harmed fingernail skin [32].

Skin Cleaning Application

The skin is secured with a hydrolipid layer that, contingent upon the territory of the
bodies, contains emissions from sebaceous organs and from apocrine and eccrine
perspiration organs. Decay items from corneocytes and cornification during the time
spent being spilled are additionally present. This film gives a characteristic safeguard
counter pathogenic life forms yet in addition draws in soil and toxins from the earth.
In some cases, the microbes there on the skin exterior follow up on segments of the
surface film and make unwanted side effects, for example, those subsequent from the
digestion of mixes found in apocrine perspiration that make stench [33]. Therefore,
occasional purifying to evacuate the useless, dirt, and smell is basic to keep up skin
well-being. Purifying is additionally important to evacuate the dirt (which may
incorporate microscopic organisms) from the skin exterior that is procured by
accidental touch or by deliberate application (prescriptions or cosmetics and other
3 New Consumer Nanoproducts: Modern Perspective 49

restorative items). Silver nanoparticles are utilized as skin disinfectants and sterili-
zation. Nano Cyclic Inc. makes nanocyclic a chemical pink cleanser which is a
deductively adjusted mix of nanosilver and characteristic fixings and cases that it
executes destructive microscopic organisms and parasites, battle skin breaks out, and
decreases age spots and sun-harmed skin [34].

Lip and Nail Care

Lip care is one more hopeful category of cosmeceuticals. Distinctive nanoparticles

can be fused into lipstick and lip sparkle which will relax or relieve the lips by
forestalling transepidermal water loss. Korea Research Institute of Bioscience and
Biotechnology possess a patent that depicted that it is conceivable to get ready
shades showing the wide scope of colors utilizing gold or silver nanoparticles by
blending in different make-up proportions and whose shading can be kept up for an
extensive stretch of time [35]. Nanoparticles of silica are utilized in lipsticks to
enhance the homogenous circulation of shades. When applied, they keep the shades
from relocating or seeping into the scarcely discernible difference of lips [36].
Nanotechnology-supported nail cosmeceuticals have different preferences over
traditional items. An examination uncovered that nail polishes having nanosized
particles increase strength, deface obstruction, and effective opposition of the human
nails. Nano Labs Corp. (a nanotechnology innovative work organization) was
granted a temporary patent for its unique nano-nail clean and polish having favorable
circumstances that it dries to a hard state, opposes stun, splitting, scratching, and
chipping and its flexibility offers prevalent simplicity of utilization without breaking.
One of the new procedures which may have the extraordinary possibility in the
cosmeceuticals is the consolidation of nanoparticles having antifungal action in nail
clean to treat parasitic toenail diseases.

Exposure and Penetration of Nanoparticles to Skin and Body

Utilization of nanoparticles has made new changes; however, it additionally presents a

few dangers and vulnerabilities. Expanding the creation and utilization of nanomaterials
brings about an expanding number of laborers and buyers presented to nanomaterials.
This shows there is a more noteworthy requirement for data on their risk paths. Human
beings’ paths of vulnerability to nanoparticles are breath ingestion, and dermal courses
[37]. Breath intake is the most widely recognized route of presentation to airborne
nanoparticles [38]. Laborers may breathe in nanoparticles while manufacturing or end
customers may breathe in on the utilization of aerosolized cosmeceuticals. The statement
of nanoparticles in the respiratory framework relies upon their associations with respi-
ratory epithelium film. Nanoparticles may move by means of the nasal nerves to the
cerebrum and access the sensory system [39]. In light of their size, these nanoparticles
can without much of a stretch access the circulation system inhalation or skin and from
that point, they are shipped to the different organs. Ingestion may happen from
50 D. V. Shastri and K. D. Arunachalam

unexpected hand to mouth movement of nanoparticles or from those cosmeceuticals that

are application close to the mouth or lips. Huge divisions of nanoparticles quickly drop
off the body after ingestion, yet a little part might be captured up by the body which
moves into the various organs [40]. Another path of introduction of nanoparticles into
the circulation is dermal ingestion. Dominant parts of cosmeceuticals are applied to the
skin. Three pathways of entrance over the skin have been recognized: intercellular,
transfollicular, and transcellular [41].
Development of the cosmeceutical sector is expanding step by step as the
cosmeceuticals advertise is exceptionally differentiated, with items originating
from major and little makers and neighborhood organizations around the globe.
Nanotechnology speaks to the key advances of the twenty-first century, offering
fantastic open doors for both exploration and enterprise. The fast spread and
marketing of nanotechnology in cosmeceuticals have offered an ascend to extraor-
dinary specialized and financial yearnings, yet additionally question about the rising
dangers to well-being and security of customers. Subsequently, cosmeceutical items
dependent on nanotechnology ought to be structured and sold in a manner that
completely regards the strength of customers and nature [42].

Innovations in Nanoconsumer Industry

Easy-to-Clean Products

The issue of exterior floor or any product surface contamination is huge, particularly
while taking into account more energy surfaces, for example, glass or metal, which
have a solid inclination to absorb different particles. Regular techniques depend on
the decrease in surface free energy without losing the material characteristics, for
example, transparent materials. By and large the water and oil repellency is
expanded when the contact edge of the water is above 100
. This wonder is used
in nonstick surfaces, for example, fricasseeing skillet (Teflon). New methodologies
depend on natural/inorganic nanocomposites which give characteristics like
perfluorinated polymers such as teflon.

Anti-Graffiti

The significant disadvantage of regular plaster, blocks, or cement is its solid

sponginess which gives an amazing substrate to extensive spray painting. A
normal way to deal with this depends on a polyurethane (PUR) covering that
gives perpetual insurance and prevents the paint from penetrating into the divider.
This can comprise a two-segment framework, which responds after applying
straightforwardly on the divider. Any spray painting on the ensured exterior
can be expelled without any problem. In any case, there is little in this covering
that is true “nano,” in spite of the fact that this term is now and again referenced in
this field.
3 New Consumer Nanoproducts: Modern Perspective 51

Antimicrobial Coating

Battling microorganisms is regularly accomplished by specific chemical agents. Two

inorganic methodologies can be utilized for cleaning surfaces. The first is in light of the
photocatalytic action of titanium dioxide as depicted underneath. The second endeavors
the toxicity of specific metallic cations, for example, silver. Silver has since quite a while
ago been familiar with its amazing antimicrobial impact because of the arrival of silver
particles which are taken up by organisms and apply a harmful impact. Present day
draws near increment its movement by scattering silver in ultrafine particles. The
outrageous increment in surface region upgrades silvers’ normal disinfecting capacity.

Anti-Fingerprint

Metallic surfaces, for example, hardened steel obtain effortlessly recolored when
contacted with exposed hands. The optical reflectivity of the material modifies
because of the exchange of oil from the skin despite the fact that the deposit of
finger grease cannot be avoided completely, an anti-fingerprint coating diminishes
the sight by cloaking their traces (refractive index) of the protecting covering
matches that of the oil. In this manner, enemies of fingerprints covered metal
surfaces show up darker contrasted with their unprotected partners.

Antifog

Bringing a cold surface into a hotter encompassing will prompt fogging. This impact is
unavoidable except if the surface is warmed. It results from the arrangement of small
beads on the reflection surface dispersing the light and nebulizing reflections. A super
hydrophilic covering can forestall drop formation partly. The droplets just converge into a
slim water layer on the mirror without modifying the reflectivity to an extreme. Photo-
catalytic TiO2 coverings are super-hydrophilic when presented to adequate UV light.

Corrosion Protection

Metallic portions in car fabricate are usually heat treatment to accomplish the wanted
form. Throughout this warming procedure the steel will erode. It very well may be
ensured against high-temperature consumption by applying a nanoparticulate covering.

Wear and Tear Protection

A decrease of abrasion on surfaces in mechanical contacts can be accomplished

likewise by diminishing grating or by hardening surfaces through coverings. The
grating coefficient can be diminished by diamond-like carbon coatings (DLC). These
52 D. V. Shastri and K. D. Arunachalam

amorphous coverings provide a hardness of around 20 GPa. One more methodology

is in view of surfaces which decrease erosion productively.

Scratch Resistance

Tough nanoparticles, for example, SiO2, can be utilized to develop scratch-safe

coverings. For instance, they can be joined in a natural framework to enhance the
scratch opposition of polishes.

Tensile Strength

Addition of nanoscale parts into composites will improve their tensile and impact
strength quality. Carbon nanotubes provide the most elevated elasticity ever
watched. Regarding this, carbon nanotubes are relied upon to be of incredible
significance in the future.

Insulation

The standard of insulating material depends on large porosity which encases as much
air as could be expected under the circumstances. The material uses the low thermal
conductivity of air, also, free wind current is repressed. In this manner, the density of
material is a significant measure. The lower the density the more air is encased and
the improved the protection will be. The protecting capacity of a provided material,
for example, glass wool, can be expanded by thickening the protecting layer. In such
a manner, nanoporous materials provide prevalent properties. Silica aerogels have
the most minimal thermal conductivity and density, everything being equal. They are
some of the time called frozen smoke. Their warm conductivity can be as low as
0.016 W/(m·K)4, with a thickness of 0.005–0.2 g/cm3. They are made by a sol-gel
process. In any case, silica aerogel is extremely fragile and costly to deliver. In this
manner, adaptable and less expensive choices have been created, which offer
predominant protection and can be a lot more slender than customary protecting
material.

Photocatalytic Surfaces

Very hydrophobic areas are tainted to a far lower degree than surfaces with a higher
interfacial pressure. Furthermore, freely reinforced dirt particles are evacuated effec-
tively by wetting. Other than this technique to build the characteristic stain repel-
lency of a surface by decreasing its free energy, we can straightforwardly assault
adsorbents by deteriorating them through photocatalysis. Consequently even a
profoundly sticky surface, for example, glass, could be outfitted with a self-cleaning
finish which is enacted with ultraviolet light.
3 New Consumer Nanoproducts: Modern Perspective 53

In any case, this methodology is just appropriate for exterior applications.

A typical material for photocatalytic coatings is titanium dioxide (TiO2). TiO2 is a
light scatter and a UV safeguard. The main property makes it an ideal element for
white paint (white color), the last gives the self-cleaning and UV-secure capacity.
TiO2 is a compound semiconductor which exists in three distinctive substance
structures: anatase, rutile, and brookite type, and just the initial two are broadly
utilized for various applications.
The photocatalytic action can be improved by bringing down the recombination
rate of electrons and holes in anatase TiO2 particles. This can be accomplished by
doping the particles with silver. The presence of silver gives an extra antibacterial
quality as recently portrayed.

Antireflective Coating

In numerous applications, a solid reflection from a flat surface is bothersome, for

example, for spectacles or displays. The reflectivity of a surface can be diminished
by two various ideas: the first presents a nanoscale and nano-roughness, which
diminishes uniform reflection through light dissipating. This idea is once in a
while alluded to as a nano-moth-eye structure in light of the fact that a similar rule
is found in insects which helps in camouflage. It can likewise be utilized to build the
affectability of solar-based cells because of the upgraded transmission. In any case,
the magnitude of a productive moth-eye structure must be in the range of
150–200 nm. The least demanding approach to acquire such a structure is decorat-
ing, which is constrained to nearly little regions.
The subsequent idea depends on the covering of alternating layers of silicon
dioxide and titanium dioxide. These two materials give a solid difference in refrac-
tive index bringing about an altogether higher transmission and diminished reflec-
tion. Despite the fact that being increasingly costly, the subsequent idea offers
superior control. Be that as it may, the thickness of the layers is in the scope of a
few hundred nanometers and in this way not really a topic of nanotechnology.

Nanophotonics and Consumer Industry

Nanophotonics is classified under nanophysics and is the unification of nanotech-

nology with photonics. On a very basic level, it is a blend of photonics and
optoelectronics at nanoscale measurements. Nanophotonics innovation is
empowering a wide scope of photonics items going from high-productivity solar
cells to ultrasecure communication followed by health care. Despite the fact that
numerous nanophotonics items are as yet under examination, numerous items, for
example, nanophotonics PV cells, nanophotonics LEDs, and nanophotonics OLEDs
are impressively driving the market development. The interest for cutting-edge
gadgets, for example, longer battery life, compacted size, more noteworthy infor-
mation transmission speed, and high usefulness can be accomplished by executing
nanophotonics innovation.
54 D. V. Shastri and K. D. Arunachalam

In the gadgets business, scaling down of segments and their integration has been
drifting for longer than 10 years. With the appearance and radical universality of cell
phones, the drive to accomplish more prominent productivity from the smallest
gadgets has additionally picked up boost and given energy to the nanophotonic
gadget to advertise the world over. As indicated by the United Nations Industrial
Development Organization (UNIDO), worldwide creation has been developing
fundamentally throughout the previous, not many years, in this way prompting an
expansion in the worldwide portion of manufacturing value added (MVA) in GDP
(gross domestic product) from 15.1% to 16.5% during 2009–2018. The MVA
development rate which shows the advancement of manufacturing enterprises pow-
ers development of the nanophotonic gear showcase. Nanophotonic gadgets are
generally utilized in ventures, for example, telecommunication, health care, semi-
conductors, aviation and defense, consumer electronics, and also in the automobile
industry.
Because of the higher switching speeds of the photonic incorporated circuits,
nanophotonic products include a more appeal inside signal processing applications.
Nanophotonics gets new possibilities in the instrumentation for nanoscale, data and
communication management, chemical and biomedical sensor application, advanced
solar cell and lighting, environmental remediation, and medical treatment. The
widespread development of cybercrime exercises across numerous divisions is the
key factor in increasing the development of the nanophotonic equipment industry.
Nanophotonic chips are picking up noticeable quality in fiber optics links of huge
server farms to forestall digital attacks. The information helped through optical fibers
is encoded, empowering a solid forward leap in cybersecurity. The nanophotonic
equipment showcase esteem is foreseen to reach $1.5 billion by 2023, developing a
compound annual growth rate (CAGR) of 21.23% over the figure time of 2018–2023
[43]. Optical filters are finding more applications in UV resistance, antireflection and
protection against scratches and abrasion etc. Many recent researchs are promising in
innovation and take consumer market in the next decade[44–46].

Advantages and Disadvantages of Nanotechnology

Since any technology comes with both pros and cons, nanotechnology also has few,
but when compared to the impact it is giving in the consumer industry or many
sectors, drawbacks are negligible.

Potential Advantages

• Nanotechnology is now producing new materials accessible that could transform

numerous zones of production. For instance, nanotubes and nanoparticles, which
are cylinders and particles just a couple of atoms over, and aerogels, materials
made out of light and solid materials with insulating properties, could make ready
for new methods and predominant items. Also, robots that are just a couple of
3 New Consumer Nanoproducts: Modern Perspective 55

nanometers long, called nanobots, and nanofactories could help build original
materials and items.
• Nanotechnology may change the manners by which we get and use energy.
Specifically, solar power may become cheaper. Energy-storing gadgets will turn
out to be increasingly productive thus. Nanotechnology will likewise start new
techniques for creating and storing energy.
• The area of gadgets is set to be reformed by nanotechnology. Quantum dots, for
instance, are minuscule light-producing cells that could be utilized for brightness
or for cause, for example, display screens. Silicon chips would earlier be able to
include a large number of parts, however, the innovation is arriving at its limit; at
one point, circuits become so little that if a molecule is out of place circuit won’t
work properly. Nanotechnology will permit circuits to be developed precisely on
an atomic level.
• Nanotechnology can possibly get significant progress in medication. Nanobots
could be sent into a patient’s arteries to gather up blocks. Medical procedures
could turn out to be a lot quicker and progressively exact. Wounds could be fixed
cell by cell. It may be possible to even repair genetic disorders. Nanotechnology
could likewise be utilized to improve drug production, fitting medications at a
molecular level to produce them progressively compelling and diminish adverse
effects.

Potential Drawbacks

• Since these particles are little, issues can really emerge from the inhaling of these
nanoparticles, much like the issues an individual gets from breathing in minute
asbestos particles.
• By and by, nanotechnology is pricey, and creating it can cost you a ton of cash. It
is likewise entirely hard to make, which is presumably why items made with
nanotechnology are increasingly costly.
• Because of very compact-sized recording devices and cameras, the possibility of
misuse of them raises privacy and security concerns.
• Due to very small particle sizes, there’s a possibility of lotions and skincare
products can get into the bloodstream; it may be a toxin.
• All things considered, nanotechnology, as different advances before it, will cause
significant changes in numerous economic zones. In spite of the fact that items
made conceivable by nanotechnology will at first be a costly extravagance when
accessibility expands, an ever-increasing number of business sectors will feel the
effect. A few innovations and materials may get out of date, prompting organi-
zations to spend significant time in those regions leaving the enterprise. Modifi-
cations in production forms realized by nanotechnology may bring about
occupation misfortunes like reduction of employment.
• Nanotechnology increases the chance of little recording gadgets, which would be
practically imperceptible. All the more genuinely, it is conceivable that nanotech-
nology could be weaponized. Atomic weapons would be simpler to make and
56 D. V. Shastri and K. D. Arunachalam

further arms may likewise be created. One chance is the purported “intelligent
bullet,” an automated projectile that could be monitored and pointed precisely.
These improvements may demonstrate an aid for the defense; yet in the event that
they fell into inappropriate hands, the outcomes would be critical.

Conclusions

The consumer products effectively accessible have just started to misuse the capa-
bility of nanotechnology. As has appeared in this chapter, most customer items right
now accessible depend on interface impacts. In any case, the significant possibility
that can be normal from the enormous research interest in nanoscience has not yet
reached the buyer. For instance, customer items that misuse quantum impacts or the
one of a kind electronic properties of carbon nanotubes have just started to scratch
the surface. Moreover, there are different impacts that show guarantee. The genuine
guarantee of nanotechnology may show up when items start to make utilization of
more than one of these impacts. For example, the fuse of carbon nanotubes into
sports items utilizes their mechanical quality and high surface region to volume
proportion, yet future items could likewise use their electronic properties and little
size, for instance interfacing various levels in coordinated circuits or for working up
novel nanotube transistors. Such an approach may prompt progressive items that can
extraordinarily improve the personal satisfaction of the normal purchaser.

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Consumer Nanoproducts: A New Viewpoint
4
Sherly Antony, Prasanth Rathinam, R. Reshmy, Raveendran Sindhu,
Parameswaran Binod, and Ashok Pandey

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Definition of Consumer Nanoproduct . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
History and Characteristics of Consumer Nanoproduct . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Effects on Health and Environment Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Database or Inventories on Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Consumer Products Inventory (CPI) of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
The Nanodatabase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Marketing of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Regulations and ISO Technical Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
GHS and Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
International Organizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
The Various Expert Committees in USA and European Continent Include . . . . . . . . . . . . . . . . . 72

S. Antony
Department of Microbiology, Pushpagiri Institute of Medical Sciences and In-charge of Microbial
Technology and Infectious Diseases Laboratory, Pushpagiri Research Centre, Thiruvalla, Kerala,
India
P. Rathinam
Department of Biochemistry, Pushpagiri Institute of Medical Sciences and In-charge of
Biochemistry Laboratory and Medical Biotechnology Laboratory, Pushpagiri Research Centre,
Thriuvalla, Kerala, India
R. Reshmy
Post Graduate and Research Department of Chemistry, Bishop Moore College, Mavelikara, Kerala,
India
R. Sindhu (*) · P. Binod
Microbial Processes and Technology Division, CSIR-National Institute for Interdisciplinary,
Science and Technology (CSIR-NIIST), Thiruvananthapuram, Kerala, India
A. Pandey
Centre for Innovation and Translational Research, CSIR- Indian Institute for Toxicology Research
(CSIR-IITR), Lucknow, India

© Springer Nature Singapore Pte Ltd. 2022 59

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_106
60 S. Antony et al.

Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

Abstract
The last two decades has witnessed several consumer nanoproducts based on
nanotechnology and nanomaterials being increasingly developed and marketed at a
fast rate. With more and more products being added each year, one needs to
understand the complexities behind the development of these products, their scope
of use, and their marketing strategies. Regulations are now put in place for the
manufacture, transportation, routine use, and disposal of these nanoproducts as they
have been noted to have a tremendous impact both on environment and human
health. Hence, newer and greener nanotechnology is the need of the hour! History of
development of these products, their ever-evolving use in daily life, and the various
inventory databases are lined out in detail in this chapter.

Keywords
Consumer nanoproduct · Nanotechnology · Nanomaterials · Nanostructured
materials · Nanoproduct database · Inventory nanoproducts

Introduction

Nanoscaling and its various scientific applications have brought forth the advent of a
new era of nanotechnology and nanoscience. This revolutionary technology comes with
a futuristic vision of societal change, economic growth, and a sustainable environment.
The myriad of possibilities for its applications as consumer products being with
nanomaterials (NMs) has been incorporated in varying order of quantity and miscellany
(Table 1). There is evident large-scale commercialization and delivery of nanoproducts
thus translating bench side research into marketed consumer products. A big multibillion
dollar industry now exists with NMs in various aspects of biomedical engineering and
healthcare, automotive manufacturing, appliance manufacturing, cosmetics, food and
beverages, energy applications, information technology, and construction. Yet, regula-
tory issues do exist with regards to toxicity, disposal, and accumulation in environment
and possible health hazards in humans and animals [11, 48].

Consumer Nanoproducts

Definition of Consumer Nanoproduct

A plethora of products available in the market contain or are derivatives of nano-

materials. Many products have used the term nano to indicate the small size without
actually having any nanomaterials [25]. Therefore, a “consumer nanoproduct” or
4 Consumer Nanoproducts: A New Viewpoint 61

Table 1 Important terminologies and their definitions used in this book [7, 19, 28, 42]
Term Definition
One nanometer One millionth of a millimeter (1 nm {metric} ¼ 109 m{SI}) “nano”
derived from the Greek word meaning dwarf
Nanoscale/Nano- Approximately diameter in the range of 1–100 nm (ISO/TS 12805:2011) or
size EC Definition (2011/696/EU)
Nanoscience The study of phenomena and manipulation of materials at atomic,
molecular, and macromolecular scales, where properties differ
significantly from those at a larger scale
Nanotechnology The design, characterization, production, and application of structures,
devices, and systems by controlling shape and size at nanometer scale [42].
Richard Feynman, a physicist in 1959 who is considered as the father of
nanotechnology, introduced this concept. But, the term was first used in
1974, by a researcher at the University of Tokyo named Norio Taniguchi
Nanomaterial EC Definition (2011/696/EU) states that NM is a natural, incidental or
manufactured material containing particles, in an unbound state or as an
aggregate or as an agglomerate and where, for 50% or more of the
particles in the number size distribution, one or more external dimensions
is in the size range 1 nm – 100 nm [18]
Nano-object Material that possesses one or more peripheral nanoscale dimensions
Nanoparticle Nano-object with three external nanoscale dimensions
Nanofiber A nanomaterial with two analogous exterior nanoscale dimensions and a
third larger dimension
Nanocomposite A multiphase structure with no less than one phase on the nanoscale
dimension
Nanostructure Composed of interconnected constituent parts in the nanoscale region
Nanostructured Materials containing internal or surface nanostructure
materials

“nanotech product” is defined as mixtures and articles containing or derived nano-

materials available in market for use by consumers [11]. This represents any product
with (or claiming to contain) manufactured nanomaterials, even small quantities
nanomaterials [10].
The product has to go through different stages of R and D, manufacturing, and
regulations before it reaches the consumer (Fig. 1). The purpose of the products is
used to define the different product categories, e.g., health and fitness products, food
and beverages, cross-cutting, automotive, and goods for children. When the product
category is subdivided, it is known as the product type, e.g., health and fitness group
includes subcategories like sporting goods, personal care, cosmetics, filtration,
clothing, and sunscreen [10]. There is definitely a gray zone in the knowledge in
various databases which all products are actually available in the market and the
source and exact quantity of nanomaterial in them [21]

Nanomaterials (NMs)
There are many loopholes for labeling nanoproducts as a well-harmonized definition
for nanomaterials still does not exist. Details are depicted in Table 1. There may be
62 S. Antony et al.

Fig. 1 Development of an ideal consumer nanoproduct through different stages of research and
development and marketing regulations

appreciable differences in many of its properties when compared to the macromo-

lecular counterpart [25, 31, 45].

Nanostructured Materials (NSM)

For definition, refer to Table 1.

History and Characteristics of Consumer Nanoproduct

The evolution of nanotechnology and nanoscience has resulted in development of

various products. The two major phases of discovery and development in nanotech-
nology were [41]:

(i) Nano-I (first foundational phase): This science centric phase occurred in the first
decade of nanotechnological advancements, i.e., 2001 to 2010, where the focus was
on research mainly inter-disciplinary research at the nanoscale. It resulted in iden-
tification and elaboration at nanoscale of new phenomena, characteristics, proper-
ties, and functions; creation of a library of modules which would be the corner stone
for future services; and gradual improvement of already existing products.
(ii) Nano-II (second foundational phase): This R and D phase driven by socioeconomic
considerations occurred during 2011 to 2020 where the focus was on more complex
nanosystems where the base is an amalgamation of science and engineering. This
has helped in a smooth transition toward measuring directly in a good time
resolution, designing of new products, and bulk use of nanotechnology.
4 Consumer Nanoproducts: A New Viewpoint 63

Composition and Classification of Nanomaterials

The major four material-based categories [31] include the following:

(i) Carbon-based: From the name itself, NMs, those containing carbon atoms,
e.g., fullerenes (C60& C70), carbon nanotubes (CNTs), carbon nanofibers
(CNFs), vapor-grown carbon fibers (VGCFs)/vapor-grown carbon nanofibers
(VGCNFs), carbon black, graphene (Gr), and carbon onions. They can be
produced by laser ablation, arc discharge method, chemical vapor deposition
(CVD), and by catalytic chemical vapor deposition (CCVD).
(ii) Inorganic-based: They comprise metal and metal oxides, e.g., gold or silver,
titanium dioxide (TiO2) and zinc oxide (ZnO), and silicon dioxide (SiO2). They
can be synthesized by precipitation of salts in aqueous medium, hydrothermal
synthesis, micro-emulsions, polyol process, etc.
(iii) Organic-based: NMs made from organic matter by help of weak interactions.
(iv) Composite-based: They are multiphase, i.e., they are made by combining NPs
with other NPs or with larger bulk-type materials.

Sources of Nanomaterials
The lines of demarcation between the three sources are often blurred resulting in
overlapping of the origins. The three sources of NPs are:

(i) Incidental nanomaterials: They are by-products of industrial processes and

rarely natural events thus produced incidentally.
(ii) Engineered nanomaterials (ENMs): They are synthetic, e.g., carbon NPs, TiO
NPs, and hydroxyapatites. They are seen in NPs in varied biomedical and
healthcare products, part of diesel, engine exhaust, cigarette smoke, building
demolition, etc.
(iii) Naturally produced nanomaterials: They are found occurring naturally in the
environment. Nanobacteria like Pseudomonas stutzeri were found to produce
metal NPs by binding to heavy metals and acts by precipitating [26]. Nanobes
are novel nano-organisms, discovered on sandstones in Western Australia
[47]. Magnetotactic bacteria produce magnetic oxide NPs which continue to
be harnessed in biomedical application [2].

Five Nanomaterial Properties

The size, agglomeration, impurity, contaminant dissociation, recycling, and disposal
are the five properties of NPs based on which there is a risk description. This is
associated with risk of corrosion, instability, degradation properties, and accumula-
tion in flora and fauna including human beings [10, 11, 27, 35].

Range of Products and Applications

First NMs to be incorporated were nanoclays into polymer resins, i.e., nylon 6-clay
hybrids in Toyota car manufacturing in 1989 which improved its overall sturdiness,
durability, and stability [39]. Following this, many metallic nano-oxides like TiO2, ZnO,
64 S. Antony et al.

SiO2 were also used widely in products with cleaning properties, in UV light protection,
or in other products with special viscoelastic behavior. The ENPs that were first
commercialized in medical field were in pharmaceuticals, for example, addition of
metallic oxide (ZnO and TiO2) in sun block creams. Following this nanoparticulate
silver was incorporated into chronic wound-care dressings owing to its antimicrobial
properties. Lately CNTs and graphene owing to their properties and unique structures
are being incorporated into various consumer products. Hence now the clearly identi-
fiable five major categories of nanoproduct composition are there. They are:

(i) Those products which have not expressed or not advertised the content
(ii) Metal and their oxides
(iii) Carbonaceous NMs
(iv) Silicon-based NMs
(v) Others like polymers, organics, ceramics, etc.

The different nanomaterials in consumer products where the majority of nano-

products have a nanomaterial composition is suspended in liquids like water, oil,
lubricants, creams, followed by solid products like mixtures of CNTs plus plastic and
surface bound like textiles, a laptop keyboard coated with AgNPs others include
bulk, nanostructured bulk (nanoscale computer processor), nanostructured surface
(nanofilm-coated products) [10, 11, 48].
The timeline for the development of various consumer nanoproducts and pro-
cesses began in the early twenty-first century. Presently there are four generations of
development of consumer nanoproducts [41].

(i) First-generation nanoproducts: During the 2000s, various passive nano-

structures were incorporated into products. The nanoscale element like NPs
or nanoclay platelet or NTs were integrated into a matrix material fit for
coatings, films, and composites or they were used as a part of a bulk NSM.
(ii) Second-generation nanoproducts, i.e., active nanostructures were used exten-
sively during 2005 to 2010. The nanoscale element is the functional structure
nanospheres and NSMs for drug delivery which would respond to external
stimuli such as pH or temperature giving a controlled release. In addition,
nanowires with amplifying mechanistic action were used as sensors and actu-
ators, transistors, and other electronics.
(iii) Third-generation nanoproducts were having mainly 3D nanosystems (2010
onwards). They were being used in bio-assembly systems (e.g., template DNA
and viruses), electrical and chemical template-guided assembly.
(iv) Fourth-generation nanoproducts (2015 until 2020): represented by an assorted
molecular nanosystems with targeted molecular level functions.

Effects on Health and Environment Safety

With the promise of benefits, nanoproducts have stormed the markets and have
found their way to our daily life. Various nanotech or nanoproducts having NMs
4 Consumer Nanoproducts: A New Viewpoint 65

or ENMs in them are integrated or laced on to our day to day usage. The critical
gaps in knowledge and the lack of uniformity in its regulations both in industry
and research globally have spelt out an impending problem. The possibility of it
being a double-edged sword need to be kept in mind, and serious consideration of
its deleterious effects on our health as well as environment need to be undertaken
before its release into the global or local markets. The process of the large-scale
manufacturing of nanoproducts, its proposed use, the exposure levels in humans,
problems faced in its discarding, and handling either in the original or modified
forms ultimately translates to no restriction for its movement, through the envi-
ronment and this foist blatant and latent health risks both in humans and in the
environment (Fig. 2) The major challenge in this is that the NMs need to be
detected and quantified to evaluate their state, the translocation phenomena, and
bio-persistence.
In humans, foreign substances or organisms normally have to face certain bar-
riers. The largest barrier is the skin unless and until a breach is there in the
epithelium, while some organs like the lung and GIT are easily susceptible. The
origin of NPs and the various routes by which they access humans includes inhala-
tion, ingestion, and direct skin contact. NPs which are inhaled or ingested can readily
spread through the circulation and reach the other sites or organs in the human body
[8, 14, 15, 48], while for the environment, exposure is related to material aging,
waste production, and disposal [35]. The probable chance of exposure to the NMs in
nanoproducts depends mainly on the site of exposure (Table 2).

Toxicology Data of Nanomaterials

A screening-based strategy is needed in real time within a bigger testing background
for environmental health and safety (EHS). This is to serve as the first impediment
that a nanoproduct and ENM-enabled product must pass before they are being
exposed to more laborious testing. Many suggestions have elaborated on a five-tier
screening process where the first tier is a routine screen based on material amount,
technology categories, size, properties, and use. This is followed by a tier 2 where
categorically a 100% release is assumed and the actual release evaluated. In tier 3,
define the free particle persistence and dissolved fractions’ fate, while in tier 4,
toxicity testing is both acute and chronic. Finally with tier 5, material-specific and
site-specific investigations are undertaken. All this provides the essential informa-
tion on taking a decision on a nanoproduct [12, 36]. In fact, a risk communication
system targeted directly at the consumers to make out the nanoproducts multiple
values and combine them into the decision-making process especially in marketing
phase [34].
The toxicity of nanoproducts is multifaceted and based on various aspects of
the NPs incorporated in them [29]. It depends on dose and exposure time effect,
i.e., molar concentration of NPs in the contiguous medium multiplied by the
contact time, while a pre-exposure effect does exist too, whereby a short contact
time or the exposure of low NP concentrations beforehand will stimulate the
cellular phagocytic activity. Another factor is the NP’s capability of aggregation
and concentration effect, where increasing the concentration results in promotion
of aggregation. Another effect is the particle size, where there is size-dependent
66 S. Antony et al.

toxicity, i.e., NPs with smaller diameter penetrate more and disrupt the cellular
systems than NPs of larger diameters. The next factor affecting toxicity is the
particle shape effect where there is a shape-dependent toxicity at different aspect
ratios. The rising hazardous effects of NPs are inversely proportional to the
particles size and directly proportional to surface area. There is also a surface
functionalization effect with definite impact on translocation and subsequent
oxidation processes at the cellular and subcellular level. In addition there exists
a crystal structure effect with minor difference in the crystal’s structure; there are
characteristic changes in the cellular uptake, oxidative mechanisms, and subcel-
lular localization [16, 23, 37].

Environmental and Human Health Hazard Profile Judging Tools

Nano-safety is a cause for concern for mainly three groups, the researcher, industrial
workers, and finally the end users the consumers. There are a host of tools to
evaluate ENM’s potential risks and help in making informed decisions. There are
many tools being developed for the same. Few of the important tools are elaborated
below.

Fig. 2 Impact of consumer-based nanoproducts linked to ultimate fate of NMs in ecological system
4 Consumer Nanoproducts: A New Viewpoint 67

Table 2 Possible cumulative risk assessment at the various sources or route of entry of Nano-
products in humans [9–11, 33]
Nanoproducts Details if any Exposure levels
I. Inhalation route:a
1. Spraying/spray products:
Spray guns Generate small aerosol particle sizes Very high exposure levels
Propellant Disinfectant sprays with nano-Ag, Significant exposure levels
sprays impregnation sprays with nano-silica and
sunscreen sprays with nano-TiO2 and
nano-ZnO generate small aerosol particle
Pump sprays Nano- Ag Low exposure level
Larger droplets/aerosols are generated
Less volatile solvents are used
2. Powders Cement with nano-TiO2 Need to measure actual
products Face powder with nano-silica exposure levels associated
Plaster/gypsum, powder paints with with specific products
nano-TiO2
3. Nanomaterials Sports equipment, electronics, and for As long as the nanomaterial
in solid surface treatment of equipment and stays embedded in the solid
matrices and buildings matrix no exposure
on surfaces But if in production, repair,
and disposal of such
products, there is possible
release of NMs high
exposure
II. Oral route: a
1. Food additives CaCO3 used as food additive (E170) ➔ High oral exposure
contains a nano-fraction
TiO2 (E171) and silica (E551) in children
specially
2. Sunscreens Intake of Nano-TiO2 and nano-ZnO High oral exposure if
incorporated sunscreen lipstick and exposed, more studies
possibly from hand-to-mouth behavior
of children
3. Medicines Lipid, polymer, and protein-based High oral exposure can lead
particles to systemic toxicity [40]
Drug delivery systems/nanocarriers of
drugs
III. Dermal:
Small wound Nano-Ag➔risks may be acceptable Systemic toxicity such as
dressings at considering the risk associated with non- argyria and elevated liver
home treatment enzyme levels
Hospital
treatment of
burns
IV. Eye: Current information does not appear that
eye exposure to NMs would lead to any
significant risks. Further information on
eye toxicity might be warranted
a
Following exposure, NPs gains accesses to other organs like the liver, brain, heart, and spleen
68 S. Antony et al.

NanoRiskCat
NanoRiskCat was the first screening tool for categorization of risk profiles to
human health and ecology. This was developed by Hansen et al. which aims to
provide a guideline for first-tier assessment companies and regulators regarding
the hazard and exposure potential of consumer products containing various
ENPs. They used five colored dots where the first three dots indicates the
exposure level for the specialized final users, major clients, and of course for
the surrounding milieus, while the latter dual dots specifically addresses the
nanoproducts humans and the environment hazard potential (Fig. 3). A frame-
work is used to determine various information of relevance to NPs, while the
assessments with regard to hazards pertaining to health and ecology was centered
on a tree with nodes dealing with the various aspects of the regulatory classifi-
cations, raw toxicity information, and other endpoints.

Life Cycle Assessment and Risk Assessment of Nanoproducts (LICARA)

nanoSCAN
This Internet-based tool was developed by European Framework 7 project to assess
the advantages and disadvantages plus threats of ENM-enabled products throughout
its stages of development, i.e., from cradle to grave.

The Nano Guidance for Risk Informed Deployment (NanoGRID)

This is an Excel app which is based on a tiered methodology to determine the
varying impacts of ENM-enabled products on environment, health, and safety. It
details if any additional tests need be done for sorting out aforementioned
concerns [24].

Fig. 3 NanoRisk categorization of a nanoproduct

4 Consumer Nanoproducts: A New Viewpoint 69

Database or Inventories on Consumer Nanoproducts

There is no clarity on what NanoTech products are really available on the market,
i.e., details regarding the nanotech product and the number and types available and
altered over time. In addition, there is hardly much data available on how much,
when, and what exactly the consumers are exposed to. This overall lack of statistics
hinders both the quality and computation aspects of consumer exposure assessment
of nanoproducts.
With the purpose of addressing these shortcomings, different databases or inven-
tories are available globally. Though the major ones include Consumer Products
Inventory (CPI) and Nanodatabase, there are many other databases available. The
product categories are uniform in CPI and Nanodatabases ranging from food and
beverages, home and garden, electronics and computers, machines, health and
fitness, cross-cutting, automotive, and goods for children. Nonetheless, there is
clear lack of uniformity in all the nanodatabases regarding the data displayed,
exposure–risk parameters evaluated and private and public information access! [6,
22, 48].

Consumer Products Inventory (CPI) of Nanotechnology

It was established in the USA in 2005 as off shoot of the Project on Emerging
Nanotechnologies (PEN) and was supported by its charitable trusts and Woodrow
Wilson International Center for Scholars. It details 1600 plus products currently
involving NPs mainly. Its frequency of updating is annually and was the first of its
kind, with focus only on the North American market [6, 43].

The Nanodatabase

The Nanodatabase was established in Europe in 2012 by DTU Environment, the

Danish Ecological Council, and Danish Consumer Council. It is an inventory
comprising of nanomaterials (NMs)-based nanoproducts. It is updated daily with
detailed information of the product, with roughly 4200 plus products with its
exposure as well as the hazard information using NanoRiskCat. It allows the user
to sort and extract data as it is equipped with different analytical tools. When the
products were analyzed, majority fell into the category which were having
unsupported claims [22, 48].

Others

Another inventory providing public information includes the Nano-

produktdatenbank, but the major disadvantage is it being in German language,
with a focus on German markets. Another inventory is The European Consumer
70 S. Antony et al.

Organisation (BEUC) which contains only nanosilver particle-based items. Few

other registries are available on a country basis like the Danish, Belgian, and France
nanoregistries in the respective countries, all of which are updated annually but
limited data available publically [22].

Marketing of Nanoproducts

Daily, new nanoproducts are being introduced in the market by following a good
nanotechnology commercialization model. The global capacity of the nanoproduct
market is estimated to a whopping $400 billion [1]. The present status and predicted
growth of the nano-industry is detailed in Table 3.
There is major investment in sales of nanoproducts, in medical, manufacturing,
and energy industries. Generally, the nanoproduct sales are anticipated to grow over
the upcoming years. The leading spots among nanocatalysts, hydrocarbon-
processing nanoproducts, are increasingly being utilized in nanoproducts pharma-
ceutical preparations and medical equipment. The market size, market potential, and
the general economic picture must be kept looked into before marketing a nano-
product. There are many barriers existing to a successful commercialization of
nanotechnology, the inability to produce a practical prototype, perform safety
testing, large-scale manufacturing, lack of funds, adverse public perception of
nanoproducts, etc. [27].

Regulations and ISO Technical Specifications

Just like two sides of a coin, though there is lot of benefits of incorporating NMs
into products, risks exist too! Just a few years back, there was a scare in Germany,
with hundred people becoming ill after using a nano-designed aerosol. This
resulted into local authorities performing a nano-recall the first of its kind. How-
ever, later, it was found that fault lied elsewhere and not with the nano component
[49]. Hence governments and international agencies need to cooperate and bring

Table 3 The present market scope for nanotechnology, nanofiber products, and in textiles
Present market Projected market Compound
value in dollars value in dollars for annual growth
Heads (year data taken) the (year) rate (CAGR) Reference
Nanotechnology $2.0 billion (2018) $2.1 billion (2023) 19.4% [4]
Nanofiber $927 million (2018) $4.3 billion (2023) 36.2% [5]
products
Nanotextiles $5.1 billion (2019) $14.8 billion 23.6% [3]
(2024)
4 Consumer Nanoproducts: A New Viewpoint 71

forth legislation, laws, and rules to be followed and enforced globally. Certain
governments and organizations have implemented this to reduce and avoid risks
associated with these products. There is no consensus internationally for the
defining the research of NPs, production, handling, labeling, toxicity testing, and
evaluation of the impact.

GHS and Labeling

The United Nations Economic Commission for Europe [44] proposed The Globally
Harmonized System of Classification and Labelling of Chemicals (GHS) which
states the chemicals cataloguing by hazard types and suggests the inclusion of labels
and data sheets pertaining to safety. [44]
Two kinds of labeling exist: mandatory and voluntary labeling. In the EU, plain
product labeling of products containing nanomaterials aims to create awareness in
consumers whether they want to buy such product or not. Few other countries do
encourage voluntary labeling [25, 32].

International Organizations

(i) Basel Convention (BC): Has taken steps to advance research to generate data
for enhanced understanding of the likely threats of discarded NMs, nano-waste,
plus best practices relating to its safe disposal.
(ii) World Health Organization (WHO) and International Labour Organization
(ILO): Main focus is to protect employees from possible hazards of mass-
produced NMs.
(iii) Food and Agriculture Organisation (FAO): Food safety assessment in food and
additives containing NMs (United Nations).
(iv) ECOSOC’s Sub-Committee of Experts: Review the GHS labeling to nano-
materials [44]
(v) Strategic Approach to International Chemicals Management (SAICM): A
global action plan was crafted by recognized thirteen activities in relation to
NP-related products and identified them as an emerging policy issue (EPI).
(vi) International Organization for Standardization (ISO): ISO/TS80004-1:2015
(en) and ISO/TS 80004-2:2015 both replaced the previous 2010 standard and
now elaborate two parted document details out the various terms used in
nanotechnology generally and nano-objects, respectively.

But one can note that though this is a global issue recognized by many international
bodies and governments, a uniform legal enforcement is lacking.
Risk assessment of NMs is one of the important regulatory aspects in marketing of
nanoproducts [13, 30–32].
72 S. Antony et al.

The Various Expert Committees in USA and European Continent

Include

• EPA facilitates innovation and ensures safety of the substances effective from
2017 entails a must reportage of the associated exposure levels and safety
information on the nanoscale substances as part of chemicals under Toxic Sub-
stances Control Act (TSCA) section 8[a] [45].
• US Food & Drug administration (FDA) created the Nanotechnology Task Force
to monitor and advice regarding the regulatory steps needed for NM-based
products [20]. Similarly, this role in Europe, are played by The European Food
Safety Authority (EFSA) and The European Medicines Agency (EMA) [20]
• The Organisation for Economic Co-operation and Development (OECD) Envi-
ronment Directorate from 2006 have a Working Party on Manufactured Nano-
materials (WPMN) which inspects the safety of manufactured nanomaterials [38].
• The United States Occupational Safety and Health Administration [46] and The
European Agency for Safety and Health at Work (EU-OSHA) both detail out the
rights of the workers which need be complied to by the employers [17, 46].
• Others include the Scientific Committee on Emerging and Newly Identified
Health Risks (SCENIHR) and The Scientific Committee on Consumer Safety
(SCCS)

Conclusion

It is well documented and proven that this wonder technology has immense poten-
tial. Nonetheless, it is vital that we harness the full benefit of it by not only
developing nanoproducts in general but also taking full responsibility by
establishing uniform guidelines and regulations globally in their production, manu-
facture, processing, waste disposal, and other parts of its life cycle. Thus, every
aspect is given its due importance and not make it a rat race for mindless develop-
ments. The target is the attainment of the betterment of mankind as a whole,
increasing shelf life of otherwise short-lived consumables and services, improving
drug delivery, and much more!

Important Websites

1. The nanodatabase. https://www.nanodb.dk/

2. National Nanotechnology Initiative (NNI) https://www.nano.gov/
3. Nanonature. https://nano.nature.com/
4. Nanotechnology Products Database (NPD). https://product.statnano.com/

Acknowledgment Reshmy P and Raveendran Sindhu acknowledge the Department of Science

and Technology for sanctioning projects under DST WOS-B Scheme.
4 Consumer Nanoproducts: A New Viewpoint 73

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embor.7400799
 Part II
Design and Engineering Technology for
Consumer Nanoproducts
Effect of Mechanical Alloying in Polymer/
Ceramic Composites 5
M. V. Khumalo and M. C. Khoathane

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Polymer Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Natural Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Classification of Ceramic Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
High-Energy Ball Milling (HEBM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Techniques and Methods of HEBM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
HEBM in Polymer-Ceramics Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
HEBM in Thermoplastic Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
HEBM in Thermoset Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
HEBM in Polymer Metal Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

Abstract
The chapter presents ceramics-polymers composites using mechanical alloying
(MA). Ceramics are classified as inorganic and nonmetallic materials that are
essential to our daily lifestyle. Many ceramics, both oxides and non-oxides, are
currently produced from polymer precursors. Ceramics generally have an amor-
phous or a nanocrystalline structure and consist of excellent structural such as
stability, oxidation resistance, creep resistance, high-temperature mechanical, and
good dielectric properties. Nevertheless, they have a fundamental weakness in
that they are easily fractured and require high-temperature processes for the
fabrication of integrated substrates. Composites are now one of the most

M. V. Khumalo (*) · M. C. Khoathane

Department of Chemical, Metallurgical and Materials Engineering, Polymer Technology Division,
Tshwane University of Technology, Pretoria, South Africa
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 79

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_4
80 M. V. Khumalo and M. C. Khoathane

important classes of engineered materials, because they offer several outstanding

properties as compared to conventional materials. Composites are fast-develop-
ing segment in the polymer industry; composites filled with materials having at
least one dimension in the micro- and nanometer-size range such as nanofillers,
nanoclays, or nanotubes and ceramics represent a step change in technology in the
composite area. MA is a solid-state powder processing technique involving
repeated welding, fracturing, and re-welding of powder particles in a high-energy
ball mill. This technique was originally developed to produce oxide dispersion
strengthened (ODS) nickel and iron-base super alloys for aerospace applications.
MA has been substantiated to be capable of synthesizing a variety of equilibrium
and nonequilibrium phases, including nanocrystalline and amorphous materials.
Recently MA has been demonstrated to be a most versatile and economical
process for synthesis of nanocrystalline materials, due to its simplicity, low
cost, and ability to produce large amount of material. The chapter focuses on
the preparation processes; general microstructures; mechanical, chemical, elec-
trical, and optical properties; and potential applications.

Keywords
Ceramics · Alumina · Polymers composites · Polymer nanocomposites ·
Mechanical alloying · Composites · Nanocomposites · Clays · High-energy ball
milling

Introduction

High-performance plastics and composites, which developed in the twentieth cen-

tury, have penetrated to the international economy and people’s lives in different
fields with an exceptional rate of development in the history. They have become the
substitutes for traditional materials, showing improved performance. Now, with the
speedy development of science and technology, materials play an important role in
the international economy. New materials are still the beginning of new technolo-
gies, and materials science, energy technology, and information science have
become the three pillars of modern science and technology [1]. Two main kinds of
polymers are thermoplastics and thermosets. According to global worldwide
researchers, production of thermoplastics is approximately 200 billion pounds per
year, or approximately 25 pounds for every person on the planet. Only a small
fraction of this amount is filled and used as a composite, but a small fraction of this
large number is still a significant amount of material [2]. By far the most important
thermoplastic composites are made from flexible thermoplastics, i.e., semicrystalline
materials with a glass transition temperature below room temperature. Thermoplas-
tics’ applications are in flexible and rigid packaging, motor industry, engineering
sector and agriculture, etc. Thermosets are simply melt resins that chemically react
from low viscosity liquids to form solid materials during a processing called curing.
Thermosets are commonly used for high-temperature applications; some of the
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 81

common products are electrical equipments, motor brush holders, printed circuit
boards, circuit breakers, etc. Commercial plastic resins may contain two or more
polymers in addition to various additives and fillers. These are added to improve
some properties such as the processability; thermal, chemical, or environmental
stability; and mechanical properties of the final products [3]. The term composite
materials was firstly used in abroad in the 1950s, and it has been used domestically
from about the 1970s. Composite material is a kind of complex multicomponent
multiphase system, and it is difficult to be defined accurately. A composites materials
is made by combining two or more materials into unique one with superior proper-
ties that cannot be met by conventional monolithic materials, such as metal and its
alloys, ceramics, and polymers [4, 5]. The purpose of composites allows the new
materials to have strengths from both materials, frequent times covering the original
materials’ weaknesses. Composites are different from alloys because they are com-
bined in such a way that it is difficult to tell one particle, element, or substance from
the other. They usually classified by the type of reinforcements they use. The
reinforcements are embedded into a matrix that holds it together and used to
strengthen the composites [6]. Composite materials have several advantages over
traditional engineering materials, which made them more attractive in many indus-
trial applications. Composite materials have superior mechanical properties and
commonly classified at following distinct two levels: The first level of classification
is usually made with respect to the matrix constituent. The major composite classes
include organic matrix composites (OMCs), metal matrix composites (MMCs), and
ceramic matrix composites (CMCs). The term organic matrix composite is generally
assumed to include two classes of composites, namely, polymer matrix composites
(PMCs) and carbon matrix composites commonly referred to as carbon-carbon
composites. The most important inorganic nonmetallic matrix composite materials
are ceramic matrix composites (CMCs) and carbon-based composite materials such
as C/C composite materials (Fig. 1).
These four types of matrices produce common types of composites. Majority of
the composites used commercially are polymer-based matrices. In a composite,

Matrices

Polymer Matrix Metal Ceramic Carbon and

Composites Matrix Composites Matrix Composites Graphic matrix
(PMC) (MMC) (PMC) composites (CGMC)

Thermosets Thermoplastics

Fig. 1 Classification of matrix materials [7]

82 M. V. Khumalo and M. C. Khoathane

matrix is an important phase, which is defined as a continuous one. The important

function of a matrix hold the reinforcement phase in its embedded place, which acts
as stress transfer point between the reinforcement and matrix and protects the
reinforcement from adverse conditions [7].

Polymer Matrix Composites

Polymer matrix composites (PMCs), because of their inherent characteristics, have

become the fastest-growing and most widely used composite materials. Compared
with traditional materials such as metals, PMCs have the following characteristics:

• High specific strength and modulus

• Excellent fatigue and fracture resistance
• Good damping characteristics
• Multifunctional performance
• Good processing technics
• Anisotropic and properties designability
• High fracture toughness
• Good puncture resistance
• Good corrosion and abrasion resistance
• Low cost
• Lower thermal expansion properties

PMCs consist of thermoset or thermoplastic matrix resins reinforced by ceramic,

metal, fibers, carbon, and graphic that are much stronger and stiffer than the matrix.
They are attractive because of lightweight, stronger, and stiffer than the unreinforced
polymers or conventional metals. PMCs have additional advantages of their prop-
erties and forms could be tailored to meet the needs of a specific application. High-
performance reinforcement materials are of the highest interest in various industries
like military and aerospace [8]. Basically all commercially important polymers have
applications where the polymer is filled, although definitely some materials are more
commonly filled than others. Typically, the reason that a specific polymer is a good
or bad candidate for use as the continuous phase of a composite is its ability to form
strong interactions with particular filler. Polymers are ideal materials as they could be
processed easily, as they are lightweight, and have desirable mechanical properties.
Both thermosetting and thermoplastic resins could be used as the polymer phase; the
former had the advantage of low viscosity while the latter had the advantage of the
possibility of recycling and reuse [9]. The use of polymer composites in various
engineering applications had become state of the art. The multiauthor volume pro-
vides a useful summary of updated knowledge on polymer composites in general,
practically integrating experimental studies, theoretical analyses, and computational
modelling at different scales, i.e., from nano- to macroscale. Comprehensive con-
sideration was given to four major areas: structure and properties of polymer
nanocomposites, characterization and modelling, processing and application of
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 83

macrocomposites, and mechanical performance of macrocomposites. It influences

the mechanical properties, shear modulus, and shear strength and its processing
characteristics. Reinforcement phase is the principal load-carrying member in a
composite. Therefore, the orientation of the reinforcement phase decides the prop-
erties of the composite [10].

Ceramics

Overview

Ceramics has been the focus of increased interest during the last century since it
exhibits better hardness, stiffness, and chemical stability compared to many other
materials. The word ceramics originated from “Keramos” meaning burnt stuff and is
derived from the Greek word keramikos. Ceramics cover a vast area of inorganic,
nonmetallic materials including white wares, structural clay products, refractories,
glass and glass-ceramics, cement, concrete, lime, foundry sand, oxide ceramics, and
non-oxide ceramics such as boride, carbide, and nitride. Developments in the
twentieth century that stimulated progress in ceramics include advances in science
and technology in general, the rise of new industries, advances in military technol-
ogy, and also the overwhelming concern for health, safety, and environment [11–
13]. Ceramics are generally categorized as conventional or traditional ceramics,
which contain clay and clay-based materials, and high-tech or advance ceramics
which are from synthetic raw materials and having specific structural and functional
properties. The highest attraction of structural ceramics has constantly been the
capability of operating at temperatures far above those of metals. Structural appli-
cations include engine components, cutting tools, and chemical process equipment.
Electronic applications for ceramics with low coefficient of thermal expansion and
high thermal conductivity include superconductors, substrates magnets, and
capacitors [14] (Table 1).
Many compounds in ceramics contained both ionic and covalent bonding. The
general properties of those materials depend on the dominant bonding mechanism.
Compounds that were either mostly ionic or mostly covalent had higher melting
points than compounds in which neither kind of bonding predominates. In polymers,
the bonding within the chains are covalent bonds (strong and directional), while the
hydrogen bonding and Van der Waals’ forces between the chains are relatively weak,
which resulted in lower melting points, higher thermal expansion coefficients, lower

Table 1 Ceramics variety Compound Melting point 0C Covalent %% Ionic %%

of chemical bonding [14]
MgO 2798 27 73
Al2O3 2050 37 63
SiO2 1715 49 51
Si3N4 1900 70 30
SiC 2830 89 11
84 M. V. Khumalo and M. C. Khoathane

stiffness, etc. In ceramics, different types of bonding mechanism could occur: ionic,
e.g., in oxides and silicates (Al2O3, MgO, SiO2, etc.); covalent, e.g., in nonmetallic
carbides and nitrides (SiC, B4C, BN, Si3N4, AlN, Si2N2O, SiO2, etc.); and metallic,
e.g., in transition-metal carbides and nitrides, etc., and they often coexist in the same
physicochemical phases.

Natural Raw Materials

It has been understood that clay mineral is an excellent raw material for various high-
temperature ceramic requirements. The ceramic properties of clays are largely
governed by the crystal structure and the crystal composition of their essential
constituents and the nature and amount of accessory minerals present. Since silicates
and alumina silicates are easily available, they are also inexpensive and thus provide
the backbone of high tonnage products in ceramic industry [15]. The principal clay
mineral groups are kaolinite, smectite, and palygorskite. Clay minerals can be
divided into chain and layer structures. The layer structures are branched into 1:1
and 2: 1 (dimorphic and trimorphic). Classification of clay minerals is indicated
below (Fig. 2).

Layer Structure

Two layer type Three layer type Regular mixed layer

(2:1) Chain structure type
(1:1) type

(Sheet structure (Sheet structure (Ordered stacking of (Hornblende like

composed of one composed of two silica alternate layers of chains) e.g. Attapulgite,
silica layer and one layers and one alumina different types e.g. sepiolite palygorskite
alumina layer) layer) Chlorite group)

Equi dimensional Elongate

Equi dimensional Elongate (montmorillonite (montmorillonite
(Kaoline group) (Halloysite group) group) group)

e.g. Kaolinite, e.g. Montmorillonite e.g.

e.g. Halloysite
Dickite Nacrite etc vermiculite, Montmorillonite,
sauconite Nontronite saponite,
hectorite

Fig. 2 The category of layer structure steps for natural raw materials
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 85

Classification of Ceramic Matrix Composites

CMP are a family of new materials which are attracting considerable industrial
interest and investment worldwide. They are defined as materials whose microstruc-
tures compromise a continuous metallic phase (the matrix) into which a second
phase, or phases, has been artificially introduced [16]. CMP can be divided into two
types: microcomposites and nanocomposites; in the microcomposites, micro-size
second phases such as particulate, platelet, whisker, and fiber were dispersed at the
grain boundaries of the matrix. Some of the more common discontinuous reinforce-
ments include whiskers, platelets, and particulates having compositions of Si3N4,
silicon carbide (SiC), aluminum nitride (AlN), titanium diboride, boron carbide, and
boron nitride. Of these, silicon carbide has been the most widely used because of its
stability with a broad range of ceramic oxide and non-oxide matrices [17]. The main
purpose of these composites is to improve the fracture toughness. On the other hand,
the nanocomposites can be grouped into three types: intragranular and intergranular
composites and nano/nanocomposite as shown in (Fig. 3). As schematically drawn
in below figure, in the intra- and intergranular nanocomposites, the nano-size
particles are disperse mainly within the matrix grains or at the grain boundaries of
the matrix, respectively. Their aim improved not only the mechanical properties such
as hardness, fracture strength, toughness, and reliability at room temperature but also
high-temperature mechanical properties such as hardness strength and creep and
fatigue fracture resistances [18].
CMPs are promising materials; by combining different ceramic matrix materials
with special suitable fibers, new properties could be created and tailored for inter-
esting technical fields [20, 21]. CMPs were established to overcome the intrinsic

Fig. 3 The classification of Inter-type Inter-type

ceramics nanocomposites [19]

Intra/inter-type Nano/nano-type
86 M. V. Khumalo and M. C. Khoathane

brittleness and lack of reliability of monolithic ceramic, with a view to introduce

ceramics in structural parts used in severe environments, such as rocket and jet
engines, gas turbines for power plants, heat shields for space vehicles, fusion reactor
first wall, and heat treatment furnaces. Ceramic matrices could be characterized as
either oxides or non-oxides and in some cases might contain residual metal after
processing [22]. Some of the more common oxide matrix includes alumina, silica,
and mullite. Among alumina and mullite had been most widely used because of their
in-service thermal and chemical stability and their compatibility with common
reinforcements.

Nanomaterials

Nano-structured (NS) materials are defined as solids having microstructural features

in the range of 1–100 nm (¼ (1–100)  10–9 m) in at least one dimension
[23]. These materials have outstanding mechanical and physical properties due to
their extremely fine grain size and high grain boundary volume fraction. When the
size of material is in range of the nano-size, the main components of the material
concentrate on the surface. For example, when the particle is 2 nm in diameter, the
surface atoms will occupy 80% overall. The enormous surface could produce surface
energy, and then nanometer-sized objects generate the strong aggregation, which
enlarges the particle size. Ceramic-based nanocomposites and metal-based nano-
composites can be made by the method of nano-phase in situ growth; their perfor-
mances were improved significantly, but there are still difficulties to accurately
control the content of reinforcements and the chemical composition of generated
products by in situ reaction. Organic-inorganic molecular interactions have covalent
bond type, coordination bond type, and ionic bond type; each type of nanocomposite
material has its corresponding preparation methods. For example, the preparation of
nanocomposites with covalent bond type adopts the sol-gel method basically. The
materials can achieve the level of the dispersion of molecular grade, so they get the
superior performance. High-energy mechanical milling can be used to produce
nanopowder. There are two routes for producing nanopowders using mechanical
milling: (a) milling a single-phase powder and controlling the balance point between
fracturing and cold welding, so that particles larger than 100 nm will not be
excessively cold welded, and (b) producing nanopowders using mechanochemical
processes [24].

High-Energy Ball Milling (HEBM)

A new process called “mechanical alloying” (MA) had been developed, which
produces homogeneous composite particles with an intimately dispersed, uniform
internal structure. Materials formed by hot consolidation of the powders achieved the
long sought-after combination of dispersion strengthening and age-hardening in a
high-temperature alloy. Mechanical milling (involving one material) and mechanical
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 87

alloying (involving two or more materials) generally refer to high-energy ball milling
techniques, employed to process materials in the solid state. Those non-equilibrium
processing routes, responsible for the early successes in oxide dispersion-
strengthening of metallic superalloys, involve a variety of metastable inorganic mate-
rials. The morphologies (both single component and alloys) are used to form extended
solid solutions, novel intermediate phases, alloys from immiscible metals and oxides,
metal-ceramic composites, and nanocrystalline materials [25, 26]. Since its inception
by Benjamin around 1966, HEBM has been used to produce oxygen dispersion-
strengthened (ODS) iron- and nickel-based alloys for aerospace engineering. Mechan-
ical alloying (attrition, also generally known as HEBM) was a multipurpose tool to
produce nanostructured materials with a wide variety of chemical compositions and
atomic structures [27]. The material/particle dimension did not matter significantly, as
long as it was smaller than the size of the balls, because material got grinded within a
very short period of time and becomes powder with the high-energy impact of the balls
[28]. Ball milling can enable the purposeful execution of physical and chemical
transformations in powdered materials.
That method confirmed that the physical and chemical behaviors of molecules
and ordered and disordered solids could be affected by non-hydrostatic mechanical
stresses and the associated strains [29]. Ball milling was performed at room temper-
ature on dry mixtures of powders, which had the undisputable advantages of
avoiding the need for high temperatures, hazardous solvents, and complex in situ
polymerization processes. In addition, ball milling not only represented an interest-
ing alternative for the mass production of hybrid organic-inorganic materials; it is
also an environmentally and economically sustainable method for fabricating nano-
composites with temperature-sensitive molecules.
For the past two decades, HEBM has broadly been used as a versatile process to
produce a variability of progressive compound powders. The core difference
between high-energy milling by planetary ball mill, Spex mill, attritor mill, and
the conventional milling was previously methods applied considerably on larger
doses of energy to the particles over time. Significant improvement in the mechan-
ical, chemical, and physical properties has been achieved, through chemistry mod-
ifications and conventional thermal, mechanical, and thermomechanical processing
methods [30, 31]. The large amount of energy consumed by high-energy mills was
possibly a burden in its industrial application of the method. That was because the
electrical energy consumed for the production of the powders by high-energy mills
was added to the final price of the products [32]. Scientific investigations by material
scientists have been directed continuously towards improving the properties and
performance of materials (Table 2).

Techniques and Methods of HEBM

Ball milling has been applied in numerous solvent-free carbon-carbon bond forma-
tions. Various types of ball mills are known, and they include ball mills (drum), jet
mills, bead mills, vibration ball mills, planetary ball mills, and horizontal rotary ball
88 M. V. Khumalo and M. C. Khoathane

Table 2 Typical capacities Mill type Sample weight

of the different types of
Mixer mills Up to 2  20 g
mills [30]
Planetary mills Up to 4  250 g
Attritors 0.5 to 100 kg
Uni-ball mill Up to 4  2000 g

mills [33]. All of these devices are based on the principle that a starting material is
placed between two surfaces and crushed because of the impact and/or frictional
forces that are caused by collisions between these surfaces. The various mills differ
in the method of how the motion causes the collisions created. Besides the intensive
grinding effect, the collisions often lead to an energy transfer, which results in an
increase of internal temperature and pressure. For the achievement of better control
of these factors, some ball mills have cooling/heating devices attached. In general,
ball mills are able to produce materials with a particle size of 100 nm. Rodriguez
et al. described a planetary ball mill that contained a main disk that can rotate at a
high rotational speed and can accommodate one to eight grinding bowls. These
bowls hold a number of balls as grinding medium and rotate around their own axes in
opposite directions, relative to the main disc. The rotational speeds are between
100 and 1000 rpm. Vibration ball mills contain only one or two grinding chambers,
which accommodate one or more grinding balls and can be shaken at a frequency of
between 10 and 60 Hz, in three orthogonal directions. Some vibration ball mills have
cooling/heating systems, which allow a temperature control while grinding [34].
Other terms found in the literature to describe the same milling technique are
high-speed ball milling (HSM), high-speed vibrational ball milling (HSVM), shaker
milling, or HEBM. Horizontal rotary ball mills have the advantage that they could be
operated at a high relative velocity of the grinding medium (up to 14 ms1) that
cannot be reached by other types (up to 5 ms1) [35].
The HEBM media comprise the milling balls, grinding vessel, vial, jar, or bowl.
The HEBM media are a major source of contamination via diffusion as well as
abrasion. Stainless steel, hardened steel, tungsten carbide (WC), and zirconia (ZrO2)
are the most commonly used HEBM media. Often, process-controlling agents (PCA)
are used to decrease the sticking of the powder to balls and walls of the milling jar.
PCA can be in solid, liquid, or gaseous form and can get adsorbed on the surface of
the metal, thereby causing a reduction in surface energy. The milling temperature is
an important variable [36]. For high-temperature requirements, electrical heating is
employed to heat the milling vial in order to increase the temperature of milling, and
this is expected to promote alloying process through diffusion. This can lead to an
increase in the minimum achievable grain size. Milling speed was varied depending
on the type of ball mill, ball-to-powder ratio, and purpose of HEBM. Usually, higher
milling speed lead to higher-impact energy caused by faster grain refinement
[37]. Aluminum (A‘) was a reactive element; therefore, milling was performed in
an inert atmosphere or in vacuum. Argon (Ar) was the most commonly used milling
atmosphere. Use of nitrogen, hydrogen, and helium was also reported. Other gases,
like NH3, could be introduced to induce chemical reactions, which lead to reactive
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 89

Fig. 4 Schematic representation of formation of nanocrystalline grains during HEBM [30]

HEBM. Ball-to-powder weight ratio (BPR) had significant effect on the kinetics of
alloying and/or grain refinement. BPR largely depended on the purpose and type of
HEBM. A small BPR might not induce any significant grain refinement. Milling
time is very important factor, which should be long enough to achieve steady-state
grain reduction and completed alloying. However, longer ball milling time increased
chances of contamination, costs time and money, and might lead to the formation of
unwanted phases (Fig. 4).

HEBM in Polymer-Ceramics Composites

HEBM is one of the effective processes for fabricating polymer-ceramic composite

powders as it allows incorporation of the ceramic phases into the polymer particles.
The technique polymer nanocomposites with nano-sized ceramic particulate rein-
forcement can be produced through numerous deformations, fracturing, and cold
welding events. After a certain period of milling, powder microstructure homoge-
neity can be achieved. In addition, simplicity, high efficiency, and low cost of ball
milling method have drawn scientist to attention [38]. Alumina is a ceramic metal
oxide of great importance. The material was used as building material, refractory
material, and electrical and heat insulator, due to its high strength, corrosion resis-
tance, chemical stability, low thermal conductivity, and good electrical insulation.

HEBM in Thermoplastic Matrix Composites

The medium-density polyethylene (MDPE) powder is reinforced with nano-sized

alumina (Al2O3) particles. SEM micrographs of pure MDPE regular shape powder
converted to flake shapes as milling time increased. Also the outcomes demonstrated
that an increase in milling time causes to decrease the agglomeration of alumina. The
DSC profiles of samples explained that ball milling has little effect on crystalline
temperature and melting point of all materials including MDPE and its nano-
composites. The nanocomposite shows more thermal stability than pure polyethyl-
ene proved by TGA tests [39]. During the HEBM process, the outcomes showed that
the consistent shape of PBT powders was converted into flakes and the nano
90 M. V. Khumalo and M. C. Khoathane

antimony oxide (Sb2O3) particles were well deagglomerated and better dispersed in
the poly(butylene terephthalate) (PBT) matrix. Mechanochemical stimulation pro-
vided by the HEBM process produced a reduction in the molecular weight of PBT,
which favors the first step of thermal degradation. Furthermore, two Tg’s were
attained in the case of the nanocomposite powders when the milling time was over
3 hours, one of them being slightly higher than that of the pure PBT, which showed
that there was a special interaction between PBT and nano-Sb2O3 particles. How-
ever, the HEBM process led to a decreasing of the PBT crystallinity [40]. The
authors further explained PBT nanocomposites contained modified nano-Sb2O3
particles were dispersed by two different dispersing techniques, which includes
high-speed rotating to disperse HSR and high-energy ball milling to disperse
HEBM. The dispersion, interfacial interaction, and mechanical properties of nano-
composites were investigated. The results showed that the dispersion and compat-
ibility of nanocomposites dispersed by HEBM were better than that of HSR. From
the analysis of interfacial interactions between nano-Sb2O3 particles and PBT
matrix, the interfacial adhesion (B) and tensile strength of interfacial (σ i) were
decreased with the increase of nano-Sb2O3 particle content.
Polymer-clay nanocomposites were fabricated from medium-density polyethyl-
ene and organically modified Na-montmorillonite (MMT) using the planetary ball
milling as a new method. The milling time and the addition of clay have not affected
on the crystal structure of MDPE matrix. The addition of clay reduces the crystalline
size of MDPE. Ball milling was also effective in reducing the crystallite size of
MDPE. The ball milling has influence on the crystallinity of MDPE, especially
during the early stage of milling. The crystallinity of MDPE decreases as the clay
contents increased. It could reduce the intensity of XRD peaks by only 5 wt% clay
[60]. The effects of HEBM under different conditions on the structure of Na+-
montmorillonite (Na-MMT) and the organo-montmorillonite (Cloisite 30B) were
investigated. Ball milling increased the structural disorder: peeling off of layers from
the particles was observed, followed by the exfoliation of the particles, indicated by
the disappearance of the (001) reflection [41]. Shao and his co-workers reported a
novel technology, solid state shear milling (S3M), to prepare poly(ethylene tere-
phthalate)/Na+-montmorillonite nanocomposites used the pristine Na+-MMT with-
out organic modification to avoid the problem that the organic modifiers [42]. The
intercalated PET/Na+-MMT co-powders could be produced under the strong shear
forces of pan-milling, increased interlayer spacing of pristine Na+-MMT from
1.17 nm to 1.48 nm, which could be further delaminated during subsequent twin-
screw extrusion. The Na+-MMT had a heterogeneous nucleation effected on the
crystallization of PET, which was strengthened by milling. Na+-MMT was incorpo-
rated into a poly(ε-caprolactone)-starch blend by means of a ball mill. The milling
time strongly influenced the mechanical and barrier properties. In particular, the best
results in terms of elastic modulus and permeability coefficient were achieved with a
complete delamination of the pristine clay structure. In summary, the milling process
not only had demonstrated to be a promising compatibilization method for immis-
cible PCL-starch blends, but it could be also used to improve the dispersion of
nanoparticles into the polymer blends [43]. Planetary ball mill was employed to
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 91

produce MDPE matrix nanocomposites reinforced with different clay contents. The
results showed the effects of milling time and clay content on the particle size of
polyethylene powder. The results showed that during milling, the regular shape of
pure polyethylene powder converts into flake shapes and the average particle size of
the powder increased upon increased milling time because the welding mechanism
was predominant. The potential of ball milling was investigated in the melt-
processing of PP/clay-based compounds to improve the clay dispersion [44].
Depends on milling parameters, the nature of the clay and the presence of other
components during milling, different changes in the clay structure such as delami-
nation and breakage has been observed. Nevertheless, the main concern was the
particle agglomeration caused by milling. Preliminary milling of clay alone led to
large particle agglomeration in case of the organoclay, which results in a poor clay
dispersion in the final compounds. Ball milling demonstrated some potential to
improve the dispersion of the clay, especially in the case of the inorganic clays,
which could be an alternative to the use of organoclays.
Based on author’s paper, PP/organophilic montmorillonite (OMMT) nano-
composites were successfully prepared without any compatibilizers by solid-state
shear compounding (S3C) using pan-mill equipment. When OMMT and PP were
co-milled, exfoliation of the OMMT layers as well as formation of nanocomposites
of OMMT with PP could be realized as a result of the weak interlayer structure of
OMMT and the fairly strong shear forces offered by pan-milling [42]. Water-soluble
PVP/MMT nanocomposites prepared via solution intercalation method were inves-
tigated. The nanocomposites prepared by attrition ball milling showed better optical
transparency than the ones by simple stirring because the more rigorous mixing
could induce the smaller sizes of tactoid or primary particle in the nanocomposites.
PVP and MMT were considerably compatible enough to form an exfoliated nano-
composite up to 20 wt% MMT contents [45]. The solid-state shear pan-milling was
employed to prepare a series of polymer/layered silicate (PLS) nanocomposites.
During the process of pan-milling at ambient temperature, poly(vinyl alcohol)/
organic montmorillonite (PVA/OMMT) was effectively pulverized, resulting in
coexistence of intercalated and exfoliated OMMT layers. Microscopy analysis
indicated that OMMT dispersed homogeneously in PVA matrix, and diffraction
analysis illustrated that pan-milling has an obvious effect on increase in the
interlayer spacing of OMMT and resulted in coexistence of intercalated and exfoli-
ated OMMT layers formed [46]. Sorrentino investigated HEBM used to prepare the
composites of poly(3-caprolactone), and modified Mg-A‘ layered double hydroxide
[47], at different inorganic content, has a number of mechanical and physical
properties enhanced in comparison to those of the pure PCL polymer. In particular,
modulus and stress at yield point resulted improved for all the composites, in spite of
the molecular weight reduction of PCL. Strain at break point and stress at break
values improved in the composite sample containing 1.4 wt% of inorganic filler. The
usage of solid-state ball milling (SSBM) for dispersed cellulose nanowhiskers
(CNWs) in starch-based thermoplastics also improve mechanical properties. Differ-
ent testing demonstrated strong correlation between mechanical reinforcement and
nanowhisker dispersion [48]. The starch-pectin-CNW nanocomposites showed high
92 M. V. Khumalo and M. C. Khoathane

dispersion of the nano-sized filler in the matrix; thus, SSBM showed great potential
when compared to sol-gel, casting/evaporation, and other methods to disperse those
promised nanoparticles. Nano-sized boron nitride (BN) powder was successfully
prepared by pulverizing micro-sized BN powder using a ball mill process without
any wetting agents. In order to enhance the dispersivity of nano-BN in the polymer
matrix, the surfaces of the nano-particles were treated with LDPE, which dissolved
in the cyclohexane solvent. In their investigation, the preparation of nano-sized BN
dispersed HDPE was successfully performed by using an organic solvent surface
treatment method together with a polymer melt mixing process, and the highly
enhanced thermal conductive characteristics for the nano-BN/HDPE composites
were observed [49]. The authors explained the effect of silica nanoparticles on
structure and morphology of LDPE which was investigated. SiO2 nanoparticles
were dispersed in a LDPE with cryogenic HEBM. Although HEBM promoted the
formation of metastable monoclinic phase in the LDPE, nanocomposites in the form
of films never showed differences in their thermal and morphological characteristics,
which suggested that there were no high interactions between the polar nano-
particles. The nonpolar polymer and thermal treatment was enough to eliminate
the specific microstructure induced by HEBM [50]. According to the studies,
PET/SiO2 nanostructure was induced by cryo-milling for 10 h. PET flakes dispersed
with the single SiO2 nanoparticles formed the primary composite particles, and
conglomerations of those primary composite particles were the secondary composite
particles [51]. The typical sizes of the single SiO2 nanoparticles, PET/SiO2 primary
composite particles, and the secondary composite particles were 30, 400, and
7.6 μm, respectively. The dispersion homogeneity of SiO2 nanoparticles in PET
matrix was far more beyond the capability of conventional methods, which was
ascribed to solid processing, high mechanical energy of ball milling, and cryogenic
temperature. It was realized from the studies that ball milling and mixing with strong
shear force and strike force were applied to get fine dispersion of nano-SiOx particles
in poly(phenylene sulfide) (PPS) powder. Ball milling increased total systematic
interface energy. The bonds allowed SiOx to dissipate and transfer energy and thus
improve PPS impact strength from the addition of nano-SiOx. Crystallization
behavior (Tc, Tm, ΔT, Xc, etc.) of nano-SiOx/PPS was influenced by ball milling.
Consequently, crystallinity of nano-SiOx/PPS was reduced by 25%, and its Izod
impact strength was increased by 89% [52].
Fumed silica nanoparticles with 14 nm of diameter were blended with PMMA, by
means of a HEBM process. It was demonstrated how possible to obtain fumed silica-
PMMA nanocomposites with a very homogeneous dispersion of the nanoparticles
within the PMMA. It has been observed that the properties of the composite were
highly dependent on the active milling time: (i) the size of the silica-PMMA
nanocomposite particles decreased and (ii) the Tg also decreased. The later result
has been assigned to a reduction in the molecular weight of the PMMA due to chain
scission during the high-energy blending process [53, 54]. It was further reported by
Gonzalez-Benito and his co-worker the effects of the presence of silica nanoparticles
in the structure, dynamics, and thermo degradation of PMMA. HEBM was used to
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 93

uniformly disperse nanoparticles within a polymeric matrix (PMMA). FTIR results

indicated no signal of degradation processes or secondary reactions induced by
HEBM was observed; there was no existence of specific interaction between the
silica nanoparticles and the PMMA polymer [55]. HEBM used co-milling in a solid
state by low-temperature MA to prepare nickel-ferrite (NiFe2O4) nanopowders and
ultrafine PMMA, dispersing nanoparticles in a polymer matrix, and a uniaxial high-
velocity cold compaction processed employed a cylindrical, hardened steel die and a
new technique with relaxation assists has been studied. It was found that a longer
mixing time gave a higher degree of dispersion of the nanopowder on the PMMA
particle surfaces [56, 57]. The results obtained from their work showed that PEEK/
SiO2 nanocomposite powder successfully produced by HEBM under ambient tem-
perature. Mechanical milling led to the deterioration of PEEK crystallites and
decreased the degree of crystallinity. Mechanical milling has major effects on
thermal behavior of PEEK. Non-equilibrium orders imposed the material by repet-
itive deformed during milling might be responsible for observed changes [58]. The
development of HEBM and the presence of TiO2 nanoparticles on the
non-isothermal crystallization and fusion behavior of the HDPE were investigated.
It has been demonstrated that HEBM was a good method to prepare nanocomposites
of well-dispersed TiO2 nanoparticles within an HDPE matrix. It was observed that
although in general there was a reduction of crystallinity of the polymer, when
nanoparticles were absent, the HEBM process induced a double crystallization
process (appearance of both the orthorhombic and metastable monoclinic phases).
The authors further explained HEBM promotes the formation of the metastable
monoclinic phase in the LDPE, nanocomposites in the form of films never showed
important differences in their thermal and morphological characteristics, suggesting
there are no high interactions between the polar nanoparticles and the nonpolar
polymer and thermal treatment was enough to eliminate the specific microstructure
induced by HEBM. The mechanical properties and morphologies of PP composites
filled with four different sizes of calcium carbonate (CC) particles were studied. It
was clear that the PP matrix and filler size have key effects on improvement of
mechanical properties of PP matrix. For all three PP matrices, the yield strength, the
flexural strength, and modulus of composites filled with CC25, CC4, and CC1.8
could be regarded as the same. And the yield strength, the flexural strength, and
modulus of composites filled with CC0.07 were obviously lower than those of
composites filled with other sizes of particles. For all particles, the flexural strength
and modulus of the composites increased with increasing filler content, while the
yield strength decreased with increasing filler content [59]. A1/PMMA composites
with low coefficients of thermal expansion were prepared by attritor milling of A1
and PMMA powders and then hot pressing the powder mixture. The resistivity drops
by about 10 orders of magnitude as AI content was increased from 20 to 40 vol. %.
The attritor milling helps in reducing the critical volume fraction of metal particles
by increasing the aspect ratio. The dielectric constant and dissipation factor of the
A1/PMMA composites increase with increase in aluminum content, which is due to
interfacial polarization [60].
94 M. V. Khumalo and M. C. Khoathane

HEBM in Thermoset Matrix Composites

According to Huang [61], UV-curable ammonium salt ([2-(methacyloyloxy)ethyl]

trimethylammonium methyl sulfate (MAOTMA) MAOTMA)-modified
MMT/epoxy nanocomposite samples were prepared with the aid of planetary
mechanical milling process. TEM microscopy revealed a uniform dispersion of
exfoliated MMT lamella in epoxy matrix, and the thermal analyses indicated a
substantial improvement on thermal properties, e.g., thermal stability and CTE, of
nanocomposites. Analytical results illustrated that the planetary mechanical milling
process adopted was a valuable tool for microstructure refinement and physical
property enhancement of nanocomposite samples. The induce MMT further exfoli-
ated and homogeneously dispersed in epoxy matrix (diglycidyl ether of bisphenol A)
curing in the presence of diaminodiphenyl sulfone and obtained improved mechan-
ical properties, a promised new method had been developed to prepare highly
reinforced epoxy/MMT nanocomposites through exerting shearing force on epoxy/
MMT solution. When the novel-structured MMTII was sheared by ball milling in
ketone/epoxy solution during the processing of novel-structured epoxy/MMTII
nanocomposites, a desirable exfoliation could be achieved in comparison with no
ball milling step. The resultant nanocomposites have a high impact toughness, and
the impact strength could be increased up to 48.1 kJm2 from 32.1 kJm2, which
was about 50% higher than that of pristine matrix by ball milling. Modifying agents,
being combined with dodecylbenzyldimethylammonium chloride and meta-
xylylenediamine, were used to organically modify the clay (MMTII) [62].

HEBM in Polymer Metal Matrix Composites

Acrylonitrile-butadiene-styrene (ABS)/iron nanocomposites have been prepared by

cryo-milling (HEBM under cryogenic temperature), and a microstructure of iron
network in ABS matrix was obtained. ABS/Fe nanocomposites have been success-
fully obtained by cryo-milling. The cryogenic temperature and cryo-milling greatly
enhances the size reduction by improving fracture and restricting cold welding. Both
particles and grains refined much faster speed rate, and the comminution limited was
moved to the finer end inaccessible to ambi-milling process. 20 hours cryo-milling
pulverizes the single ABS/Fe composite particle smaller than 100 nm and refined Fe
grains about 20 nm [63]. The authors further explained PANI/iron nanocomposites
with both conducting and magnetic properties had been prepared by cryo-milling
(HEBM under cryogenic temperature), in which the average size of iron grains
attains 20 nm. After cryo-milling for 20 h, the average size of Fe grains was refined
to 20 nm; besides, many of Fe particles were dispersed in PANI matrix. It only
needed to take 2 or 5 hours to get them dispersed homogeneously in the PANI matrix
[64], but the conductivity decreases gradually with the cryo-milling time after 2 h
due to the dedoping of DBSA from PANI matrix. Pan-milling technique was
developed to prepare ultrafine PP/Fe composite powders, in which the average
grain size of the iron particles attained a nanoscale level. An average grain size of
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 95

iron below 100 nm was obtained and reached 28 nm after 30 milling cycles while
co-milling with PP. The experimental results showed that co-milling benefited the
size reduction both for PP and iron [65]. Microstructural and phase transformation of
magnitute induced by HEBM and influence of conducted polyaniline (PANI) on
Fe3O4 particles in system of Fe3O4-polyaniline were investigated. Through diffrac-
tion analysis, it was found that after HEBM the crystallite size of Fe3O4 particles was
rapidly reduced to about 21 nm. Broken PANI chains reacted with the Fe atoms in
the surface of Fe3O4 particles formed some paramagnetic phase and a small number
of superparamagnetic α-Fe2O3 particles. The magnetic properties of the composites
were also changed [66]. Ethylene vinyl acetate (EVA) copolymer, a thermoplastic
semicrystalline polymer, has been blended with barium titanate submicrometric
particles (BaTiO3) by means of HEBM to obtain composites in the form of films
by hot pressing. Two different milling conditions have been considered: room
temperature and cryo-milling [67]. The characterization of the samples as powders
and films showed the lack of strong interactions between the matrix and the BaTiO3
and that the cryogenic conditions were the most suitable to achieve a uniform
dispersion of the nanofiller without altering the structural and morphological prop-
erties of the base materials. Magnetic nanocomposites composed of cobalt ferrite
(CoFe2O4) nanoparticles and polyvinyl alcohol (PVA) polymer were obtained using
a two-step mechanical milling, and the effects of milling time and polymer content
were investigated. It was found that single-phase cobalt ferrite of 20  4 nm particle
size was distributed uniformly by increasing PVA amount and milling time up to
80 wt.% and 30 hours, respectively; however, the size and shape of particles were not
changed drastically. The interaction of PVA chains and magnetic phase has been
confirmed in nanocomposite samples. The obtained results in their work prove that
mechanical alloying could be an efficient way to yield such advanced functional
magnetic nanocomposites [68]. The structural, morphological, dielectric, magnetic
properties of CoFe2O4 and various PS concentrations added to CoFe2O4 nano-
particles prepared by coprecipitation method [69]. Characterization results indicated
the addition of PS in CoFe2O4 nanoparticles remarkably modified the size of the
prepared nanoparticles. Structural analysis by XRD confirms the formation of
single-phase cubic spinel structure, and vibrational spectral analysis confirms the
Fe-O symmetrical stretching vibrational mode. Hence, from the obtained overall
results, it could be concluded that the addition of PS in CoFe2O4 nanoparticles
controlled the size of the particles and thus enhanced the dielectric and magnetic
properties of CoFe2O4 nanoparticles which would be useful for high-frequency and
data storage applications. A polymer nanocomposite of nanocrystalline nickel ferrite
and polyethylene (PE) was successfully synthesized using the ball milling process
[70]. The ball milling process did not significantly influence the crystallite size of
nanocrystalline nickel ferrite in the composite. Magnetic measurements carried out
at room temperature suggested characteristics of superparamagnetism, i.e., absence
of hysteresis, remanence, and coercivity and lack of saturation magnetization. The
nickel ferrite-polyethylene nanocomposite exhibited a blocking temperature of
20 K. The lack of saturation magnetization at high field occurs in association
with high field irreversibility and open loop at 50. Rashidi and Ataie [71] reported
96 M. V. Khumalo and M. C. Khoathane

that magnetic nanocomposites composed of mixed cobalt ferrite nanoparticles and

PVA or poly ethylene glycol (PEG) polymer were synthesized using a two-step
mechanical alloying method. PEG not undergo the local temperature risen and
induced heat during milling process melt in both moderate and slow milling condi-
tions. Although nanocomposites, cobalt ferrite nano-particles embedded entirely in
melted polymer matrix and the initial hours of milling, obtained composite changes
to bulk in ball mill. PVA was properly mixed with cobalt ferrite particles the
dispersion of particles with interaction between polymer chains and cobalt ferrite
nano-particles obtained in the moderate milling condition. HEBM using co-milling
in a solid state by low-temperature mechanical alloying to prepare nickel-ferrite
(NiFe2O4) nanopowders and ultrafine poly-(methyl methacrylate) (PMMA), dispers-
ing nanoparticles in a polymer matrix, and a uniaxial high-velocity cold compaction
process using a cylindrical, hardened steel die and a new technique with relaxation
assists has been studied. Experimental results for different milling systems were
presented showing the effects of milling time and material ratio. It was found that a
longer mixing time gives a higher degree of dispersion of the nanopowder on the
PMMA particle surfaces. Furthermore, with increasing content of NiFe2O4 nano-
powder, the reduction of the particle size was more effective. Different post-
compacting profiles, i.e., different energy distributions between the upper and
lower parts of the compacted powder bed, led to different movements of the various
particles and particle layers. Uniformity, homogeneity, and densification on the
surfaces in the compacted powder are influenced by the post-compacting magnitude
and direction [72, 73]. Raju and Murthy [74] explained a series of nanocomposites of
nickel-zinc ferrite plus paraformaldehyde which was successfully synthesized using
the mechanical milling process. The milling process significantly influenced the
crystallite size of nanocrystalline nickel-zinc ferrite in the composite. With the
increases in the volume of polymer, the permittivity, permeability, and dielectric
and magnetic loss of all the composites decreased. The permittivity and permeability
of all the composites have shown good frequency stability and low dielectric and
magnetic losses within the measurement range.

Conclusion

In the past years, the interest in the production of polymer nanocomposites by ball
milling has considerably increased as the number of publications with related subject
has increased. Mechanical alloying is a simple, sophisticated, and convenient pro-
cessing technique that continues to attract the serious attention of researchers. MA is
a complex process that involves many variables, and many of them are
interdependent. Therefore, modelling of the MA process is very difficult. Uniform
dispersion can be achieved using various types of mechanical methods, including
ultrasonication, shear mixing, calendaring, ball milling, stirring, and extrusion. It has
become a major potential process for processing advanced materials which awaits to
be used in industry. It is now time for material scientists who are interested in
developing high-energy mechanical milling into an industrial process to learn from
5 Effect of Mechanical Alloying in Polymer/Ceramic Composites 97

researchers who have mastered the art of low-energy mechanical milling. Selection
of a proper method or a combination of several methods as well as their processing
conditions has to be based on the desired properties of end products. Undoubtedly
HEBM valuable equipments to study polyesters materials with different nanofillers
and clays there’s least research on this field. The polymer-nanoparticle systems that
have been studied this far provided a basis for refinement, and further work will
furnish valuable insight into the mechanisms of reinforcement and new methods of
nanocomposite design.

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Identification and Quantification
of Nanomaterials in Consumer Product 6
Pratap Kumar Deheri and Biswabandita Kar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Defining Nanomaterials: What Are Nanomaterials? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Nanomaterials in Consumer Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Potential Health Risk of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Sample Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Characterization Techniques for Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Dynamic Light Scattering (DLS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Surface Charge (Zeta Potential (ζ)) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
BET-Surface Area Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
FTIR and UV-Visible Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
X-Ray Diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy
(TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

Abstract
It is the age of nanotechnology. Development in the field of nanotechnology and
nanomaterials and its applications in the field of materials science, electronics,
optics, energy, medicine, and consumer product are growing rapidly. Nano-
materials are widely being used in agricultural products, food packing materials,
cosmetic, medicine or pharmaceutical products, food materials, textiles, automo-
biles, and household chemicals. Use of nanosized materials or nanoparticles
(NPs) opens a broad prospect of new materials with improved properties,
increased lifetime, better packing materials, new nano-nutrient forms that have
high bioavailability, effective food additive, nano-coating with better abrasion

P. K. Deheri · B. Kar (*)

Kalinga Institute of Industrial Technology (KIIT), Bhubaneswar, Odisha, India

© Springer Nature Singapore Pte Ltd. 2022 101

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_6
102 P. K. Deheri and B. Kar

resistance, nano-coating with super-hydrophobic properties, and lightweight

nanomaterial composite with increased mechanical properties, just to name a
few. However, nanomaterials have some risk factor due to skin contact and
ingestion that may lead to possible health hazard such as fibrosis, inflammation,
carcinogenicity, etc.

Keywords
Nanomaterials · Consumer products nanomaterials · Nanomaterials helth risk ·
Nanomaterials identifications and characterizations

It is a fact that nanomaterial developments and uses in various fields including

consumer products are increasing and so is the consumer exposure too. If the
nanomaterials have any health hazardous properties, the risk related to nanomaterial
exposure would also be increasing. Hence, the accurate evaluation of the benefits as
well as risks associated with any nanomaterials or the engineered nanomaterials is
highly desirable for consumer’s protection. Nanomaterials in any products can be in
dispersed form in bulk or on surface, as individual particles (particulates), as
intercalated particles, as solid solutions, and as agglomerates. This complex struc-
tural inhomogeneity or distribution of nanomaterials in consumer products is key to
property control. An in-depth analysis of this complex structure will be helpful in
property as well as adverse effect determination of the product. However, nano-
particles or nanomaterials usually make a very low percentage in most of the
consumer products. At the same time, proper analysis and characterization of these
nanomaterials are complex, due to the complex structures. Furthermore, the in situ
analysis of these products is complicated due to incompatibility nature of the
characterization equipments that can be used for nanomaterial detection and
analysis.
Consumer products nanomaterials characterization includes physicals, chemicals
and biological properties evaluations. The morphological evaluations such as size,
shape, dispersion state, surface area and surface morphology, elemental analysis, it's
stability and leachability, interaction with living organism or biological response and
quantitative analysis are important for any consumer product applications. Here,
some analytical techniques suitable for the detection, characterization, and quantifi-
cation of nanomaterials in consumer’s products such as food, cosmetic products,
packaging materials, medicines, etc. are discussed. It is difficult to get complete
information about the nanomaterials used in products by using a single characteri-
zation technique. The use of two or more characterization techniques that can
complement each other to extract the complete information needs extensive knowl-
edge in equipments and data interpretation. The principal objective of this study is to
discuss the principles of operations for different characterization techniques, uses in
the analysis of nanomaterials in the consumer products, advantages and weakness of
these techniques, and some of the emerging techniques that can be used to nanopar-
ticle characterization and can be used as complementary information.
6 Identification and Quantification of Nanomaterials in Consumer Product 103

Introduction

Improved physical and chemical properties of nanomaterials (NMs) as compared to

their micro or bulk materials make them attractive to a wide range of applications in
different fields. Today over 1000 consumer products are available globally that
utilize nanomaterials, and it is finding more and more applications daily. Looking
at the broad application areas, the most important questions need to be answered are;
(1) the potential benefit of nanomaterials when included in consumer products, (2)
what are the characteristic properties should be considered for applications in
consumer products and (3) what are the adverse effects on health and environment
associated with it. Humans and the environments are constantly exposed to these
engineered nanomaterials during the production, during use, and after disposal too.
To evaluate the benefits of nanomaterial inclusion in consumer product to that of the
adverse health effects is the key in nanomaterial selection in any applications. For
this, the detailed characterization of nanomaterials is required. In this section of the
book, some appropriate analytical techniques for the detection, characterization, and
quantification of nanomaterials in food, cosmetics, paints, packaging materials, and
textile products are discussed.

Defining Nanomaterials: What Are Nanomaterials?

Nanomaterials are typically materials with at least one dimension in the size range of
1–100 nm (1 nm–109 m). Nanomaterial classification based on dimensionality is
more concise and clear by taking into consideration confinement of electrons in a
nanostructure system [1, 2]. The classifications based on dimensionality and exam-
ples are illustrated in Fig. 1 [2].

1. Zero-dimensional nanostructure (e.g., quantum dots, nanosphere): electron

movement is confined in all three dimensions.
2. One-dimensional nanostructure (e.g., nanofibers, nanowires, nanorods): the elec-
trons are free to travel in one direction and confined in the other two directions.
3. Two-dimensional nanostructure (e.g., nanofilms, nanoplates): the electrons can
easily move in two directions and are confined in third direction.
4. Three-dimensional nanostructure (e.g., polycrystalline nanostructure, nano-
powders, multilayer films). In 3-D nanostructures, 0-D, 1-D, and 2-D nano-
structures are interconnected through interface. In this nanostructure system, the
electrons are free to move in all three directions, and there are no confinement and
limitations.

Even though the nanomaterial’s elemental compositions and crystal structures are
same as the bulk materials, nanomaterials often show different chemical, physical,
and biological properties. Properties include optical properties, chemical and bio-
logical reactivity, permeability through membranes, magnetic properties, thermal
and electrical properties, etc. Some of the nanoscale properties can be extrapolated
104 P. K. Deheri and B. Kar

Fig. 1 Nanoparticles based on dimensionality and examples [2]

from their bulk properties, whereas some other properties may drastically change
below a certain size as compared to the bulk properties. For example, nanoparticles
have an increased surface to volume ratio compared to bulk materials. Nanomaterials
can be much more reactive as chemical reaction rates often related to surface area.
Due to increased surface area, nanomaterials have increased catalytic activity. This
large increase in catalytic effect can be considered as “true” nanoscale features.
However, all nanomaterials may not necessarily have such size reduction effects.
But, these nanomaterials have different properties than their bulk material properties
and are due to size reduction.
Nanomaterials are also classified based on their elemental compositions and
physiochemical properties. The properties of a nanomaterial can be affected by its
stability, dispersion or agglomeration state, the stability of a colloidal dispersion, or
the surface charge. The properties are also largely determined by the properties of
matrix materials in which nanoparticles are embedded. Hence, in order to understand
the behavior of a nanomaterial, it is often necessary to consider the matrix in which it
is embedded. This has an important impact on stabilities, properties, applications,
and even the safety of nanomaterials.
6 Identification and Quantification of Nanomaterials in Consumer Product 105

Nanomaterials come from a broad range of materials of different elementals and

chemical composition. Hence, properties are different and they are used in a wide
range of applications. Nanotechnology itself is a vast area that uses nanomaterials of
wide range and manipulation at the nanoscale that has a potential influence on almost
all technological applications. Nanomaterials are utilized in a wide range of products
that include medical devices (diagnostics, drug delivery), medicinal products, cos-
metic products (antimicrobials, UV absorbers in sunscreens, nano-tag for
bio-imaging, targeted drug delivery), food and food packaging (enhanced flavor,
texture, encapsulation of micronutrients), electronics (data storage, displays), energy
and environmental applications (catalysts, photovoltaics, fuel cells), automotive
(coatings, tyres, composite body parts), construction (thermal insulation), and
advanced materials in general. With their widespread use and diverse applications,
there is a large, developing, and valuable global market for nanotechnology. Some of
the nanomaterial characteristics and their commercial applications are listed in
Table 1.

Nanomaterials in Consumer Products

Nanoparticles and engineered nanomaterials can be resulted in smarter, lighter,

stronger, and cleaner systems and material. At the nanoscale, the properties of
particles may change that can be modulated depending on the requirements.
Nanoparticles are widely used in the manufacture of self-healing polymer, paints
that are scratch-resistant, anti-fouling, and high light-reflecting, scratch-proof
eyeglasses, transparent sunscreens, water/dust-repellent fabrics, self-cleaning win-
dows and solar cells, UV-blocker fabrics and body lotion, sports materials and
equipments with better performance and durability, etc. [55–58]. Automobile tyres
with nanoparticle fillers can improve adhesion to the road and can be resulted in
reducing the stopping distance even in wet conditions. Nanoparticle-strengthened
steels are used in manufacturing car body for lightweight but better strength and
stiffness. Nano-SiO2 coating can improve antireflection, and the transmittance can
be increased up to 95%. Application on solar cell panel will increase the efficiency
by minimizing the solar light reflection and producing a high photovoltage current
[59, 60]. Doped tin oxide provides scratch resistance and offers transparent
protection from ultraviolet radiation, not observed in micron size particles
[61, 62].
TiO2 in consumer product: TiO2 nanomaterials in the form of nanospheres,
nanowires, nanotubes, nanorods, and nanoflowers are synthesized and are used in
many consumer products [63]. TiO2 is frequently used as a “natural coloring agent”
and is well accepted by consumers. TiO2 due to its brilliant white color, high
brightness, and high refractive index (>2.4) is used as a colorant in many drugs,
food products, paints, and cosmetics. It is also used in wide variety of confectionary
foods, toothpastes, cottage, mozzarella cheeses, sauces, lemon curd, and low-fat
106 P. K. Deheri and B. Kar

Table 1 Types of nanomaterials and their applications

Characteristic properties and
Nanomaterials Elements/compounds applications area References
Metallic Silver (Ag), gold (Au), Antimicrobial agents [3–12]
nanomaterials platinum (Pt) Bio-imaging (nano-tag)
Catalyst, fuel cell catalyst
Biomedicine
Silicon (Si) Luminescent display devices [13–15]
Micro and integrated
semiconductors
Solar energy cells
Catalyst, semiconductor (light
energy harvesting)
Copper (Cu) Antimicrobial [16–19]
Antifungal
Conductive ink
Catalysis
Zinc (Zn) Antimicrobial, antibiotic, and [20]
antifungal coatings, UV filtering,
biomarkers, biodiagnostics, and
biosensors
Nickel (Ni), iron (Fe), Magnetic materials [21–24]
cobalt (Co) Targeted drug delivery
Super-paramagnetic
Bio-imaging (MRI)
Data storage
Efficient catalyst, electrode
materials
Metal oxide TiO2 Photocatalyst, semiconductor, [25–28]
nanomaterials and cosmetics
ceramic Antimicrobial coating, UV
nanomaterials protection coating, abrasion and
scratch resistance
TiO2 is mostly used as white
pigment in paint, textile, plastics,
and paper
ZnO2 Photocatalyst, semiconductor, [29–33]
cosmetics, UV filtering,
antimicrobial coating, flame-
retardant coating
SiO2 Photocatalyst, semiconductor, [34–36]
catalyst, sensor, cosmetics
Drug delivery
Optical imaging coating
Flame-retardant coating
Abrasion and scratch resistance
Fe3O4 and Fe2O3 Imaging (MRI), biosensors, [37–42]
targeted drug delivery, cell
labeling
Magnetic fluid, hyperthermia as
cancer therapeutic treatment
(continued)
6 Identification and Quantification of Nanomaterials in Consumer Product 107

Table 1 (continued)
Characteristic properties and
Nanomaterials Elements/compounds applications area References
Rare earth oxide such Solid electrolyte in solid oxide [43–45]
as Nd2O3, Dy2O3, fuel cells, fluorescent materials,
CeO2 luminescence, and
electroluminescent devices,
special optical glass and plasma
display panels, solid oxide fuel
cell, UV detectors
Nanoclays Mechanical and rheological [46–49]
property modifier, flame
retardant, reinforcement in
polymer, decrease in oxygen
permeability, as pollutant
remover (radioactive and dye
pollutant)
Carbon-based Carbon nanotubes, Excellent mechanical, electrical, [48, 50–
nano materials fullerene, graphene, thermal, optical, and chemical 53]
graphene oxide, carbon properties
black Cell/tissue imaging
Biosensor, drug delivery, cancer
therapy, water purification
(organic and inorganic pollutant
removal), in battery and capacitor
Polymer-based Antibacterial applications, [54]
nanomaterials vaccine carrier/drug delivery
system

products such as skimmed milk and ice cream as texture modifier [64, 65]. The
bandgap of nanoTiO2 is usually ~3.0 eV. Hence, it absorbs light in the UV-visible
regions and shows the most promising applications in photocatalytic and photovol-
taic applications. TiO2 is an environmentally friendly and efficient material that is
extensively used in the photodegradation of numerous organic pollutants and is used
in water purification. Moreover, TiO2 nanomaterials are a good choice for UV
protecting applications. It has also been used in light-assisted H2O splitting reaction
to produce H2 gas for green energy technology. Nano-TiO2 functions as UV filter
protecting the paints’ binder material. At the same time, it degrades organic materials
via generation of radicals (photocatalytic), which is used for self-cleaning surfaces
and antimicrobial coatings [66, 67]. The number of products containing TiO2 is
considerable and increasing with time. However, limited information about the
physicochemical properties of nanosized TiO2 such as quantity, particle size, size
distribution, and particle structure is made available in the product even when the
product is labeled as containing TiO2.
SiO2 in consumer product: Highly pure, spherical, and microporous SiO2 parti-
cles are the most common support for the stationary phase in column chromatogra-
phy. SiO2 are permeable to many solvents and have a surface area of several hundred
square meters per gram.
108 P. K. Deheri and B. Kar

Silicon dioxide (SiO2) nanoparticles are used in coating materials too. It improves
scratch and abrasion resistance, barrier properties, and total transparency of the
coating without reducing gloss and also improves adhesion on substrates with
hydroxyl functions. Silicon dioxide (SiO2) nanoparticles reduce shrinkage during
curing of polymer composite. There are various forms of synthetic amorphous silica
(SiO2) available on the market suitable for food applications. Silica gels are widely
employed in food industry as flavor carriers as it is considered nontoxic and safe and
can entrap chemicals in its inner pores which results in pronounced flavor
stabilization.
Nano-silica as filler in polymer matrix is highly promising in improving oxygen
and moisture barrier properties that help in extending shelf-life of food products in
food packaging technology. Nano-layer silica coating protects the surface of alumi-
num from oxidative reaction and reduces its reflectivity. High efficiency of nano-
sized silica compared to that of micron size as anti-caking, clarifying, and adsorption
agents has attracted more and more applications [68]. Stabilized silica colloids
(5–100 nm) are used in the food industry as an aid for clarifying wine, beer, fruit
juices, etc. Magnesium, calcium, and aluminum silicate have been used as anti-
caking agents in food industries to prevent caking in food products. They are used in
healthcare products such as toothpastes, detergents, and cosmetics. They are also
used as antifoaming agent in decaffeinated coffee and tea, as carrier for active
ingredient, and as antistatic agent in food packaging plastics. SiO2 nanosized
particles have been used to construct nanobiosensors. Pt nanoclusters (~2 nm)
mixed with the nanoscale SiO2 particles (~10 nm) are used as a glucose oxidase
immobilization carrier and to fabricate the glucose biosensor. The sensitivity and
performance of biosensors are improved by using nano-SiO2. SiO2 used in concrete
and cement pastes improved the particle packing. It acts as a nanofiller and strong
binding agent and increases the cohesion between the cement and the aggregate [69].
The detection and quantification of SiO2 nanomaterials could be done quite easily
from simple food matrix such as instant tea and coffee. The quantification of SiO2
nanomaterials in tea and coffee can easily be achieved by acid digestion followed by
elemental analysis using ICP-MS or ICP-OES spectroscopy. However, this method
fails to differentiate natural SiO2 from the additive one. However, identification,
separation, sampling, and quantification is complicated if it is from a complex matrix
like coating and paints. The separation of SiO2 nanomaterials from the matrix
materials involves complicated steps and is different for different matrix materials.
ZnO in consumer product: Zinc oxide (ZnO) is a hexagonal crystal that exists in
white dusty powder. It has a very broad and versatile range of applications in the field
of cosmetics, pharmaceutical, and many engineering uses. Nanosized zinc oxide is
transparent for visible light spectrum but block or reflected back the UV light, which
makes it interesting to use UV filter in sunscreens. However, ZnO particles used for
sunscreens are in the range of 20–60 nm and can easily penetrate human skin. To
overcome this hazardous effect, ZnO nanoparticles are coated with SiO2 or Al2O3
and coalesce into aggregates sized 200–500 nm. Such particles cannot penetrate the
body through the healthy skin and hence are not hazardous to the health of con-
sumers. Nano-zinc oxide also possesses antimicrobial actions against some bacteria
6 Identification and Quantification of Nanomaterials in Consumer Product 109

and fungi and is used by the pharmaceutical industry for manufacturing zinc
ointments, zinc pastes, adhesive tapes, and bandages for skin and wound treatment
[70, 71]. Moreover, zinc oxide-based semiconductors are used as transparent con-
ductive layers in blue light-emitting diodes, liquid-crystal screens, and thin-film
solar cells [72, 73]. Zinc oxide is used as catalyst to activate vulcanization process
[74]. It promotes the process of vulcanization in rubber that is used for tire
manufacturing. In addition, its good thermal conductivity improves the removal of
heat generated during the friction of the tires. ZnO nanomaterials in cement increase
the water resistivity and prolong the processing time.
Clay nanoparticles in consumer product: Nanoclays are nanoparticles of layered
silicates. The clay layers could be 2:1 (one octahedral layer sandwiched between two
tetrahedral layers) or be 1:1 (one octahedral and one tetrahedral joined together).
Depending on chemical composition and morphology, clay minerals are classified as
montmorillonite, bentonite, kaolinite, hectorite, and halloysite. Montmorillonite
consisted of ~1 nm thick aluminosilicate layers and stacked in ~10 μm size. The
clay structure is agglomeration/systematically arranged nanostructure plates. Nano-
clays are the most commonly used commercial additive used for preparation of
nanocomposites used in automotive, aeronautical, and packaging industries.
Nanoclay-polymer composites have been often used as rheological modifiers in
paints, inks, greases, and cosmetics. It has been used as carriers and delivery systems
for the controlled release of drugs. Nanoclays have also been used in water retention
application in agriculture field, drilling mud to maintain viscosity, as solid adsorbent
to retain dye and inorganic pollutant for water purification applications, as filler in
paper and rubber to improve mechanical strength and fire retardancy, and also as
base materials in many medicines and cosmetics [75–77]. Furthermore, the bentonite
clay has applications across the pet food products, as it is a mineral-rich naturally
occurring compound, which provides added supplements to pet food. The addition
of nanoclay to pervious concrete has improved the compressive and flexural strength
and durability [78].
Metallic nanoparticles in consumer product: Electronics, optics, fluorescent
materials, biosensors, as well as catalysts are main applications of metal nano-
particles. Noble metal nanoparticles (Ag, Au, Pt) have been used for several bio-
medical applications such as anticancer, radiotherapy enhancement, drug delivery,
thermal ablation, antibacterial, diagnostic assays, antifungal, and gene delivery
[79]. Various functional group compounds such as peptides, antibodies, RNA, and
DNA along with biocompatible polymer can be used for surface functionalization to
target different cell. Depending on the shape and symmetry, silver and gold nano-
particles show surface plasmon resonance and are used for sensor device fabrica-
tions. Silver nanoparticles are employed as conductive fillers in electronically
conductive adhesives [80]. Metal nanoparticles also have very important catalytic
properties. Ag, Au, Au/Pd, and Pd/Pt bimetallic nanoparticles work as effective
catalysts for hydrogenation of olefins [81].
Carbon nanostructure in consumer product: Carbon atom has the ability to form
single, double, and triple covalent bonds with another carbon and with other
elements. This variable valency enables carbon to form fullerene, carbon nanotubes
110 P. K. Deheri and B. Kar

(CNTs), graphene, carbon nanodiamonds (CNDs), and carbon dots (CDs). Carbon
nanomaterial development and industrial uses are currently evolving at a rapid pace.
Applications in the field of nanoelectronics, gas storage, production of conductive
plastics, composites, paints, textiles, batteries with enhanced lifetimes, biosensors,
etc. are growing rapidly [82]. Carbon nanomaterials possess good electrical conduc-
tivity, heat conductivity, and mechanical properties. They are highly stable and
environmentally friendly too [83].
Carbon nanotubes possess high surface areas, high aspect ratios, and high
mechanical strength. CNT’s electrical and thermal conductivity is very high (equiv-
alent to copper). The tensile strength is also almost 100 times greater than that of
steel. All these unique properties’ combination makes CNT as very good filler
materials in polymers and ceramics to make desirable consumer products. Due to
high surface curvature, electron can easily be emitted from CNT by little application
of potential and hence can be used in electric devices as field emission sources. With
the hollow cylindrical nature, CNTs can be used as efficient gas and metal container/
storage [84]. Large surface area and high charge carrier mobility make it potential
candidates for application in various sensors. The mobility of electrons in the layers
of graphene is more than that in silicon and is explored to replace silicon in the
electronic industry.

Potential Health Risk of Nanomaterials

Nanotechnologies bring benefits and promises along with combination of risks and
uncertainties. Nanotechnologies have revolutionized many industrial sectors, such as
the electronics, agriculture, food, food safety, medicine, pharmacy, cosmetic, and
personal care, and have become an indispensible part of our everyday life, hence the
potential risk of exposure of workers, consumers, and the environment. Human body
part such as the skin, intestinal tract, and lungs are in direct contact with the
environment. Passive and/or active transport of various substances like water,
nutrients, or oxygen occurs through these three points. These three ways are the
most possible points of entry for nanoparticles. Nanoparticle injections and implants
made up of engineered nanomaterials are other possible routes of exposure [85–
88]. All nanomaterials on exposure will immediately adsorb onto human body
surface and due to the smaller size translocate easily to body tissues and organs.
The adsorption process will depend on the surface chemistry, surface energy, and
surface functionalization. The adverse effect to human health and the environment
depends on possible hazards of nanomaterials. The nanomaterial toxicity is directly
linked to the physicochemical differences from the bulk materials, their ability to
pass biological barriers, and possibility of bioaccumulation. Inhaled nanoparticle
causes asthma, bronchitis, emphysema, lung cancer, and neurodegenerative diseases
(Parkinson’s and Alzheimer’s diseases). Nanoparticles in the gastrointestinal tract
have been linked to colon cancer. Nanoparticles in the circulatory system cause
arteriosclerosis, blood clots, arrhythmia, heart diseases, and ultimately cardiac death.
Translocation to other organs such as the liver and spleen may damage these organs
6 Identification and Quantification of Nanomaterials in Consumer Product 111

as well. Exposure to some nanoparticles may lead to autoimmune diseases, such as

systemic lupus erythematosus, scleroderma, and rheumatoid arthritis [85].
The inhalation of metallic nanomaterials or other dusts causes lung disease, and
the type and severity of lung diseases depend on the nature of the material, exposure
duration, and dose. The inhalation of metal fumes like zinc and copper leads to metal
fume fever, an influenza-like reaction [85, 87]. Inhaled or ingested lead nano-
materials enter blood circulation system and end up in bone and other tissues as
deposition. Lead nanomaterial toxicity includes mental function impairment,
impaired visual motor performance, memory loss, as well as anemia, fatigue, lack
of appetite, abdominal pain, and kidney disease. Nickel nanomaterial exposure via
inhalation as dust and fumes is associated with lung and sinus cancer. Excessive
amounts of iron nanoparticles increase risk of adenocarcinomas, colorectal tumors,
hepatomas, mammary tumors, mesothelioma, and renal tubular cell carcinomas.
Organic nanoparticles could be of animal or plant origin and contain fragments
and fibers from wood, bone, fur, skin, leather, brooms, flour, grains, tobacco, carpets,
paper, etc. These nanostructures can cause the upper respiratory system, eyes, and
skin irritation and may lead to bronchitis, allergic reactions, asthma, and dermatitis.
In humans, most inhaled carbon nanoparticles get accumulated in the lung where
they induce oxidative stress and inflammation (only less than 1% get translocated).
However, nanoparticle inhalation and translocation study is challenging due to the
small size of particles and the low deposited mass. It requires extremely sensitive 13C
radio labeling [89]. Only at high exposures did the 13C label start to accumulate in
the liver, heart, olfactory bulb, brain, and kidney. It is also observed that inhalation of
iron oxide-based magnetic nanoparticles (~50 nm) for weeks leads to liver, spleen,
lung, testis, and brain deposition. The results indicated that both the blood-brain
barrier (BBB) and the blood-testis barrier (BTB) were penetrated by the magnetic
nanoparticles.

Sample Preparations

When working with pure nanomaterial characterization, sample preparation is

straightforward. However, detection, characterization, and quantification of nano-
materials in consumer product is highly challenging due to complex matrix chem-
istry and very low concentrations of nanomaterials in the matrix materials. Sample
preparations that involve removing the matrix or separating the nanomaterials from
the matrix for both qualitative and quantitative analysis are tedious tasks
[90, 91]. The physical and chemical properties of nanomaterials depend on the
surrounding matrix and can change if the matrix is removed. Unlike their bulk
counterpart, nanomaterials are highly reactive and quickly change their physical
and chemical properties when separated from matrix. Thus, the characterization of
nanomaterials in consumer products requires sample treatment techniques that are
able to separate nanomaterials from complex matrices which may contain particles
of similar composition. At the same time, sample surface chemistry manipulation
should be minimized to guarantee analytical accuracy and reduce the risks of
112 P. K. Deheri and B. Kar

artifacts. The sample preparation, storage, and measurements conditions are other
important parameters to be investigated in order to remove the undesired interaction
effect with the matrix extract. Another point of consideration is the sample quantity
that should be processed in order to be representative for the whole sample.
Although a number of techniques are available, their applications in complex
situations and at trace levels of nanomaterials are not feasible in most cases. The
necessary steps that may be required in nanomaterial characterization in consumer
products are (1) digestion, (2) concentration (centrifugation, filtration), and (3) liquid
phase extraction or solid phase extraction [91]. In every step of sample preparation
from sampling, particle extraction, or matrix removal till final quantitative analysis, a
number of quality check criteria should be in place to assess particle stability and
recovery.
Digestion: Chemical digestion involves the use of strong mineral acids (HCl,
HNO3, HF) or may be in combination with hydrogen peroxide and high temper-
atures by conventional heating or microwave heating in ambient conditions.
However, it can cause the dissolution of nanomaterials, thus losing information
about their phase purity, size, and concentration in the sample. As an alternative,
alkaline digestions have recently been proposed. Alkaline reagent Tetra-
methylammonium hydroxide (TMAH) is often employed for degradation of
organic matrices. Tetramethylammonium hydroxide (TMAH) is able to efficiently
digest organic matrix such as soft tissue and selectively extract nanomaterial
without dissolving it to free ions [92]. Enzymatic digestions have been proposed
as an effective alternative for the analysis of reactive nonmaterial in biological
tissues and meat [93, 94]. Enzymatic digestions by proteases or pectinases have
also been used to solubilize biological tissue (mammal/plant tissues) [95, 96]. How-
ever, the residue of matrix or partially degraded matrix makes the nanomaterial
analysis more complex or some time impossible causing many unresolved peaks.
Reactive metallic nanoparticles like Zn, Cu, Fe, and Ag can be digested to their
corresponding salt solution by using HCl, HNO3, and H2SO4 acid in concentrated
or dilute form. However, inert metal like Au and Pt needs aqua regia for dissolu-
tion. Dissolution of metal oxide like TiO2, SiO2, and CeO2 can be achieved by
strong HF. These acid-based digestions along with ICP-MS/ICP-OES are required
to get information of the total element content from the nanomaterials, except if the
nanomaterials are insoluble in acids.
Sample concentration: The concentrations of nanoparticles from the matrix
materials may not be in the detection limit of characterization requirements. Centri-
fugation can be considered the simplest approach to concentrate and isolate partic-
ulates from a suspension. However, unwanted solids are also isolated along with the
nanoparticles. Thus centrifugation is not an efficient technique for the fractionation
but is useful for isolation of nanomaterials from a dissolved species when ultrafil-
tration fails [90]. Performance of centrifugation depends on the size and density of
the samples. Ultrafiltration and dialysis are based on the use of nanoporous mem-
branes of different materials for nanomaterial separation. Ultrafiltration is based on
isolating dissolved species from nanoparticles; hence, dissolution of nanomaterials
in the exposure media is studied using it [97]. However, dialysis works on diffusion
6 Identification and Quantification of Nanomaterials in Consumer Product 113

principle and takes long time to achieve separation [90]. Hence, ultrafiltration is
preferred over the dialysis. Depending on composition and surface functionality of
engineered nanomaterials and the corresponding dissolved species may interact with
the membrane surfaces, affecting their recoveries. The filtration retention and elution
of an analyte depend on the size of membrane pores [98].
Isolation of NMs from the matrix: There are very few extraction procedures for
the isolation of nanomaterials from the matrix discussed in literature [91]. Cationic
surfactant in combination with an ionic liquid is used in a liquid-liquid extraction to
isolate gold nanoparticles from water and liver [99]. Ag and TiO2 hydrophobic
nanoparticles present in water samples can be quantitatively extracted into organic
solvent like hexane by surface functionalization using mercaptocarboxylic acid and
alkyl amine [100]. By adding complexing agents such as thiosulfate, EDTA, and
thiocyanate, selective extraction of Ag, AU, CuO, and ZnO nanoparticles in pres-
ence of respective cations can be performed [90]. This technique can be used to
quantify the nanomaterials from the soluble metal ions. Sample separation of organic
nanoparticles from matrix materials is very tricky. Procedures to isolate intact
organic nanomaterials from organic matrices are lacking. Solvent extraction of
organic nanomaterials generally leads to a breakup of the structure [101].

Characterization Techniques for Nanomaterials

To understand and for correct evaluation of benefits vs. risks of nanomaterials and
engineered nanomaterials, it is necessary to identify, quantify, and evaluate the
chemical and physical properties. However, characterization of nanomaterials in
food matrices and in cosmetic and personal care products poses significant chal-
lenges, due to low concentration levels and complex nature of interaction with
matrix materials. Furthermore, the interdisciplinary nature of the field makes nano-
material characterization more challenging. Analytical techniques suitable for the
detection, characterization, and quantification of nanomaterials in consumer prod-
ucts such as food and cosmetics products have been discussed in elaboration. Several
techniques have been used to characterize the nanomaterials’ shape, size, size
distribution, crystal structure, elemental composition, and other physical properties.
Most of the time, a combinatorial characterization approach is required to extract
complete information of nanomaterials used. The chemical compositions, phases
and phase compositions and crystal structure of the nanomaterials are thoroughly
investigated as a first step after synthesis. Size, size distribution, degree of agglom-
eration, surface chemistry and surface charge are then evaluated. However, till today,
there are no standardized procedures for it. The challenge with most of the nano-
material characterizations in natural environment is difficult because of the unstable
physical and chemical characteristics of nonmaterial. In colloidal system or in
solvent dispersion, nanomaterials tend to (1) interact with the surrounding solvent
molecules and other chemical compounds in natural environment, thereby acquiring
surface charge, and (2) agglomerate to substantial size and (3) sediments. Thus,
measurement of nanomaterials by one single method is a daunting, irreproducible
114 P. K. Deheri and B. Kar

Table 2 List of experimental techniques used for nanomaterial characterization

Technique Information that can be derived
Dynamic light scattering Size (hydrodynamic size), size distribution, detection of
(DLS) agglomerates
(Surface charge) Zeta Nanoparticle stability in matrix
potential, ζ
BET-surface area analysis Surface area, can differentiate nanosized materials
FTIR and UV-visible Functional group, nanomaterial surface interaction with organic
analysis compounds
X-ray diffraction (XRD) Crystal structure, phase composition (crystallinity and amorphous
content), crystalline grain size
Small angle X-ray Size, shape, size distribution, core shell structure
scattering (SAXS)
Scanning electron Secondary electron imaging (shape, size), back scattered imaging
microscopy (SEM) (phase), energy dispersive X-ray analysis (elemental analysis,
semi-quantitative)
Transmission electron Bright-field/dark-field analysis (size, shape, crystallinity),
microscopy (TEM) selected area diffraction, SAD (phase composition)

task. Nanomaterial properties can be evaluated by more than one technique that
complements each other, and all the characterization techniques have their own
strengths and limitations [64, 102]. The physical and chemical parameters of a
nanometer and the required characterization techniques are listed in Table 2 [64,
102–104].

Dynamic Light Scattering (DLS)

Light scattered when it interacts with matter and carries information related to the
physical characteristics of the sample. The scattering can be divided into three
different types and is expressed as α, a dimensionless constant that is directly related
to size parameter (Eq. 1) [105]:

πDp
α¼ ð1Þ
λ
where πDp is circumference of a particle and λ is wavelength of incident radiation.
Based on the value of α, scatterings have three different types [105]: α, Rayleigh
scattering (particles are smaller in size compared to wavelength of light, λ); α ≈ 1,
Mie scattering (particles are about same in size of the wavelength of light, λ); and
α  1, geometric scattering (particle size is much larger than wavelength of light, λ).
Particles in suspension are in constant random motion (Brownian motion) due to
interaction with the surrounding molecules of the suspending fluid. The suspended
particles are illuminated with a coherent light source (laser light). The laser light
scattering (LLS) is assumed to be Mie scattering, and both diffraction and scattering
(absorption, refraction, and reflection) of the light around the particle in its medium
6 Identification and Quantification of Nanomaterials in Consumer Product 115

are taken into account. Light scatters in all directions, and scattering intensity is a
function of the size and shape of the particles. The intensity fluctuations (caused by
Brownian motion of molecules in solution) of scattered light are analyzed. The
diffusion coefficient (Dτ) of suspended particles that is related to hydrodynamic
size of macromolecules can be obtained. The relation between the speed of the
particles (diffusion coefficient, Dτ) and the particle size is given by the Stokes-
Einstein equation (Eq. 2) [106]:

kB T
Dτ ¼ ð2Þ
6πηRH
where Dτ is translational diffusion coefficient [m2/s] – “speed of the particles,” kB is
Boltzmann constant [m2kg/Ks2], T is temperature (K), η is solvent viscosity, and RH
is hydrodynamic radius. A basic requirement for the DLS measurement is constant
Brownian motion of molecules/particles. Larger particles settle down very quickly
due to gravitational force and loss random movement (Dτ ¼ 0) that would lead to
inaccurate results. The onset of sedimentation indicates the upper size limit for DLS
measurements. On the other hand, smaller particles do not scatter much light, and
hence insufficient measurement signal leads to noise only. Signal-to-noise ratio
defines the lower size limit in DLS. In DLS, high particle concentration causes
multiple scattering so a relatively low concentration is needed to have better signal
[107]. The advantages of this technique are (1) can measure a broad range of particle
size (2–3000 nm), (2) highly reproducible and reliable as the size is from average
value of a large number of particles, (3) size data can be obtained as intensity and/or
volume distribution, and (4) almost all automated process and less labor intensive.
Disadvantages are (1) measure hydrodynamic size not actual size, (2) DLS principle
is valid for single scattering but in practice light is multiple scattered and the
contribution cannot be ignored, and (3) it cannot resolve particle mixtures of
different size.
Guideline for proper size analysis of nonmaterial using DLS [108]: To obtain a
reliable size data that can be comparable with other size analysis techniques, the
following points must be taken into consideration during sample preparation:

(a) Colored sample: If the test sample is colored, it is always recommended to check
the absorption of the laser light by the sample. Recording of transmission
spectrum of the test sample is recommended. If it is strongly absorbing, DLS
is not a recommended technique for size analysis.
(b) Sample concentration: In DLS, laser light scattering intensity will depend on
particle size, refractive index of solvent, and concentration of measuring sample.
Here, we cannot do much with size and RI of solvent; only concentration can be
personalized for analysis. Too high concentration causes multiple scattering and
high interparticle interaction, while too low concentration results in high signal-
to-noise ratio and leads to inconsistent results. It is therefore necessary to work
out to find the concentration-independent size by analyzing the size and size
distribution with various concentrations.
116 P. K. Deheri and B. Kar

(c) Effect of salt concentration: If the test particle surface is charged, electrical
double layer is formed in aqueous solution. This electrical double layer increases
viscous drag with the surrounding solvent molecules. This decreases the diffu-
sion coefficient and hence increases the hydrodynamic size. Addition of a small
amount of monovalent neutral salt (such as NaCl) will diminish this effect by
screening the electrical double layer. A high concentration of salt induces
aggregate formation in charge particles and hence results in increased particle
size and poly-dispersity. DLS measurements with some inert monovalent elec-
trolyte are highly recommended, and pure deionized or distilled water should
generally be avoided as dispersion medium.
(d) Proper equipment handling and sample preparation: The laser should be
switched on 30 min prior to measurements. It allows a stable and consistent
laser source. The cuvette, solvent measuring chamber should be dust free.
Multiple scan should be averaged out to have a consistent result.
(e) Concentration effects: In DLS measurement of an optimum concentration is
required to have reliable, error-free size data. Too high concentration causes
multiple scattering, while too low concentration does not produce enough
scattering and error in size data. Moreover, at high concentration, the particle
might not be freely mobile due to the strong interparticle interactions. This is
especially true for magnetic nanoparticles due to high dipole-dipole
interactions [109].

Analysis of nanomaterials in consumer products by DLS: Nanomaterial analysis

present within consumer products and nanocomposites is challenging for detection
and analysis. DLS technique is highly suitable for nanomaterial analysis in the liquid
phase. So, frequent sampling and treatment of consumer products before their
analysis is required. This increases error in quantitative analysis but also prevents
in situ analysis of the NPs in the environment resulting in unrealistic analysis of NPs
[105]. Furthermore, DLS measurement requires RI and viscosity value as input. It is
difficult to find and often not available for environmental samples.
The applications of engineered nanoparticles in drinking water treatment to
remove heavy metals, microorganisms, and organic pollutants appear as a very
dynamic branch of nanotechnology [110]. Hence, accurate detection of nonmaterial
in drinking water is vital in assessing the risk to the environment and human health,
as well as to control nonmaterial discharge. DLS offered good advantages as a
technique to analyze the dispersion of carbon black and carbon nanotubes in the
aquatic environment [111]. Zero-valent iron nanoparticle can be used for ground-
water remediation [105]. However, being magnetic iron highly tends to agglomerate.
Addition of guar gum can improve the stability and is monitored by DLS. The
cytotoxicity of copper nanoparticles against Escherichia coli was studied using a
designed experiment using DLS so that a correlation was obtained between toxicity
and particle size [112]. Particle size change is highly effected by the change of pH
and temperature and hence the cytotoxic effect. The changes can be tracked using
DLS. DLS was used to establish in vitro toxicology assessment of metal oxides.
Metal oxide suspensions in culture medium were studied for cytotoxicity effects.
6 Identification and Quantification of Nanomaterials in Consumer Product 117

Evaluation of particle size and formation of secondary larger nanoparticles due to

protein encapsulation was confirmed by DLS [113].
Nanomaterial uses in food supplements and food packaging include [105, 114]
(1) nanoclays as diffusion barriers as clay-polymer composite; (2) nano-silver as
antimicrobial agents; (3) TiO2 as food whitening and brightening especially for
confectionary, white sauces and dressings, and certain powdered foods; and (4) sil-
icates and aluminosilicates used in the food industry as anti-caking agents. Silicates
and aluminosilicates are also used in pharmaceuticals or nutraceuticals and tooth-
paste products. Significantly less information of DLS as analytical method to foods
is available in the literature. Almost all food materials need sample preparation for
the nanomaterials/engineered nanomaterial detection and characterization. Method
development is needed to extract nanoparticles from complex matrices without
affecting the nanomaterial surfaces as they exist in the native environment. Oxida-
tion reactions can be used in converting organic carbon to carbon dioxide or other
volatile gases. Oxidative degradation of organic matters using H2O2 at 60  C can be
helpful in extracting nonmaterial without affecting the physical properties much.
Concentrated acid (HNO3, HCl) can also be used to oxidize the organic content.
However, it may result in acid leaching of the nanoparticles [115]. Complete diges-
tion of nonmaterial using strong acid or maybe combination of acid could be useful
for total elemental analysis. However, size/shape information is lost. NaOH diges-
tion of SiO2-soap dissolves the silicon dioxide. However, acid digestion using HCl
separates SiO2 without damaging it [115, 116]. Further development is essential to
develop reliable size and size distribution analysis techniques.

Surface Charge (Zeta Potential (ζ))

The surface charge controls the nanoparticles’ interaction with themselves and with
the surrounding environment and influences their physical state in solvent, in
emulsion, or even in a solid matrix. The ζ-potential value provides indirect infor-
mation on the net surface charge on nanoparticles. Zeta potential is a physical
property exhibited by all solid-liquid and liquid-liquid colloidal systems. For nano-
particle stability, highly positive or highly negative ζ-potential value is desired. Zeta
potential of nanoparticles with the value of 25 mV has high stability [117]. High
surface charge tends to repel and doesn’t agglomerate.
Suspended particles are surrounded by a layer of opposite charge of the particle’s
surface called the Stern layer (Fig. 2) [118]. In Stern layers ions are strongly bound.
An additional layer of more loosely associated ions of opposite charge to the surface
is formed that moves with the particle and is termed as diffused layer. The whole
system forms an electrical double layer. The interface between the electrical double
layer and surrounding environment is termed as slip plane, and potential on slipping
plane is zeta potential (ζ).
During measurements, nanoparticles are made to move across an externally
applied electric potential. The velocity of particle movement is measured from the
intensity of scattered laser light. The velocity at different voltage is measured and is
118 P. K. Deheri and B. Kar

Fig. 2 Charge distribution and electrostatic potential around a negatively charged particle [118]

used to calculate zeta potential. Electrophoretic mobility (μe) is then measured and
converted to the zeta potential (ζ) using the Henry equation (Eq. 3) [118]:

2   ζ  f ðk  αÞ
μe ¼ ð3Þ
3η
where μe is electrophoretic mobility and is ratio between the nanoparticle velocity
and the external applied field. ε and η are the dielectric constant and the absolute
zero-shear viscosity of the medium respectivly. f(k  α) is known as “the Henry
function,” where α is the radius of the particle and k is known as the Debye
parameter, which represent the thickness of the electrical double layer. The
ζ-potential value is dependent on the concentration of the suspension, type of
solvent, and other additives if any. DLS can be combined with ζ-potential measure-
ments for a more complete characterization. Zeta potential measurements are rele-
vant only for sub-micron particles. Sedimentation or aggregation of the
nanoparticles leads to error in zeta potential measurement, since electrophoretic
mobility is strongly changed. Nanoparticle concentration should be in an optimum
range that must result in high signal-to-noise ratio and minimize multiple scattering
interferences.
There are many consumer products such as cosmetics, paints, inks, paper, drug
delivery, personal care, and food products that either exist in emulsion form or their
preparation steps may involve emulsion formation. The suspensions or dispersions
require stability in emulsion in order to meet expected performance criteria. Zeta
potential measurements provide information about the surface/interfacial and can
predict dispersion stability. Dispersion stability is important to prevent aggregate
6 Identification and Quantification of Nanomaterials in Consumer Product 119

formation and it controls. It is important for the ease of spreading of a paint on

substrate surface to produce a thin even film, limited spreading in the case of inks,
lipsticks and sunscreens. Even-film coverage, drug suspensions or food dispersions
must maintain stability when are stored on the shelf and prevent settling. Zeta
potential of TiO2 nanoparticle can be manipulated with the addition of surfactants
and by changing pH [119]. Optimized surfactant amount and pH can result in stable
TiO2 nanoparticle aqueous suspensions [120]. Untreated SiO2 nanoparticle surfaces
were determined to be highly negatively charged and have stable hydrodynamic
sizes in a wide pH range. In an aim to make it biocompatible, introduction of amine-
containing molecules as coating agents induces positive charge on the silica surface
that leads to agglomeration and gel-like network formation [121]. Study shows that
L-arginine coating at pH 5.5–6.5 resulted in a 15 mV zeta potential and hence a
stable colloid. Change of pH values has large effects on oxide nanoparticles’ (such as
TiO2, Fe2O3, Al2O3, ZnO, and CeO2) zeta potential values and hence their stability
in solution and even the nanotoxicity [122, 123].

BET-Surface Area Analysis

The Brunauer-Emmett-Teller (BET) technique is also used for the characterization of

nanoscale materials. It is based on the principle of physical adsorption of a gas on a
solid surface. Nitrogen is usually used because of its availability and purity. The
amount of nitrogen adsorbed to the surface of the particles is measured at 196  C
(boiling point of N2). The sample is cooled using liquid nitrogen to facilitate the gas
adsorption. The sample is then removed from the nitrogen atmosphere and heated to
facilitate the adsorbed nitrogen to be released. The amount of released/desorbed
nitrogen gas is directly related to the total surface including pores in particles. The
calculation is based on the BET theory (Eq. 4) [124]:

P=P 1 C  1
P 

0
¼ þ =P0 ð4Þ
n 1 P=P
0
nm C nm C

where n is the amount of gas adsorbed at the relative pressure P/P0, nm is the amount
of adsorbed gas needed to form monolayer, P is the pressure, and P0 is the saturation
P=
pressure of adsorption. To calculate the BET specific surface area, n 1PP=0 is plotted

ð P0 Þ
as a function of P=P0 ). From the value nm, the specific surface area (m2/g) can be
calculated [124]. Here, C is the BET constant and is related to the energy of
monolayer adsorption. From C value the shape of an isotherm in the BET range
can be obtained. The volume-specific surface area (VSSA) can be obtained by
multiplying the specific surface (S) by its density [125]. It is conventionally stated
in units of m2/cm3. When the VSSA is larger than 60 m2/cm3, the material is
considered as nonmaterial according to EC (European Commission) definition
[125, 126]. It is based on the hypothesis that nonporous and monodisperse spherical
particles of 100 nm constituent particle size have SSA of 60 m2/cm3.
120 P. K. Deheri and B. Kar

FTIR and UV-Visible Spectroscopy

Fourier transform infrared (FTIR) and UV-visible spectroscopy are one of the most
important techniques available for material analysis. The techniques are based on
the absorption or scattering of electromagnetic (EM) radiation when passed
through materials. In its simplest form, an EM is passed through the analytes and
the intensity of a beam of light is measured before and after passing through the
sample. The difference of the intensity is plotted as a function of wavelength. The
electromagnetic (EM) radiation gets absorbed due to change in electronic transi-
tion in materials (UV-visible spectroscopy) or change in dipole moment in matter
(Fourier transform infrared spectroscopy). Infrared spectroscopy (FTIR) measures
the absorption of electromagnetic radiation in the mid-infrared region (4000–
400 cm1). The qualitative aspects of FTIR spectroscopy are one of the most
versatile analytical techniques to identify functional group and bond. It is possible
to deduce whether specific functional groups such as CO, NH, NH2, C¼C,
aromatic ring, etc. are present or not. However, it is not always possible to fully
characterize a compound only by examining its IR spectrum. Chromatography,
mass spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and various
other spectroscopic techniques in combination with FTIR can be used to get much
information needed for nanomaterials or the functional group attached to
nanomaterials [127].
The IR spectra of clay nanoparticles show well-defined absorption bands
corresponding to OH and Si-O stretching and bending vibrations. The OH group
stretching vibrations absorb in the 3700–3500 cm1. Bending vibrations of OH
groups absorb in the 950–650 cm1 regions. The Si-O stretching appears in the
1050–1000 cm1, while strong bending vibrations appear in the 550–400 cm1
region [128].
Incorporation of clay (montmorillonite) up to 5% into plastic can reduce the water
and oxygen permeability and can preserve food materials for longer time. FTIR
spectra can be helpful in identifying Si-O stretching that corresponds to clay. Along
with it, asymmetric Si-O-C stretching at 1000 cm1 and Si-CH2-R deformation at
1250 cm1 are useful information in deducing clay-polymer structure
[129, 130]. The FTIR spectrum of ZnO nanoparticle band at 1608 cm1 is due to
the OH bending of water. This indicates the presence of a small amount of water
adsorbed on the ZnO nanocrystal surface. A strong band at 465 cm1 is attributed to
the Zn-O stretching band [131], while Mn-O stretching vibration appears at 560–
530 cm1 and Ti-O stretching vibration appears at 800–450 cm1 [132, 133]. For
surface functionalization of TiO2 for UV protection applications, FTIR study can
provide a clear bonding nature in it [134–136]. The disappearance or peak shifting of
functional groups of organic compounds confirms the interactions of nanomaterials
with the surface active agent. In general a free carboxylic acid C¼O stretching
appears at ~1750 cm1. The broad shoulder peaks at ~1650 cm1 in TiO2-citric acid
composite confirm the interaction [137]. This shift in CO stretching is due to the
6 Identification and Quantification of Nanomaterials in Consumer Product 121

M-CO bonding that weakens the C¼O bond strength and results in shifting to low
energy band. Incorporation of nanoparticles into fabric materials can be confirmed
by FTIR analysis. For example, coating of TiO2 nanoparticles on polyester (PET)
fabrics resulted in 415, 484, and 494 cm1 compared to untreated PET. Moreover,
ZnO nanoparticle coating on PET shows new IR bands at 419, 441, and
484 cm1 [138].
The most important application of UV-visible spectroscopy is to give the infor-
mation about the nonmaterial’s interaction with light and to determine the functional
group in the material. It confirms the presence or absence of a chromophore in the
sample which is responsible for the color of the compound. The ability of a fabric
treated with nanoparticles or a sunscreen containing nanomaterials to block UV light
can be estimated by the ultraviolet protection factor value (UPF) using Eq. 5. The
measurement of UPF value can be performed using a UV/visible spectrophotometer
[139, 140]:
P400nm
280 nm Eλ Sλ Δλ
UPF ¼ P400nm ð5Þ
280 nm Eλ Sλ T λ Δλ

where Eλ is relative erythemal spectral effectiveness, Sλ is spectral irradiation of the

skin in UV region (280–400 nm), Tλ is spectral transmittance of the fabric, Δλ is
increment relating to wavelength, and λ is wavelength in nanometer.
UV-visible spectroscopy too plays an important role in characterizing polymer
matrix nanocomposite. PMC with tunable optical properties such as refractive index,
UV absorption, transparency, luminescence, etc. are of great significance to develop
materials for potential applications. Applications include light-emitting diodes, solar
cells, polarizer, color filters, optical communication, data storage devices, and
optical sensors and in the biomedical field [141]. Isotropic metal nanoparticles can
be distinguished from the anisotropic one by UV-visible spectrometry. The surface
plasmon resonance (SPR) of spherical metal nanoparticles produces a single absorp-
tion peak. However, asymmetric particles such as ellipsoid and nanorod produce two
absorption peaks and are independent of aspect ratio. Moreover, the FWHM (full
width half maxima) of the peak carry the nanoparticle size information
[142, 143]. UV-Vis spectroscopy is one of the important techniques to understand
the optical properties of semiconductor nanomaterials too. One such most frequently
used method is Tauc plot [144, 145]. The absorption coefficient (α) is related to the
optical bandgap energy and is expressed as (Eq. 6):


ðαhνÞ2 ¼ constant  hν  Eg ð6Þ

where Eg is the bandgap energy, h is the Planck constant, and ν is the electromagnetic
radiation frequency. For direct bandgap calculation, (αhν)2 have to be plotted against
hν and bandgap can be derived by extrapolating the linear portion of the curve to
zero absorption.
122 P. K. Deheri and B. Kar

X-Ray Diffraction (XRD)

X-ray diffraction is based on constructive interference of monochromatic X-rays

when it is reflected from an ordered crystalline solid. The scattering is coherent and
intensity is significant only along a few well-defined directions stated as Bragg’s law
(Eq. 7):

nλ ¼ 2dhkl sin θ ð7Þ

where n is integer, λ is the X-ray wavelength, dhkl is interplanar distance of (hkl)

plane, and θ is the angle between incident beam and the crystallographic plane,
which is equal to half of the scattering angle 2θ. This law relates the wavelength of
electromagnetic radiation to the diffraction angle and the lattice spacing in a crys-
talline sample. Bragg’s law can be deduced from Fig. 3. If we compare the X-ray line
path length, it is cleared that line 2 is travelling 2dsinθ length more than the line
1. So, both the line will be in phase and form a constructive interference if only
2dsinθ is equal to integral multiple of λ. X-ray is generated using an X-ray generator
and passes through a monochromator. The monochromatic X-ray is then incident on
sample to be analyzed, and the diffracted rays are collected through a range of 2θ
angles. A plot of intensity vs. diffraction angle is obtained as diffractogram. The
XRD plot can be represented as intensity vs. d spacing too. d-Spacings allow
identification of the mineral as each mineral has a set of unique d-spacings. Typi-
cally, this is achieved by comparison of d-spacings with standard reference patterns.
X-ray diffractometer has three main components: X-ray tube, sample holder, and
an X-ray detector. X-ray is produced in a cathode-ray tube; a high-voltage applica-
tion between hot anode and water-cooled cathode produces electrons and accelerates
toward target cathode. In collision with the cathode materials, electrons lose energy
and the lost energy radiates out as white X-ray. When electrons have sufficient energy
to knock inner shell electrons of the target material, characteristic X-ray spectra are
produced. The produced X-rays are characteristic of target metal (Cu, Mo, Fe, Cr).

Fig. 3 Bragg’s law;

scattering and diffraction of
X-ray
6 Identification and Quantification of Nanomaterials in Consumer Product 123

These spectra consist of several components (Kα, Kβ) and have to be passed through
monochromator to obtain the desired monochromatic X-ray.
X-ray powder diffraction is most widely used for identification of unknown
crystalline materials and measurement of sample purity. In combination with
Rietveld refinement techniques, quantitative analysis such as phase percentage and
amorphous content and determination of unit cell parameters can be performed. The
XRD technique can be used to extract informations of nanomaterial with no signif-
icant difference from the microcrystallines. However, it should be noted that there is
considerable peak broadening with size reductions and it can be used for crystallite
size determination. The crystallite size D is related to FWHM of the XRD peaks
(Eq. 8) [146]:

Kλ
D¼ ð8Þ
β cos θ
where D is average crystallite size, K is Scherrer constant and is 0.9, β is FWHM, and
θ is the Bragg angle. However, for accurate crystallite size estimation, the instru-
mental peak broadening has to be considered. The size obtained from XRD peak
broadening is from crystallite size. So, don’t confuse it with particle size unless it is
cross verified with electron microscopy imaging or any other direct imaging
techniques.
The phases in a nonmaterial or in composites present can be confirmed from the
comparison of experimental data with the standard XRD pattern. The phase per-
centage can be obtained by comparing the intensity of the peaks. However, manual
comparison can lead to lot of errors as amorphous content is unknown; the intensity
also depends on the X-ray absorption coefficient. Rietveld refinement is an effective
way of analysis to extract all these information with minimum error. In this method
the experimental XRD is compared with a simulated pattern using FullProf/TOPAS
software. The experimental data is fitted with the standard pattern using the non-
linear least squares approach. Instrument parameters are kept constant, and sample
displacement error, lattice parameters, crystallite size, and intensity (scale factor) can
be refined to calculate the simulated patterns.
For untreated commercial sunscreens, XRD analysis confirms the presence of
TiO2 and ZnO nanoparticle with the size information from the peak width
[147]. However, the TEM analysis returns a different size value. The atomic
arrangement of a nanoparticle surface is not in order and does not diffract or result
in incoherent diffraction. Hence, in XRD, size analysis excludes the surface
amorphous-like structure part. Hence it is expected that the XRD size estimation
always gives smaller in size value than a direct imaging technique. XRD has the
limitation to determine particle size, and even crystallite size larger than 200 nm
cannot be calculated. XRD cannot detect materials if the weight percentage is below
0.5–1 wt% depending on XRD equipment power and sensitivity. Such difficulty can
be overcome by using any other complementary techniques such as SEM and TEM.
Polymer-clay nanocomposites enhance the polymers’ mechanical, gas barrier,
flame-retardant, electrical, and biodegradable properties. However, the properties’
124 P. K. Deheri and B. Kar

Fig. 4 (a) Clay-polymer composite, tactoid, intercalation, and exfoliation, (b) XRD pattern of
clay-polymer composite (clay, intercalation, and exfoliation) [148]

enhancement depends on the clay nanomaterial dispersion in polymer matrix. The

composite can be [148] (a) tactoid, (b) intercalation, and (c) exfoliation (Fig. 4). The
classification is based on the interaction of polymer with clay nanoparticles and the
extent of clay layer separation. In tactoids, polymers are bound to clay nanoparticle
surfaces. So, the layer structure is intact and resulted in a well-defined XRD peak
along (001) plane (Fig. 4). But as polymer molecules enter the clay layer, the basal
plane d001 spacing increases and hence the XRD peak position shifts to a lower
value. In the third case (exfoliation), clay layer structure is completely lost and hence
the XRD peak disappears [148]. Surface functionalizations/modifications of textile
fabrics with metal oxide, clay, and metal nanomaterials are carried out to improve
UV-blocking, fire-retardant, and antimicrobial properties. The presence or binding of
these nanomaterials on textile surface is confirmed by XRD analysis
[149, 150]. Even XRD study is a very handy tool in analyzing the surface oxidation
of stabilized metallic nanoparticles [151].
Small angle X-ray scattering (SAXS): In small-angle X-ray scattering (SAXS)
techniques, elastic scattering of X-rays by a sample is recorded at 0.1–10 measured
from the incident beam axes. This scattered X-ray contains information regarding the
structure of scattering particles [152]. SAXS can resolve structural information of
nanomaterial size ranges between ~0.5 and ~100 nm. The size resolution limits
depend on the X-ray wave length (λ ¼ 1.5406 Å, copper target), sample-to-detector
distance (SDD), the pixel size and geometry of the X-ray detector, and size of the
beam stopper (SAXS setup is shown in Fig. 5) [152].
The scattering intensity I(q) from a collection of particles can be expressed as
[153]:

I ðqÞ ¼ NS ðqÞPðqÞ ð9Þ

where N is number of particles, S(q) is structure factors and carries the spatial
arrangement information of particles, and P(q) is form factor and is related to spatial
6 Identification and Quantification of Nanomaterials in Consumer Product 125

SDD

-ray
red X
X-ray beam Scatte q
2θ

Sample

Beam
stoper

2D detec
tor

Fig. 5 Schematic of a SAXS setup [152]

electron density. Hence, it carries the influence of particle shape and size distribu-
tions in small-angle scattering intensity. q is diffraction vector and is given by:

4π
q¼ ð10Þ
λ sin θ
A proper data processing obtained from SAXS measurement allows to calculate
an overall picture of the nanoparticle sizes, shapes, and/or relative position of
nanoparticles [152]. In SAXS data simulation, each nanoparticle is assumed to
have simple geometrical shape, such as sphere, ellipse, or rod. Still, the SAXS
technique has proven to be a powerful tool to determine the mean size, size
distribution, shape, and the surface structure. As nanoparticles are increasingly
incorporated into many of consumer products, it is more important to gain a deep
understanding of their structure-property relationships in the matrix itself. Modern
SAXS techniques are effective in situ characterization. Iron oxide core with PEG
shell is well characterized by SAXS [154]. The core size and size distribution
information is obtained along with the shell (PEG) swelling behavior using this
technique. SAXS analysis of carbon nanotube (CNT) embedded in resin matrix can
be able to distinguish the alignment of CNT and can be used to interpret the obtained
properties [155]. Conventional nanoparticle characterizations present in aerosol
involve separation of nanoparticle from the matrix materials. So, correct measure-
ments are difficult as it may change the physical and chemical properties. This
shortcoming can be addressed by usage of synchrotron-based in situ SAXS tech-
nique and can be successfully used to differentiate individual particles from the
aggregates [156]. The distribution, layer orientation, and degree of intercalation into
clay layers in a polymer-clay composite can well be studied using directional SAXS
technique [157, 158]. SAXS results are more statistically average than TEM imaging
126 P. K. Deheri and B. Kar

as sample size is high in SAXS. Moreover, the estimated size is found to be in good
agreement with other imaging techniques such as TEM [153].

Scanning Electron Microscopy (SEM) and Transmission Electron

Microscopy (TEM)

Electron microscopy helps to observe materials at a nanometer level with high

resolution. It is considered one of the most powerful techniques for its capability
to visualize nanoparticles size, shape, or aggregation state. This information can be
used as complementary information to interpret results from other techniques. The
combination of electron microscopy with complementary techniques such as energy
dispersive X-ray spectroscopy (EDXS) and electron diffraction (ED) is even more
informative. However, there are some limitations to these techniques: (1) high
energy of the electron beam can cause damage to biological specimens, (2) high
vacuum may cause biological specimen cell wall disruption, and (3) sample prepa-
ration for TEM is complex and multiple steps are involved such as sample thinning,
fixation, sectioning, and grinding to make electron transparent.
Scanning electron microscopy (SEM): In scanning electron microscopy (SEM),
a high energetic electron beam is generated at the top using electron gun (Fig. 6a)
[159]. There are two types of electron gun: field emission guns (tungsten tip coated
with ZrO2, strong electrostatic field induces electron emission) and thermionic guns
(tungsten filament, LaB6 is heated to emit electrons). The emitted electron is
accelerated and focused on sample surface using a series of electromagnet. The

a Electron b First condenser lens

source

Second condenser lens

Anode Anode
Condenser aperture

Electron beam

Condenser First condenser lens

lens
Sample
Scan coils Objective lens
Select area aperture
ele ndary
det tron

Objective
or

First intermediate lens

ect
o

lens
c
Sec

Sample Second intermediate lens

Projector lens

Screen

Fig. 6 (a) Schematic of scanning electron microscopy (SEM) and (b) transmission electron
microscopy (TEM) [159]
6 Identification and Quantification of Nanomaterials in Consumer Product 127

sample surface is scanned using the high-energy focused electron beam by the help
of a scanning coil. Magnification is the ratio between scanning sample area (Raster)
to the image display area. When high energy electrons collide with the sample, four
different types of interaction are observed: (1) knockout inner shell electron (sec-
ondary electron, low energy electron, 10–50 eV), (2) elastic scattering electron
(BSE, high energy equivalent to primary source electron, >50 eV), (3) characteristic
X-ray is emitted (EDXS analysis), and (4) Auger electrons. Secondary electrons are
generated at the sample surface and carry the morphological information such as size
and shape. BSEs are elastically scattered electrons and are directly related to atomic
number Z (gives atomic number contrast). Heavier elements resulted in brighter
images than the light elements. The ejected secondary electron leaves an empty
space in inner (K, L) shell. To fill the empty shell, an outer orbital electron leaps from
high energy level and the energy difference is emitted as X-ray. This X-ray is
fingerprint to each element and can be used for qualitative and semi-quantitative
analysis called EDX/EDS analysis.
The size/shape analysis of bare nanoparticles is much easier in terms of sample
preparation, characterization, and analysis. The characteristic features are prominent
(Fig. 7a, b) [160]. However, it does not confirm the phase present. XRD analysis can
be used as complementary information for phase formation and purity. EDX analysis
can be also carried out to confirm the elements present. Fabric treated with 2 wt% of
ZnO2 and TiO2 shows excellent UV light blocking (UPF greater than 50). The
hydroxyl and carboxylic acid groups are anchoring the nanoparticles on fabric.
The uniform coating is confirmed by SEM imaging (Fig. 7c, d) [138]. The uniformly
distributed brighter spot is presumed to be nano ZnO2 and TiO2 particles. BSE
imaging along with EDX analysis could have been used to extract more information
in characterizing these nanomaterials bonded to fabrics. In BSE the nanoparticles
will be resulted in brighter spot than the fabric due to high atomic number (Z) value.
EDX can be used in elemental analysis. XRD analysis of this composite can be a
handy technique too to prove the presence of ZnO2 and TiO2 particles. But XRD has
its limitation in detection below ~0.5 wt percentage that may vary depending on
equipment. Ag nanoparticles-treated fabrics are good as antibacterial and antifungal
properties and can be used for wound dressing. From the secondary electron imaging
of silver-cellulose composite, it is difficult to infer the presence of silver nano-
particles (Fig. 7e) [161]. However, the EDX analysis confirms the presence of Ag
elements (Fig. 7f) [161].
Transmission electron microscopy (TEM): Electron beam is transmitted
through the sample, and the interference of the transmitted and the diffracted electron
beams forms the basis of bright-field imaging. Bright-field image can be formed by
selecting the centered electron beam. The image contrast is originated from the
thickness and phase difference. The deflected electrons only can also be used to form
an image by blocking the centered beam using select area aperture known as a dark-
field image. In this imaging technique, the crystalline phase will form brighter region
than the amorphous phase. The objective lens form diffraction pattern at back focal
plane with electron scattered from crystal planes of crystallites. Both image and
diffraction patterns are formed simultaneously in TEM, but it depends on the
128 P. K. Deheri and B. Kar

Fig. 7 SEM imaging of consumer products. Secondary electron imaging of ZnO (a) nano-pencil,
(b) nano-flowers, (c) nano-TiO2-coated fabrics, (d) nano-ZnO-coated fabrics. (e) Secondary elec-
tron imaging of Ag NPs-cellulose composite and (f) EDX analysis of Ag NPs-cellulose composite
[138, 160, 161]

focusing of intermediate lens to form/see image or diffraction pattern on the viewing

screen. TEM is widely used as a complementary tool to XRD to help determine the
nature of polymer-clay nanocomposites. Figure 8 shows typical images of an
intercalated and an exfoliated nanocomposite [148].
As discussed earlier, the XRD peak of (001) plane shifts to a lower two-theta
value due to polymer insertion in layer structure. The same can be confirmed from
the TEM image (Fig. 8a). The layer spacing of (001) plane is ~1.6 nm and
increases to ~2.9 nm due to intercalation. However, in exfoliation stacking of
(001) plane is lost and corresponding XRD peak disappears. From Fig. 8b, one
can infer that the stacking of (001) plane is lost completely and clay layers are
uniformly dispersed in polymer matrix. This exfoliation state resulted in achiev-
ing maximum mechanical properties with low clay loading. Even the gas and
moisture barrier property is improved for a composite and can preserve food for
long time without any deterioration to food quality. Figure 9a shows the bright-
field imaging of TiO2 separated from commercial sunscreen [162]. The presence
6 Identification and Quantification of Nanomaterials in Consumer Product 129

Fig. 8 Bright-field imaging of polymer-clay composite: (a) intercalated and (b) exfoliated com-
posite [148]

Fig. 9 (a) Bright-field TEM micrograph of TiO2 separated from commercial sunscreen, (b) EDX
analysis, (c) silver nanoparticle in antimicrobial solution, and (d) size distribution calculated using
Image J software [162, 163]
130 P. K. Deheri and B. Kar

of Ti is further confirmed by EDX analysis (Fig. 9b). Commercially available

sunscreen product has very low quantity of nano-TiO2. Sample separation/con-
centration is required prior to TEM analysis. The observed high aggregation
might be as a result of removal of surfactant/stabilizing agent from the sunscreen
lotion. Furthermore, antimicrobial liquid products intended for humans contain
silver nanoparticles. The TEM analysis shows ~12 nm particles with a narrow
size distribution (Fig. 9c, d) [163]. In this case there was no need to separate the
nanomaterials from its original dispersion solution. And hence a well-dispersed
particle can be observed with a very narrow size distribution.
A number of analytical methods have been discussed that are used in nano-
material characterization. Each technique has its strengths and drawbacks. The
information that can be obtained includes elemental compositions, phase/phase
purity, size/shape, size distribution, and physical state of it in matrix materials. It is
impossible to get all the information regarding the nanomaterials present in any
product using just one or two characterization techniques. It can only be character-
ized fully by a combination of analytical techniques. There are several factors that
complicate the development of methods to detect and to measure nanomaterials in
consumer products: (i) the complex interaction with matrix and the need of special
sample preparation procedure; (ii) the lack of standard characterization procedure;
and (iii) the development of new analytical techniques and strategies. Most of the
research is focused in the area of detection and characterization of nanomaterials.
Separating the nanomaterials from the product matrix alters the physicochemical
characteristic of nanomaterials. More development in sample preparation method is
needed.
The current most widespread technique that is used for size/shape and state of
dispersion is electron microscopy. However, in electron microscopy
(SEM/TEM), the sample size is too low to be considered as the representative
of any product. The observation must be substantiated with other techniques like
DLS or XRD technique. However, XRD results give crystallite size, not particle
size. Again, DLS measure hydrodynamic size, not the actual particle size. So, the
investigator has to be careful in comparing both results. Coupled with other
characterization methods, UV-Vis spectroscopy is an essential tool to evaluate
optical properties of nanomaterials in consumer products. FTIR spectroscopy is a
very strong analyzing tool to identify surface functional group. The same
UV-Visible and FTIR equipment can be used to study UV and/or IR blocking
capacity of any materials for different applications. However, it may not produce
the same result for bare nanoparticles as well as for nanoparticles in matrix
materials. SAXS is another effective analytical tool in determining the size and
shape of nanomaterials and core-shell structures. However, it involves complex
mathematical modeling for data interpretation. So, it is always better to comple-
ment the observation with electron microscopic imaging study which is direct
evidence to microstructure. Moreover, the microstructural study in combination
with SAD pattern and EDX analysis further confirm phases and elements present
in the nanomaterials.
6 Identification and Quantification of Nanomaterials in Consumer Product 131

Conclusions

The characterization of nanomaterials in consumer products such as food, cosmetic/

personal care products, textiles, and paint is tricky and needs extensive work. Sample
preparation often is the most challenging step. Nanomaterials in consumer products
are very difficult to characterize due to complex interactions with the matrix mate-
rials as well as very low concentration in some product. Separation of nanomaterials
for characterization involves basically three steps: (1) digestion, (2) concentration,
and (3) separation. However, taking out the nanomaterials and characterization may
not give the exact physicochemical properties.
DLS in combination with zeta potential can be used for size, size distribution, and
stability of nanoparticle analysis. UV-Visible spectra can be utilized to determine UV
blocking capacity of nanomaterials present in consumer product. X-ray diffraction
(XRD) is helpful in phase identification and crystallite size determination. The
information can be used as complementary information to the microstructural
image from electron microscopy. Small angle X-ray (SAXS) is also a powerful
technique in nanomaterial size and shape determination in the matrix material itself.
So, it gives more reliable information that can be correlated to the physicochemical
properties of nanomaterials in matrix materials. However, one single characteriza-
tion technique is not sufficient to extract all information of a nanomaterial that is
required for applications in any product. Hence, a combination of analytical tech-
nique is usually required. So, the researcher or investigator’s strong understanding in
this field is required to choose the correct set of characterizations to get all the
necessary and reliable information for any specific application.

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 Part III
Consumer Nanoproducts Based on Polymer
Films and Bio-hybrid Polymer Nanofiber
Polymer-Hybrid Nanocomposites Films
and Fiber-Based Nanoproducts 7
Kamlesh Kumar and Sunita Mishra

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
Packaging Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Sensor and Actuators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
Electronic Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
Filters and Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Energy Storage and Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Thermal Barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Electromagnetic Interference (EMI) Shield Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

Abstract
Polymer hybrid nanocomposite films and fibres have many industrial applications
in packaging, sensors and actuators, electronics, biomedical, energy storage,
filters and separators, etc. Different polymers and their hybrid composites with
metal, and ceramics are used to produce various products for variety of applica-
tion in different sectors. In present chapter, we discuss the polymer and polymer-
hybrid nanocomposite film and fibres-based materials and their products. The
chapter start with application of different polymer and hybrid nanocomposites
films and fibres in packaging, sensor, biomedical and electronic industries.

Keywords
Polymer · Hybrid nanocomposite · Films · Fibres · Nanoproducts

K. Kumar · S. Mishra (*)

CSIR-Central Scientific Instruments Organisation, Sector-30, Chandigarh, India
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India
e-mail: [email protected]; [email protected]

© Springer Nature Singapore Pte Ltd. 2022 143

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_15
144 K. Kumar and S. Mishra

Introduction

Polymer hybrid nanocomposite films and fibers have many industrial applications
due to their low cost, light weight, and easy production. They are extensively used
for packaging, sensors and actuators, electronics, biomedical, energy storage, filters,
and separators [1–10]. Polymers such as polyimide, polyethyleneimine, polyvinyl
alcohol, poly(4-vinyl pyridine), and polyimide along with nanomaterials such as
metal oxide nanoparticles, carbon nanotubes, graphene, and multi-walled carbon
nanotube can be used to produce polymer hybrid films and fibers, and their proper-
ties such as thermal, electrical, mechanical, and rheological can be tailored according
to the application in various sectors [11–16]. In the present chapter, we discuss the
polymer and polymer-hybrid nanocomposite film and fiber-based materials and their
products. An example of practical application of polymer-hybrid nanocomposite for
wireless pressure sensor monitoring system is shown in Fig. 1 [17].

Fig. 1 Wireless blood pressure sensor (a) sensor matrix, (b) optical images of a PVDF-HFP/PEDOT
array on an inkjet-printed electrode PEDOT:PSS/PET film, (c) pressure mapping with custom-made
Bluetooth board (bottom), (d) spatial pressure mapping of sensor array, (e) blood pressure sensor on
wrist band, (f) display using smart phone. (Reprinted with permission from ref. [17])
7 Polymer-Hybrid Nanocomposites Films and Fiber-Based Nanoproducts 145

Different applications of polymer nanocomposites films and fibers are discussed

in details in the subsequent sections.

Packaging Products

Petroleum resources are widely used to make traditional polymer packaging mate-
rials; however, these materials do not have environmental sustainability. The poly-
mer hybrid nanocomposite thin film has replaced the traditional packaging materials
due to their better properties and multifunctionalities. The environmental issue and
human health threat can be solved by using biodegradable polymer packaging films.
Different biodegradable polymer hybrid materials have been prepared for packaging
applications [18].Wang et al. have reviewed the applications of different chitosan
biopolymer composite films showing various properties used for food packaging
applications [19]. Moreover, polymer hybrid nanocomposite materials can provide
new sensing and food packaging solutions. For example, polylactic acid hybrid
nanocomposite films are lightweight, have different colors, and are superior
thermo-mechanical resistant for food packaging applications [20].
The conductive paper made of natural cellulose fibers and conductive polymers
have potential to be used as packaging material for electronic equipments or anti-
bacterial applications [21] (Fig. 2).
The polymer matrix with uniformly dispersed nanoparticles in the polymer results
in a high matrix-filler interfacial area with enhanced thermo-mechanical properties
[22]. A wide range of polymer nanocomposites fibers using nanoparticle and poly-
mer matrix are used for nanofillers. These nanofillers can be utilized in civil
structures, automobiles, aerospace packaging, thermal materials, and other consumer
products.

Fig. 2 Polymer inorganic hybrid composite film for food packaging applications. (Reprinted with
permission from ref. [18, 19])
146 K. Kumar and S. Mishra

Sensor and Actuators

Polymer films are useful materials to make rapid and reversible sensors due to low
cost, light weight, simple fabrication techniques, and easy tunable physical proper-
ties. Polymer film can be deposited or mixed with various substances like inorganic
and ceramic materials. Sensing effects by polymer film demonstrate the relationship
between physical and chemical phenomena in terms of electrical or optical signal.
The sensing mechanism can be generated by ion exchange membrane, conductive,
dielectric polymer, and optically sensitive polymers to measure humidity, bioactive
molecules, pH, temperature, and presence of specific ions [23]. Conjugated poly-
mers have tremendous potential as a chemosensor for onsite monitoring of the food
quality and safety in the food processing industry [24]. Moreover, formaldehyde can
be sensed in seafood products by a biodegradable hybrid polymer film [25]. Hydro-
gen gas sensor can be prepared by polymer palladium nanocomposite materials
[26]. Siloxane polymer film containing gold nanoparticle enhanced colorimetric
detection of cardiac troponin [27] (Fig. 3).
Polymer hybrid nanocomposite film can be used as actuators to give response to
external stimuli such as light, magnetic, electrical, temperature, or pH [28]. This
actuation effect is useful for the tissue engineering, drug delivery, soft robotics, and
micro-mechanical applications. Some polymer thin film-based actuators such as a
UV-visible light-driven liquid crystal polymer-based photomechanical motor [29],
natural sunlight response actuator [30], and a polymer-based flexible solvent respon-
sive membrane[31]are shown in Fig. 4.
Due to the large surface area and enhanced electrical and electrochemical prop-
erties, polymer hybrid nanofibers are used as sensing materials for high sensitivity
and fast response for determining humidity hydrogen peroxide, glucose, and

Fig. 3 (a) Conjugated polymer film-based chemical sensors. Reprinted with permission from ref.
[24], (b) polymer membrane-coated palladium nanoparticle and graphene hybrid sensor for highly
sensitive hydrogen gas sensing with gas selectivity. (Reprinted with permission from ref. [26])
7 Polymer-Hybrid Nanocomposites Films and Fiber-Based Nanoproducts 147

Fig. 4 (a) Electroactive polymer composite artificial muscles. Reprinted with permission from ref.
[29]. (b) Sunlight actuating polymer film. Reprinted with permission from ref. [30]. (c) Actuating
flexible nanoporous poly(ionic liquid) paper-based hybrid membranes. (Reprinted with permission
from ref. [31])

pH. The piezoresistive pressure sensors were used to develop the wearable device
using 3D membranes of conductive polymer nanofibers [17]. Nanofiber composites
made of conducting polymers, polyelectrolytes, and semiconductors are used for the
development of various types of gas sensors, and these sensors have more sensitivity
and faster responses, compared to the thin film sensors [32]. The magnetic polymeric
composite nanofibers can be used to design sensor and actuators depending on their
magneto-optical and magnetoresistive properties [33]. Nanofibers composed of
polyaniline, chitosan, and single-walled carbon nanotubes have been used as dual-
mode actuators based on pH and redox reactions [34]. A self-powered pressure-
sensitive polymer composite nanofiber-based fabric sensor was developed for the
human health monitoring applications [35].

Electronic Applications

The polymer hybrid nanocomposite films have attracted significant attention in

electronic industries due to their better flexibility, low density, low manufacturing
cost and better optical parameters. Conductive polymers composites films are used
to fabricate flat, flexible screen for computer and televisions. Flexible electronic
circuits are prepared by depositing conductive polymer film on the flexible substrate.
These flexible electronic materials can be bent and stretched into any shape at any
time. These kinds of devices can be used on curved substrates and easy to roll and
pack when not required [36, 37] (Fig. 5).
148 K. Kumar and S. Mishra

Fig. 5 Future flexible, bendable, rollable, and foldable touch panel. (Reprinted with permission
from ref. [36–38])

Fig. 6 Different uses of polymer composite for biomedical applications. (Reprinted with permis-
sion from ref. [39])

Biomedical Applications

Polymers are broadly utilized for biomedical applications such as for tissue engi-
neering, scaffolds, and implants, but its mechanical properties are not comparable to
the natural bone and tissues. Polymer hybrid nanofibers and films with optimal
mechanical and biological features can be used to overcome the limitations of
polymers. Polymer composite films have advantages for biomedical application
due to good biocompatibility, biodegradability, highly smooth surface, high corro-
sion resistance, chemical inertness, and nontoxicity [39]. Control drug delivery and a
variety of medical products such as disposable surgical cloths, gloves, medical bags,
and dialysis bags are some of examples in this category (Fig. 6).
7 Polymer-Hybrid Nanocomposites Films and Fiber-Based Nanoproducts 149

Polymer nanocomposites fabricated ceramic/metallic nanoparticles in the poly-

mer matrix are promising material for tissue engineering, bone regeneration, and
drug delivery applications [40]. Studies on the lipid-coated nanofibers drug-loaded
nanocomposite have shown an improvement in the drug sustained release profile
[41]. Polymer nanofibrous scaffolds exhibited excellent mechanical properties for
various vascular tissue engineering applications due to their reliable
cytocompatibility and hemocompatibility [42]. The combination of CNT with bio-
molecules such as chitosan or heparin can be used to develop novel scaffolds with
the properties of expediting cell growth [43]. Biodegradable polymer nanofibrous
scaffolds of poly(D,L-lactide-co-trimethylene carbonate) with impressive shape
memory properties have been found to have bone-forming ability [44].
Poly(ε-hydroxybutyrate-co-ε-hydroxyvalerate) PHBV–gelatin fibers can be used as
an alternative carrier for ocular surface tissue engineering and as an alternative
substrate to amniotic membrane [45]. PLGA–tussah silk–graphene oxide have
excellent protein and bacterial antifouling characteristics suitable for bone tissue
engineering [46].

Filters and Separators

Polymer composite membranes have various applications in water purification, food

processing, and gas separation. Depending on the pore size, these membrane can be
used for microfiltration, ultrafiltration, nanofiltration, and reverse osmosis [47]. Poly-
mer-inorganic composite hybrid membranes exhibit extraordinary gas separation
properties for vapor–gas separation applications [48]. Polymer hybrid nano-
membrane can be used for airborne nanoparticle filtration [49] as well as water
purification [50] (Fig. 7).
A reusable membrane was developed by using polysulfone with NaOH nano-
particles and a thin layer of polyamide polymer for oil–water separation process
[51]. The cellulose/polyvinylidene fluoride-co-hexafluoropropylene nanofibers hav-
ing super oleophobic properties can be used for selective separation of water from oil
[52]. Different combinations of polymers, ceramics, metal oxides, and carbonaceous
material can be used to fabricate nanofiber membranes for removing wastes from
water [53].

Energy Storage and Generation

Conductive polymer composite materials are fascinating for high-energy storage

applications owing to their light weight, flexibility, low cost, controllable resistance,
and excellent electrochemical properties. Composites of conductive polymers with
flexible substrates are used to make flexible supercapacitors [54]. Moreover, flexible
piezoelectric polymer-based energy-harvesting systems can be used for roadway
applications [55]. Polymer hybrid composites nanofibers are widely used in batte-
ries, supercapacitors, water desalination, hydrogen production and energy harvesting
[56]. The supercapacitive behavior of polymer composite-based electrodes can be
150 K. Kumar and S. Mishra

Fig. 7 (a) Hybrid monolithic aerogel of syndiotactic polystyrene and polyvinylidene fluoride for
airborne nanoparticle filtration. Reprinted with permission from ref. [49]. (b) Polymer inorganic
hybrid nanocomposite materials for water purification applications. (Reprinted with permission
from ref. [50])

optimized for the energy storage applications due to improved cyclic performance
and reversible capacity [57]. Dielectric nanocomposites have shown high ability to
store and discharge electrical energy [43] due to their interior hierarchical interfaces
that lead to the high energy density without the adverse effect of coupling of electric
displacement and breakdown strength [58]. A polymer-based nanocomposite with
controlled orientation of one-dimensional nanofibers has demonstrated an impres-
sive energy storage performance [59] (Fig. 8).
7 Polymer-Hybrid Nanocomposites Films and Fiber-Based Nanoproducts 151

Fig. 8 Conductive polymer-based flexible, thin all-solid-state supercapacitor. (Reprinted with

permission from ref. [54])

Textiles

The nanofiber materials have created a niche area in textile industry by improving
the comfort and thermal properties of the textile materials. The variation of pore size
with the density of electrospun web area is the controlling parameters for the level of
protection and thermal comfort of any fabric [60]. Self-cleaning coatings of polymer
nanofibers can be used to reduce contamination on surgical tools and protective
clothes by optimizing the surface chemistry and topography of the nanofiber mem-
brane. The cotton fabric modified by TiO2 and TiO2/Ag/PVP nanocomposites has
displayed a better antimicrobial activity for self-cleaning fabric applications
[61]. Thermomechanical properties of monofilaments from polymeric nano-
composites of nano-clay in polyamide (PA) and polypropylene (PP) matrices have
shown better tensile performances with high elastic response and can be a potential
material in upholstery and automobile reinforcement tires [62]. The fibers composed
of polybutylene terephthalate (PBT) and TiO2 have shown significant improvements
in the self-cleaning properties under UV radiation and can be used in textile products
[63]. The nanostructured piezoelectric poly nanofibers exhibited excellent durability
152 K. Kumar and S. Mishra

Fig. 9 All-fiber e-textile with high thermal-moisture stability and comfortability. (a) The e-textile
with good wearability. (b) Schematic diagram of air permeability and moisture permeability of the
e-textile. (c) Schematic diagram of the moisture wicking function of the e-textile in sweating state.
(d) SEM micrographs and contact angles of hydrophilic PAN and PA6 fibers. (e) Pore size
distribution of hydrophilic PAN and PA6 fibers. (f) Water evaporation rate of cotton fabric,
cotton-PAN fabric, and cotton-PA6-PAN fabric (the moisture-wicking fabric). (Reprinted from
Copyright (2018), with permission from The Royal Society of Chemistry [66])

and can be used for mart upholstery for car seats or portable materials [64]. The
polymeric piezoelectric nanofibers yarns were woven by twisting it that resulted in
an increase in its overall strength and toughness along with an achieved energy up to
98 J/g with high stretchability [65] (Fig. 9).

Thermal Barriers

Thermal barrier material made from polymer nanofiber composites can be used as a
passive thermal insulator or an active temperature regulator. Composites of nano-
fibers with other materials may take advantage of the better insulation property of
nanofibers while providing greater resilience to the composite material. The polymer
composite was formed by infiltration of Sn-Ag-Cu matrix into the polyamide fibrous
mesh to exhibit a high heat transfer capability with a through-plane and in-plane
thermal conductivity [67]. Polyethylene nanofibers with diameters ranging from
10 to 100 nm with ultra-high strength (11 GPa) can be used as thermal conductor
with increased dielectric constant over a broad temperature range (20 K–320 K)
[68]. A biocompatible and biodegradable polymer composite nanofibers composed
7 Polymer-Hybrid Nanocomposites Films and Fiber-Based Nanoproducts 153

Fig. 10 Schematic illustrating the action of thermal interface material, which fills the gaps between
two contacting surfaces and conducts the heat produced by electronic drives [70]. (Copyright
(2012) the American Chemical Society) [70]

of poly(ε-caprolactone) and Fe3O4 nanoparticles coated multiwalled carbon nano-

tubes have shown an excellent shape memory effect under heat and magnetic field
[44, 69] (Fig. 10).

Electromagnetic Interference (EMI) Shield Materials

The day-by-day increase in the electrical equipment has raised a threat to environ-
ment and people from electromagnetic interference (EMI). The capability for EMI
shielding can be further enhanced by making composites of polymers with different
materials making it suitable for shielding material. The composites based on poly
(ε-caprolactone) along with multiwalled carbon nanotube have shown excellent EMI
shielding properties (exhibiting a reflectivity lower than 10 dB), with a shielding
effectiveness >20 dB [71]. The overall shielding efficiency (SE) of the polymer
composites can be enhanced by using more than one type of nanofillers. Nanoscale
silver flakes and multiwalled carbon nanotubes were used with nitrile butadiene
rubber to get higher SE with a broad frequency range and high flexibility [72] and the
similar properties have been shown by the MWCNTs/Au/polyaniline nano-
composites [73]. The modified carbon fiber/magnetic graphene/epoxy composites
have resulted in higher SE over a broad frequency range of 8.2 to 26.5 GHz
[74]. Study has found that high SE is not only due to the addition of high conducting
fillers but also by adding different types of fillers and its distribution, and extending
the conducting network [21]. Polyacrylonitrile nanofiber/metal nanoparticle hybrid
membranes have shown better EMI shielding effect compared to pure metal and
other synthesized EMI shielding materials (Fig. 11).

Conclusions

There is a huge potential of poly nanocomposites film and fibers for various
applications such as for textile, electromagnetic shielding, biomedical, thermal,
energy harvesting and storage, filter membranes, sensor and actuators. By optimiz-
ing the synthesis process parameters and including different polymers and nano-
materials, it is possible to improve the material properties of these materials as per
154 K. Kumar and S. Mishra

Fig. 11 (a) fabrication process of CPAN NF/MNP hybrid nanofiber membranes for EMI shielding.
FE-SEM images (Inset with magnified SEM); (b) PAN NF membranes, (c) CPAN NF membranes,
(d) CPAN NF@Ag seed, (e) CPAN NF/Ag NP, (f) CPAN NF/Cu NP, and (g) CPAN NF/Ni
NP. (Reprinted with permission from ref. [75])

required applications. It is expected that a wide range of polymer nanocomposite

materials will continue to grow in the future that will be driven by the consumer
product requirements and the market potential.

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 Part IV
Consumer Nanoproducts Based on Polymer
Nanocomposites Matrices
Consumer Nanoproducts Based on Polymer
Nanocomposites Matrices 8
María Paula Guarás and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
Nanocomposites of Polymer Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Polymer/Clay Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Polymer/BaTiO3 Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Polymer/Hexagonal Boron Nitride Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Polymer/Carbon Nanotubes Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Polymer Matrices from Sustainable Renewable Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Starch-Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
PLA-Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
PCL-Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Commercial Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

Abstract
In the last years, the development of polymeric-based nanocomposites has been a
relevant area with high scientific and industrial interest. This is related with numer-
ous improvements achieved in these materials, derived from the combination of one
or more polymeric matrices and the incorporation of an inorganic or organic
nanomaterial. The enhanced performance of those materials generally includes
better mechanical strength, toughness, and stiffness, improved electrical and thermal
conductivity, superior flame retardancy, and higher barrier properties (to moisture

M. P. Guarás (*)
Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones en Ciencia y
Tecnología de Materiales (INTEMA), Facultad de Ingeniería, Universidad Nacional de Mar del
Plata (UNMdP) y Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Mar del
Plata, Argentina
V. A. Alvarez
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina

© Springer Nature Singapore Pte Ltd. 2022 161

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_17
162 M. P. Guarás and V. A. Alvarez

and gases). Polymeric nanocomposites can also display unique design possibilities,
offering advantages for the production of functional materials with specific and
desired properties for different kinds of applications. In addition, the opportunity to
use natural resources together with their environmental friendship has also open new
and different opportunities for applications of those materials.
This contribution revises the advances in consumer nanoproducts based on
polymeric matrix nanocomposites. Nanomaterials have been increasingly inserted
into consumer products, although research is still ongoing on their possible effects
on the environment and human health. The consumer nanoproducts that are
present in the market include cosmetics, clothing, food, electronic equipment,
etc. At the same time, this has triggered the development of databases and
inventories with information on engineered nanomaterials (ENM) embedded in
nanoproducts. The objective of the next chapter is to describe the consumer
nanoproducts based on polymer nanocomposites matrix present in the market
and to evaluate their advantages and disadvantages and their consumption risks.

Keywords
Nanoproducts · Polymer matrices · Filler · Nanocomposites

Introduction

To understand the structure and properties of nanocomposites, it is necessary to

define some basic concepts in advance. Contrary to popular belief, composite
materials are as old as nature itself. A clear example of this is wood, the structure
of which consists of tubular-structure cellulose fibers wrapped in a lignin matrix.
Another example of man-made composite materials in the early days of civilization
is the adobe and straw huts, which laid the foundations for the current constructions.
A composite material is defined as any system or combination of materials made up
of a union (nonchemical, insoluble with each other) of two or more components,
which gives rise to a new material with new, characteristic, and specific properties.
The properties of the new material depend, then, on the type of interface and the
characteristics of the components [16]. Particles such as CaCO3, silica, clay and
carbon black, and glass and carbon fibers have been widely used in recent times to
improve the mechanical properties of elastomers and polymers. For example, tires
have 10–100 nm diameter carbon black particles as filler, epoxy resins are reinforced
with 10–20 μm diameter fiberglass used in boat hulls, and compounds filled with
carbon fibers 5–20 μm meet the performance demands for applications such as
aircraft bodies and sports equipment. Composite materials reinforced with micron-
sized particles have a small-volume fraction at the filler/polymer interface, compared
to nanocomposites. Consequently, nano- and microscale fillers have very different
effects on the final properties of a polymer (C. M. [36]).
In general, nanotechnology is one of the most interest fields of research since the
last century. The general definition of nanotechnology is that technology in which a
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 163

group of processes, materials, applications, and concepts are defined by size. Nano-
technology, more specifically, is defined as the study, design, creation, synthesis, and
manipulation of materials creating functional systems through the control of matter
at the nanoscale, generating good mechanical and thermal properties with respect to
pure polymers and composite materials [62]. The extraordinary potential of this new
technology promotes new development routes for high-performance materials. Dur-
ing recent years, nanocomposites have generated much research interest owing to
remarkable enhancements in the composites final properties and its applications,
using very low-volume fractions of fillers. The term nano is used as a prefix for any
unit and means one billionth (10
9) of that unit. Generally speaking, nanomaterials
are materials that have at least one dimension in the range of 1–100 nm. A nanometer
is approximately the length equivalent to ten hydrogen or five silicon atoms aligned
in a line. When some outstanding property of a material, whose organization,
random or well-ordered nanopatterns is evidenced, the resulting material is called
a nanostructure or nanostructured material (Rajendra Kumar [25]). Nanomaterials
exhibit highly attractive multifunctional properties that are clearly different from
those of bulk materials. Nanomaterials are generally classified based on their
dimensionality, morphology, composition, uniformity, and agglomeration.
Depending on the dimensionality of the nanoparticles, the nanomaterials can be
classified into 0D, 1D, 2D, and 3D as seen in Fig. 1.
Phase-separated polymer blends naturally reach nanoscale phase dimensions. The
morphology of the block copolymer domain is generally at the nanoscale level.
Asymmetric membranes often have an empty nanoscale structure, mini-emulsion
particles, and interfacial phenomena in mixtures and compounds that involve nano-
scale dimensions [81]. Polymer nanotechnology is primarily developed to improve
performance in terms of gas barrier properties such as oxygen and carbon dioxide. It
has also been shown to improve the performance of UV barrier properties. On the
other hand, they also improve resistance, rigidity, dimensional stability, and

Fig. 1 Examples of nanoparticles classified according to their dimensionality

164 M. P. Guarás and V. A. Alvarez

temperature resistance (thermal stability) [83]. There has also been a growing
interest in polymer matrix-based nanocomposites initially due to successful studies
involving exfoliated clay and other more recent studies involving carbon nanotubes,
carbon nanofibers, exfoliated graphite (graphene), nanocrystalline metals, and a
large number of nanoscale inorganic reinforcements [37].
Nanomaterials, due to their improved properties over their matrices (without
nanofillers), have been increasingly incorporated into consumer products and have
provided solutions in many diverse fields. Nowadays, nanotechnology is an emerg-
ing area for research and development, basically in most of the disciplines of science
and technology. Fields of application include nanoelectronics, polymer-based nano-
materials, nanoparticle drug delivery, polymer-bonded catalysts for fuel cell elec-
trodes and self-assembled layer-by-layer polymer films, nanofibers, printing
lithography, polymer blends, and nanocomposites [34].
A common question is “with all the interest and associated large R&D expendi-
tures in nanotechnology (including polymer matrix nanocomposites), why is there
not more commercial impact?” Nowadays there are available in the market a number
of polymeric matrix nanocomposites. Some important ones are summarized in the
final part of the present chapter.

Nanocomposites of Polymer Matrix

Polymers today are the materials of choice over metals and ceramics. This is due to
its low-density properties, high specific rigidity, high specific resistance (resistance/
density ratio), and ease of manufacturing complex parts on a large scale using
traditional injection molding, at low cost and low energy consumption. However,
they have very low electrical conductivity, mechanical properties (resistance and
Young’s modulus) and low thermal conductivity, and a relatively high coefficient of
thermal expansion (CTE) [25]. These properties can be improved by adding an
appropriate reinforcing (or filler) volume fraction (i.e., fibers or particles) in the
polymer matrix, giving as the final product what are called polymer matrix com-
pounds or nanocomposites, depending on the size of the constituents in matrix.
Numerous studies have shown that compared to conventional polymer composites,
polymer nanocomposites show improved mechanical and tensile strength, lower
scratch and wear resistance, higher thermal distortion temperature, and noise
damping. The problems that composites normally present are associated with high
reinforcement content, such as decreased toughness, poor optical clarity, and higher
melt viscosity [38]. These aspects are less problematic in the production of nano-
composites since a nano-reinforcement volume fraction of less than 10% by weight
is enough to produce high-performance polymer nanocomposites [4]. For example,
to improve properties likewise in a polymer matrix, the addition of only 1–5% by
volume of nanoparticles is required versus 15–40% by volume of micron-sized
particles or fibers. However, dispersing nanoparticles or nanofibers is not always
an easy task. Modification of the surface with chemical groups compatible with the
polymer matrix is often required to avoid (or minimize) agglomerations. Otherwise,
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 165

Fig. 2 Advantages and disadvantages of polymer nanocomposites

nanoparticles tend to clump together and ultimately become responsible for stress
concentration and crack formation in polymeric nanocomposites [29].
Polymeric nanocomposites are a blend of two or more constituents or phases, which
exhibit different properties from their individual constituents. It is a necessary condition
that the constituents dispersed in the polymer matrix have at least one dimension in the
range of 1 to 100 nm. Furthermore, these constituents or phases present in the
nanocomposite must be insoluble with each other. The size and distribution of the
nanofiller are of great importance. As mentioned above, as the specific contact surface
area between nanoparticles and polymer chains increases, the interaction within the
nanocomposite is more intense. Depending on the nano-reinforcement used in the
polymer matrix, improvements such as high-temperature capability, corrosion resis-
tance, noise damping, low cost/manufacture, ductility, high specific stiffness and
strength, high thermal conductivity, and low coefficient of thermal expansion can be
obtained, compared to the unreinforced polymer [17] (Fig. 2).

Polymer/Clay Nanocomposites

Polymeric nanocomposites reinforced with clay nanoparticles are among the first
polymeric nanomaterials to emerge on the market as materials for a wide spectrum of
applications. Nanoclays are the most widely investigated nanoparticles as reinforce-
ment of different polymer matrices, since they are a readily available and low-cost
alternative compared to other nano-reinforcements [59].
Phyllosilicates (2:1) are layered silicates, widely studied. The nanoclay most
frequently used is the montmorillonite (MMT). MMT is a hydrated alumina silicate
mineral which consists in platelets of an octahedral sheet of alumina sandwiched
166 M. P. Guarás and V. A. Alvarez

between two sheets of tetrahedral silicate. When certain aluminum atoms are
replaced by magnesium atoms, the valence difference between Al and Mg creates
negative charges (called cation exchange capacity (CEC)) which are distributed
within the plane of the nanoclay layers, balanced by positive counterions (Na+,
Li+, Ca2+), typically sodium ions, located between the galleries. Naturally, clay
platelets have a thickness of 1 nm and have the other dimensions (i.e., length
and width) in the order of 150 nm, up to a size of 1 or 2 μm. Hydration of the sodium
ions causes the galleries (or interlayer spacing) to expand and the clay to swell.
MMT can absorb large amounts of water (> 20 times its volume) and polar liquids,
causing separation of the silicate layers [62].
One strategy to improve the compatibility of clays with polymeric matrices is the
organic treatment (chemical modification). It is carried out by ion exchange between
inorganic alkali cations on the clay surface with the desired organic cation. This type
of modification increases the interlaminar spacing of natural clays, thus favoring
dispersion in the polymer matrix [42]. There are diverse clay surface treatments;
among the most prominent are the treatments with quaternary ammonium salts,
alkylimidazoles, coupling and anchoring agents, reactive diluents, and functional
amino compounds.
Particularly, sodium ions can be exchanged with organic cations such as ammo-
nium salt to form an organoclay (o-clay). The ammonium cation is known as a
“surfactant” due to its amphiphilic nature. The resulting modified clay has a mostly
hydrophobic character. Longer alkyl tails (of surfactant) give a more hydrophobic
o-clay. Commercially, a variety of modified clays are available (Cloisite TM Na+,
10A, 15A, 20A, 25A, 93A, and 30B). Longer alkyl tails (of surfactant) give a more
hydrophobic o-clay. Commercially, a variety of modified clays are available
(Cloisite TM Na+, 10A, 15A, 20A, 25A, 93A, and 30B).
In its original state, MMT is only miscible with hydrophilic polymers, such as
poly(ethylene oxide), polyamide, polyurethane, and poly(vinyl alcohol). In order to
make MMT miscible with other polymers such as polypropylene (PP) or polyethyl-
ene (PE), the polymers must be modified by grafting a small amount of a modifier
such as maleic anhydride (MA). Typically ~1% of MA by weight is used, which acts
as a compatibilizer and is very effective dispersing the modified clay into the original
polyolefin.
Depending on the physical state of the polymer, the clay can be incorporated into
the matrix through different mechanisms [25]:

• Polymer Intercalation: it is based on a solvent system in which polymer is

soluble and also the clay is capable of swelling. Firstly, swelling of the clay in the
solvent (water, chloroform, toluene) is generated, increasing the interlaminar
space. When the polymer and swollen clay are mixed in the solvent, the polymer
chains are sandwiched within the interlaminar space displacing the solvent. Then
evaporation of the solvent occurs under suitable conditions according to the
formulation.
• In Situ Polymerization: clay swells within the liquid monomer or the monomer
in solution so that polymerization occurs between the clay sheets. The
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 167

polymerization can be initiated by heat or radiation, by diffusion of a suitable

initiator, or by an initiator or organic catalyst pre-fixed by cation exchange within
the clay layers.
• Melt Intercalation: in this method, both the polymer and the clay are fed in solid
state into a discontinuous (Brabender type) or continuous mixer (twin screw
extruder). By applying shear stress and temperature, it is possible to transform
to the polymer to the melt state and, on the other hand, to increase the interlaminar
spacing of the clay to facilitate the intercalation of the polymer chains in the
molten state between the filler galleries. This mechanism has certain advantages
with respect to those previously mentioned. First, it is environmentally benign
due to the absence of organic solvents. Second, it is compatible with the industrial
processes currently in use, such as extrusion and injection molding (Fig. 3).

Depending on the interactions between the polymer and the layered silicate (mod-
ified or not) and also on the method used for the preparation of the nanocomposites,
three types of structures can be differentiated to mix polymers and clays (Fig. 4):

• Microcomposite-aggregate morphology: When the polymer chains are not

capable of intercalating in the interlaminar space of the clays, a microcomposite

Fig. 3 Processing of polymer/clay nanocomposites

168 M. P. Guarás and V. A. Alvarez

Fig. 4 Possible morphologies of a polymeric nanocomposite

is obtained, and the final properties of the material will be the same as those
expected for traditional composite materials.
• Nanocomposite-intercalated morphology: One or more polymer chains are
inserted between the sheets of the nanoclay, maintaining the parallel arrangement
of the lamellar structure. Intercalation of polymer chains increases the basal
spacing of the clay flakes.
• Nanocomposite-exfoliated morphology: It occurs when the clay sheets are
completely dispersed in the polymer matrix, losing the ordered structure of
stacked layers.

Epoxy-clay nanocomposites, for example, are generally prepared by in situ poly-

merization. The first step is to disperse the clay into the epoxy resin before curing. This
dispersion will later influence the morphology of the resulting nanocomposite. A
homogeneous dispersion of the clay in the epoxy matrix will improve the degree of
exfoliation; however, the poorly dispersed clay will generate agglomerations, resulting
in a final product with poor mechanical and barrier properties [88]. The most widely
used methods for dispersing clay in the epoxy resin are mechanical stirring, ultrasound
and high shear mixing, ball milling, high-pressure mixing, and the suspension process.
These dispersion methods can be more efficient if solvents are used to facilitate
dispersion. Brown et al. studied the efficiency of the use of acetone as a solvent;
however it did not result in appreciable changes in the morphology and properties of
the resulting nanocomposite; it only served to facilitate the processability of the
nanocomposite due to a reduction in the viscosity of the system [10].
Today, the possibility of preparing filaments of clay/PLA nanocomposite raw
material for use in 3D printing using the fused deposition modeling (FDM) tech-
nique has been demonstrated. 3D-printed nanocomposites showed advantages,
mainly related to improved shape stability and mechanical properties, over samples
without reinforcement. Furthermore, Cicala et al. have reported that the presence of
filler in the PLA matrix modifies the rheology of the polymer matrix and improves
the share thinning [14].
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 169

Polymer/BaTiO3 Nanocomposites

Integrated capacitors perform a major role in the miniaturization of electronic/electri-

cal devices, as they have substantial advantages over traditional discrete capacitors.
The possible materials usable in integrated capacitors should be easily processable at
low processing temperature. Furthermore, they must be strong and flexible to be
compatible with PCB (printed circuit boards) manufacturing processes. Polymers
have a low dielectric constant; therefore, they do not have the requirements for
capacitors. On the other hand, ferroelectric ceramics have a high dielectric constant
but require high processing temperatures. Polymer/ceramic nanocomposites present a
decent alternative for manufacturing integrated capacitors due to the unique combina-
tion of properties in terms of good processability, flexibility, high dielectric constant,
low processing temperature, and low cost. Ferroelectric ceramics, including barium
titanate (BaTiO3), are the materials specifically chosen in capacitors due to their high
dielectric constant [75]. BaTiO3 is a ferroelectric ceramic with the perovskite structure
with a chemical formula of ABO3 (A ¼ Ba, Sr . . .; B ¼ Ti, Zr . . .). The crystal
structure of which consists of AO12 cuboctahedra and BO6 octahedra. Depending on
the temperature, it can be shown five different crystal arrangements (hexagonal, cubic,
tetragonal, orthorhombic, and rhombohedral). All structures present ferroelectric
properties, with the exception of the cubic structure. Also, it has low coefficient of
thermal expansion and high thermal and chemical stability.
Specifically, the electrical properties of polymer/BaTiO3 nanocomposites are an
active field of research in various electronic applications, especially for the manu-
facture of passive components integrated into electronic devices [57]. Depending on
the properties such as grain size, purity, crystallographic direction, measurement
temperature range, and preparation method, the BaTiO3 dielectric constant can reach
values of up to 5000. Among its properties, low direct current leakage, low loss
tangent (0.009), low coefficient of thermal expansion, and high thermal and chem-
ical stability stand out. However, at the same time, it has disadvantages such as
brittleness and the requirement of high processing temperatures to compact it. These
drawbacks can be overcome by adding a certain amount of ceramic powder to a
polymer matrix (R. K. [26]). Several BaTiO3-filled composites with polymers such
as epoxy [67], polyimide (PI) [64], polystyrene [21], cyanoethyl ester of poly(vinyl
alcohol) (CEPVA) [46], and polyvinylidene fluoride (PVDF) [87, 93] have been
studied. This type of compound can be used in applications such as integrated
capacitors, electronic packaging, piezoelectric capacitors/transducers, multilayer
ceramic capacitors, microwave substrate applications, and pressure-sensitive and
chemocapacitive sensors. The dielectric constant of nanocomposites can be adapted
according to user requirements.
The advantage of this type of polymer/ceramic nanocomposite is its ease of
processing and low weight compared to all ceramic materials. These factors are highly
attractive for energy storage applications. However, there is an intrinsic difficulty in
correctly dispersing ceramic nanofillers within polymeric matrices resulting in an
aggregated nanocomposite with high presence of agglomerations, especially when
the concentration of ceramic nanofillers is high. The lack of homogeneity and the poor
170 M. P. Guarás and V. A. Alvarez

dispersion of the particles result in negative influences on the dielectric properties and
the electrical decomposition properties of the nanocomposites. As already stated, the
dielectric performance of BaTiO3 particles depends on the particle size. Usually, the
dielectric permittivity of BaTiO3 nanoparticles decreases when particle size is reduced,
because it occurs at the transition of structural phase from tetragonal to cubic. Similar
results have been found, regarding the dependence of dielectric properties as a function
of the size of the reinforcement, in studies of polyvinylidene fluoride (PVDF)/
BaTiO3nanocomposites (B. H. [23]). Other polymer/BaTiO3 systems have been
studied, such as the PI/BaTiO3 nanocomposites, and it has been found that the
dielectric properties are also affected by the volume fraction of BaTiO3 (B.-H. [22]).
However, large particles with higher dielectric permittivity did not lead to increased
dielectric permittivity of the resulting polymeric nanocomposites. This result was not
completely unexpected, since a large number of factors are those that affect the
dielectric properties of polymer nanocomposites.
As explained previously, another difficulty that arises is correct dispersion and
interface interactions, which are also critical for dielectric relaxation behaviors. By
decreasing the particle size to nanoscale, the surface area of the ceramic particles
increases, which in turn produces an increase in surface energy and therefore a
tendency to agglomerate. Both factors can influence interfacial polarization in
nanocomposites.
Intensive work has been done to develop methods to improve the dispersion of
ceramic nanofillers in the polymer matrix [15]. An effective route by which good
results have been obtained is the modification of the surface of the ceramic nanofillers.
This technique is useful to modify the interface areas between ceramic nanofillers and
polymer matrix and to improve the homogeneity of the nanocomposites [86].
Surface modification of nanofillers has always been a subject of great importance
for the manufacture of high-performance polymer nanocomposites. Not only it fulfils
the function of improving the dispersion of nanomaterials and the interfacial bond
between the polymer matrix and nanomaterials, but it is also important in the dielectric
relaxation of nanocomposites since it has an impact on interfacial polarization
[71]. Numerous studies have been carried out to understand the behavior and proper-
ties of superficially modified nanoparticles. A comparative study evaluated the dielec-
tric properties of modified and unmodified BaTiO3 nanoparticles (6 nm in size). The
modifier used was n-hexylphosphonic acid (HPA) [9]. As a result, it was found that the
modification of the surface led to significant changes in the dielectric properties: the
modified nanoparticles presented a lower dielectric constant and dielectric loss than
the unmodified nanoparticles, as well as weaker temperature sensitivity.
Since BaTiO3 particles have surface groups such as hydroxyl, they have a polar
character on their surface. This fact facilitates the grafting of different types of
surfactants on the surface of the particle and favors the formation of a dielectric
layer. In order to increase the reactive sites of the nanoparticles, they are often
hydroxylated in a H2O2 solution. In this way, it is possible to increase the grafting
rate of surfactants (Y. [91]). In the resulting nanocomposites, it has been found that
hydroxylation successfully improved dielectric strength, in turn showing a decrease
in dielectric permittivity and dielectric loss. In addition, studies show that both
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 171

pristine BaTiO3 and hydroxylated BaTiO3 could be modified by surfactants, such as

silane coupling agents [39]. The popularity of silane coupling agents is due to their
high reactivity, and, at the same time, they have various functional groups that
interact or react with the polymer matrix. Studies conducted on the effects of
different silane coupling agents on the performance of BaTiO3/epoxy nano-
composites have shown that these agents played a critical role in their thermal and
dielectric properties [31, 32]. Other efficient surfactants for BaTiO3 modification are
phosphonates and phosphonic acids [19]. These surfactants have a strong binding
affinity for oxides [9]. Another advantage is that they do not present the problems
that occur with silane coupling agents, that is, the self-condensation of silane
molecules, nor do they react with water. Finally, carboxylates or carboxylic acids
also act as commonly used surfactants [79]. By chemisorption they bind with
BaTiO3 and other oxides.
Another option lies in polymeric surfactants (Fig. 5). They have proven to be an
attractive alternative for modifying the surface of nanoparticles. The advantages of
using polymers include:

1. The polymer surfactant is able to form a surface layer with different thicknesses
and thus create a nucleus-covered structure together with the nanoparticles. It is
possible to control the coating structure (especially thickness) by controlling the
polymerization processes.
2. The polymer chains favor the formation of interactions with the polymer matrix,
thus resulting in more intense interfacial bonds.

A distinction needs to be made between the grafting methods. On the one hand,
there is the “grafting to” method, which uses the polymer to modify the surface of the
nanoparticle to form a shell around it. On the other hand, the “grafting from” method
uses the surface of the nanoparticles as nucleation points for the initiation of
polymerization of the monomers. Controlled core-shell structures can be made
using atomic transfer radical polymerization (ATRP) and reversible addition-
fragmentation chain transfer polymerization (AFT) techniques [20]. The application
of the “grafting from” method may be limited since both polymerizations are limited
to the synthesis of certain polymer structures. For the “grafting to” method, the
polymer coating can be done in two ways: (1) by physical absorption, caused by
electrostatic and van der Waals interactions, and (2) by chemical reaction between
the polymer chains and the surfaces of the nanoparticles [84].

Polymer/Hexagonal Boron Nitride Nanocomposites

The continuing trend of miniaturization of electronic devices and the increasing

power output of electrical equipment have posed the challenge of creating packaging
and insulating materials. The main objectives are to develop materials with high
thermal conductivity, low coefficient of thermal expansion (CTE), low dielectric
constant, high electrical resistivity, high resistance to rupture, and low cost.
172 M. P. Guarás and V. A. Alvarez

Fig. 5 Methods to design and build core-shell nanoparticles for high-permittivity polymer
nanocomposites

Polymeric materials present an attractive alternative to develop this type of material,

due to its excellent processability and low cost. However, most polymers are
thermally insulating and have a thermal conductivity between 0.1 and
0.5 W·m
1·K
1. One approach to increasing the thermal conductivity of polymers
is to introduce inorganic fillers with high thermal conductivity, such as aluminum
oxide, aluminum nitride, boron nitride, silicon nitride, beryllium oxide, or diamond.
Thermally conductive nanoparticle-reinforced polymeric compounds can be eas-
ily processed. This fact led to the obtaining of nanocomposites with improved
thermal conductivity due to the type of reinforcement used, and therefore they
have been widely used for the thermal management application. Among the nano-
particles used for the processing of heat-conducting polymeric compounds, boron
nitride (BN) dielectric ceramic particles are an increasingly attractive option. This is
because the resulting heat-conducting compounds can simultaneously provide elec-
trical insulation (wide bandgap of 6 eV) in electronic devices and equipment [48].
Hexagonal boron nitride (h-BN) is an attractive nanofiller for reinforcing poly-
mers due to its properties. Firstly, it has low density (2.1 g/cm3); it also has high
mechanical resistance (Young’s modulus, 0.7–0.9 TPa; elastic limit, 35 GPa),
thermal stability (stable up to 1000  C under atmospheric conditions), and chemis-
try; and finally it is intrinsically an electrical insulator [33]. Moreover, h-BN is
structurally analogous to graphite and has equally good thermal transport properties.
These characteristics make BN-based composite materials perform their great poten-
tial in applications for the thermal management of energy systems, such as solar
cells, light-emitting diodes, etc. Numerous studies have been developed on BN
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 173

nanomaterials, for example, nanotubes (BNNT) and nanosheets received much

attention due to their great performance in improving the thermal conductivity of
polymeric compounds while maintaining the electrical insulation properties of a
polymeric matrix [13].
Song et al. have studied the exfoliation of h-BN in an organic medium, with the
aim of obtaining sheets of nanometric thickness and, subsequently, dispersing the
resulting nanosheets in matrices of poly(vinyl alcohol), PVA, and epoxy [72]. Supe-
rior thermal transport performance has been obtained in the thus manufactured
polymer/h-BN nanocomposite films. The results demonstrate that nanometric-thick
h-BN sheets can hold promise with metallike heat transfer performance, as has
already been achieved in graphene sheet-reinforced polymer nanocomposites
[78]. Zhi et al. have developed a method of preparing thermally conductive thermo-
plastic nanocomposites with high-volume filler fractions. A 24% by weight h-BN-
reinforced poly(methyl methacrylate) (PMMA) nanocomposite was reported to have
a thermal conductivity of 3.16 WmK
1 [92].
Although significantly improved thermal conductivities were achieved, there are
still challenging problems that limit the practical applications of BN-based polymer
nanocomposites. First, they have poor post-processing capacity. This problem orig-
inates from two critical points: the thermoset matrices adopted and the strong
dominant fill-to-fill interactions, especially in highly charged compounds [49]. On
the other hand, the other problem with this type of nanocomposites is related to the
weak interactions between matrix/polymer filler and interfaces, which generally
dramatically impair the final performance. Often this can result in a nanocomposite
with high thermal resistance between the charge and the polymer matrix and/or cause
deterioration in mechanical and electrical insulation properties simultaneously.
Actually, two techniques for processing polymeric h-BN nanocomposites have
been developed. On the one hand, most of the methods used involve adding h-BN
nanoparticles to a commercial thermoplastic polymer matrix or to a curable thermo-
rigid prepolymer, which has resulted in the aforementioned problems. On the other
hand, after several years of research, controlled in situ polymerization techniques
have been developed. In situ polymerization is believed to be a very promising
technique for preparing nano-BN/polymer nanocomposites. The use of this pro-
cessing method has certain advantages: (i) the growing polymer chains covalently
bond with the BN nanoparticles, which favors the interaction between the nano-
particles and the polymer matrix; (ii) the polymer chains as they grow act as
modifiers and polymer matrix, which significantly suppresses the aggregation of
nanoparticles and, therefore, results in an excellent dispersion of nanoparticles and
favors the reduction of filler interactions to fill in the nanocomposite.

Polymer/Carbon Nanotubes Nanocomposites

Carbon-reinforced nanomaterials have had an unprecedented impact in recent

decades in terms of their technological scope and their applications in the field of
nanotechnology. Carbon is a molecule whose unique catenation properties allow it to
form covalent bonds with other carbons in different states of hybridization (sp, sp2,
174 M. P. Guarás and V. A. Alvarez

and sp3) and thus form a variety of small molecules with long-chain structures.
Carbon is a highly versatile material with good mechanical, chemical, optical, and
electrical properties. These properties can be adapted according to the final applica-
tion by manipulating its structure and surface chemistry. Carbon-based materials
include a wide range of structures such as graphite, diamond, amorphous carbons,
fullerenes, graphite, nanotubes, nanohorns, nanocones, carbynes (linear carbon
chains), and carbon onions. The industrially used structures are activated carbon,
carbon black, graphite, glassy carbon, diamond, and carbon fibers. The other struc-
tures (nanotubes, nanodiamonds, nanocones, nanofibers, whiskers, nanorings, and
nanohorns) are in continuous optimization for use in technological applications [40].
Graphite, carbon black, carbon nanofiber (CNF), and carbon nanotubes (CNTs)
are carbonaceous inclusions commonly used to develop polymer matrix nano-
composites. Carbonaceous materials are known for their thermal and electrical
conductivity properties. According to their dimensions, they can be classified into
three groups: (1) carbon black and round silica particles have three dimensions at the
nanoscale; (2) CNT and CNF have two dimensions at the nanoscale; and (3) graphite,
known to be a layered material, exhibits one dimension at the nanoscale. Carbon
black is basically amorphous carbon and has a high surface/volume ratio, which
gives it good adhesion to polymer matrices. However, carbon black grains tend to
agglomerate and therefore require preprocessing treatments to obtain a correct
dispersion in the matrix. CNTs are carbonaceous nanofillers that have attracted
considerable attention in recent years because they have been shown to improve
the inherent mechanical and electrical properties of nanocomposites compared to
unreinforced polymer. Graphite consists of sheets of graphene bound by covalent
bonds in the plane and van der Waals forces outside the plane between each layer.
The graphene layers are stacked in AB sequences linked by weak van der Waals
interactions, which are produced by a delocalized orbital π (Rajendra Kumar [25]).
After the identification of their unique structure in the early 1990s, carbon
nanotubes (CNTs) have attracted a lot of attention [2]. The basic structure of CNTs
is graphene sheets, which are rolled up, with a length-diameter ratio significantly
greater than that of any other material, which gives it its extraordinary properties.
CNTs are classified as single-wall CNTs (SWCNTs), double-wall CNTs (DWCNTs),
triple-wall CNTs, and multiple-wall CNTs (MWCNTs). In particular, CNTs have an
extremely high Young’s modulus ( 1 TPa) and tensile strength of 150 GPa. On the
other hand, it reaches intrinsic electrical conductivities of approx. 105–106 S/m for
metallic CNTs and 10 S/m for semiconductor CNTs and high thermal conductivities
(3000–6000 W/mK). These properties are combined with high flexibility, low
density (1.3–1.4 g/cm3), and high aspect ratios (up to 1000 or more).
Due to the unique combination of properties, the addition of CNT can greatly
improve the thermal, mechanical, and electrical properties of the polymer matrix
nanocomposites. However, their applications have been limited by their low solu-
bility in commonly used solvents and their difficulty in dispersing in both solvents
and polymeric matrices [43]. One of the most effective methods to improve the
dispersion of nanotubes in the polymer matrix is the modification of CNTs by
polymers. This modification can be classified according to its chemical union: the
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 175

non-covalent or the covalent bond between the CNT and the polymer. Non-covalent
modification of CNT consists of the physical adsorption and/or polymer coating to
the surface of the CNT. On the other hand, covalent modification of CNTs is the
chemical covalent bonding (grafting) of polymer chains onto the surface of the
CNTs. Grafting is a very effective process, which produces a dramatic improvement
in the interfacial interactions between the nanotubes and the polymer matrix. Inter-
facial interaction is one of the most critical fields in polymer/CNT compounds [66].
Polymer/CNT compounds can be processed in solution (thermoset and thermo-
plastic matrices), mass mixing (thermoplastic matrices), melting (thermoset and
thermoplastic matrices), and in situ polymerization (thermoset and thermoplastic
matrices). The most commonly used polymer matrices for nanocomposites are
epoxy resins, polyamide-6 (PA-6), polyacrylonitrile (PAN), polycarbonate (PC),
polyethylene (PE), ultrahigh molecular weight polyethylene (UHMWPE), poly-
imide (PI), poly(methyl methacrylate) (PMMA), polypropylene (PP), polystyrene
(PS), polyurethane (PU), and poly(vinyl alcohol) (PVA), among others.
The industrial and technological applications related to epoxy/CNT nano-
composites have led to their being widely researched. These nanocomposites are
processed using melt or solution blending methods. The typical processing by melt
mixing of epoxy/CNT consists of three steps: firstly the CNTs are added directly to
the resin, and the mixture is sonicated in an ultrasonic machine at high temperature;
secondly a curing agent is added and the mixture is degassed in a vacuum oven; and
finally the mixture is placed in molds and cured in an oven [28]. The method is as
follows when processing is by solution: the CNTs are dispersed in the solution using
sonication; on the other hand, the epoxy resin and curing agent are dissolved in
acetone and mixed with the CNT suspension. The mixture is then mechanically
agitated and sonicated in a water bath. Finally, the acetone present in the system is
removed by rotary evaporation, and the mixture is cured in an oven [50]. Liu et al.
studied MWCNT-reinforced epoxy nanocomposites using polyethylenimine as a
dispersing agent (covalent modification). The nanocomposites whose nanoparticles
were covalently modified showed higher strength and higher storage modulus, due
to improved nanotube/polymer interaction [50]. Similar results were observed by
Spitalsky et al. in H2O2/NH4OH-modified nano-reinforcements for the production of
MWCNT/epoxy nanocomposites [73].
PA-6/CNT compounds are often processed using the fusion method or by capro-
lactam polymerization. Generally, the melt method consists of the following steps:
PA-6 is extruded together with CNTs, using a twin-screw corotating extruder at a
barrel temperature of 260  C and a throughput of 5 kg/h. They are pelletized and
processed by injection molding [55]. On the other hand, for processing by polymer-
ization, it is as follows: first the CNTs and caprolactam are blended, and the blend is
sonicated at 80  C for 2 h; then 6-aminocaproic acid is added to the suspension. This
suspension is heated to 250  C with mechanical agitation under an argon atmo-
sphere. After 6 hours of agitation, the blend is removed and poured into water,
causing the precipitation of the polymer. The precipitate is pelletized and washed
with hot water for subsequent molding [24]. Meincke et al. developed PA-6/CNT
compounds processed on a twin-screw extruder. At low percentages of
176 M. P. Guarás and V. A. Alvarez

reinforcement, the nanocomposite evidences electrical conductivity. In addition,

Young’s modulus showed a 27% increase compared to the unreinforced matrix
[55]. Gao et al., on the other hand, studied the chemical processing technology,
which allowed them to perform continuous spinning of PA-6/SWCNT fibers by in
situ polymerization of caprolactam in the presence of amide-functionalized
SWCNTs. It was possible to control the number of PA-6 chains grafted onto the
SWCNT nanoparticles by controlling the concentration of the initiator. Fibers with
improved mechanical resistance and thermal stability were obtained [24].
Pristine CNTs (P-CNTs) present a difficulty in being dispersed in polymer
matrices, as previously mentioned. Therefore, numerous processing techniques
have been developed, to effectively reduce the aggregation of nanotubes within
matrices. Acid oxidation is a method by which reactive oxygen-containing groups
such as carboxyl, carbonyl, and hydroxyl are introduced to the surface of CNTs. For
this, the use of strong acids, such as HNO3 and H2SO4, is necessary. The final
oxidized polymer/CNT nanocomposites (O-CNT) have exhibited better dispersion
and interfacial behavior within multiple polymer matrices. Lateral functionalization
of CNTs using organic chains or functional groups is another effective way to
improve the dispersion of CNTs. Reactive oxygen-containing fractions produced
by acid oxidation can be transformed into other functional groups using acrylic,
chloridization, amination, esterification, and a variety of other methods [8].
Among the most important applications of CNT/polymer nanocomposites are
electromagnetic interference (EMI) shielding, supercapacitor electrodes, photovol-
taics devices, thermoelectrics devices, water purification, and gas and chemical
vapor sensors, among others.

Polymer Matrices from Sustainable Renewable Sources

Biodegradable polymers or biopolymers are polymers capable of being degraded

through the metabolism of natural organisms [63]. This process produces gases
(CO2, N2), water, biomass, and inorganic salts [5]. It is possible to classify biodegrad-
able polymers in different ways, according to their chemical composition, synthesis
method, processing, economic importance, and application, among others. The clas-
sification according to the source they come from is divided into (i) polymers from
biomass such as agro-polymers (starches or cellulose and proteins), (ii) polymers
obtained from microbial production such as polyhydroxyalkanoates (PHAs) (micro-
bial polyesters are produced by biosynthetic function of a microorganism), (iii)
conventional polymers and chemically synthesized from monomers from agro-
resources (polylactic acid, PLA), and (iv) polymers obtained from fossil resources
[70]. To achieve full biodegradability, proper handling of waste products must be
carried out; that is, after being used, plastics must be properly disposed of in order to
allow for biological decomposition (i.e., composting) (Prof. [12]).
Among the most important biodegradable polymers, thermoplastic starch (TPS),
polylactide (PLA), polycaprolactone (PCL), and polyhydroxybutyrate and poly-
hydroxyalkanoate (PHA) are especially found due to their promising properties.
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 177

Starch-Based Nanocomposites

Thermoplastic starch (TPS) is a promising material for the development of biodegrad-

able polymers. Currently, due to its abundance, it is one of the biodegradable polymers
from the cheapest renewable resources available on the market. Depending on the
botanical origin of the plant, the starch granules can have different shapes (spheres,
platelets, polygonal) and size (from 0.5 to 175 μm). Its chemical composition consists
of two components: amylose, composed of 1,4-α-D-glucose bonds in straight chains,
and amylopectin, in which the glucose chains are highly branched [58].
The main disadvantages exhibited by thermoplastic starch are poor mechanical
properties, high hydrophilicity (which produces changes in properties with humid-
ity), high viscosity (which limits its processing), and high susceptibility to
retrodegradation (the material recrystallizes with time, becomes opaque, and suffers
exudation of plasticizer to the environment). The mechanical properties of thermo-
plastic starch evolve over time due to molecular rearrangement, which depends on
the processing method and the conditions of storage. When samples are stored below
the Tg, they can suffer physical aging with material densification [76]. When
T > Tg, the samples are retrograded by increasing their crystallinity [51]. Aging
the physical properties are observed for materials with a plasticizer content of less
than 25% by weight [54]. This phenomenon induces an increase in the resistance of
the material and a decrease in the deformation at break.
It is possible to combine thermoplastic starch with other compounds in order to
eliminate the disadvantages associated with their properties. These disadvantages
can be overcome by using different strategies through physical or chemical means,
including chemical modification [56], copolymerization of grafts [41], mixing with
other synthetic polymers [27], and the incorporation of fillers such as clay [1] and
nanocrystalline cellulose [77]. The incorporation of nanofillers to the polymer blends
produces enhancements in the mechanical and barrier properties, driving to materials
with high performance/cost ratio. The addition of a certain amount of nanofillers can
significantly improve the physicochemical properties of the starch, and the size of
the filler can also influence the biological activities of the starch-based materials.
Starch-based nanocomposites can generally be processed using two different
techniques, casting and extrusion. Although starch offers advantages in biomedical
applications in other ones, as in the packaging and automotive industries, are limited
and there are not capable of satisfying most of the necessary requirements. For this
reason it is essential to incorporate some ecological filler to improve the properties of
the starch. Among the different fillers, clay is the most abundant, biomass-based and
low-cost filler that is frequently used in many applications. Kaolin is also used as a
backing to prepare nanocomposites using thermoplastic starch (TPS) [53].
Often, it is necessary to modify the clay in order to increase its interlayer spacing
and thus allow the polymer to be sandwiched between the clay sheets. Although clay
modification is a means of increasing interlaminar spacing (d001) to possibly facilitate
molecular intercalation of starch, it is demonstrated that the structure of the resulting
compounds is more dependent on the hydrophilicity of MMT. The morphology of
TPS-based nanocomposites will be highly dependent on the hydrophilicity of the
178 M. P. Guarás and V. A. Alvarez

MMT and the chemical modification of the TPS. It has been shown that the incorpo-
ration of MMT hydrophobic nano-reinforcements such as Cloisite 15A, 6A, and 10A,
Nanomer I.30E, etc. led to the formation of microcomposites, showing unaltered
interlaminar spacing (d001), using TPS with 30% glycerol [90]. When Cloisite 30B,
a more hydrophilic OMMT, was used, higher values of d001 were obtained,
corresponding to a higher dispersion of the nano-reinforcement in the TPS. Exfoliated
nanocomposites have also been produced with MMT-Na+ due to the more hydrophilic
character that makes it more compatible with thermoplastic starch. Uniform dispersion
of MMT in thermoplastic starch can be achieved in this case due to polar interactions,
especially the hydrogen bonds formed between the MMT-OH groups and the starch
molecules [82]. When starch is chemically modified to decrease its hydrophilicity,
apolar interactions with MMT can be achieved and as a result a lower dispersion of the
reinforcement in the matrix [3].
Nanocellulose (NC) is a rigid particle that appears in the form of a rod and that has
high strength and rigidity. Often, it has been used to improve the mechanical properties
of various biocomposite materials, processed in different ways, such as films, gels, and
foams, and notably to reinforce biopolymer-based electrospun fibers [44]. As is
known, both cellulose and starch are biodegradable and belong to the polysaccharide
family. The general chemical formula of cellulose and starch is (C6H10O5) and the
structural unit is D-glucose. They are isomers with different glycosidic bond connec-
tions. Taking advantage of chemical similarity between both polymers, cellulose
nanofibers (CNF) are commonly used to reinforce starch resulting in good interfacial
bonds. Recently, starch/CNF-based nanocomposites have become increasingly popu-
lar in the paper, food, and adhesive manufacturing area, due to their excellent
mechanical properties, low cost, and mainly biodegradability [65].
Chang et al., in their work, have impregnated cellulose nanoparticles in a starch
matrix, and the compounds containing 5% by weight of cellulose nanoparticles
showed a 248% increase in the elastic limit [11]. Patil and Netravali impregnated
microfibrillated cellulose (MFC) with starch resin to take advantage of the chemical
similarity between starch and cellulose, and the resulting starch/MFC biocomposites
showed markedly improved thermal and tensile properties, comparable to the prop-
erties of compounds based on edible starch [60].

PLA-Based Nanocomposites

Polylactide or poly(lactic acid) (PLA) is a biodegradable thermoplastic polyester that

is manufactured using biotechnological processes from renewable resources.
Although it can be manufactured from numerous biomass sources, corn has the
advantage of providing the highest purity lactic acid required. In order to resurrect
the costs of the manufacturing process, alternative starting materials (e.g., woody
biomass) are continually being studied; however, due to the complexity of extrac-
tion, it is still expensive.
In addition to its biodegradability and renewability, PLA exhibits interesting
mechanical properties, its Young’s modulus is about 3 GPa, and the tensile strength
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 179

is between 50 and 70 MPa with an elongation at break of about 4% and an impact

strength of about 2.5 kJ/m2 [52]. Compared to conventional polymers such as PE,
PP, PS, and PET, the mechanical properties of semicrystalline P(l-LA) are attractive,
making it an excellent substitute for short-life packaging applications. However,
PLA is a brittle material with low-impact resistance, which is one of its main
limitations. In addition, the main issue regarding the use of PLA relates to its low
capacity and degree of crystallization, which significantly limits its industrial appli-
cation in durable applications such as automotive and electronics [61]. One solution
widely developed in recent years has been to incorporate nano-reinforcements into
the PLA matrix. Several types of nanofillers have been considered as reinforcing
agents in order to improve their thermomechanical properties, as well as to provide
additional functionalities such as fire resistance.
PLA-based nanocomposites have been extensively researched in the presence of
layered silicates, in order to obtain highly exfoliated structures.
The preparation of PLA-based silicate nanocomposites with improved mechan-
ical and barrier properties, in which highly exfoliated structures were obtained, has
been successfully obtained using the solvent interleaving processing technique.
Pochan and Krikorian investigated the effect of organic modifiers derived from
three commercial organophilic clays (Cloisite 30B, Cloisite 25A, and Cloisite
15A) during the formation of PLA matrix nanocomposites. Given the compatibility
between the matrix and the Cloisite 30B clay modifier, the mechanical properties of
these compounds were improved, showing a 61% increase in Young’s modulus
when 15% of Cloisite 30B was added to the matrix [47]. Although PLA is an
interesting candidate for use as food packaging in relation to its biodegradability,
the oxygen permeability of PLA must be reduced in order for it to be competitive in
the oxygen-sensitive food area. Svagan et al. developed layer-by-layer nano-
composites based on PLA films and chitosan/montmorillonite layers. During this
procedure, thin-film multilayer structures of chitosan and montmorillonite were
assembled mainly by means of electrostatic forces in the extrusion of PLA films.
Compared to pure PLA, montmorillonite/chitosan bilayer-coated PLA films
achieved almost two orders of magnitude lower oxygen permeability [74].
Due to its unique structural and electronic characteristics, graphene as nanofiller
finds promising applications in the field of polymer nanocomposites. Recently, the use
of functionalized graphite nanofillers with tricobalt tetraoxide has been developed to
increase the fire resistance of PLA [80]. Co3O4/graphite nanofillers were synthesized
by an in situ chemical reduction process and redistributed in the PLA matrix by the
melt method. As expected, the incorporation of Co3O4/graphene into PLA increased
the initial degradation temperature, while slowing down the thermal decomposition
process. Also, the heat release rate of the nanocomposites was reduced by 40%
compared to pure PLA. The emissions of gaseous products such as hydrocarbons,
carbonyl compounds, and carbon monoxide were in turn reduced with the addition of
Co3O4/graphene, which was attributed to the combined properties of the barrier effect
and the high catalytic activity for CO oxidation of Co3O4/graphene.
Historically, silver compounds (neutral or ionic forms) have been widely used for
both hygienic and healing purposes. When silver has a nanometer size, its total surface
180 M. P. Guarás and V. A. Alvarez

area becomes larger, and in this context the antibacterial efficacy increases accord-
ingly. Furthermore, for various applications (water/air treatment and purification,
health industry, electronics, textiles, shoe industry, packaging, etc.), there is a growing
demand for polymer materials with antimicrobial properties. Since Ag nanoparticles
form large aggregates and agglomerates very easily, the preparation of polymer
nanocomposites/silver nanoparticles requires them to be properly pre-dispersed, spe-
cific surface treatments or the functionalization of the nanoparticles with organic
molecules, and/or their incorporation into suitable polymer matrices [18].
Ag nanoparticles with diameters in the range of 3–5 nm were synthesized by Kamyar
et al., by a chemical reduction method using silver nitrate and sodium borohydride (as a
reducing agent), in a PLA-based solution composed of two solvents (DMF and
CH2Cl2). The PLA films after evaporation of the solvents showed a uniform distribution
of Ag-NP nanoparticles in the PLA matrix and strong antibacterial activity against
E. coli and Staphylococcus aureus bacteria, respectively [68]. Furthermore, following a
similar procedure, biodegradable PLA fibers containing nanosilver particles were pre-
pared by electrospinning. These fibers showed a strong bacterial reduction of 98.5% and
94.2% against S. aureus and E. coli, respectively [85].

PCL-Based Nanocomposites

Poly(e-caprolactone) or PCL is a semicrystalline, biodegradable polyester derived

from petroleum. PCL has good resistance to water, oil, solvent, and chlorine, a low
melting point, and low viscosity and is easily processed using conventional polymer
processing techniques. It has low mechanical resistance but high flexibility, and its
elongation at break can reach values of up to 700% [27].
The recently developed nanocomposite technology consisting of the addition of
nanoparticles derived from biomass such as starch or cellulose is of particular
interest. Compared to other types of inorganic nanofillers, this type of polymer-
based nanoparticles has been given great attention due to its sustainability, biode-
gradability, and economic benefits. Several methods have been developed to prepare
starch-based nanoparticles (SNPs), including precipitation by organic solvents, high-
pressure homogenization method, and lyophilization method, among others
[69]. SNPs were reported to produce significant improvements in the mechanical
and water vapor barrier properties of starch films. Biosource nanocomposites based
on PCL/SNP by melt mixing and different SNP contents (2.5 to 10 wt.%) have been
prepared, obtaining a very good dispersion of the SNPs in the PCL matrix. Further-
more, great improvements were observed in the mechanical properties of the
resulting nanocomposites. Even with the addition of 10% by weight of SNP, the
nanocomposite still demonstrated good ductility [45].
Poly(e-caprolactone) (PCL)/carbon nanotubes (CNTs) have potential applications
in the biodegradable materials market and in the biomedical field [30]. CNTs can
help overcome the disadvantages of PCL with respect to mechanical properties and
thermal stability. Further studies address the addition of CNT to the PCL matrix and
have found that CNTs could improve biodegradation rate, mechanical performance,
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 181

and thermal stability [7]. An alternative “grafting” approach based on in situ ring
opening polymerization of e-caprolactone has been successfully developed to cova-
lently graft biodegradable poly(e-caprolactone) onto CNT surfaces. The content of
grafted PCL can be easily controlled by adjusting the ratio of CNT-compatible
monomers and macroinitiators. After PCL was injected onto CNT surfaces, the
core-shell structures with nanotubes promise good solubility/dispersibility of
CNT-PCL adducts in low boiling point organic solvents. CNT-injected PCL retains
the biodegradability of conventional PCL and can be completely biodegraded by PS
lipase in 4 days [89].

Commercial Nanoproducts

Nanoproducts market development does not confine itself to the rippling effect; it’s a
much more complicated and country-specific process. It is important to take in mind
that the key demand-driving factor is offering radically new value to a consumer. In
this sense, nanotechnology and nanoproducts not only develop the existing markets
but also create new, high-capacity ones (P. C. M. [35]).
The annual global market growth rate is averaging 17%. The growth in question
is not gradual. There are tens of promising product niches boasting accelerated
growth, for example, solar energy conversion (300% annual growth rate); optical
electronics, 53%; medical research, clinical diagnostics, and medical equipment
using nanotechnology, 32%; fuel nanocells, 23%; nanocomposites, 20%; etc. In
2015 global market capacity is expected to reach a $500 billion mark and surpass $1
trillion if the full cost of consumer nanoproducts is taken into account [6].
Some important polymeric matrix-based nanocomposites available in the market
are summarized in Table 1.

Conclusions

In this chapter, we have shown that the addition of nanoparticles to polymer matrices
produces nanocomposites, a new generation of composite materials, with enhanced
but also novel properties. Polymer-based nanocomposite is still a technology revo-
lutionizing the world of material.
Nonetheless, there are still several unresolved issues and new challenges in the
field of polymer nanocomposites. One really important is the influence of prepara-
tion and processing techniques and methodologies on the generation of morphol-
ogies and their dependence on the final properties of the system that make it suitable
for a required application.
The polymer-based nanocomposites still have a huge potential that can be exem-
plified by the massive investment from government but also companies throughout the
entire world. Finally, although there are several commercially available products based
on this kind of materials, it is expected a big growth on the next decades together with
the generation of a big impact on world business and economy.
182 M. P. Guarás and V. A. Alvarez

Table 1 Examples of commercial nanoproducts and its applications, characteristics, and producers
Commercial polymer nanocomposites
Product Characteristics Applications Producer
Vestamid Electrically conductive Industrial parts Creanova
(Nylon
12/CNTs)
Nylon Improved modulus, Automotive parts (e.g., Bayer, Honeywell
nanocomposites strength, heat distort timing belt cover, Polymer, RTP
temperature, barrier engine cover, barrier, Company, Toyota
properties fuel line), packaging, Motors, UBE, Unitika
barrier film
Durethan Doubling of stiffness, Barrier films, paper Bayer
KU2-2601 high gloss and clarity, coating
(nylon 6) reduced oxygen
transmission rate,
improved barrier
properties
Aegis NC Doubling of stiffness, Medium barrier bottles Honeywell Polymer
(nylon 6/barrier higher heat distort and films
nylon) temperature, improved
clarity
Polyolefin Stiffer, stronger, less Step-assist for GMC Basell, Blackhawk
nanocomposites brittle, lighter, more Safari and Chevrolet Automotive, Plastics
easily recycled, Astro vans, heavy-duty Inc., General Motors,
improved flame electrical enclosure Gitto Global
retardancy Corporation,
Southern Clay
Products
Imperm ® Improve barrier Multilayer PET bottle Nanocor Inc.
properties and sheets
M9 High barrier properties Juice or beer bottles, Mitsubishi Gas
multilayer films, Chemical Company
containers
Aegis TM OX Highly reduced oxygen High barrier beer Honeywell Polymer
transmission rate, bottles
improved clarity
Forte Improved temperature Automotive furniture Noble Polymer
nanocomposite resistance and stiffness, appliance
very good impact
properties
Commercial nanofillers
Product Characteristics Applications Producer
Carbon High electrical and Additives and Bayer, Hyperion
nanotubes thermal conductivity, reinforcements Catalysis
low thermal expansion International,
coefficient Nanocyl,
Zyvex Corp.
Nanomers Microfine powder Nylon, epoxy, Nanocor
unsaturated polyester,
engineering resins
(continued)
8 Consumer Nanoproducts Based on Polymer Nanocomposites Matrices 183

Table 1 (continued)
Commercial polymer nanocomposites
Product Characteristics Applications Producer
Cloisite Hydrophilic Additives, enhance Southern Clay
Organophilic flexural and tensile Products
modulus, barrier
properties and flame
retardance of
thermoplastics
Dellite Hydrophilic Cables and wires, Laviosa
Organophilic packaging
Automotive, rubbers,
Bentone With a broad range of Additives to enhance Elementis Specialties
polarity mechanical, flame-
retardant, and barrier
properties of thermoset
and thermoplastics
Masterbatches Pellet Thermoplastic olefin PolyOne Corporation,
and urethane, styrene- Clariant Corporation,
ethylene-butylene- RTP Company
styrene, ethylene-vinyl
acetate
NanoFil Improve the Thermoplastics and Sud-Chemie
mechanical, thermal, thermosets
and barrier properties
Planomers Additive, enhance Electric and electronic, TNO
mechanical barrier medical and healthcare,
properties, thermal adhesive, building and
stability, and flame construction materials
resistance
PlanoColors Nanopigments, e.g., Decorative coloring, TNO
blue, red, green, yellow, UV-stable coloring,
high UV stability heavy metal-free
coloring
PlanoCoatings Additive, excellent Transparent packaging TNO
transparency and materials, protective
improved barrier coatings, transparent
properties barrier coatings

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Polymer Nanocomposites for Futuristic
Energy Storage Applications 9
A. K. Nath and J. M. Kalita

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Layered Silicates and Polymer-Layered Silicate Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . 194
Ionic Liquids and Ionic Liquid-Based Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Swift Heavy Ion Irradiation and Effects on Polymer Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . 198
Ionic Transport and Electrochemical Properties of Ionic Liquid-Based
P(VdF-HFP)-Layered Silicate Nanocomposite Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
Swift Heavy Ion Irradiation Effects on Polymer-Layered Silicate Nanocomposite
Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223

Abstract
Electronic devices play a continuously increasing role in today’s modern society
and the demands of wireless devices being rapidly growing. To ensure a stable
current power supply, on board energy storage is essential, and therefore, energy
storage devices are of great importance in today’s world. Traditional devices with
liquid electrolytes have several limitations due to their bulky size and carry the
inherent risk of leakage and safety. With a view to overcome the difficulties
associated with bulky size and leakage, solid electrolytes have been emerged. Out
of all kinds of solid electrolytes, polymer electrolytes have got utmost importance
as they offer several advantages such as structural and chemical stability, shape
versatility, low toxicity, etc. Therefore, burgeoning research is going on in the
field of polymer electrolyte to get enhanced ionic conductivity and electrochem-
ical stability which facilitate miniaturization, create more flexibility for the design
of stand-alone microelectronic devices, and enhance the applicability in diversi-
fied fields. Swift heavy ion (SHI) irradiation is a novel technique to improve

A. K. Nath · J. M. Kalita (*)

Department of Physics, Cotton University, Guwahati, India

© Springer Nature Singapore Pte Ltd. 2022 189

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_18
190 A. K. Nath and J. M. Kalita

electrical, electrochemical, and optical properties of different polymeric mate-

rials. Irradiation by high energy ion beam leads to fluence-dependent chain-
scission and/or cross-linking of the polymer chains which change the molecular
weight distribution and molecular structure of the host polymer, which in turn
affect electrical and mechanical properties. Considering all these developments in
the field of energy storage materials, different polymer electrolyte nanocomposite
systems, effects of SHI irradiation, and their probable applications have been
reported in this chapter.

Keywords
Polymer electrolyte · Nanocomposite · Energy storage · Layered silicate · Swift
heavy ion irradiation

Introduction

One of the main challenges of today’s information rich technology world is to

provide efficient, portable, low-cost, and ecofriendly electrochemical energy con-
version and storage devices such as rechargeable batteries. Rechargeable batteries
based on liquid electrolyte have several restrictions on their design and size and carry
the inherent risk of leakage. The replacement of liquid electrolytes with polymer
electrolyte thin films offers numerous advantages to battery technologies in terms of
structural and chemical stabilities, shape versatility, low toxicity, etc. and has
potential advantages in the continuing trend toward miniaturization. A polymer
electrolyte consists of an inorganic salt dissolved in a polymer matrix. The history
of polymer electrolytes leads back to 1973 when P.V. Wright and his group observed
ionic conductivity in their trail blazing work on poly(ethylene) oxide (PEO)
complexed with sodium and potassium thiocyanates and sodium iodide [1]. The
electrical properties of these electrolyte systems were studied later by P.V. Wright
which established a correlation between ionic conductivity and amorphous phase of
the polymer [2, 3]. In 1979, Armand [4] first proposed the use of these electrolyte
systems as solid polymer electrolytes for rechargeable batteries which opened a
window to the emerging field of polymer electrolytes. The oxygen atoms in PEO
have high electron donor power with suitable interatomic separation enabling them
to form multiple intra-polymer coordination bonds with cations. The low bond
rotation barriers allow segmental motion of the polymer chain providing a mecha-
nism for ion transport [5]. Since the first proposal by Armand in 1979, polymer
electrolytes have been adopted in a wide variety of applications. The largely attracted
applications of polymer electrolytes are in rechargeable batteries, sensors, fuel cells,
supercapacitors, actuators, electrochromic displays, etc. The role of polymer elec-
trolytes in these applications is to separate the electrodes, allow fast and selective
transport of ions, and provide electronic insulation between the electrodes. To be
suitable for the above-mentioned applications as given in Fig. 1, a polymer electro-
lyte must satisfy the following important requirements:
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 191

Fig. 1 Polymer electrolyte and applications

(i) Polymer electrolytes should have adequate ionic conductivity (~ 10
3 S cm
1)
and should be electronically insulator so that ion transport can be facilitated and
self-discharge can be minimized. In general, the electrolyte is the component of
192 A. K. Nath and J. M. Kalita

an electrochemical device that sets the upper limit of output power. Therefore,
higher electrolyte conductivity implies that a higher output power can be
obtained from the device [6].
(ii) Another important requirement of polymer electrolyte is wide electrochemical
stability which is important for energy storage devices such as supercapacitors
and rechargeable batteries [7]. Polymer electrolyte should have electrochemical
stability extending from 0 V up to as high as 5 V to be compatible with
electrode materials.
(iii) A polymer electrolyte should possess high thermal stability as during the
functioning of the device, it may release heat that may result in degradation
of the device. The polymer electrolyte used as a component in a device must be
capable of maintaining its rated performance and withstand the device operat-
ing conditions, particularly the operating temperature.
(iv) Polymer electrolyte should be robust against electrical, mechanical, or thermal
abuses. It must possess good mechanical strength as to achieve various favor-
able electrochemical properties. Polymer electrolyte films should be flexible for
miniaturized applications.

Polymer electrolytes can be primarily classified into three categories: (i) solid
polymer electrolytes, (ii) gel polymer electrolytes, and (iii) composite polymer
electrolytes. “Solid polymer electrolytes” are solvent-free systems with an ionic
conducting phase formed by dissolved salts in a polar polymer matrix [8]. The
ionic conductivity of solid polymer electrolytes is typically low, generally lower than
10
6–10
8 S cm
1 at room temperature. In order to increase the ionic conductivity,
“gel polymer electrolytes” have been developed by incorporating liquid plasticizer
and/or solvents to a polymer-salt complex that is capable of forming a stable gel with
the polymer host structure [9]. Gel polymer electrolytes are characterized by a higher
ambient ionic conductivity but poorer mechanical properties compared to solid
polymer electrolytes. The “composite polymer electrolytes” are prepared by adding
inorganic material to the polymer-salt complex [10]. The combination is expected to
improve ionic conductivity and electrochemical stability of the polymer electrolyte.
The development of polymer electrolytes with high ionic conductivity and
electrochemical properties has been an intensive area of research driven by the
need to find new electrolytes for miniaturized applications [11]. Classical polymer
electrolytes based on a polymer matrix and a solid salt offered low room temperature
ionic conductivity restricting them from practical applications. High crystallinity of
polymers is the key factor of low ionic conductivity (~10
7 S cm
1) in traditional
polymer electrolytes. In this scenario, nanocomposite polymer electrolytes came as a
rescue offering higher ionic conductivity (~10
3 S cm
1). Nanocomposite polymer
electrolytes are produced by dispersing nanoscale fillers such as Al2O3, TiO2, SiO2,
and clay in the polymer matrix [12, 13]. The nanofillers hinder the recrystallization
of the polymer chains promoting localized amorphous regions which facilitates the
movement of the ions through the polymer matrix leading to enhancement in ionic
conductivity. It has been observed that particle size and the type of polymer-filler
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 193

system play a significant role in enhancing electrochemical, thermal, and mechanical

properties of nanocomposite polymer electrolytes [14].
One important advancement in the field of polymer electrolytes is the develop-
ment of polymer-layered silicate nanocomposites. These nanocomposites are formed
by the intercalation of polymers inside the interlayer galleries of layered silicate and
are gaining great deal of research interest because of their potential importance in the
development of polymer electrolytes with enhanced properties for applications in
solid-state batteries [15, 16]. Intercalating polymer in layered silicate can produce
polymer electrolyte nanocomposites with huge interfacial area which not only
reduces the crystallinity of the polymer resulting in higher ionic conductivity but
also sustains the mechanical stability [17]. Among the most commonly used inor-
ganic layered hosts, montmorillonite (MMT) is a favored choice in view of its
special features of high aspect ratio and high cation-exchange capacity
(CEC 80 mequiv./100 g). The high swelling capacity of MMT is significant for
the efficient intercalation of polymer inside the interlayer galleries. Aranda and
Ruizhitzky [18] have found that intercalated poly(ethylene oxide) (PEO) molecules
between silicate galleries impede polymer crystallization, resulting in higher ion
conductivity compared with systems without clays. R.J. Sengawa et al. [19] reported
that the dispersion of nanoscale MMT clay in poly(vinyl alcohol) (PVA)-poly
(ethylene oxide) (PEO) blend matrix produces a large hindrance to the polymer
chain dynamics.
In recent times, the use of non-volatile, non-flammable ionic liquids (ILs) in
polymer electrolytes has emerged as a very promising approach to replace traditional
solid salts to improve the ionic conductivity and the interfacial property of polymer
electrolytes as it can act both as ion supplying material (salt) and plasticizer which
collectively enhance the ionic conductivity of the polymer electrolyte [20, 21]. Ionic
liquids are organic salts that exist in liquid state at temperature lower than 100  C
[22]. They have engrossed much attention due to their unique properties such as
non-volatility, non-flammability, negligible vapor pressure at room temperature,
wide electrochemical stability window (~4.5 V), high ionic conductivity
(~10
2 S cm
1), excellent thermal and chemical stability, etc. [23, 24]. The polymer
gel electrolytes based on ILs have a unique hybrid structure, which possesses
cohesive properties of solids (due to polymer matrix) and diffusive properties of
liquids (due to IL) simultaneously. Recent works done by many research groups
demonstrated that ionic conductivity and electrochemical stability of polymer elec-
trolytes are enhanced by the addition of ILs [24, 25]. For example, P. Yang et al. [26]
reported room temperature ionic conductivity of 2.1  10
4 S cm
1 for the IL-based
gel polymer electrolyte with poly(vinylidene fluoride-co-hexafluoropropylene)
(P(VdF-HFP)) as polymer matrix and 1-butyl-4-methylpyridinium bis
(trifluoromethanesulfonyl)imide (B4MePyTFSI) as ionic liquid. J. Pitawala et al.
[27] have studied the properties of polymer gel electrolytes based on P(VdF-HFP)
and ionic liquids of the pyrrolidinium cation and the bis(trifluoromethanesulfonyl)-
imide anion and obtained maximum room temperature ionic conductivity of
1.6  10
3 S cm
1.
194 A. K. Nath and J. M. Kalita

Swift heavy ion (SHI) irradiation is another novel technique to improve material’s
properties. Electrical, electrochemical, and optical properties of different polymeric
materials can be selectively modified by ion irradiation [28]. Irradiation by high
energy ion beam leads to fluence-dependent chain-scission and/or cross-linking of
the polymer chains which change the molecular weight distribution and molecular
structure of the host polymer, which in turn affect electrical and mechanical prop-
erties. When energetic ions penetrate into a polymer material, they lose energy
during their passage through the material mainly by two different processes:
(i) elastic collisions with the nuclei known as nuclear energy loss and (ii) inelastic
collisions with the atomic electrons of the material known as electronic energy loss
[29]. In SHI irradiation, electronic energy loss dominants and the kinetic energy of
the ejected electrons is transmitted to the lattice by electron-phonon interactions
leading to increase of local lattice temperature above the melting point of the
material. The melting of the material is followed by a rapid quenching resulting in
amorphous columnar structure when the melt solidifies and the material’s properties
get modified. SHI irradiation has been reported to increase hardness, strength and
wear resistance, ionic conductivity, and density and change the chain length and
crystallinity of polymers [30, 31]. Considering the above-mentioned assessment, the
present chapter describes works on electrochemical properties of ionic liquid-based
polymer electrolyte nanocomposites and the effect of SHI irradiation.

Layered Silicates and Polymer-Layered Silicate Nanocomposites

The layered silicates commonly used in the nanocomposites belong to the structural
family known as 2:1 phyllosilicates [32]. Their crystal lattice consists of a
two-dimensional, 1 nm thick layers which are made up of two tetrahedral sheets of
silica fused to an edge-shaped octahedral sheet of alumina or magnesia. The lateral
dimensions of these layers vary from 300 Å to several microns depending on the
particular silicate. Stacking of the layers leads to a regular van der Walls gap between
them called the interlayer or gallery. Isomorphic substitution within the layer (e.g.,
Al3+ replaced by Mg2+ or by Fe2+ or Mg2+ replaced by Li+) generates negative
charges that are normally counterbalanced by hydrated alkali or alkaline earth
cations residing in the interlayer. As the forces that hold the stacks together are
relatively weak, the intercalation of small molecules between the layers becomes
easier [33].
The commonly used layered silicates of 2:1 phyllosilicates family are montmo-
rillonite, hectorite, and saponite. The chemical formulae for montmorillonite,
hectorite, and saponite are Na0.33((Al1.67Mg0.33)(OH)2(Si4O10)), Na0.33((Mg,
Li)3(OH, F)2(Si4O10)), and (Ca, Na)0.33((Mg, Li)3(Mg, Fe)3(OH)2(Al0.33Si3.67O10)),
respectively. All these clays have layered structures with exchangeable cations in the
interlayer galleries. Polymers can also be intercalated into the interlayer galleries of
these clays.
The naturally occurring layered silicates are hydrophilic in nature and not misci-
ble with most of the polymers. In order to mix these hydrophilic layered silicates
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 195

with polymers, it has to be modified to organophilic (organoclay) by exchanging the

cations of the interlayers with organic cationic surfactants such as alkylammonium
or alkylphosphonium (onium) salts. Because the modified clay (organoclay) is
organophilic, its surface energy is lowered and is more compatible with organic
polymers. The modification of layered silicates to organoclay not only matches the
clay surface polarity with the polarity of the polymer but also expands the clay
galleries. This facilitates the penetration of the gallery space by either the polymer
precursors or preformed polymer. The maximum extent to which the cations inside
the interlayer galleries can be exchanged is called cation exchange capacity and
generally expressed in mequiv/100 g. Montmorillonites, hectorite, and saponite are
the most commonly used layered silicates.
Layered silicates have layer thickness of the order of 1 nm and very high aspect
ratio of ~10–1000. Only a few weight percent of properly dispersed layered silicates
create much higher surface area for polymer-layered silicate nanocomposites com-
pared to conventional composites. Depending on the nature of the components used
(layered silicate, organic cation, and polymer matrix), the strength of interfacial
interactions between the polymer matrix and the layered silicates, as well as their
methods of preparation, three different types of polymer-layered silicate nano-
composites can be thermodynamically obtained:

(i) Phase separated: When the polymer is unable to intercalate between the
silicate layers, a phase-separated composite is obtained whose properties
remain in the same range as traditional microcomposites.
(ii) Intercalated nanocomposite: In intercalated nanostructure, a single or some-
times more than one extended polymer chain is intercalated between the silicate
layers resulting in a well-ordered multilayer morphology with alternating
polymeric and inorganic layers.
(iii) Exfoliated nanocomposite: These nanocomposites are formed when the sili-
cate monolayers individually dispersed in polymer matrix, the average distance
between the segregated layers being dependent on clay loading. The separation
between the exfoliated nanolayers may be uniform (regular) or variable (disor-
dered), and the stacks of the original clay structure are lost.

The systematic studies on the interaction between a clay mineral and a macro-
molecule dates back to 1949, when Bower [34] described the absorption of DNA by
montmorillonite (MMT). In 1963, Greenland [35] synthesized poly(vinyl alcohol)/
montmorillonite nanocomposite system and demonstrated that a polymer could be
directly inserted in a clay in an aqueous solution. However, the field of polymer-
layered silicate nanocomposite was widely introduced to the academic and industrial
laboratories by a group of Toyota researchers in 1995 [36]. The Toyota research
group reported improved methods for producing nylon 6 clay nanocomposites using
in-situ polymerization. Their work revealed that polymer-clay nanocomposites
exhibit superior strength, modulus, heat distortion temperature, water, and gas
barrier properties with comparable impact strength as neat nylon 6. They also
reported on various other types of polymer-clay hybrid nanocomposites. The
196 A. K. Nath and J. M. Kalita

pioneering work done by Giannelis and his colleagues [37] revealed that intercala-
tion of polymer chains into the interlayer galleries of an organoclay can occur
spontaneously on heating a mixture of polymer and silicate clay powder above the
polymer glass transition or melt temperature. They explored the possibility of
intercalation on the basis of thermodynamical free energy considerations and simu-
lation studies to investigate the conformational and structural arrangement of poly-
mer chains between successive clay layers [38]. Polymer electrolytes based on MMT
clay and polymers such as poly(ethylene oxide) PEO and polyacrylonitrile (PAN)
showed enhanced ionic conductivity compared to conventional polymer electrolytes
[39]. Fan et al. [19] studied the Li-MMT/Na-MMT and PEO16LiClO4 composites
and reported 30 times enhancement in room temperature ionic conductivity for the
composite polymer film (3.5  10
6 S cm
1) compared to that of the pure
PEO16LiClO4 (1.2  10
7 S cm
1). H.W. Chen et al. [40] showed that modified
MMT enhances the ionic conductivity of PEO-based polymer electrolytes by
16 times than plain system. The conductivity increase is due to the well-dispersed
clay in the system, which tends to disrupt the association of lithium cations and
anions. Raghavan Prasanth et al. [13] prepared PVdF-clay nanocomposite PGEs
containing 0–4 wt. % clay loading and studied their electrochemical properties. The
intercalation/exfoliation of the clay into the polymer matrix was confirmed by XRD.
The highest achieved ionic conductivity was 3.08  10
3 S cm
1 at room temper-
ature for PGE containing 2 wt. % of nanoclay [13].

Ionic Liquids and Ionic Liquid-Based Polymer Electrolytes

Ionic liquids are a class of materials which have attracted tremendous research
interest as holding a great promise for green chemistry applications. Ionic liquids
(ILs) are salts of organic cations and anions with melting temperatures below 100  C
[41]. Ionic liquids are characterized by weak interactions due to the combination of a
large cation and a charge delocalized anion. This results in a low tendency to
crystallize due to flexibility of the anion and dissymmetry of the cation [24]. Ionic
liquids are liquid electrolytes composed entirely of ions. In recent years, ionic liquids
have been the subject of extensive investigation due to their unique properties such
as negligible vapor pressure, non-flammability, high ionic conductivity, wide elec-
trochemical stability window, and good chemical and thermal stability [42]. Unlike
inorganic salts, which require solvation by a solvent to dissociate into an ion pair,
ionic liquids do not require solvation and exist as completely dissociated ion pairs in
the liquid state. Ionic liquids can reduce the use of hazardous and polluting organic
solvents due to their unique characteristics as well as taking part in various new
syntheses.
On the basis of their composition, in general ionic liquids can be classified into
three different classes, namely, aprotic, protic, and zwitterionic. Aprotic ionic liquids
do not contain any acidic proton, while protic ionic liquids contain an acidic proton
on the cationic species. Zwitterionic ionic liquids have a positive and a negative
electrical charge at different locations within the molecule. On the basis of
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 197

R2
R1 N + N
Suitable for Li batteries and supercapacitors
X–

Aprotic

H
R1 N + N
Suitable for fuel cells
X–
Protic

( ) X–
R1 N + N n Suitable for IL based membranes

Zwitterionic

Fig. 2 Different types of ionic liquids and their applications

composition and types, different ionic liquids are suitable for different applications
as highlighted in Fig. 2 [24].
Ionic liquids possess several advantages over conventional organic solvents that
make them environmentally benign solvents. Different kinds of organic, inorganic,
and organometallic compounds are soluble in ionic liquids. Ionic liquids are highly
polar and consist of loosely coordinating bulky ions and mostly have a liquid range
up to 300  C. The wide liquid range of ionic liquids is distinct advantageous over
traditional solvents which have narrow liquid range. The ionic liquids have low
volatility which makes them easy to contain and transfer and can be used under high
vacuum conditions. The unique properties of ionic liquids such as non-flammability,
high ionic conductivity, electrochemical, and thermal stability make them ideal
electrolytes in electrochemical devices like in batteries, capacitors, fuel cells, actu-
ators, and electrochemical sensors [43, 44].
For applications in rechargeable batteries, ionic liquids should have high ionic
conductivity. Ionic liquids have reasonably high ionic conductivity of the order of
~10
2 S cm
1 compared to other organic solvents or electrolyte systems [45]. Ionic
liquids have advantages over general solvents as they have intrinsic ionic conduc-
tivity and do not require additional electrolyte. Ionic liquids also have higher density
of ions, and they are denser than water from 1.0 to 1.6 g cm
3 depending on the
structure of the ion. Ionic liquids have high thermal stability up to around 450  C.
Ionic liquids generally exhibit a wide potential window of around 4.5–5.0 V [46] and
large electrochemical stability window up to 7.0 V for some ionic liquid such as
1-butyl-3-methyl-imidazolium tetrafluoroborate [47].
The unique properties of ionic liquids such as high ionic conductivity,
non-flammability, and low volatility are significant assets for applications of ionic
liquids in polymer electrolytes. The replacement of the conventional, flammable, and
volatile, organic solutions in gel polymer electrolyte (GPE) with ionic liquid-based
198 A. K. Nath and J. M. Kalita

polymer electrolytes can greatly reduce the risk of thermal runaway and enhance the
conductivity. Scott et al. [48] have reported that imidazolium-based ionic liquids
served as excellent plasticizers for poly(methyl methacrylate) with improved thermal
stability and ability to significantly reduce the glass transition temperature. Md. Abu
Bin Hasan Susan et al. [23] prepared ionic liquid-based polymer electrolytes by in
situ free radical polymerization of compatible vinyl monomers in a room tempera-
ture ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)imide
(EMITFSI). They obtained ambient temperature ionic conductivity close to
10
2 S cm
1 and thermal stability up to ~400  C. J. Fuller et al. [49] reported
P(VdF-HFP)-based polymer electrolytes incorporated with hydrophilic 1-ethyl-3-
methylimidazolium tetrafluoroborate (EMIBF4) and hydrophobic 1-butyl-3-
methylimidazolium hexaflorophosphate (BMIPF6) room temperature ionic liquids.
They found that ionic liquid-based polymer electrolytes with ionic liquid to P
(VdF-HFP) mass ratios of 2:1 exhibited ionic conductivities of >10
3 S cm
1 at
room temperature and > 10
2 S cm
1 at 100  C. The pioneering work of A. Noda
and M. Watanabe [50] showed that in situ polymerization of suitable vinyl mono-
mers in ionic liquids such as 1-ethyl-3-methylimidazolium tetrafluoroborate
(EMIBF4) and 1-butylpyridinium tetrafluoroborate (BPBF4) formed mechanically
strong and highly conductive polymer electrolyte films exhibiting an ionic conduc-
tivity of 10
3 S cm
1 at room temperature. S.A. Hashmi and co-workers [51]
extensively studied ionic liquid-based polymer electrolytes for applications in
rechargeable batteries and supercapacitors. They obtained high room temperature
ionic conductivity of ~3  10
4 S cm
1 with PEO-based lithium ion-conducting
polymer electrolytes complexed with lithium trifluoromethanesulfonate (LiCF3SO
or LiTf) plasticized with an ionic liquid 1-ethyl 3-methyl imidazolium tri-
fluoromethanesulfonate (EMITf). Magnesium ion-conducting electrolyte films com-
prising of PEO complexed with magnesium trifluoromethanesulfonate
(or magnesium triflate) added with different amount of ionic liquid, 1-ethyl-3-
methylimidazolium trifluoromethanesulfonate (EMITf) was prepared by Y. Kumar
et al. [52].

Swift Heavy Ion Irradiation and Effects on Polymer Electrolytes

Swift heavy ion (SHI) irradiation is a special technique for inducing physical and
chemical modification in bulk materials. High energetic ion beams have been
exploited by researchers in different ways in the field of materials science to induce
the desired properties in a material. SHI irradiation can modify the molecular
structure in polymers in a controlled way leading to changes in their chemical,
electronic, electrical, tribological, and optical properties [53]. SHI (energy
>1 MeV/u) irradiation deposits the energy in the material in the near surface region
mainly due to the electronic excitation [54]. Ion irradiation of polymers can induce
irreversible changes in their macroscopic properties. Electronic excitation, ioniza-
tion, chain-scission and cross-links, and mass losses are the events that give rise to
the observed macroscopic changes [55]. The SHI has large range typically a few tens
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 199

of μm due to which the impinging ions do not get implanted in the material if the
thickness of the material film is smaller than the ion range. Ionization trail produced
by SHI causes bond cleavages producing free radicals, which are responsible for
most of the chemical transformations in polymers, namely, chain-scission, cross-
linking, and double and triple bond formation. When an energetic ion penetrates
through a material, it loses energy mainly by two nearly independent processes:
(i) elastic collisions with the nuclei known as nuclear energy loss (dE/dx)n, which
dominates at an energy of about 1 keV/amu, and (ii) inelastic collisions of the highly
charged projectile ion with the atomic electrons of the matter known as electronic
energy loss (dE/dx)e which dominates at an energy of about 1 MeV/amu or more. For
an SHI, the inelastic collision is the dominant mechanism for transfer of energy to
the material for producing tracks when its value crosses a threshold value for track
formation. In SHI irradiation, the modification of thin films or the near-surface
region of the bulk samples is due to the electronic excitation. In this case, the
impinging ions do not get embedded in the film due to their large range (typically
a few tens of m or larger).
SHI irradiation is an up-to-the-minute technique to improve the ionic conductiv-
ity and other properties of polymer electrolytes. The changes induced by SHI
irradiation depend on the sample parameters like composition, molecular weight,
temperature, and ion beam parameters such as energy, mass, and fluence. SHI
irradiation has been reported to increase hardness, strength and wear resistance,
ionic conductivity, density, change the chain length, and crystallinity of polymers
[56]. These modifications result from the changes of the chemical structure caused
by changing the chemical bonding when the incident ion breaks the polymer chains,
breaks covalent bonds, promotes cross-linking, and liberates certain volatile
species. J. Singh et al. [57] studied the effect of electron beam irradiation on the
properties of PEG-LiClO4 polymer electrolyte films and reported that ionic conduc-
tivity of the unirradiated electrolyte increases from 7.27  10
7 S cm
1 to
1.31  10
5 S cm
1 after irradiation.

Ionic Transport and Electrochemical Properties of Ionic

Liquid-Based P(VdF-HFP)-Layered Silicate Nanocomposite
Electrolytes

Polymer-layered silicate nanocomposites formed by the intercalation of polymers

inside the interlayer galleries of layered silicate have been gaining great deal of
research interest because of their potential importance in the development of poly-
mer electrolytes with enhanced properties for applications in solid-state batteries. In
this chapter, discussion has been confined to poly(vinylidene fluoride-co-hexa-
fluoropropylene) P(VdF-HFP) polymer matrix only. The copolymer P(VdF-HFP)
consists of crystalline vinylidene fluoride (VdF) and amorphous hexa-
fluoropropylene (HFP) units. The VdF unit provides an excellent chemical stability
and mechanical strength to P(VdF-HFP). The amorphous HFP unit helps in trapping
more liquid electrolyte. Hence, polymer electrolytes with P(VdF-HFP) as polymer
200 A. K. Nath and J. M. Kalita

matrix provide high ionic conductivities together with high mechanical stability. The
ionic liquid used is 1-butyl-3-methyl imidazolium bromide (BMIMBr). 25–30 wt. %
octadecylamine modified montmorillonite (MMT) has been used as the layered
silicate. Out of the commonly used layered silicates, modified MMT has been
selected because of its special features such as high aspect ratio (~1000), high
cation-exchange capacity (CEC ~ 80 mequiv./100 g), large specific surface area
(~ 31.82 m2 g
1), and appropriate interlayer charge (~ 0.55) and length scale (clay
channel width ¼ 16 Å).
At first calculated amount of P(VdF-HFP) was dissolved in acetone and stirred for
6 h at 50  C. Modified MMT was dispersed in 5 ml of tetrahydrofuran (THF) by
ultrasonication, and the dispersed MMT solution was then mixed with P(VdF-HFP)
solution by magnetic stirrer at 50  C. After 15 h of stirring, ultrasonication was done
for 30 min. The viscous slurry thus obtained was cast on petri dishes, and the
samples were dried for 2–4 days at room temperature and then kept in vacuum to
get flexible, free standing, and rubber-like films. Different P(VdF-HFP)-MMT
nanocomposite films were prepared by varying the concentration of modified
MMT w.r.t. P(VdF-HFP) as 1.5, 2.5, 5, 7.5, and 10 wt. %. The P(VdF-HFP)-MMT
intercalated nanocomposite films were then immersed in ionic liquid BMIMBr for a
period of 5 h. The IL, BMIMBr got soaked in the nanocomposite films leading to the
formation of P(VdF-HFP)-BMIMBr-MMT intercalated nanocomposite electrolytes.
Figure 3 shows a photograph of P(VdF-HFP)-BMIMBr-MMT intercalated nano-
composite electrolyte.
Electrochemical and thermal properties of the layered silicate nanocomposite
electrolytes have been studied. First of all, nanocomposite formation has been
confirmed from HRTEM image as shown in Fig. 4a. The HRTEM micrograph
shows that layered silicate forms ordered intercalated tactoids that consist of many
parallel silicate layers. It is evident that platelets are oriented edge on and reveal the
existence of small thin bundles with each platelet of 3 nm thickness. Direct

Fig. 3 A photograph of
P(VdF-HFP)-BMIMBr-MMT
intercalated nanocomposite
electrolyte
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 201

Fig. 4 (a) HRTEM of P(VdF-HFP)-BMIMBr-5% MMT nanocomposite polymer electrolyte.

(b) Shows selected area electron diffraction (SAED) pattern. (Reproduced from Ref. [15] with
permission of Springer)

observation of HRTEM image revealed unambiguous evidence of the MMT stacks

being intercalated and uniformly distributed. It is noteworthy that a somewhat
parallel arrangement of several neighboring platelets is maintained. Similar micro-
graphs showing layered silicate structures have been obtained for all MMT loadings.
Selected area electron diffraction pattern (SAED) of the area is shown in Fig. 4b.
The SAED shows diffuse rings representative of amorphous phase. SAED confirms
the highly amorphous nature of the electrolyte system.
XRD studies have been carried out in order to monitor the formation of the
polymer-layered silicate intercalated nanocomposites. Figure 5 shows the XRD
patterns of modified MMT, pure P(VdF-HFP), and nanocomposite polymer electro-
lytes. The intercalation of P(VdF-HFP) into the interlayer galleries of modified
MMT has been confirmed from the shifting of characteristic (001) basal reflection
of modified MMT at 2θ ¼ 4.1 to lower angle side in case of nanocomposite
electrolyte system. Modified MMT exhibits (001) peak at an angle 2θ ¼ 4.1
corresponding to the interlayer spacing (d001) of 2.15 nm. In case of P(VdF-HFP)-
BMIMBr-x% MMT electrolyte system, the peak position of (001) plane shifts
toward the lower angle side indicating an increase in d001. The values of d-spacing
(d001) have been calculated using Bragg’s law, 2dsinθ ¼ nλ, and the values are given
in Table 1. An increase in d-spacing of the (001) plane of MMT with increasing
concentration of MMT shows that P(VdF-HFP) intercalates into the interlayer
galleries of MMT and the intercalation increases with increasing concentration of
MMT. Beyond 7.5 wt. % of MMT, intercalation saturates, and no further shifting in
(001) peak has been observed. Moreover, Fig. 5 also shows that with increasing
concentration of MMT, crystallinity of the nanocomposite electrolyte system
decreases. As P(VdF-HFP) intercalates into the interlayer galleries of MMT, the
recrystallization of the P(VdF-HFP) chains decreases resulting in decreased
202 A. K. Nath and J. M. Kalita

Fig. 5 XRD patterns of (a)

pure modified MMT, (b) pure
P(VdF-HFP) and P
(VdF-HFP)-BMIMBr-x%
MMT nanocomposite
polymer electrolytes where
(c) x ¼ 1.5, (d ) x ¼ 2.5,
(e) x ¼ 5.0, ( f ) x ¼ 7.5, and
(g) x ¼ 10.0

Table 1 d-spacing, microstrain, and ionic conductivity of nanocomposite polymer electrolytes at

different concentrations of MMT
Wt. % of MMT d001 (nm) Microstrain (%) Ionic conductivity (mS cm
1)
1.5 2.19 0.26 1.53
2.5 2.29 0.32 4.34
5.0 2.67 0.35 9.80
7.5 2.80 0.37 6.51
10.0 2.80 0.37 1.51
Reproduced from Ref. [15] with permission of Springer

crystallinity. It is observed that lowest crystallinity has been obtained for the
nanocomposite electrolyte containing 5 wt. % of MMT. On further increase in
MMT concentration, agglomeration of MMT takes place, and the excess MMT
remains as a separate phase in the system which is confirmed from the increased
intensity of the (001) peak at 7.5 and 10 wt. % of MMT concentration. Due to phase
separation of MMT, the crystallinity of the nanocomposite electrolyte system
increases at higher (> 5 wt. %) concentration of MMT.
As polymer intercalates into the galleries of MMT, a significant compressive
strain is expected in MMT layers. This strain arises due to the dislocation of crystal
layers of MMT from their regular crystal lattice upon polymer insertion. The single-
line approximation method [58] has been employed to calculate microstrain. This
procedure involves the extraction and analysis of Gaussian (βG) and Lorentzian (βL)
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 203

components of integral breadth of a single Bragg peak corrected for instrumental

broadening. After correcting the instrumental broadening, the remaining line broad-
ening (β) is believed to be due to crystallite size (βcryst) and retained strain (βstrain)
broadening. Therefore,

β ¼ βcryst þ βstrain ð1Þ

e ¼ βstrain =4 tan θ ð2Þ

The calculated microstrain and d spacing of (001) peak are given in Table 1. As
d spacing increases, microstrain increases confirming intercalation.
Ionic conductivity is a fundamental important property of a polymer electrolyte,
and in a gel electrolyte, conductivity is achieved due to the movement of the ions
through the interconnected pores of the polymer matrix. Accordingly, the porous
structure is one of the important factors in determining the ion transport properties of
an electrolyte. The porous structure of the nanocomposite electrolyte system has
been confirmed from scanning electron microscope (SEM) micrographs. Figure 6
shows the SEM micrographs of nanocomposite films containing different amounts
of MMT. IL is trapped in the pores making conducting pathways for the ions to

Fig. 6 SEM micrographs of P(VdF-HFP)-BMIMBr-x% MMT nanocomposite polymer electro-

lytes where (a) x ¼ 1.5, (b) x ¼ 2.5, (c) x ¼ 5.0, and (d) x ¼ 7.5. (Reproduced from Ref. [15] with
permission of Springer)
204 A. K. Nath and J. M. Kalita

Fig. 7 Elemental analysis of P(VdF-HFP)-BMIMBr-5% MMT nanocomposite polymer electro-

lyte for C, F, Al, Br, Mg, and Si. (Reproduced from Ref. [15] with permission of Springer)

move. In the sample containing 5 wt. % MMT, the polymer domain seems to be
more interconnected and uniform with respect to the other composition which is in
agreement with the maximum conductivity at this composition. At 7.5 wt. % of
MMT, agglomeration of MMT takes place, and the porosity decreases as observed
from Fig. 6d.
The electrolyte film containing 5 wt. % of MMT was subjected to elemental
analysis as shown in Fig. 7. Figure 7 shows the distribution map of C, F, Si, Al, Mg,
and Br which comes from P(VdF-HFP), MMT, and IL. Except Br (anion of the IL),
all elements are distributed uniformly indicating homogeneous dispersion of all the
moieties. Br is present only in some specific regions suggesting that IL is basically
present in the pores and the Br
ion moves through the interconnected pores
(as confirmed from SEM).
Knowing the hydrophilicity of the polymer electrolyte is important for certain
applications. Contact angle measurements have been conducted in order to know
whether the nanocomposite polymer electrolyte films are hydrophilic or hydro-
phobic, and the results are shown in Fig. 8. For the MMT concentration of 1.5 wt.
%, the contact angle is 39 suggesting that the nanocomposite electrolyte is
hydrophilic at that concentration of MMT. With increasing concentration of
MMT, the contact angle increases becoming 50 , 64 , and 70 for the MMT
concentrations of 5.0, 7.5, and 10.0 wt. %, respectively. The increase in contact
angle with increasing concentration of MMT suggests that the hydrophilicity
decreases as the concentration of MMT increases. The MMT used in the present
system is octadecylamine modified, and hence it is hydrophobic due to the pres-
ence of alkyl ammonium cations [59].
On the other hand, the ionic liquid, BMIMBr, is hydrophilic [60], and due to its
presence in the pores of the polymer matrix, the nanocomposite films behave as
hydrophilic. As the concentration of hydrophobic MMT increases, the hydrophilicity
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 205

Fig. 8 Contact angle measurements of P(VdF-HFP)-BMIMBr-x% MMT nanocomposite polymer

electrolytes where (a) x ¼ 1.5, (b) x ¼ 5.0, (c) x ¼ 7.5 and (d) x ¼ 10.0

decreases and the nanocomposite films tend to become hydrophobic. This means
that increasing MMT content imparts anti-wetting property to the nanocomposite
electrolyte films.
Ionic conductivity of a polymer electrolyte is the most crucial parameter for
practical applications. The ionic conductivity of the nanocomposite polymer elec-
trolytes has been evaluated using the electrochemical impedance spectroscopy.
Figure 9 shows the room temperature Nyquist plots of the nanocomposite polymer
electrolytes. The plots show a depressed semicircle in the high-frequency region and
a spike in the low-frequency region. It is widely accepted that the high-frequency
semicircle is due to the parallel combination of bulk resistance and capacitance of the
polymer electrolytes, whereas the low-frequency spike is ascribed to the charge
transfer resistance and capacitance of the electric double layer formed at the elec-
trode/electrolyte interface. The migration of the ions is represented by the resistance
Rb, and the dielectric polarization of the polymer chains is represented by the
capacitor Cg. The response of the electrode/electrolyte/electrode cell can be simu-
lated as an equivalent circuit consisting of bulk resistance Rb in parallel with
geometrical capacitance Cg in series with the constant phase element (CPE) as
shown in inset of Fig. 9. The total impedance of the equivalent circuit can be
expressed as
206 A. K. Nath and J. M. Kalita

Fig. 9 Nyquist plots of P

(VdF-HFP)-BMIMBr-x%
MMT nanocomposite
polymer electrolytes where
(a) 1.5%, (b) 2.5%, (c) 5.0%,
(d ) 7.5%, and (e) 10.0%. Inset
shows equivalent circuit
representing actual cell
assembly

 
1
1
Z Total ¼ þ iωCg
ZCPE ð3Þ
Rb

where ZCPE is the impedance of the constant phase element. The CPE is a “leaky
capacitor” which is attributed to the capacitive dispersion at the electrode/electrolyte
contact and is given by the relation [61]

ZCPE ðωÞ ¼ 1=ðiωCdl Þn ð4Þ

where Cdl is the double layer interfacial capacitor independent of angular frequency
(ω) and ½ < n < 1. So, the total impedance of the equivalent circuit corresponding to
that of the electrode/electrolyte/electrode cell can be given as
 
1
1
Z Total ¼ þ iωCg
1=ðiωCdl Þn ð5Þ
Rb

At high frequencies, bulk resistances and the capacitances are of comparable

magnitude and 1/ωCg ≈ Rb, both the bulk resistance and capacitance are the
contributing factors to the overall impedance of the cell. Therefore, at high frequen-
cies the equivalent circuit reduces to a parallel RbCg combination giving rise to a
semicircle. At low frequencies, dielectric polarization is high corresponding to high
value of Cg and hence 1/ωCg < Rb; so the contribution of Cg becomes negligible to
the overall impedance, and the equivalent circuit behaves as a series combination of
Rb and a CPE giving an inclined spike displaced by Rb along the real axis. The bulk
resistance (Rb) is determined from the intercept of the semicircular arc with the real
axis. It is observed that Rb decreases with increasing MMT concentration attaining
minimum value at 5.0 wt. % of MMT concentration. On further increase in MMT
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 207

Fig. 10 Variation of ionic

conductivity at ambient
temperature and IL uptake of
P(VdF-HFP)-BMIMBr-MMT
nanocomposite polymer
electrolytes with varying
MMT concentration.
(Reproduced from Ref. [15]
with permission of Springer)

concentration, Rb again increases. The room temperature ionic conductivity values

have been evaluated from the measured values of Rb, and the variation of room
temperature ionic conductivity and IL uptake with different MMT concentration is
shown in Fig. 10. Room temperature ionic conductivity of P(VdF-HFP)-BMIMBr
electrolyte without addition of MMT is 5.63  10
4 S cm
1. On addition of 1.5 wt. %
of MMT, ionic conductivity increases to 1.53  10
3 S cm
1. Room temperature
conductivity increases with increasing MMT content and attains a value of
9.8  10
3 S cm
1 for 5.0 wt. % of MMT content. The enhancement of conductivity
by adding MMT to the polymer matrix is a combined effect of high aspect ratio of the
MMT clay particles and increased uptake of ionic liquid, 1-butyl-3-methylimi-
dazolium bromide by the nanocomposites. The IL uptake of the nanocomposites
increases with increasing time as well as MMT concentration. At 5.0 wt. % of MMT,
the uptake as well as conductivity is maximum. The IL acts both as salt and plasticizer
and hence due to plasticization conductivity increases. The intercalation of P
(VdF-HFP) into the MMT galleries suppresses the crystallization of the polymer
due to steric hindrance produced by MMT layers to the polymer chains leading to the
increased uptake of ionic liquid in the amorphous phase which results in enhanced
ionic conductivity. Room temperature ionic conductivity of the order of 10
8 to
10
6 S cm
1 has been obtained for conventional electrolytes with general salts.
Room temperature ionic conductivity of 9.8  10
3 S cm
1 is obtained in
P(VdF-HFP)-BMIMBr-5 wt. % of MMT electrolyte system which is much higher
as compared to conventional polymer electrolytes.
The gel formation process is composed of two distinct steps. First, the electrolyte
solution would mainly enter into the cavities, which are present in the porous host
polymer because this process provides the lowest energy barrier for the solution to
flow from the outside. In the next step, the temporarily trapped solution in the
cavities penetrates into the polymer chain to produce saturation. Finally, the fully
swollen polymer reaches an equilibrium condition which provides the maximum
conductivity. The nanocomposite films have highly porous morphology as
208 A. K. Nath and J. M. Kalita

confirmed from SEM micrographs. IL, 1-butyl-3-methylimidazolium bromide fills

the pores and makes highly conducting pathways for movement of ions. This is the
reason of very high ionic conductivity. In spite of having such highly porous
structure, free standing films have been obtained as intercalation of P(VdF-HFP)
into MMT increases mechanical strength. Hence by intercalation as well as using
ionic liquid, highly conducting gel electrolytes have been obtained with good
mechanical strength. Beyond 5 wt. % of MMT, certain amount of MMT remains
outside in the P(VdF-HFP) phase. Due to the presence of excess MMT, the porosity
of the system decreases as evident from SEM micrographs (see Fig. 6). The excess
MMT increases the viscosity of the system and hence conductivity decreases.
Moreover, the phase-separated MMT blocks the pores as observed in SEM micro-
graphs and hinders the movement of the ions leading to decrease in conductivity.
In order to know that the charge transport in the nanocomposite polymer electro-
lyte films is predominantly ionic in nature, total transference number has been
measured. Total transference number is a fraction of the total current carried by the
ions, and it has been estimated using Wagner’s polarization technique. The measured
values of transference number of P(VdF-HFP)-BMIMBr-MMT nanocomposite
polymer electrolytes are 0.91, 0.94, 0.96, 0.95, and 0.90 for the MMT concentrations
of 1.5, 2.5, 5.0, 7.5, and 10.0 wt. %, respectively. The transference number increases
with increasing concentration of MMT attaining the highest value at 5.0 wt. % of
MMT. This reveals that at 5.0 wt. % of MMT concentration, ionic contribution to the
total current is maximum which is due to the easier movement of ions at that
concentration of MMT. Beyond 5.0 wt. % of MMT, agglomeration of MMT takes
place which hinders movement of ions and therefore ionic contribution to current
decreases. The high values of ionic transference number (0.90–0.96) suggest that
current in the nanocomposite polymer electrolyte films is predominantly ionic in
nature.
Figure 11 shows the temperature dependence of ionic conductivity of the nano-
composite films. The variation of ionic conductivity with temperature suggests that

Fig. 11 Temperature
dependence of P(VdF-HFP)-
BMIMBr-x% MMT
nanocomposite polymer
electrolytes where (a) x ¼ 1.5,
(b) x ¼ 2.5, (c) x ¼ 5.0, (d )
x ¼ 7.5, (e) x ¼ 10.0
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 209

the ionic conduction in the nanocomposite gel polymer electrolyte system obeys the
Vogel-Tammann-Fulcher (VTF) relation [62] given by

σ ¼ A T
1=2 exp ½
B=kðT
T o Þ ð6Þ

where A is the pre-exponential factor, B is pseudo-activation energy for conduction, k is

the Boltzmann constant, T is the temperature in K, and To is a quasi-equilibrium glass
transition temperature usually 30–50 K lower than glass transition temperature, Tg. The
VTF relation describes the transport properties in a viscous matrix, and its applicability
suggests that the ion transport in the nanocomposite polymer electrolyte system occurs
in the amorphous phase assisted by the segmental motions of the polymer chains.
As the temperature increases, the polymer chains flex and expand producing more
free volume leading to an increase in segmental motion of the polymer chains which
facilitates ion transport.
The electrochemical stability of the nanocomposite electrolytes at room temper-
ature has been studied by linear sweep voltammetry, and the results are shown in
Fig. 12. The decomposition voltage limit can be defined as the potential at which a
rapid rise in current was observed and continued to increase as the potential was
swept. It can be observed from Fig. 12 that neat ionic liquid, 1 butyl 3 methyl
imidazolium bromide has low decomposition voltage of 3.5 V. The electrochemical
stabilities of the nanocomposite gel electrolytes are larger compared to pure ionic
liquid. With increasing concentration of MMT, the electrochemical stability
increases attaining highest value of 5.5 V at 5.0 wt. % of MMT concentration.
Beyond 5 wt. % of MMT concentration, electrochemical stability decreases reaching
to the values of 5.2 and 4 V for the MMT concentrations of 7.5 and 10 wt. %,
respectively. Generally, the irreversible oxidation of the salt anion limits the anodic
oxidation window. The Lewis acid sites on the anionic surface of MMT can interact
with Br
(Lewis base) of the IL and retard the decomposition of the anion of the IL
enhancing the electrochemical stability.

Fig. 12 Linear sweep

voltammetry plots of (a) pure
ionic liquid and P(VdF-HFP)-
BMIMBr-x% MMT
nanocomposite polymer
electrolytes where (b) x ¼ 1.5,
(c) x ¼ 2.5, (d ) x ¼ 5.0, (e)
x ¼ 7.5 and ( f ) x ¼ 10.0.
(Reproduced from Ref. [15]
with permission of Springer)
210 A. K. Nath and J. M. Kalita

Fig. 13 Interfacial stability

of (a) P(VdF-HFP)-BMIMBr
electrolyte without MMT and
(b) P(VdF-HFP)-BMIMBr
electrolyte containing
5.0 wt. % of MMT

Compatibility of polymer electrolytes with electrode materials remains an acute

problem for their application in high power rechargeable batteries. Electrolytes lead
to the formation of solid-state interface (SEI) layer, and a dendritic growth of lithium
occurs at the electrode-electrolyte interface, which results in the decay of ionic
conductivity and internal short circuiting of the cell during charge-discharge cycles
of the cell. In order to examine the interfacial stability of nanocomposite gel polymer
electrolytes before and after addition of MMT, the evaluation of the interface
characteristics has been carried out by monitoring the time evolution of ionic
conductivity of symmetrical cells of stainless steel/nanocomposite gel polymer
electrolyte/stainless steel, stored at room temperature for 20 days. Polymer electro-
lytes without MMT and containing 5.0 wt. % of MMT (as it has highest conductiv-
ity) have been selected to observe the effect of MMT on interfacial stability, and
the results are shown in Fig. 13. It is observed that ionic conductivity of both the
electrolytes decreases with time but, the decrease of ionic conductivity in the MMT
free polymer electrolyte is much larger as compared to that of the P(VdF-HFP)-
BMIMBr-MMT nanocomposite electrolyte. Moreover, ionic conductivity of the
polymer electrolyte without MMT is continuously decreasing up to the 20th day of
observation. However, the ionic conductivity of the nanocomposite electrolyte
containing 5.0 wt. % of MMT becomes constant after 15th day, and no further
decrease in ionic conductivity has been observed. In case of the electrolyte without
MMT, the electrode directly comes in contact with the electrolyte, and corrosion
reaction takes place easily and the passivation of electrode may eventually produce
thick, high-resistive layers resulting in continuous decrease of ionic conductivity.
However, in case of the intercalated nanocomposite electrolyte with MMT, the
electrode/electrolyte contact area decreases as the presence of high aspect ratio
MMT in the polymer matrix can prevent the electrode material to come in direct
contact with the electrolyte and hence protect them from further reaction leading to
increase in interfacial stability.
Studies on thermal properties have been carried out using thermogravimetric
(TG) analysis, and Fig. 14 shows TG curves of pure P(VdF-HFP), ionic liquid
(BMIMBr), modified MMT, and P(VdF-HFP)-BMIMBr-MMT nanocomposite
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 211

Fig. 14 TG curves of
(a) P(VdF-HFP), (b) ionic
liquid, (c) MMT and P
(VdF-HFP)-BMIMBr-x%
MMT nanocomposite
polymer electrolytes where
(d ) x ¼ 1.5, (e) x ¼ 2.5, ( f )
x ¼ 5.0, (g) x ¼ 7.5 and
(h) x ¼ 10.0. (Reproduced
from Ref. [15] with
permission of Springer)

polymer electrolytes with varying concentration of MMT. There is essentially no

weight loss for the polymer electrolytes when they are heated from room temperature
up to 238  C indicating that no component is volatile inside the electrolytes. From
Fig. 14, it is observed that there are three decomposition ranges for the nanocomposite
electrolytes. The first range (235–325  C) corresponds to the decomposition of
[BMIM]+ cation of 1-butyl-3-methylimidazolium bromide (BMIMBr), the second
range (335–505  C) occurs due to decomposition of P(VdF-HFP), and the third
range (515–760  C) corresponds to the decomposition of anion [Br]
. It is observed
that addition of IL in polymer reduces the decomposition temperature of the electrolyte
system which may be attributed to the complexation of [BMIM]+ cations of IL with
the polymer that destabilizes the C-H bonds of the polymer. Moreover, with increasing
concentration of MMT, the decomposition temperature decreases attaining lowest
value at the 5 wt. % of MMT concentration. This can be attributed to the fact that
with increasing MMT concentration, amorphicity increases (confirmed from XRD
analysis) resulting in decreased thermal stability. It is known that amorphous materials
have lower decomposition temperature compared to crystalline materials. Beyond
5.0 wt. % of MMT, agglomeration of MMT takes place leading to increase in
crystallinity of the system as confirmed from XRD and SEM studies. Due to increase
in crystallinity, thermal stability increases beyond 5.0 wt. % of MMT concentration.
The onset decomposition (Tonset) and rapidest decomposition (Trpd) of P-
(VdF-HFP), ionic liquid, modified MMT, and P(VdF-HFP)-BMIMBr-MMT poly-
mer electrolytes have been calculated by plotting the derivative thermographs of
TGA curves. The derivative TG curves are shown in Fig. 15, and the calculated
values of Tonset, Trpd, and wt. loss from Tonset to Trpd are summarized in Table 2. For
pure P(VdF-HFP), Tonset ¼ 425  C and Trpd ¼ 489  C and from Tonset to Trpd, 50%
wt. loss has been observed. With increasing concentration of MMT, Tonset and Trpd
decreases attaining lowest values at 5.0 wt. % of MMT concentration. On the other
hand, wt. loss from Tonset to Trpd increases with increasing concentration of MMT
attaining highest value at 5.0 wt. % of MMT concentration. This shows that thermal
stability of the nanocomposite electrolyte system decreases with increasing concen-
tration of MMT which is due to increase in amorphicity of the system. Beyond
212 A. K. Nath and J. M. Kalita

Fig. 15 Derivative of TG
curves of (a) P(VdF-HFP),
(b) ionic liquid, (c) MMT and
P(VdF-HFP)-BMIMBr-x%
MMT nanocomposite
polymer electrolytes where
(d ) x ¼ 1.5, (e) x ¼ 2.5, ( f )
x ¼ 5.0, (g) x ¼ 7.5 and (h)
x ¼ 10.0

Table 2 Tonset, Trpd and wt. loss from Tonset to Trpd of P(VdF-HFP), IL, MMT, and nanocomposite
polymer electrolytes containing different concentrations of MMT
Weight loss from Tonset to Trpd
Sample Tonset ( C) Trpd ( C) (%)
P(VdF-HFP) 425 489 50
Ionic liquid 238 318 59
MMT 300 375 11
P(VdF-HFP)-BMIMBr-1.5% 290 351 24
MMT
P(VdF-HFP)-BMIMBr-2.5% 280 336 25
MMT
P(VdF-HFP)-BMIMBr-5.0% 238 303 30
MMT
P(VdF-HFP)-BMIMBr-7.5% 248 311 27
MMT
P(VdF-HFP)-BMIMBr-10.0% 294 364 19
MMT

5.0 wt. % of MMT, agglomeration of MMT takes place increasing crystallinity of the
system resulting in increase in thermal stability. The agglomerated 2D MMT layers
act as mass and heat transport barriers to the volatile species generated during
decomposition giving rise to an overall increase in thermal stability of the nano-
composite electrolytes.

Swift Heavy Ion Irradiation Effects on Polymer-Layered Silicate

Nanocomposite Electrolytes

The detailed results on P(VdF-HFP)-BMIMBr-MMT nanocomposite electrolyte

system with varying concentration of modified MMT as discussed in preceding
section reveal that the nanocomposite electrolyte containing 5.0 wt. % of modified
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 213

MMT has the best properties. Therefore, this sample has been chosen to irradiate
with 100 MeV Si9+ swift heavy ions with a view to further enhance the properties.
The ion irradiation of nanocomposite polymer electrolyte films was performed at the
15 UD Pelletron accelerator available at the Inter-University Accelerator Centre
(IUAC), New Delhi, India, using Materials Science beam line facilities. The nano-
composite electrolyte films were irradiated by 100 MeV Si9+ ion beam with four
different fluences of 5  1010, 1  1011, 5  1011, and 1  1012 ions cm
2 keeping
the ion current constant at 0.6 pna. The energy of the Si9+ ion beam was chosen as
100 MeV so that the ion beam completely penetrated the nanocomposite electrolyte
films and the films undergo uniform irradiation effects as the projected ion range of
80 μm, as calculated by using SRIM (stopping and range of ions in matter) software,
was larger than the nanocomposite polymer electrolyte films of thickness ~ 30 μm.
For ion irradiation, the polymer electrolyte films were cut in 1 cm  1 cm area
and fixed on the sample holder (ladder) made up of copper. The ladder in the MS
chamber is rectangular, and 24 samples can be loaded with six samples on each
side at a time. After sample loading, the ladder is inserted in the MS vacuum
chamber. Figure 16 shows the photographs of pristine and irradiated P
(VdF-HFP)-BMIMBr-MMT intercalated nanocomposite electrolyte films
containing 5.0 wt. % of MMT. Six pieces of each sample were fixed on the ladder
and irradiated with different fluences. It is observed that with increasing ion
fluence, the irradiated portion gets darker due to heat generation during the
irradiation process.
To study the effect of SHI irradiation, firstly XRD studies were carried out, and
Fig. 17 shows the XRD patterns of pristine and 100 MeV Si9+ ion irradiated
P(VdF-HFP)-BMIMBr-MMT nanocomposite electrolytes. It is observed that with
increasing Si9+ ion fluence, (001) peak shifts toward lower angle side indicating
higher gallery spacing of MMT and larger intercalation of P(VdF-HFP). At the ion
fluence of 5  1011 ions cm
2, the characteristic MMT peak completely disappears
confirming that exfoliation of MMT layers has taken place at that ion fluence. During
irradiation, each ion creates a cylindrical molten zone of a few nanometers, tran-
siently along its path, during which the temperature of the sample is quite high and
the low viscous polymer has enough time to diffuse into the gallery to cause higher
intercalation. It has to be mentioned here that the higher the fluence, the higher is the
time of SHI exposure. So, the polymer gets more time to diffuse inside the gallery at
higher fluence. Hence, intercalation of the polymer gradually increases with increas-
ing fluence eventually leading to exfoliation at the ion fluence of 5  1011 ions cm
2.
As observed from XRD results, upon ion irradiation with increasing ion fluence, the
peak (020) broadens and its intensity decreases, which indicates that upon irradiation
the larger size polymer chains change into smaller size due to chain-scission [63] and
amorphicity of the system increases. The smaller chains with low molecular weight
easily intercalate into the interlayer galleries of modified MMT resulting in increased
amorphicity.
The surface morphology of the pristine P(VdF-HFP)-MMT-IL nanocomposite
electrolyte and that of irradiated with fluence 1  1012 ions cm
2 are shown in SEM
micrographs in Fig. 18. Pristine P(VdF-HFP)-BMIMBr-MMT nanocomposite
214 A. K. Nath and J. M. Kalita

Fig. 16 Photographs of P(VdF-HFP)-BMIMBr-MMT intercalated nanocomposite electrolyte

fixed on the ladder and irradiated at different fluences of (a) pristine, (b) 5  1010, (c) 1  1011,
(d) 5  1011, and (e) 1  1012 ions cm
2

electrolyte has porous structure with uniform pores of diameter around 5 μm as

observed from Fig. 18a. On SHI irradiation, the porosity increases significantly and
the pores get more interconnected. Figure 18b shows the morphology of the elec-
trolyte film irradiated at the fluence of 1  1012 ions cm
2, and it is observed that the
irradiated film has pores of diameter 10 μm. Thus, on irradiation with high fluence,
the pore size has become double and the pores get highly interconnected.
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 215

Fig. 17 XRD patterns of P

(VdF-HFP)-BMIMBr-5 wt. %
MMT nanocomposite
polymer electrolytes where
(a) pristine and irradiated with
different ion fluences of
(b) 5  1010, (c) 1  1011,
(d ) 5  1011, and (e) 1  1012
ions cm
2. (Reproduced from
Ref. [28] with permission of
Elsevier)

Fig. 18 SEM micrographs of P(VdF-HFP)-BMIMBr-5% MMT nanocomposite polymer electro-

lytes where (a) pristine and (b) irradiated with the fluence of 1  1012 ions cm
2. (Reproduced from
Ref. [28] with permission of Elsevier)

Contact angle measurements have been conducted on pristine and irradiated

nanocomposite polymer electrolyte films and are shown in Fig. 19. It is observed
that with increasing ion fluence, contact angle increases suggesting that the films
tend to become hydrophobic after irradiation. Pristine and the films irradiated up
to the fluence of 1  1011 ions cm
2 are hydrophilic in nature since the contact
angle is less than 90 . However, the films irradiated at higher fluences of
5  1011 and 1  1012 ions cm
2 are hydrophobic as the contact angles are
greater than 90 . The transition from hydrophilic to hydrophobic occurs due to
the combined effects of the smoothing of surface due to increased porosity on
SHI irradiation and increased abundance of hydrophobic MMT on the surface
216 A. K. Nath and J. M. Kalita

Fig. 19 Contact angle measurements of P(VdF-HFP)-BMIMBr-5% MMT nanocomposite poly-

mer electrolytes irradiated with different ion fluences of (a) pristine (b) 5  1010, (c) 1  1011, (d)
5  1011, (e) 1  1012 ions cm
2. (Reproduced from Ref. [28] with permission of Elsevier)

due to exfoliation caused by SHI irradiation at and beyond the fluence of

5  1011 ions cm
2.
Wenzel [64] predicts that the contact angle depends on surface roughness and the
contact angle at a surface is given by

cos θ ¼ r cos θ0 ð7Þ

where θ is the contact angle at the surface, θ0 is the contact angle for the perfectly
smooth surface, and r is the ratio of the areas of the rough and the corresponding
smooth surface. With increasing ion fluence, surface roughness decreases and the
contact angle θ increases.
At the fluence of 5  1011 ions cm
2 and beyond, exfoliation of MMT layers
takes place as confirmed from XRD analysis, and the MMT platelets get dispersed in
the polymer matrix. As the modified MMT is hydrophobic, the hydrophobicity
increases at higher fluences due to exfoliation of MMT layers. According to Cassie
[65], the contact angle at a heterogeneous surface depends on the fractional areas of
different components of the surface. If the solid surface is composed of two
materials, then the contact angle is a function of the two separate contact angles on
the pure substrates such that

cos θ ¼ f a cos θa þ f b cos θb ð8Þ

fa and fb are the fractional areas of the two compounds, and θa and θb are the contact
angles on smooth heterogeneous surfaces of pure a and pure b materials, respec-
tively. After exfoliation, hydrophobic MMT becomes more abundant at the surface,
and the electrolyte film turns hydrophobic from hydrophilic.
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 217

Fig. 20 Variation of room

temperature ionic
conductivity of P(VdF-HFP)-
BMIMBr-5% MMT
nanocomposite polymer
electrolytes with varying ion
fluences. (Reproduced from
Ref. [28] with permission of
Elsevier)

The SHI irradiation increased the room temperature ionic conductivity of pristine
electrolyte from 9.8  10
3 S cm
1 to 2.26  10
2 S cm
1 after irradiation with the
fluence of 5  1010 ions cm
2. Further, the conductivity increases with increasing
ion fluence as shown in Fig. 20. The highest room temperature ionic conductivity of
4.96  10
2 S cm
1 is obtained at the highest fluence (1  1012 ions cm
2) used in
the present study. On further increase in fluence, the nanocomposite electrolyte films
get burnt. The increasing trend of ionic conductivity with increasing ion fluence can
be attributed to the fact that polymer chains are broken on irradiation due to the heat
generated in thermal spike that occurred during ion irradiation. The smaller chains
with lower molecular weight easily intercalate into the interlayer galleries of mod-
ified MMT resulting in increased amorphicity as confirmed from XRD studies. The
ionic motion becomes easier in the amorphous phase and the ionic conductivity
increases.
It is well known that porosity plays an important role in determining the ionic
conductivity in polymer electrolytes [66]. Polymer electrolytes having large and
interconnected pores have high ionic conductivity as the ions can easily move
through the interconnected pathways. From the morphological studies shown in
Fig. 18, it is observed that with increasing ion fluence porosity increases and the
pores get more interconnected. Large interconnected pores facilitate easier ionic
movements leading to increased ionic conductivity.
Generally, ionic conductivity depends on mobility and number of charge carriers,
and the relationship is governed by

σ ¼ nqμ ð9Þ

where n, μ, and q are the concentration, mobility, and charge of the ions, respectively
[67]. With increasing intercalation, mobility of the ions increases as the ions can
migrate through the intercalated polymer chains easily. As fluence increases, inter-
calation also increases as observed from XRD results leading to increase in ionic
218 A. K. Nath and J. M. Kalita

mobility, and consequently, ionic conductivity also increases. At sufficiently high

fluence ( 5  1011 ions cm
2), exfoliation of MMT layers takes place, and the
exfoliated MMT layers suppress recrystallization of polymer chains leading to
increase in ionic conductivity. Ionic mobility is high in amorphous region, and
Eq. (9) corroborates increase in ionic conductivity. Moreover, the activation energy
(Ea) required for an ion jump is low in case of IL as the salt is in liquid state. Ea can
be written as a sum of two terms which are denoted by binding energy (Eb) and strain
energy (Es). Eb is the average energy an ion requires to leave its site, and Es is the
average kinetic energy an ion needs to structurally distort its surroundings to create a
“doorway” through which it can jump to another site. The IL and SHI irradiation
induces expansion of the polymer matrix leading to decrease in Es part of activation
energy thereby enhancing the ionic conductivity.
The total transference number of the pristine nanocomposite polymer electrolyte
containing 5.0 wt. % of MMT is 0.96 indicating that the charge conduction is
predominantly ionic. On SHI irradiation, the total transference number increases
following an increasing trend with increasing ion fluence. At the highest fluence of
1  1012 ions cm
2, the total transference number is 0.98. The increase in the total
transference number for the pristine electrolyte from 0.96 to 0.98 for the SHI
irradiated electrolyte films indicates that on irradiation the movement of the ions
becomes more facile and the contribution of ionic current to the total current
increases.
The results for temperature dependence of conductivity are shown in Fig. 21. The
conductivity of the electrolytes increases with an increase in temperature suggesting
that the ionic transport occurs through the carrier ions assisted by the segmental
motions of the polymer chains. With increasing temperature, segmental motion
increases indicating increase in free volume, and the temperature dependence of
conductivity can be related by VTF equation (Eq. 6). VTF behavior indicates that
ionic conduction in highly amorphous system is strongly coupled with polymer
segmental motion. SHI irradiation makes the system amorphous, and the

Fig. 21 Temperature
dependence of ionic
conductivity of P(VdF-HFP)-
BMIMBr-5% MMT
nanocomposite polymer
electrolytes irradiated with
different ion fluences of
(a) pristine (b) 5  1010,
(c) 1  1011, (d ) 5  1011,
(e) 1  1012 ions cm
2.
(Reproduced from Ref. [28]
with permission of Elsevier)
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 219

temperature dependence of conductivity follows VTF behavior for the amorphous

electrolyte system.
The VTF parameters A, B, and T0 have been estimated for the pristine and the SHI
irradiated nanocomposite polymer electrolyte films using curve fitting method and
are presented in Table 3. It is observed that the pre-exponential factor A increases
from 0.68 S cm
1 K1/2 to 4.0 S cm
1 K1/2 for the pristine electrolyte irradiated with
the highest fluence of 1  1012 ions cm
2. As pre-exponential factor A is propor-
tional to the carrier concentration, its increase with increasing ion fluence corrobo-
rates the fact that carrier concentration increases on SHI irradiation giving rise to an
increase in ionic conductivity. The decreasing trends of B and To with increasing ion
irradiation fluence reveal that hopping of ions through the segmental motion of the
polymer chains becomes easier and ionic conductivity increases on SHI irradiation.
The electrochemical stability window of pristine and SHI irradiated IL-based
nanocomposite polymer electrolytes have been determined by linear sweep
voltammetry, and the results are shown in Fig. 22. It is observed that for the pristine
electrolyte, there is no apparent current through the working electrode from open
circuit potential up to 5.5 V, and then the current increases gradually when the
electrode potential is higher than 5.5 V. This result reveals that the electrochemical
stability window for the pristine electrolyte is up to 5.5 V. On irradiation with
100 MeV Si9+ ions, the electrochemical stability window increases, and a continuous

Table 3 VTF parameters Fluence (ions cm
2) A (S cm
1 K1/2) B (eV) To (K)
of pristine and 100 MeV
Pristine 0.66 0.17 201
Si9+ ion irradiated
nanocomposite polymer 5  1010 0.88 0.14 197
electrolyte films with 1  1011 1.00 0.10 192
different fluences 5  1011 3.00 0.09 183
1  1012 4.00 0.08 180
Reproduced from Ref. [28] with permission of Elsevier

Fig. 22 Interfacial stability

of P(VdF-HFP)-BMIMBr-5%
MMT nanocomposite
polymer electrolytes
irradiated with different ion
fluences of (a) pristine
(b) 5  1010, (c) 1  1011,
(d ) 5  1011, (e) 1  1012 ions
cm
2. (Reproduced from Ref.
[28] with permission of
Elsevier)
220 A. K. Nath and J. M. Kalita

increasing trend has been observed with increasing ion fluence attaining maximum
value of 6.5 V at the highest fluence of 1  1012 ions cm
2. With increasing ion
fluence, intercalation of P(VdF-HFP) into MMT layers increases, and the Lewis acid
sites on the surface of MMT interact more easily with the Lewis base (Br
) of the
ionic liquid and retard the decomposition of the anion leading to enhanced electro-
chemical stability window. After exfoliation at and above the fluence of 5  1011
ions cm
2, the Lewis acid-base interactions become more significant, and very high
(6.5 V) electrochemical stability has been achieved.
The results show that electrochemical stability up to 6.5 V has been obtained for
the polymer electrolyte irradiated with the fluence of 1  1012 ions cm
2.
Electrode-electrolyte compatibility is another important area of concern for the
applicability of polymer electrolytes in rechargeable batteries. The reactivity of
electrode with most electrolytes leads to the formation of solid-state interface layers
which result in the decay of ionic conductivity [68]. The interfacial stability of the
pristine and irradiated polymer electrolytes has been demonstrated by monitoring
ionic conductivity at room temperature for a period of 20 days, and the results are
shown in Fig. 23. Comparing the results, it is observed that the decrease of room
temperature ionic conductivity with time is much larger in pristine electrolyte than
the irradiated electrolytes. Moreover, ionic conductivity of pristine electrolyte con-
tinuously decreases for a period of 15 days and then becomes stable. However, for
the electrolyte irradiated with the fluence of 1  1012 ions cm
2, stability in ionic
conductivity has been obtained after 8 days as observed from Fig. 23b. This confirms
that 100 MeV Si9+ ion irradiation enhances the interfacial stability of the electrolytes
with electrodes. It is also observed that interfacial stability increases with increasing
ion fluence. The reason for this can be attributed to the fact that on irradiation
intercalation increases finally leading to exfoliation at higher fluence ( 5  1011
ions cm
2). Due to increased intercalation and exfoliation, MMT clay comes in
between electrode and electrolyte and reduces the formation of passivation layers on
the electrode leading to better interfacial stability.

Fig. 23 (a) Interfacial stability of pristine nanocomposite polymer electrolyte. (b) Interfacial
stability of 100 MeV Si9+ ion irradiated nanocomposite polymer electrolytes irradiated with
different ion fluences of (a) 5  1010, (b) 1  1011, (c) 5  1011, (d) 1  1012 ions cm
2.
(Reproduced from Ref. [28] with permission of Elsevier)
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 221

Studying the thermal properties of nanocomposites is very important to observe

the safety and environmental effect [69, 70]. Thermal properties have been studied
by thermogravimetric analysis, and the results are depicted in Fig. 24. In case of pure
P(VdF-HFP), only one decomposition range is observed; however, for pristine and
irradiated nanocomposite electrolytes, two decomposition ranges are observed. The
first range (186–284  C) corresponds to the decomposition of [BMIM]+ cations, and
the second range (320–430  C) occurs due to decomposition of P(VdF-HFP). The
derivative thermographs of TG graphs as shown in Fig. 25 exhibit one peak in case
of pure P(VdF-HFP) corresponding to one decomposition range and two peaks in
case of pristine and irradiated nanocomposite electrolytes corresponding to two
decomposition ranges. It is observed from TGA plots that decomposition tempera-
ture (Td) decreases after irradiation. Td for pure P(VdF-HFP) is 435  C and for
pristine P(VdF-HFP)-BMIMBr-MMT nanocomposite electrolyte is 265  C. After
irradiation, Td decreases as given in Table 4 and becomes 185  C for the electrolyte

Fig. 24 TG plots of P
(VdF-HFP)-BMIMBr-5%
MMT nanocomposite
polymer electrolytes
irradiated with different ion
fluences of (a) pristine (b)
5  1010, (c) 1  1011, (d )
5  1011, (e) 1  1012 ions
cm
2. (Reproduced from Ref.
[28] with permission of
Elsevier)

Fig. 25 Derivative of TG
plots of P(VdF-HFP)-
BMIMBr-5% MMT
nanocomposite polymer
electrolytes irradiated with
different ion fluences of (a)
pristine (b) 5  1010, (c)
1  1011, (d ) 5  1011, (e)
1  1012 ions cm
2.
(Reproduced from Ref. [28]
with permission of Elsevier)
222 A. K. Nath and J. M. Kalita

Table 4 Tonset, Trpd, and wt. loss from Tonset to Trpd of nanocomposite polymer electrolytes
irradiated with different ion fluences
Fluence (ions cm
2) Tonset ( C) Trpd ( C) Weight loss from Tonset to Trpd (%)
Pristine 238 303 30
5  1010 170 243 22
1  1011 166 241 21
5  1011 160 234 20
1  1012 158 230 19
Reproduced from Ref. [28] with permission of Elsevier

irradiated with fluence 1  1012 ions cm
2. Addition of IL in pure P(VdF-HFP)

reduces the decomposition temperature (Td) of P(VdF-HFP) which may be attributed
to the complexation of [BMIM]+ cations of IL with the polymer that destabilizes the
C-H bonds of the polymer. On SHI irradiation, amorphicity of the nanocomposite
polymer electrolyte films increases as confirmed from XRD studies. SHI irradiation
decreases the decomposition temperature by making the electrolyte films more
amorphous as the decomposition temperature for amorphous materials is lower
than that of the crystalline materials.
The derivative thermographs of TG graphs are shown in Fig. 25 which gives the
onset decomposition (Tonset) and rapidest decomposition (Trpd). The values of Tonset
and Trpd are summarized in Table 4. For pure P(VdF-HFP), Tonset ¼ 425  C and
Trpd ¼ 489  C and from Tonset to Trpd, 50% wt. loss has been observed. For the
pristine nanocomposite electrolyte, the values of Tonset and Trpd are 238 and 303  C
and 30% wt. loss has been observed. From this result it is observed that the rate of
decomposition is low in case of nanocomposite electrolyte compared to pure P
(VdF-HFP), which is required for practical applicability over large temperature
range. Similarly, for the SHI irradiated electrolyte films, the Tonset, Trpd, and %
wt. loss decrease as observed from the data given in Table 4. The increased
intercalation and exfoliation upon SHI irradiation lead to decrease in the decompo-
sition rate, which can be attributed to the fact that 2-D MMT layers act as mass and
heat transport barriers to the volatile species generated during decomposition giving
rise to an overall increase in thermal stability of the nanocomposite electrolytes.

Conclusion

The field of polymer electrolyte nanocomposites is an emerging area of research as

they find widespread applications in energy storage and conversion devices. In this
chapter, the properties of polymer electrolyte nanocomposites for futuristic energy
storage applications have been discussed. Ionic liquids have shown promise as vital
materials of electrochemistry owing to the prospects of offering efficient ion con-
duction. Incorporation of ionic liquids into polymer networks furnishes a compatible
combination resulting in some polymer electrolytes with relatively higher ionic
conductivity and electrochemical stability and thus expanding their applications in
9 Polymer Nanocomposites for Futuristic Energy Storage Applications 223

rechargeable batteries, fuel cells, and solar cells. The chapter describes the effect of
modified MMT on electrochemical properties of P(VdF-HFP)-BMIMBr-MMT
nanocomposite polymer electrolytes. The electrolyte system containing 5.0 wt. %
MMT shows ionic conductivity of 9.8  10
3 S cm
1 and thermal stability up to
238  C confirming that the electrolyte is usable over a wide temperature range.
The use of swift heavy ion irradiation technique to enhance the morphological,
structural, and electrochemical properties has been discussed. The nanocomposite
polymer electrolyte containing 5 wt. % of modified MMT has been irradiated with
100 MeV Si9+ ion with different fluences. The room temperature ionic conductivity
increases with increasing ion fluence attaining the highest value of
4.96  10
2 S cm
1 at the highest fluence used (1  1012 ions cm
2). Further, the
electrochemical stability window increases with increasing ion fluence attaining the
highest value of 6.5 V at 1  1012 ions cm
2 irradiation.
Despite numerous studies on polymer electrolyte nanocomposites, a polymer
electrolyte with high room temperature ionic conductivity is still outstanding.
There is a whopping scope for further development of the polymer electrolyte
nanocomposites with higher room temperature ionic conductivity for practical
applications in rechargeable batteries. The ion conduction mechanism inside the
interlayer galleries of MMT has not been thoroughly understood as yet which can
further be investigated to tune the properties of the polymer electrolyte nano-
composites. Extensive research is going on to develop single ion-conducting poly-
mer electrolyte; however, the researchers are far away from achieving the goal. Swift
heavy ion irradiation with different ion beams and energies can be a promising tool
for enhancement of the electrochemical properties of polymer electrolyte
nanocomposites.

Important Websites

https://www.sglcarbon.com/en/
https://www.iuac.res.in/
https://www.alliedmarketresearch.com/polymer-nanocomposites-market

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Metal Organic Framework Nanoparticles-
Based Polymeric Membrane for Industrial 10
Mixture Separation

Dipeshkumar D. Kachhadiya and Z. V. P. Murthy

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Factors Affecting the Properties of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Methods MOF Incorporating into the Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Various Applications of MOFs Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
Pervaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
Desalination Via Pervaporative Route . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Conclusions and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
For Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
Important Journals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
Important Books . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

Abstract
Metal organic frameworks (MOFs) are defined as solid crystalline materials
synthesized in situ by the interaction of metal ions with organic linkers. MOF
nanoparticles (NPs) have been widely used in various industrial separations,
mainly membrane-based separation, because of their distinct properties such as
narrow pore size, unique chemical features, and availability in multiple shapes.
Both organic-inorganic and polymeric materials can be used as support materials.
There is good compatibility between the MOFs and polymers. So MOFs can be
used as fillers to prepare mixed matrix membranes. In this chapter, special
attention is given to the fabrication of MOF membranes and application in the
field of liquid mixture separations, such as water/wastewater treatment, nano-

D. D. Kachhadiya · Z. V. P. Murthy (*)

Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat,
Gujarat, India
e-mail: [email protected]; [email protected]

© Springer Nature Singapore Pte Ltd. 2022 227

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_86
228 D. D. Kachhadiya and Z. V. P. Murthy

filtration, desalination, and pervaporative separation. This review gives a sum-

mary for the synthesis of MOF membranes and their applications in various fields
and the challenges for developing MOFs membranes for liquid mixture
separation.

Keywords
MOFs · MOF membranes · Liquid mixture separation · Pervaporation ·
Desalination

Abbreviations
2-MeIM 2-methylimidazol
BSA Bovine serum albumin
CA Cellulose Acetate
CNT Carbon Nanotubes
DI Deionized water
DMF N, N dimethylformamide
GO Graphene Oxide
GOQD Graphene Oxide Quantum Dots
IP Interfacial Polymerization
LBL Layer-by-Layer
MIL-101 Material institute lavoisier-101
MMM Mixed Matrix Membrane
MOF Metal Organic Framework
NMP N-Methyl-2-pyrrolidone
NPs Nanoparticles
PA Polyamide
PAN Polyacrylonitrile
PBI Polybenzimidazole
PDA Polydopamine
PDMS Polydimethylsiloxane
PEA Polyetheramine
PEBA Polyether-Block-Amide
PEI Polyetherimide
PI Poly imide
PSF Polysulfone
PVA Poly(vinylalcohol)
PVDF Polyvinylidene Fluoride
rGO Reduced Graphene Oxide
SR-AOP Sulfate Radical Based Advanced Oxidation Processes
TFC Thin Film Composite Membrane
TFM Thin Film Membrane
UiO-66 Universitetet i Oslo - 66
ZIF Zeolitic Imidazolate Framework
10 Metal Organic Framework Nanoparticles-Based Polymeric Membrane for. . . 229

Introduction

Metal organic framework (MOF) consists of metal centers and organic binders that
have high surface areas and distinct pore structures. As compared to conventional
porous materials such as zeolites, carbon-based materials, metal oxides, and
graphene, MOFs are extensively favored for various applications because of having
unique tunable properties and different pore structures [1]. The control of pore
structures is easier for MOFs as compared to other nanoporous materials. Nowadays,
MOFs incorporated with polymers have gained remarkable attention to enhance
MOF porosity and performance in various applications [2].
Membrane material and its properties have a considerable impact on the perfor-
mance and separation efficiency of the membrane. Polymers, for example, cellulose
acetate (CA), polyamide (PA), polysulfone (PSF), polyimide (PI), poly-
dimethylsiloxane (PDMS), and polyvinylidene fluoride (PVDF), are commonly
used to fabricate membranes. Polymer materials have several irreplaceable advan-
tages, especially high processability and low production cost [3]. A disadvantage of
polymeric membranes is that it generally suffers between selectivity and permeabil-
ity [4]. The polymer properties hydrophobicity/hydrophilicity and structure stability
are crucial for the separation performance of the MOF membrane. Hydrophilic poly-
mers such as polyacrylonitrile (PAN), poly(vinylalcohol) (PVA), and chitosan are
generally used because they selectively allow water molecules to pass through it [5].
Hydrophobic polymers like PDMS, polyether-block-amide (PEBA), and poly-
benzimidazole (PBI) are used to remove organic compounds from the aqueous stream
[5]. To enhance the separation efficiency of the membrane, micro/nanoparticles (NPs)
are blended into polymeric material to alter the crystal growth mechanism, composi-
tion, and pore structure of the membrane, thereby resulting in high performance
mixed-matrix membranes (MMMs) [6]. MOFs incorporated membranes are mostly
applied for various membrane separation processes like in gas permeation, H2 purifi-
cation [7], CO2 separation [8], hydrocarbon separation [9]; in pervaporation, for
dehydration of solvent [10], removal of dilute organic compound [11], organic-organic
mixture separation [12]; nanofiltration [13]; desalination [14]; membrane distillation
[15]; etc.
Hydrophilicity and hydrophobicity of the membranes plays an essential role in
the separation performance for solvent dehydration. Hydrophilic membranes allow
water molecules to diffuse through them. PVA, chitosan, and sodium alginate show
excellent attraction toward water molecules. The major issue of hydrophilic mem-
brane is its stability and mechanical strength when water concentration is high in the
feed solution. Hydrophobic membranes are generally used for the separation of
dilute organic species from an aqueous mixture. PDMS, PEBA, and PBI have
been commonly used for the separation of an organic-organic mixture. Hydrophobic
polymers possess high thermal stability with better mechanical strength. Membrane
swelling is the major issue, which can enhance the flux bot lowering the separation
factor. It can be minimized by cross-linking or blending the appropriate NPs with the
polymer chain [16]. The polymer characteristics are different at below and above the
230 D. D. Kachhadiya and Z. V. P. Murthy

glass transition temperature (Tg). To increase the mechanical properties of the

polymer, Tg is being modified by blending some NPs with the polymer chain [17].

Factors Affecting the Properties of MOFs

While preparing the MOFs with controlled morphology and structure, the most
considerable factors are temperature, additives (types of salts), composition (molar
ratio), and solvent. Figure 1 shows some typical structures of MOFs used in the
pervaporation membrane.
Temperature plays a significant role in preparing MOFs by temperature-sensitive
methods such as hydro/solvothermal or microwave-assisted methods. Most of the
MOFs are prepared in the temperature range of 60–160  C in a closed system to
achieve high-quality crystals. The synthesis temperature can play an important role in
controlling the crystals’ growth and size. The optimized temperature of the system can
result in nano-size crystals. For example, Koshhal et al. [19] prepared CuBTC MOFs
at different temperatures and studied their effect on the final product. As per their

Fig. 1 Some typical

structures of MOFs.
(Reproduced with the
permission Elsevier [18])
10 Metal Organic Framework Nanoparticles-Based Polymeric Membrane for. . . 231

results, lower relative crystallinity and reduction in specific surface area were observed
[19]. The solvent selection is another crucial factor for MOFs preparation. It directly or
indirectly affects the interaction between metal ions and organic linkers. They may act
as structure-building mediators for MOFs crystals [20]. The different studies showed
that the use of other solvents results in different sizes of crystals. Some solvents such
as dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), methanol, ethanol,
mixed solvent, and water are used to prepare MOFs [20]. For example, Ghorbani
et al. [21] prepared a ZIF-8 with different solvents (DMF, DI water, ammonia, and
acetone) and studied their effects on crystal growth. The obtained results showed that
the solvent with higher polarity achieved nano-sized crystals [21]. Different studies are
available on the impact of solvent for different MOFs (ZIF-8, CuBTC, UiO-66,
MIL-53 (Al), and HKUST) [22]. There is an effect of molar ratio and type of metal
salt on the size and structure of the MOFs crystals [23]. Zhang et al. [24] explained that
with the increase in the linker to the salt ratio (Hmim/Zn+2), size reduction was
observed for ZIF-8 crystals. Schejn et al. [25] prepared a ZIF-8 with different Zn
salts. They concluded that the more reactive metal source is responsible for faster
nucleation; thus, a reduction in the particle size was observed from 211 (ZnSO4) to
45 nm (Zn(NO3)2) [25]. There is also an effect of additives on the crystal growth,
uniformity, and shape of crystals. We can control the crystal growth and structure
coordination by adjusting the reaction kinetics [26]. Various additives are available
with different acidity, polarity, and ion strength, such as trifluoroacetic acid, cetyltri-
methylammonium bromide, amines, glycerol, benzoic acid, and pyridine [26].

Methods MOF Incorporating into the Polymer

Permeability and selectivity of the MOF membranes depend on the size and pore
structure of the MOFs. Two types of MOF membranes available for the application:
(1) Pristine MOFs membranes and (2) MOFs composite membranes. Pristine mem-
branes are defined as thin-film membranes (TFM) and are mostly prepared by the in
situ route [27]. The in situ route is used to prepare continuous MOFs membranes.
This can be categorized into direct crystallization, seeded or secondary crystal
growth, and liquid phase epitaxy.
In situ growth is termed as substrate directly immersed into the MOFs solution. In
this method, nucleation and crystal growth takes place on the modified or unmodified
substrate during the preparation time. Many researchers have developed MOF mem-
branes on various inorganic materials and polymeric substrates [28]. Kang et al. [29]
prepared a microporous MOF membrane on nickel mesh by seeded growth technique in
the autoclave. Some defects and cracks on the membrane’s surface occurred due to weak
bonding between the MOF layer and substrate [29]. To overcome this problem,
secondary growth or seeded technique is developed to prepare continuous MOFs
membranes [30]. Zhu et al. [31] prepared a polydopamine grafted ZIF-8 MOF mem-
brane on the modified ceramic α-Al2O3 support. Modification with PDA promotes
directly in situ growth to the surface of the substrate [31]. Pan et al. [32] prepared a
ZIF-8 membrane on nano-sized ZIF-8 seeded α-Al2O3 substrate via secondary growth
232 D. D. Kachhadiya and Z. V. P. Murthy

Fig. 2 Schematic of the thin-film composite membrane. (Reproduced with the permission Elsevier
[23])

by immersing the top layer of the porous substrate into the ZIF-8 solution [32]. The
layer-by-layer technique is another technique to prepare MOFs membrane. Shekhah
et al. [33] developed the thin film layer of HKUST by liquid phase epitaxy method. Liu
et al. [34] have developed novel Fe3O4@HKUST-1/MIL-100(Fe) MOFs via a combi-
nation of epitaxial growth and layer-by-layer deposition. Blending is another technique
to prepared thin film MOF-based MMM. With this method, we can prepared a 1–30 μm
thick MOFs layers on the porous substrate. Three steps involved in this process to
prepare a membrane: (1) blending the polymer and MOFs particles into the solvent;
(2) casting the dope solution on the substrate by doctor blade; and (3) drying process to
remove the excess solvent. Liu et al. [35] prepared 2.5 μm thick organophilic layer of
ZIF-8@PMPS on the inside surface of Al2O3 capillary by blending process. We can
improve the membrane design by adding a thin layer of MOFs as a top selective layer
via interfacial polymerization process (IP) (Fig. 2). This thin layer plays a significant role
in the selective separation performance of the membrane. In the IP technique, reaction of
nucleophile and electrophile reactant is taking place onto the porous substrate, which
results into the formation of uniform polymeric chain [36]. To enhance the membranes
properties, some additives of fillers have been added to prepare TFNC such as zeolites
[37], CNTs [38], GO [39], rGO [22], GOQD [40], TiO2 [41], halloysite [42, 43], and
cellulose and silica materials [43]. Other than these fillers, various MOFs such as the ZIF
series, CuBTC series, and MIL series have been used as fillers or used as active skin
layers to the porous substrates. Figure 3 represents the schematic of preparation of the
membrane via different methods.

Various Applications of MOFs Membranes

Pervaporation

The applications of PV are mainly in three areas: (1) removal of dilute species from
the mixtures, (2) recovery of organic solvents, and (3) separation of an organic-
organic mixture. In the pervaporation, separation of the selected component is
accomplished by the difference in sorption and diffusion through the membrane
10 Metal Organic Framework Nanoparticles-Based Polymeric Membrane for. . . 233

Fig. 3 Schematic diagram of membrane preparation by various methods. (Reproduced with the
permission Elsevier [30])

surface [44]. Recently various MOFs such as ZIF-8, ZIF-71, UiO-66, MAF-6, and
MOF-5 are widely used in pervaporative separations. To remove organic contami-
nants from the water, sulfate radical (SO4* ) based advanced oxidation processes
(SR-AOP) have been widely used [45].
Zhang et al. [46] prepared a polyamide composite membrane with an interlayer of
poly (4-styrenesulfonic acid) modified ZIF-8 for ethanol/water mixture separation
(Fig. 4). Obtained results described that the prepared membrane MZIF-8/PA exhibited
good separation performance with flux enhancement of 0.81–4.47 kg/m2h. Also, it was
found that by decreasing ethanol concentration in the feed, the separation factor
decreased from 318 to 127 [46]. Jin et al. [47] synthesized microwave-assisted a
234 D. D. Kachhadiya and Z. V. P. Murthy

Fig. 4 Schematic representation of a modification of ZIF-8 particles. (Reproduced with the

permission Elsevier [46])

hydrophilic CAU-10-H MOF membrane on the Al2O3 disc via secondary crystal growth
for dehydration of ethanol. Wei et al. [48] prepared MOF membrane embedding the
ZIF-90 particles onto the surface of the PVA membrane for ethanol dehydration. The
prepared hybrid membrane showed 268 g/m2h of flux with a separation factor of 1379
for 90% ethanol-water solution. Pan et al. [49] synthesized a ZIF-90 and its derivative-
based membrane for ethanol separation by incorporating the ZIFs particles with PDMS/
PVDF matrix. The prepared membrane showed almost double the total flux of
846 g/m2h with a 15.8 separation factor for 5% of ethanol/water aqueous mixture.
Ibrahim and Lin [50] prepared a MOF-5 seeded α-Al2O3 supported membrane of
organic mixture separation. Li et al. [51] prepared a hydrophobic membrane for recovery
of butanol by incorporating silane-modified ZIF-8 NPs into the PDMS polymer. The
prepared membrane showed 480 g/m2h of flux and a separation factor of 56, which is
23% higher than that of unmodified membrane for 1.5 wt% butanol solution
[51]. Dehghankar et al. [52] prepared hydrophilic MMM by incorporating the UiO-66
and MIL-101 as nanofiller with PVDF matrix via phase inversion technique. Pure water
flux of 360 LMH with 100% BSA rejection was obtained for 0.1 wt% loadings of
MIL-101 [52].
10 Metal Organic Framework Nanoparticles-Based Polymeric Membrane for. . . 235

Desalination Via Pervaporative Route

We can obtain highly pure water flux through pervaporation due to the nonvolatility
of salts in the feed solution [53]. Highly hydrophilic membranes such as PVA,
PEBA, PEA, and cellulose are used in the pervaporative desalination process.
Different nanomaterials such as GO [54], CNTs [55], SiO2 [56], Al2O3 [57], nano-
laponite clay [53], and cellulose nanocrystals [58] have been used to prepare a
nanocomposite membrane for pervaporative desalination [59].
Halakoo et al. [60] prepared TFC Cl-PA membrane for pervaporative desali-
nation via LBL deposition of the PEI as a positive charge and GO as negatively
charged on the surface of the membrane. Obtained water flux and salt rejections
were 8 kg/m2h and > 99.9% of salt rejection. Nigiz et al. [61] prepared GO
incorporated NaAl membrane for the desalination process. Prihatiningtyas et al.
[62] prepared a CTA/CNCs nanocomposite membrane for saline water treatment.
To improve the water flux without lowering the selectivity, a time-controlled
alkaline treatment is given to the membranes. Alkaline-treated membrane showed
high water flux of 107.5 kg/m2h than that of the original membrane without
losing the selectivity (Fig. 5) [62]. Selim et al. [63] developed a low-cost
glutaraldehyde cross-linked laponite/PVA membranes with water flux of
31.2 kg/m2h and 99.98% salt rejection. Zeolitic materials can also be used for
saline water treatment [64].

Water flux Rejection (%)

150 100
Water flux (Kg.m-2.h-1)

Rejection (%)

100
98

50

96

0
Untreated 6 20 30 60
Alkaline time (min)

Fig. 5 Performance data of CTA/CNCs membrane for pervaporative desalination. (Reproduced

with the permission Elsevier [62])
236 D. D. Kachhadiya and Z. V. P. Murthy

Conclusions and Future Perspectives

Different types of MOFs and MOFs membranes have been successfully developed
in the last 5 years. Membrane-based separation has been discovered as a promising
process without compromising membrane permeability and selectivity [23]. There
are n numbers of MOFs available with low hydro-stability and large pores, which is
not suitable for monovalent ion separation results in poor quality water. Despite this,
the literature reported that MOF membranes exhibited good performance in terms of
flux and selectivity compared to the commercial membrane. However, till date, no
large-scale production of MOFs membranes is reported. Scientists are working on
the development of commercial MOFs membranes with better flux, higher selectiv-
ity, and thermal/chemical stability for various applications. Future researchers can
work on improving the surface area and size distribution of MOFs that can enhance
the interfacial compatibility between polymer matrix and nanofillers. There is much
scope in MOFs stability and their integration with polymers, which opens many new
applications in various fields [65].

For Further Reading

Important Websites

1. https://www.borsig.de/en/products-and-services/membrane-technology-for-liq
uid-separation/pervaporation
2. https://pervaporation-membranes.com/products/modules
3. https://permionics.com/membranes

Important Journals

1. Journal of Membrane Science

2. Separation and Purification Technology
3. Desalination
4. Chemical Engineering Science

Important Books

1. Membrane Processes: Pervaporation, Vapor Permeation and Membrane Distilla-

tion for Industrial Scale Separations
(URL:https://onlinelibrary.wiley.com/doi/book/10.1002/9781119418399)
2. Polymer Nanocomposite Membranes for Pervaporation
(URL: https://www.sciencedirect.com/book/9780128167854/polymer-nano
composite-membranes-for-pervaporation)
10 Metal Organic Framework Nanoparticles-Based Polymeric Membrane for. . . 237

3. Pervaporation, Vapour Permeation and Membrane Distillation

(URL: https://www.sciencedirect.com/book/9781782422464/pervaporation-
vapour-permeation-and-membrane-distillation)
4. Current Trends and Future Developments on (Bio-) Membranes
(URL: https://www.sciencedirect.com/book/9780128163504/current-trends-
and-future-developments-on-bio-membranes)

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 Part V
Consumer Nanoproducts Based on Composites
Based on Shape Memory Alloys
Polymer Nanocomposite Matrix-Based
Nanoproducts 11
Ihsan Flayyih Hasan AI-Jawhari

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Ecofriendly Polymer Nanocomposite (EPN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Nanocellulose Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
Applications of Nanocellulose in Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Industrial Effluents and Contaminated Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Polymeric Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Use of Nanomaterials in Environmental Health (Nanoremediation) . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Wood Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Bio-based Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Application of Wood Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

Abstract
In this chapter, a review of several researches is done on the development and
characterization of polymer nanocomposites. Polymer nanocomposite is a prom-
ising multidisciplinary material research activity that could expand the use of
polymers for various industrial applications and also in environment to remove
pollutants. Polymer nanocomposites are a radical alternate to conventional poly-
mer composites, where large amount of fillers are added to improve the proper-
ties. For polymer composite applications, the use of natural fibers is preferred to
efficiently reduce the dependence on petrochemical-based plastics. The utiliza-
tion of renewable materials has attracted researchers because of its easy avail-
ability and low cost. They can potentially remove the harmful effects of
petroleum-based materials and thus show a greener path in the fields of applica-
tion of composites. In recent years were used developing nanotechnological
I. F. H. AI-Jawhari (*)
Department of Biology, Faculty of Education for Pure Sciences, University of Thiqar, AL-Nasiriya,
Iraq

© Springer Nature Singapore Pte Ltd. 2022 243

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_21
244 I. F. H. AI-Jawhari

methods based on adsorption capabilities of cellulosic nanoparticles for monitor-

ing hazardous substances in the environment. Along the examples are the benefits
and implications of sustainable design and the use of nanocellulose in environ-
mental applications. The discussion will be focused on structural, mechanical, as
well as degradation of cellulose. Nanocellulose, wood polymer nanocomposites
have renewability, availability, light weight, low cost, and most importantly
minimum environmental impact (Ecofriendly) and have little effect on animal/
human health. The general properties of cellulose include extensive ability of
chemical modification and very high aspect ratio leading to the formation of
versatile semi-crystalline fibers which is the unique characteristic of nano-
materials as reinforcing agents. There is the presence of strong and complex
network of hydrogen bonds which are stabilized by the ordered regions of chain
packages of cellulose that resembles nanocrystalline rods.

Keywords
Composite · Degradation · Ecofriendly · Environment · Nanocellulose ·
Nanocomposite · Polymer · Renewability

Introduction

Ecofriendly Polymer Nanocomposite (EPN)

A composite is defined as a combination of two or materials with different physical

and chemical properties and distinguishable interface. In most composite materials,
one phase is usually continuous and called matrix, while the other face called the
dispersed phase. Nanocomposites refer to composites having one phase nanoscale
morphology such as nanoparticles, nanotubes, or lamellar nanostructure. Polymer
nanocomposite (PNC) is a promising multidisciplinary material research activity that
could expand the use of polymers for various industrial applications and also in
environment to remove pollutants [17, 29, 39]. In general, the desirable properties
that are needed for many advanced applications, including low gas permeability,
high mechanical strength, light weight, high chemical resistance, etc., are not found
in commercial polymers. Polymer service has been extended in various fields as PNS
enhances the properties of polymer in order to obtain the product with essentially
new set of properties. Cellulose is one of the renewable resources and has been
identified as a source of biopolymer that can be used as a substitute for petroleum
polymers. EPN has been successfully synthesized from cellulose acetate, triethyl
citrate plasticizer, and organically modified clay [35]. The polymer matrix for
nanocomposite contains 80 wt% pure cellulose acetate and 20 wt% triethyl citrate
plasticizer. Results show that better exfoliated and intercalated structure were
obtained from nanocomposites containing 5 and 10 wt% organoclay compared
with that of 15 wt% organoclay. Tensile strength of cellulosic plastic reinforced
with 10 wt% organoclay improved by 180% and thermal stability of the cellulosic
11 Polymer Nanocomposite Matrix-Based Nanoproducts 245

plastic also increased. Recently, an active antimicrobial packaging material has been
successfully synthesized using methyl cellulose (MC) as the matrix with montomor-
illionite (MMT) as reinforcement [54]. Carvacrol was then added to the as-prepared
MMT/MC composite material to form nanocomposites.

Nanocellulose

Nanocelluloses, elemental nano-sized constituents of plant fibers, have acquired an

extra reputation relative to conventional cellulose fibers due to their huge surface
area, high aspect ratio, and high Young’s modulus of 145 GPa [22] resulting from
high crystallinity [1, 18, 25]. Furthermore, considered natural materials, nano-
celluloses are biodegradable, biocompatible, and renewable [18].
The lateral size of cellulose molecule chains is about 0.3 nm, and these chains
form bundles of elongated fibrils still with nano-scale diameters. The cellulose
chains are stabilized laterally by hydrogen bonds between their hydroxyl
groups [56].
There are three main categories of nanocelluloses [25]: nanofibrillated celluloses,
nanocrystalline celluloses, and bacterial celluloses. Nanofibrillated celluloses are
elongated strains of superfine fibrils, while nanocrystalline celluloses are rod-like
particulates consisting of crystalline cellulose [1, 49, 56]. Bacterial cellulose is
produced by down-to-top synthesis, where specific bacteria synthetize bundles of
cellulose nanofibrils from low molecular sugars and alcohols [25].
Nanocelluloses can be produced from cellulose pulp using pure mechanical or
combined chemical or enzymatic and mechanical treatments. The chemical and
enzymatic pretreatments reduce the energy needed for individualization of the
nanofibrils. These treatments typically reduce the hydrogen bonds and/or add a
repulsive charge, or else reduce the DP or the amorphous part between the individual
nanofibrils [26]. One of the most widely used chemical pretreatment is TEMPO
(2,2,6,6 tetramethyl-1-piperidinyloxy)-mediated oxidation; another potential chem-
ical oxidation pretreatment reaction for the production of nanocelluloses is periodate
oxidation. In this reaction, the C2 and C3 bonds of cellulose are selectively cleaved,
yielding 2,3-dialdehyde cellulose, which can be further derivatized with functional
groups such as carboxylic acids [31], sulfonic groups [30, 32, 41], or imines
[51]. Only a few previous studies of the use of nanocelluloses as water chemicals
exist, and they mainly address adsorption applications. TEMPO-oxidized nano-
celluloses have been used for the adsorption of various metals from aqueous
solutions, most efficiently with lead, calcium, and silver [43]. Succinic anhydride-
modified mercerized nanocellulose [14] and amino-modified nanocelluloses [15]
showed high efficiency in the removal of metal ions, with good regeneration ability,
while Kardam et al. [23] achieved improved heavy metal adsorption capacity
subjecting rice straw cellulosics to acid hydrolysis, which produced rod-like cellu-
lose nanocrystals. Yu et al. [55] used carboxylated cellulose nanocrystals for the
adsorption of heavy metals with good results, as adsorption was fast, with high
capacity, and the adsorbent was easy to regenerate. In flocculation applications,
246 I. F. H. AI-Jawhari

TEMPO-oxidized nanocelluloses with CPAM were used to flocculate kaolin clay

suspensions, whereupon relative turbidity decreased greatly and the resulting flocs
were stronger than with CPAM alone [18].
Nanocelluse has been the topic of a broad range of research as reinforcing agents
in nanocomposites because of their nanoscale dimension, renewability, availability,
light weight, and low cost, and most importantly, they have minimum environmental
impact and have little effect on animal/human health [27, 28]. They offer significant
properties of cellulose including its extensive ability of chemical modification, very
high aspect ratio leading to the formation of versatile semicrystalline fibers which is
the unique characteristic of nano-materials as reinforcing agents. There is a presence
of strong and complex network of hydrogen bonds which are stabilized by the
ordered regions of chain packages of cellulose [13] that resembles nanocrystalline
rods. Based on their preparative methods and structure, there are two main types of
nanocellulose: (i) nanocrystalline and (ii) microfibrillated cellulose.

(i) Cellulose: Nanocrystalline cellulose, which is extremely crystalline and rigid

nanoparticles, is also called cellulose nanowhiskers or cellulose nanocrystals
(Fig. 1). This can be prepared from native fibers through acid hydrolysis. A new
class of bio-based products with a broad range of applications including auto-
motive industry, construction material, etc. have been developed by using
nanocrystals as reinforcing agents. Addition of small amount of nanocrystal
can increase the strength, stiffness, and resistance of the material to stress
threefold its original strength. Thus, incorporation of nanocrystal makes the
nanocomposites an interesting high-performance material. It is also a promising

Fig. 1 Structure of cellulose nanocrystals

11 Polymer Nanocomposite Matrix-Based Nanoproducts 247

Fig. 2 Structure of cellulose fibrils

green substitute for carbon nanotubes as reinforcing agents in polymer nano-

composites and concrete. Nanocrystal reinforced nanocomposites are used in a
variety of applications such as biodegradable plastic bags, textiles, wound
dressings, etc.
(ii) Microfibrillated cellulose (MFC): The constituent of MFC is nano-sized cel-
lulose fibril having high aspect ratio (Fig. 2). The fibrils are extracted from
wood pulp through high-temperature, high-pressure, and high-velocity impact
which can be employed in polymer nanocomposites of high mechanical
capacity [36].

The strength properties of these nanocomposites are very high, and the Young’s
modulus is found to be approximately 20 GPa. Thus, MFC-based nanocomposites
that are derived from wood pulp are promising class of substance with outstandingly
high mechanical performance. The Young’s modulus of the cellulose crystal is about
134 GPa; therefore, MFC nanofibers are estimated to provide high stiffness to the
resultant nanocomposites [44].
However, another type of nanocellulose is known as bacterial cellulose (Fig. 3).
Specific bacteria mainly Gluconacetobacter strains secret these cellulose nanofibers
extra- cellularly [4, 24, 50]. These bacterial celluloses have exceptional mechanical
and physical properties due to its special fibrillar nanostructure. Its properties include
high strength, high porosity, high crystallinity (up to 84–89%, [6]), and high elastic
modulus [12]. Currently, bacterial cellulose is the topic of research in several fields
of applications, reinforcement in nanocomposites [21, 38], bio-medical applications,
and fuel cell membranes [10].
248 I. F. H. AI-Jawhari

Fig. 3 Secreted of nanofibrils

from bacteria

Nanocellulose Applications

Polymer nanocomposites are a radical alternate to conventional polymer composites,

where large amount of fillers are added to improve the properties. For polymer
composite applications, the use of natural fibers is preferred to efficiently reduce the
dependence on petrochemical-based plastics [53]. Natural fibers obtained from
various plant sources as such or in the form of extracted cellulose have been
frequently used for this application [48]. Cellulose in nanodimensions generated
from cellulose fibers has much higher mechanical properties than those of natural
fibers. Hence, CNs have attracted a great deal of interest in the polymer nano-
composite field. Due to their nanodimensions, high surface area, low density, ability
to functionalize, and sufficient strength, they proved to be a better reinforcing
material than conventional fibers. Like any other multiphase material, the properties
of nanocomposite depend on the morphological aspects and their interfacial inter-
actions. There are four different factors that can affect the performance of CN-based
water-soluble polymer nanocomposites [33]. The first, and most critical, is the
compatibility of CNs with polymer matrix. This is essential to allow uniform
dispersion of reinforcing element into the matrix. The main challenge in attaining
excellent performance lies in attaining homogenous dispersion of nanocrystals
within the polymer matrix by avoiding the aggregation of nanocrystals. The second
factor is the molecular structure of the matrix, which influences the interaction
between matrix and CN and their interfacial properties. This is also important in
obtaining a good matrix-filler interaction. Here also since both the polymer matrix
and reinforcing components are hydrophilic in nature, their interactions can be
reasonably good. The third is the aspect ratio of CN particles, which is determined
by the origin of the cellulose source and the manufacturing conditions. Since the
reinforcing filler used is possessing nano-dimensions, the reinforcing effect is better.
Fourth factor is the method of polymer nanocomposite fabrication. Solvent interca-
lation is the most widely used preparation method for these types of polymers. It is
having both advantages and disadvantages. Ease of preparation, control over the
nanocrystal aggregation, better dispersion, less damage to the nanocrystals, cost
effectiveness, etc. are the advantages, while their inefficiency for large-scale pro-
duction is a limitation. Several water-soluble polymer-based nanocomposites have
been prepared by solvent intercalation method, and their details are briefly
highlighted below.
11 Polymer Nanocomposite Matrix-Based Nanoproducts 249

Applications of Nanocellulose in Environment

This section describes a variety of developing nanotechnological methods based on

adsorption capabilities of cellulosic nanoparticles for monitoring hazardous sub-
stances in the environment. Along the examples, the benefits and implications of
sustainable design and the use of NC in environmental applications are also
addressed in order to understand and control their properties. In this regard, biode-
gradable NC can be used in different formats such as template, solid fibers, mem-
branes, films, and 3D networks with low density and thermal transport but high
surface area (aerogels, also referred to as sponges) in separation techniques for
pollutant remediation. A wide variety of cellulosic nanoparticles isolated from
various resources such as sludge, bio waste, plants, and bacteria with low-cost
production are used for bioremediation.

Industrial Effluents and Contaminated Waters

Nanotechnology actually has applications in all fields of research. Water purification

and the treatment of industrial wastewater are at a crucial juncture of vision,
ambition, and technological innovation. Contamination of arsenic and heavy metals
to groundwater and drinking water is an enormous challenge which has produced a
need for nanotechnology, materials science, and nanomaterial nanomanufacturing
[52]. The chemicals currently used for wastewater treatment are mainly based on
synthetic inorganic or organic compounds. Oil-derived polyelectrolytes are used for
the removal of colloidal solids from wastewater by flocculation and coagulation, for
example, while activated carbon adsorbents are typically used to remove soluble
impurities such as heavy metals and recalcitrance organic matter. Many of these
chemicals have associated negative health impacts, and use of activated carbon has
proved to be expensive. Moreover, the present synthetic chemicals are not readily
biodegradable or renewable. Thus there is a high demand for “green” water
chemicals which could offer a sustainable solution for achieving high-performance,
cheap water purification.
Water chemicals of a new type based on nanoscale particles (nanofibrils) derived
from cellulose, i.e., nanocelluloses, are examined as possible bio-based chemicals
for wastewater treatment. Two anionic nanocelluloses (dicarboxylic acid, DCC, and
sulfonated ADAC) were tested as flocculants in the coagulation-flocculation treat-
ment of municipal wastewater, while the flocculation performance of cationic
nanocellulose (CDAC) was studied with model kaolin clay suspensions, and nano-
celluloses produced from sulfonated wheat straw pulp fines (WADAC) were tested
for the adsorption of lead (Pb(II)). The anionic nanocelluloses (DCC and ADAC)
showed good performance in treating municipal wastewater in a combined
coagulation-flocculation process with a ferric coagulant. In the case of both anionic
nanocelluloses, the combined treatment resulted in a lower residual turbidity and
COD in a settled suspension with highly reduced total chemical consumption
relative to coagulation with ferric sulfite alone.
250 I. F. H. AI-Jawhari

On the one hand, NC materials were used to fabricate absorbent material to

control and avoid eutrophication from occurring. Different requirements for a
substrate to be considered as a sorbent material include a high adsorption efficiency
with a fast adsorption kinetics for selectively hazardous substances, low chemical
reactivity, high stability and regeneration capacity with the lowest loss of adsorption,
and, finally, good resistance to different matrices such as wastewaters or other more
complex aqueous samples. Different functions of NC for creating sorbent materials
are addressed.
On the one hand, the wide variety of products containing pigments and dyes are
of great concern since their waste is released as water containing ionic species into
the environment. This class of contaminant is difficult to degrade and produces acute
and chronic toxicities and hinders the purification of water following the conven-
tional methodologies. It is estimated that around 20% of such water-insoluble
compounds are discharged into the environment as aqueous effluents. Thus, the
government agencies are imposing restrictions on colored waste disposal. For these
reasons, biocompatible technologies based on NC have been proposed to econom-
ically avoid such contaminations to some extent. In the first place, anionic dyes were
removed by NC grafted with positively functional groups. In this regard, well-
dispersed NC containing amine groups were used as excellent sorbent material,
achieving the maximum removal efficiency of three different dyes under acidic
conditions [19]. In fact, the highest removal efficiency reported for Congo red 4BS
is almost 100%.
On the other hand, one of the most promising applications of the biocompatible
nanofibers lies in the removal of other hazardous nanoparticles released into the
environment. Among engineering nanomaterials, AgNPs are the most largely used
in everyday items by virtue of their antimicrobial and optical properties; however,
they are also considered to be highly toxic to humans and the environment. There-
fore, sulfonate-modified NC has been proposed for adsorption of such metallic
nanoparticles in aqueous solutions [42]. Thus, dispersive NC was treated with
cetyltetramethylammonium salt to achieve good adsorption efficiency, whereas the
regeneration of the sorbent material could be easily reached by simply adding
thioctic acid solution. This method was automated by packing the nanofibers into
a SPE column and applied to waters.
Other membrane application for purification of water consists of the removal of
virus such as MS2 virus and bacteria such as Escherichia coli [45], which is of great
interest in water scarce and stressed areas. In this case, ultrafine cellulose nanofibers
prepared by electrospun and modified with different functionalization (with carboxyl
and amine ending groups) were used to fabricate filtration membranes. The mem-
brane composed of positively charged amine-modified nanofibers satisfies the
National Sanitation Foundation Standards, as regards the good adsorption of viruses
and bacteria (slightly negatively charged) via electrostatic interactions. Furthermore,
removal of micotoxins was achieved by using NC grafted with fatty acids by
interaction of their hydrophobic tails [16].
11 Polymer Nanocomposite Matrix-Based Nanoproducts 251

Polymeric Nanomaterials

Biopolymer has hydrophilic nature, poor water vapor, oxygen, and other gas barriers
and poor mechanical properties [3, 11, 40]. Additionally, the properties and efficien-
cies of biopolymer films can be changed by making a bend as well as a nano-
composite mixture of polymer and a filler (a non-sized component such as nano-clay
or nano-sized silica) [3, 11, 40]. Nanotechnology has been used to produce
biocomposite materials to increase the toughness of traditional polymer matrices
[47]. The composites can be constructed from opposite changed counterparts
through electrostatic interactions.

Use of Nanomaterials in Environmental Health

(Nanoremediation)

Nanoremediation is the application of nanomaterials for environmental remediation.

The nanomaterials are used to treat groundwater, polluted air, sediments, soil, and
other contaminated materials. For example, titanium oxide (TiO2) is a good candidate
for wastewater treatment. Nanomaterials are widely used in various environmental
applications with a good success rate in cleaning up oil spills, water disinfectant, air
pollution control, and much more. Thus nanomaterials have given rise to a new
technology for the purpose of creating a healthy environment, that is, green nanotech-
nology [37]. It is defined as the science and technology used to introduce nanoparticles
into the environment with safe and premeasured harmful effects. Nanoremediation is
the application of nanomaterials for ecological remediation. It is being used to treat
wastewater, soil, and various other environmental contaminants.

Wood Polymer Nanocomposites

Wood polymer nanocomposites (WPNC) are a novel class of wood products with
significantly enhanced physical, biological, mechanical, and chemical properties
[7, 34]. Besides this, the wood fibers were also used as polymer reinforcing agents
to develop wood polymer composite (WPC). In the polymer matrix, the reinforcing
filler is pressed and molded in the presence of high temperature and pressure. Using
various additives such as binding agents, plasticizer, and flame retardant along with
nanoparticles helps to get the finished product tailor-made according to end use
application [2, 8]. For a certain period of time, the wood polymer nanocomposite in
powder form is put under pressure and temperature in the compression molding press.
The WPNC sheets are then cooled to obtain at room temperature [9]. The chemicals
used in WPNC formation have to be selected appropriately. The prepared WPNC
should not discharge any hazardous substances in the service period and at the end of
service life and can be recyclable or easily discarded at the end of service life.
252 I. F. H. AI-Jawhari

Bio-based Polymers

Wood polymer nanocomposites are typically prepared with thermoplastics or

thermosetting resin. The steady rise in crude oil prices, the problem of rising
large-scale waste, and the exhaustion of fossil fuels have caused attention in the
use of natural sources. A “greener” approach to these problems depends on the use
of renewable energy. Easily available are the biopolymers obtained from renew-
able agricultural feedstock [20, 46]. Since the biopolymers are extracted from
renewable resources, the degree of these polymers bio-degradability depends on
their chemical structure. The higher the biodegradability, the lesser the degree of
cross-linking. Such green polymers provide perceptible advantages over tradi-
tional polymers in terms of toxic gas effluence during their service state, energy
consumption when synthesizing, and waste output. Several of the desirable char-
acteristics of the biopolymers are biodegradability, high compatibility with other
polymers, and low melting temperatures.

Application of Wood Polymer Nanocomposites

WPNC has similar functions to solid wood but requires less maintenance and has a
much lower strength to – strength ratio and increased service life. It is an excep-
tional composite material, experimenting with high rates of expansion worldwide
and consisting in various proportions of wood, polymer, and other additives.
WPNC may be suitably used for indoor and outdoor applications. WPC are
produced commercially using radiation process from the mid-1969s. But very
few bio-based polymer wood nanocomposites have been developed, with most
of other technologies remaining in the stages of research and development. These
ecofriendly composites endow new substitutes with the designers to meet the
demanding requirements. WPNC products can be useful in telecommunications,
manufacturing, automotive, and other applications. The bio-based WPNC can be
used as an alternative to steel and fiberglass and can therefore be used as a
replacement for automotive parts, the most important market known for the use
of WPCs [5]. These composite materials have been used successfully in many
applications including the furniture industry and measurement engineering build-
ing industry, construction technologies automotive industry, flooring such as solid
plank flooring, laminated flooring, and parquet flooring fillets. The key advantages
of parquet floors are their abrasion resistance and toughness, which is useful in
commercial traffic installations. Although it has high costs, its ease of maintenance
and long service life have justified the high parquet flooring price over conven-
tional flooring. They can successfully make various sports equipment, such as
baseball bats, hockey sticks, golf heads, etc., and musical instruments such
stringed instrument finger boards, wind instruments, flute and trumpet mouth-
pieces, etc.
11 Polymer Nanocomposite Matrix-Based Nanoproducts 253

Conclusion

Polymer nanocomposite (PNC) is a promising material that is used in various

industrial applications and also in environment to remove pollutants. Cellulose is
one of the renewable resources which has been identified as a source of biopolymer
that can be used as a substitute for petroleum polymers. EPN have been successfully
synthesized from cellulose acetate, triethyl citrate plasticizer, and organically mod-
ified clay. Nanocellulose has been the topic of a broad range of research as
reinforcing agents in nanocomposites because of their nanoscale dimension, renew-
ability, availability, light weight, and low cost, and most importantly, they have
minimum environmental impact and have little effect on animal/human health.
Nanoremediation is the application of nanomaterials for environmental remediation.
The nanomaterials are used to treat groundwater, polluted air, sediments, soils, and
other contaminated materials. Nanomaterials are widely used in various environ-
mental applications with a good success rate in cleaning up oil spills, water disin-
fectant, air pollution control, and much more. Thus, nanomaterials have given rise to
a new technology for the purpose of creating a healthy environment, that is, green
nanotechnology.

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Polycarbonate Nanocomposites for High
Impact Applications 12
Vishwanath Dagaji Jadhav, Akhil Jayawant Patil, and
Balasubramanian Kandasubramanian

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
Vacuum Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
Role of Vacuum Pressure in Product Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
Mold Materials in Vacuum Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
Silicon Rubber Mold in Vacuum Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
Epoxy Resin Mould in Vacuum Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Master Model Manufacturing Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Three-Dimensional Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Stereolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Casting Materials in Vacuum Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Acrylonitrile Butadiene Styrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Polyurethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Polycarbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Processing Techniques for Manufacturing Polycarbonate Nanocomposites . . . . . . . . . . . . . . . . . . . 273
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277

V. D. Jadhav
Plastic and Polymer Engineering Department, Maharashtra Institute of Technology, Aurangabad,
Maharashtra, India
A. J. Patil
Department of Mechanical Engineering, Birla Institute of Technology and Science, Pilani, Goa,
India
B. Kandasubramanian (*)
Polymer Processing Laboratory, Department of Metallurgical and Materials Engineering, Defence
Institute of Advanced Technology (DU), Ministry of Defence, Pune, Maharashtra, India

© Springer Nature Singapore Pte Ltd. 2022 257

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_22
258 V. D. Jadhav et al.

Abstract
Polycarbonate, an engineering thermoplastic polymer, has sought attention in
recent times from industries to academia, owing to the presence of carbonate
group in its structure which imparts properties like high toughness, transparency,
and high impact resistance. The versatility of polycarbonate polymer can be
observed from its applicability from products in variegated sectors such as
automobile parts like helmets, bulletproof glasses in vehicles, bumpers, and
headlamp lenses, and it also finds applications in electronics such as capacitors,
etc. Contouring of these products is generally conducted by using conventional
methods like injection molding, extrusion molding, blow molding, transfer mold-
ing, and compression molding. Products fabricated via conventional methods
tend to exhibit process defects such as voids in matrix, sink marks, and burn
marks which can be overcome by adapting the alternative methodology – “vac-
uum casting,” which imparts the ability to manufacture products from a range of
materials such as thermoplastics, thermosetting resins, and elastomeric materials.
Vacuum casting has been adopted for manufacturing products like engineering
micro-gears, micro turbines, and pump impellers in automobile sectors. In this
review chapter, we present consolidated state of the art on vacuum casting while
simultaneously proposing the application of polycarbonate and its composites for
manufacturing products in engineering sectors with the aid of vacuum casting in
place of conventional methodologies for avoiding engineering drawbacks.

Keywords
Polycarbonate · Nanocomposites

Introduction

Over the few decades, polymer products and their processing have sought demand
due to their properties such as durability, light in weight, and low cost as compared to
metallic materials [1]. The fabrication of the polymeric products can be accom-
plished by techniques such as injection molding [2], extrusion molding, blow
molding, and compression molding [3] which are widely used in variegated sectors
for large-scale production in applications such as bumpers and helmets for the
automotives, rigid and hose pipes for household and agricultural sector, capacitors
and sockets for electrical as well as electronics sectors, etc. However, products
fabricated by these techniques can have defects like voids in matrix due to air
entrapment, sink marks on product surface due to less cooling time [4], and flow
marks on the product. One of the major drawbacks of these methodologies is their
selectivity to either thermoplastic or thermosetting resins, which imparts limitation
during the processing of polymers.
Vacuum casting can be one of the efficient alternatives for overcoming these
defects due to primarily utilization of vacuum during processing of polymers,
thereby giving high-quality finished products (Fig. 1). In this methodology, silicon
mold is produced on the basis of a master model which reflects the prototype
12 Polycarbonate Nanocomposites for High Impact Applications 259

Fig. 1 Vacuum casting setup

geometry through a replication [5]. Master models are created by rapid prototyping
techniques, such as three-dimensional printing and stereolithography [6]. Materials
used in this technique could be as polyester, polyurethane, epoxy resin, acrylonitrile
butadiene styrene, polycarbonate, as well as composites.
Polycarbonate has been extensively examined as an imperative polymer for
applied and fundamental research due to its various considerable properties, such
as ductility, higher glass transition temperature (~147
C), high impact resistance
(~600–820 J/m), optical transparency (n ~ 1.6), and blending ability with other
polymers, e.g., polyethylene, polypropylene, and polyethylene terephthalate. These
inherent properties of polycarbonate are attributed to the presence of carbonate
group (O(C¼O)  O) in its main chain structure. Polycarbonate shows higher
thermal stability due to the presence of rigid molecular backbone of bisphenol A
[7]. Consequently, polycarbonate has been widely exploited in applications like
bulletproof glasses, headlamp lenses for vehicle, electronics, architecture, and
aerospace.
Trautmann et al. have used vacuum casting for the fabrication of polycarbonate
material and demonstrated its use for a microneedle array of the prick test for testing
of skin allergic application [8]. Moreover, Tang et al. have used vacuum casting for
the fabrication of polyurethane material for micro-gears and studied the dimensional
accuracy required in micro-gear cavities as compared to master gear, and they
showed that gear manufactured by vacuum casting gives 51.7% more surface finish
than its master gear model, thereby implying that vacuum casting could be an
alternative for micro parts manufacturing without compromising the quality of
product [9]. Zhao et al. have used vacuum casting for the fabrication of micro-
riblets using silicone rubber on shark skin for drag-reduction applications via
unsaturated epoxy resin mold. Moreover, their calculations for drag-reduction rate
for water flow velocity, i.e., 0.45 m/s to 0.9 m/s, demonstrate the viability of vacuum
casting for practical drag-reduction applications in aircrafts and ships [10].
260 V. D. Jadhav et al.

This review aims to highlight the state-of-the-art progress in vacuum casting for
polycarbonate material; its fundamentals; the effects of processing parameters of
vacuum casting process such as mold temperature, rate of vacuum, and curing
temperature; as well as the benefits of vacuum casted products such as surface finish
and dimensional accuracy as compared to conventional methodologies. This review
also highlights viability of vacuum casting for the fabrication of polycarbonate
material and its composites reinforced with materials such as carbon fibers, pineap-
ple leaf fibers, glass fibers, Kevlar fibers, fly ash, calcium carbonate, montmorillon-
ite, and nano-materials such as carbon nanotubes and graphene and graphene oxide;
for the enhancement in properties such as electrical conductivity, impact strength,
Young’s modulus, tensile strength, flame retardancy, scratch resistance, etc.; and for
various engineering applications and materials for mold manufacturing such as
silicon rubber and epoxy resin in vacuum casting along with the case studies.

Vacuum Casting

Vacuum casting is a replicating method designated by utilization of a vacuum during

the processing of mold and casting of commodities. The molds are fabricated using
materials like silicon or epoxy resin. The casting materials used in vacuum casting
are engineering thermosetting resins such as epoxy resin, polyester, as well as
thermoplastics like acrylonitrile butadiene styrene, polypropylene, and polycarbon-
ate. The casting material and mold are processed in an inert environment under
vacuum chamber whose pressure is maintained at ~0.1 Pa [11] that helps in
degassing the mold and casting the material. The degassing of the materials helps
to enhance the properties and to remove air entrapped into molds which is one of the
drawbacks of conventional methodologies.
Vacuum casting is included in the indirect tooling methodology because it
exhibits the necessity of master model before fabrication of any commodity. This
master model is fabricated mostly by using the techniques like three-dimensional
printing and stereolithography; these processes are part of the rapid prototyping.
Rapid prototyping is a group of systems used to rapidly manufacture a master model
of a physical part or assembly using three-dimensional computer-aided design
(CAD) [12].
In the view of the aesthetic purpose offered by vacuum casting, it shows high
accuracy, dimensional and color stability, and finishing. Applying these strengths of
vacuum casting, fabrication of the composites for different applications has been
reported and tabulated in Table 1 and Fig. 2.

Role of Vacuum Pressure in Product Casting

Vacuum pressure present in chamber plays an important role for processing and
quality of the product. The rate and time of vacuum pressure depend on the casting
material, thickness of the product, etc. The low vacuum pressure can exhibit defects
12 Polycarbonate Nanocomposites for High Impact Applications 261

Table 1 Vacuum casted products and application

Serial
no. Materials Product Application References
1 Polycarbonate Microneedle array Biomedical [8]
2 Polyurethane EEG electrode Biomedical [13]
3 Polyurethane Micro-gear Automobile [9]
4 Silicon rubber Riblets on shark Aerospace, marine [10]
skin application
5 Polyurethane Turbocharger Household and [14]
impeller electronics sector
6 Acrylonitrile Connectors, Electronics and [12]
butadiene styrene Battery cover telecommunication
8 Polyester Impeller Mechanical [15]

Fig. 2 Vacuum casted products

like shrink marks and insufficient injection; moreover, air pocket and spilling can
occur due to high vacuum pressure [16].
During the casting and filling of mold by casting material, it is controlled by
filling speed, time, and speed of pressure; whenever there is a longer pressure time,
there is a small pressure speed. Pressure time controls the pressure speed and filling
speed, and the flow of filling material which is viscous in nature is calculated by
using the following equation [17]:
Formula for viscous flow of filling material
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
" #

1=k u
u 2K RT
K1
Q ¼ APa
P t : 1
P K
ð1Þ
Pa K1 M Pa

Flow formula under vacuum condition

262 V. D. Jadhav et al.

PV
Q¼ ð2Þ
t
Differential of Eq. (2)

VdP
dt ¼ ð3Þ
Q
Both sides integrated for getting formula (4) of airtime during vacuum process

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

K1
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

K1
V 2K M P1 K
P K
t¼ : 1 1 ð4Þ
A K  1 RT Pa Pa

where

P1 ¼ initial pressure
P ¼ pressure after gas filling into vacuum
M ¼ gas molar mass
V ¼ vacuum container volume
T ¼ gas temperature in formula
t ¼ filling time of the vacuum
R ¼ gas constant
A ¼ cross-sectional area
K ¼ adiabatic exponent
Pa ¼ atmospheric pressure

Zang et al. have fabricated motorcycle headlamp shells by using vacuum casting
and observed the quality of product for pressure time of 5 and 10 sec respectively,
wherein they observed that the product by 5 sec pressure time in which mold was not
filled properly exhibited defects such as short shot, which was overcome by 10 sec of
pressure time [17].

Mold Materials in Vacuum Casting

Silicon Rubber Mold in Vacuum Casting

Silicones, otherwise called as polysiloxanes, are polymers made up of repeating

units of siloxane, which is utilized in the variegated sectors such as automotives,
waterproof connectors, hoses, gaskets, sportswear, footwear, electronics, and as
mold materials. In vacuum casting process, the applications are attributed to the
properties of silicon rubber such as excellent resistance to higher temperatures
(37
C to 260
C), elongation, tear strength (~25 to 40 N/mm), compression set
(60
C to 250
C), and tensile strength (2.6 MPa) [18], as compared to conven-
tional rubbers like natural rubber, styrene butadiene rubber, etc. The drawbacks
12 Polycarbonate Nanocomposites for High Impact Applications 263

which occur in the organic rubber are low ozone resistance and thermal stability and
aging factor.
The prevalent properties of silicon rubber have made it feasible to be employed as
a material for mold in vacuum casting. Silicon rubber has two classes with a
perspective of industries: high-temperature vulcanizing silicon rubber (~70
C),
also termed as malleable silicone rubbers because of its high viscosity in uncured
state, and room temperature vulcanizing silicon rubber (28–40
C), also named as
pourable silicone rubbers because of presence in liquid state owing to its low
viscosity. Room temperature vulcanizing silicone rubbers are commonly used in
fabrication of molds [19]. Molds manufactured by silicon rubber have the capability
for the processing of thermoplastics and thermosetting resins. On the view of the
productivity, it can produce up to 20 pieces, which depend on the surface finish of
product [20].

Epoxy Resin Mould in Vacuum Casting

Epoxy resins are low or high molecular weight polymers which ordinarily contain at
least two epoxide groups. The epoxide group is also sometimes called as glycidyl or
oxirane group, which is the thermosetting polymer and widely used in the aerospace
application, surface coating, as well as for fabrication of the mold in the vacuum
casting.
Vacuum casting process starts with a master model which is fabricated with the
help of the three-dimensional printing and stereolithography [11]. The master model
is buried in a clay or plaster up to the parting line in the master model. Alternatively,
one can use a prototype model for the first half of the part. After coating the master
model with a release agent, epoxy resin is poured into the mold box and then cured.
The same procedure is repeated for the second half. Runners and gate are added to
the master model prior to casting or machined after casting. Air vents are included in
the mold because thermosetting resin releases the gases when they are processed.
Epoxy mold can be kept at low injection and packing pressure with low infusion and
pressing weights. Contingent upon the unpredictability of the part and the material,
the mold life is from 50 to 500 pieces [21].

Master Model Manufacturing Technique

Three-Dimensional Printing

Three-dimensional printing comes under rapid prototyping methodology, which was

patented by Sachs et al. in the year 1994. In three-dimensional printing, the model is
sliced into two-dimensional layers via computer controlled program [22]. The parts
are built using the powdered material, which is spread in the form of the layer
structure, and the hardener is added to the powdered material by drops like in an
inkjet printer. Currently used three-dimensional technologies used thermoplastic
264 V. D. Jadhav et al.

polymer filaments for precision accuracy and dimensional stability. Three-

dimensional printing has the capability to fabricate products of engineering plastics
such as polylactic acid, acrylonitrile butadiene styrene, polycarbonate, metal, metal-
ceramic, and composite. This technique can be applied in areas like designing of
complex products, biomedical sector for bio-printing tissue and organ, anatomical
model for surgical preparation, drug delivery devices. Along with the master model
for vacuum casting, three dimensional printing utilised in various sectors due to its
advantages like costly mould is not required, milling is not required, recycle material
can be use, automated manufacturing [23].

Stereolithography

Stereolithography (SL) is the first rapid prototyping technique invented in the year
1984 by Charle Hull, which is the first commercially available prototyper. Stereo-
lithography is a technique that has the capability to fabricate three-dimensional
prototype models by using designing software such as computer-aided design and
computer-aided modeling [24]. Materials used in stereolithography technique are
polymeric resinous materials which are classified into two categories such as radical
reaction type like urethane acrylate and cation reaction type like epoxy resin. They
are widely used, because it shows high accuracy and dimensional stability in
products. Resins used in stereolithography need low viscosity and hardening agents
for better processability. Curing time is important to complete the product in a
minimal period of time [25], which are cured using laser beam of ultraviolet rays
or LED by which it forms the layers. Stereolithography technique is used in various
applications such as master model in vacuum casting, three-dimensional copy for
shoe model, prototyping diecast parts, investment casting master models, and
biomedical parts [26].

Casting Materials in Vacuum Casting

Acrylonitrile Butadiene Styrene

Acrylonitrile butadiene styrene (ABS) is an engineering thermoplastic, which is

synthesized by the polymerization of styrene, an organic compound derived from
benzene, and acrylonitrile, a colorless volatile liquid, in presence of polybutadiene a
synthetic rubber. The monomer proportion of styrene (~40–60%), acrylonitrile
(~15–35%), and butadiene(~5–30%) in acrylonitrile butadiene styrene can vary
from grades to grades. Acrylonitrile butadiene styrene has excellent properties
such as higher impact strength [27], toughness, and resistance to chemicals.
Owing to the properties, acrylonitrile butadiene styrene is used in various sectors
such as pipes, safety helmets, telephone switchboard panels, automobile panels, and
submersible pumps. The ABS materials for various applications can be fabricated
12 Polycarbonate Nanocomposites for High Impact Applications 265

using injection molding, extrusion molding, blow molding, as well as rapid pro-
totyping technique such as vacuum casting (Fig. 3).
Howe et al. have fabricated connector used in telecommunication switching
systems by using vacuum casting of acrylonitrile butadiene styrene, and the
comparative study for the stereolithography and the vacuum casting with the
view of the time to fabricate the article was reported. They observed that result
time required for the fabrication of the product in stereolithography was compar-
atively more than vacuum casting. They also concluded that stereolithography
cannot be used directly due to its demerits such as short shot and flashes on the
surface of the product [28].

Polyurethane

Polyurethanes (PU) are polymerized using the isocyanate and diol compounds,
which form a linkage of the urethane group ((-NH-C(¼O)-O-) [29]. They are utilized
in applications such as footwears, seals and gasket in the automobile sector, foams in
water filters, and nonwoven medical covers. PU exhibits these multifunctional
applications due to properties such as hardness (20 shore A – 80 shore D), high
load-bearing capacity, elongation (640%), impact resistance (1.04 kJ/m2), and tensile
strength(~38 MPa) (Fig. 4).
Seet et al. have fabricated the micro-spike EEG electrode by using vacuum
casting of polyurethane via master model, where they observed an improvement in
the sensing performance of the electrode, along with higher efficiency [13].

Fig. 3 Structure of acrylonitrile butadiene styrene

O H O H H

C N C N C O C C O

H H H H H
n

Fig. 4 Structure of polyurethane

266 V. D. Jadhav et al.

Fig. 5 Structure of
polycarbonate

Polycarbonate

Polycarbonate is polymerized using bisphenol A and phosgene [7], via ester

exchange and phosgenation process. Polycarbonate exhibits properties like high
melting point (~250
C) and impact strength due to the rigid backbone of bisphenol
A [7]; the polar group present in polycarbonate imparts chemical solubility. It also
exhibits higher optical transparency, due to internal transmission of light nearly same
as glass. Polycarbonate possesses drawback such as low scratch resistance; however,
its properties can be enhanced with the aid of inorganic fillers and fibers via
fabricating into nanocomposites, which has been studied by various researchers
(Fig. 5).

Fillers in Polycarbonates

Fly Ash
Fly ash is by-product as a result of the combustion of the coal in thermal power
plants, which is generated in an enormous amount every year. As per a survey, India
produces ~112 million tons of fly ash every year [30]. This fly ash shows some
adverse effect on the environment like contamination of the water by the presence of
the heavy metals such as copper, arsenic, lead, zinc, mercury and uranium that are
hazardous to the health of humans as well as animals. The aim of minimizing as well
as disposing enormous fly ash is carried out via utilization in various sectors like
road construction (~35–40%), cement manufacturing (~35%), lightweight blocks
(~25%), and bricks manufacturing (~40–70%), for polymeric composites, and in
electrical and household applications such as fire retardancy.
Makoto et al. have studied the flame retardancy of polycarbonate with fly ash as a
filler and concluded that the presence of the hydroxyl group in the fly ash enhances
flame retardancy, wherein thermal degradability was measured with the help of
thermal gravimetric analyzer (TGA) which shows an augmented resistance to
degradability; also they attributed the thermal stability to hydrogen bond between
the fly ash and carbonate group. They also reported flexural strength and observed
that the flexural strength is directly proportional to weight loading of fly ash.
Flexural strength of polycarbonate/fly ash composite with respect to 10 wt% and
25 wt% was found to be ~90 MPa and ~ 99 MPa showing an enhancement of 10%
compared to pristine polycarbonate [31].
12 Polycarbonate Nanocomposites for High Impact Applications 267

Fig. 6 Structure of calcium

carbonate O

-
+2 C O
Ca

-
O

Calcium Carbonate
Biominerals are present in an enormous quantity in the environment, which are
observed in the form of hills, caves, and rocks. Calcium carbonate (CaCO3) is one of
those biominerals, which endures in the form of calcite rock. Calcium carbonate is
exploited in various sectors from the last few decades, and due to its properties as
well as its availability in extensive amount, they are employed in various applica-
tions such as construction industries for self-compacting concrete, asphalt mixture in
road construction, food packaging, as well as polymeric composites [32]. Calcium
carbonate has been used as an inorganic filler for polycarbonates for enhancing the
properties of the material such as flame retardancy, tensile strength, bending mod-
ulus, and impact strength (Fig. 6).
Wang et al. have proven that mechanical properties of polycarbonate can be
enhanced by incorporation of calcium carbonate (CaCO3). The tensile strength,
i.e., ~ 91.29 MPa and ~ 87.20 MPa for pristine polycarbonate, was augmented up
to ~4% for polycarbonate/calcium carbonate composite as compared to pristine
polycarbonate. They also examined elongation at break for polycarbonate/calcium
carbonate composite which was found to be 63.28% and 165.06% for pristine
polycarbonate. Considering the presence of calcium carbonate aid leads to increase
in the brittleness in the composite, thereby decreasing elongation at break [33].
Charde et al. have fabricated polycarbonate and calcium carbonate composite and
examined results for glass transition temperature and observed ~145
C for poly-
carbonate/calcium carbonate composite and ~ 150
C for the pristine polycarbonate.
They attributed the decrease in glass transition of calcium carbonate particles in
polycarbonate. They also studied load-bearing capacity for glassy, rubbery, as well
as transition region, wherein glassy region augmented ~12% load-bearing capacity
than that of pristine polycarbonate. The observed that scratch resistance of polycar-
bonate can be overcome in polycarbonate/calcium carbonate composite [34].

Montmorillonite
Montmorillonite is a naturally occurring mineral, in which phyllosilicate group is
present, and is found mostly in rocks, sediments, and soils. Considering the avail-
ability, montmorillonite is utilized in various applications such as soil additive in the
drought-prone areas, a binder for the mud, and heavy metal remover for water and
extensively used for polymeric composites [35]. Montmorillonite shows
268 V. D. Jadhav et al.

Table 2 Polycarbonate properties with fillers

Serial Polymeric
no. material Fillers Properties Result References
1 Polycarbonate Fly ash Flame retardancy Improved [31]
Flexural strength Improved
(99 MPa)
2 Polycarbonate Calcium Tensile strength Improved [33, 34]
carbonate Elongation at break Improved
Load-bearing Improved
capacity (12%)
Scratch resistance Improved
3 Polycarbonate Montmorillonite Young’s modulus Decrease [39]
Storage modulus Decrease [38]
(816Mpa)
Onset temperature Improved
(537
C)
Heat stability

improvement in optical and thermal properties as well as mechanical properties for

the polymer composite, which is attributed to the strong interaction between the
montmorillonite and the polymeric matrix when incorporated [36].
Chow et al. have incorporated polycarbonate with montmorillonite and observed
thermal stability for the two-phase transition, via glassy phase with temperature of
50
C100
C and rubbery phase with temperature of 150
C which showed that
storage modulus is inversely proportional to weight loading of montmorillonite,
leading to decrease in stiffness of the composite. They also tested storage modulus
for the composite for 3 wt% of montmorillonite incorporated with polycarbonate and
observed an onset temperature of ~533 °C and storage modulus of ~715 MPa at
(30
C). Similarly, 10 wt% of montmorillonite resulted in ~537
C of onset temper-
ature and ~ 816 MPa of storage modulus for 30
C [37]. Huang et al. have observed
that Young’s modulus value is inversely proportional to the percentage of montmo-
rillonite for polycarbonate/montmorillonite composite [38] (Table 2).

Fibers in Polycarbonate

Kevlar Fiber
Kevlar (-CO-C6H4-CO-NH-C6H4-NH-) is a synthetic aramid fiber, which was
introduced by DuPont in the year 1970, which is polymerized by using 1, 4-phenyl-
ene-diamine or para-phenylenediamine and terephthaloyl chloride. These fibers are
manufactured by extrusion process with the help of small hole called as spinnerets
which forms a filaments. Spinnerets are classified according to wet, dry, melt, and gel
spinning. The filament fabricated by these techniques is Kevlar fiber, available in
eight grades such as Kevlar 29, Kevlar 49, Kevlar 100, Kevlar 129, Kevlar AP,
Kevlar XP, Kevlar KM2, and Kevlar 149 [40]. They exhibit properties like higher
tensile strength (~2.7GPa), higher stiffness, higher Young’s modulus (~120GPa),
12 Polycarbonate Nanocomposites for High Impact Applications 269

Fig. 7 Structure of Kevlar fiber

relative density (~1.44 gm/cm3), low electrical conductivity, high dimensional

stability [41], and high strength to weight ratio (~5) times in comparison with
steel, and due to their versatile properties, they are used in various sector such as
defense for armor products like helmets and ballistic vests, gloves and jackets for the
protection of user from the cut and abrasion, rope and cables, power transmission
belts, cycle tires for resistance against puncture, as well as polymeric composites to
enhance properties of matrix materials. The incorporation of the polycarbonate with
Kevlar fiber shows the enhancement in the properties like ballistic protection and
increase in crystallization (Fig. 7).
Raerinne et al. have fabricated polycarbonate/Kevlar fiber composite which
resulted in improved ballistic protection of ~5.7% to that of pristine polycarbonate
[42]. Blumentritto et al. have concluded that properties of composites show more
dependency on the fibers and lesser on the matrix where fibers act as a primary load-
bearing element [43]. Takayanagi et al. have fabricated polyethylene/Kevlar com-
posite and contemplated thermodynamic properties such as crystallization which
was ~36% compared to pristine polyethylene and also concluded that these proper-
ties can be improved by the incorporation of Kevlar fibers into the polyethylene
matrix [44].

Carbon Fiber
Carbon fibers are the synthetic fibers, which is mostly fabricated by using a colorless,
volatile liquid acrylonitrile (CH2CHCN) and polyacrylonitrile precursor which
involves oxidative stabilization and carbonization [45]. Stabilization is important
for balancing quality of the fiber. The cost of carbon fibers is high due to raw
materials used like acrylic fiber as well as processing methodology. To overcome
this drawback, cheaper commercial acrylic fibers are utilized for the fabrication of
the carbon fibers nowadays. These are fabricated by using three steps such as
pretreatment stabilization (300
C), carbonatization at 1700
C, and graphitization
at higher temperature (2800
C); fibers fabricated by these techniques exhibit
properties such as electrical conductivity, high tensile strength (~600 MPa), chemical
stability and corrosion resistance, good processability, and recyclability. Considering
their properties, they are used in applications such as lightweight automotive parts,
manufacturing of parts in aircrafts, wind turbine blades, conductive plastics for the
electrical and electronic applications, as well as for the manufacturing of the
270 V. D. Jadhav et al.

polymeric composites [46]. Polycarbonate is one of the materials in which carbon

fibers can be incorporated for the enhancement in mechanical properties like tensile,
impact strength, as well as rheological properties.
Haung et al. have fabricated polycarbonate/acrylonitrile butadiene styrene/nickel
coated- carbon fiber composite, in which they observed increase in tensile strength
with increase in carbon fiber loading and also observed that electromagnetic inter-
ference shielding was increased along with electrical conductivity [47].
Carneiro et al. have fabricated polycarbonate with the carbon fiber which
exhibited improved storage modulus (39%) and yield strength (17%) as compared
to pristine polycarbonate. They also observed a decrease in impact strength due to
poor adhesion of carbon fiber with polycarbonate matrix. Viscosity was examined at
a typical shear rate of 1–103 s1 where they observed a decrease in viscosity with the
incremented loading of carbon fiber [48].

Glass Fiber
Glass fiber is one of the synthetic fiber, which is conventionally manufactured by the
silica (SiO2) sand, by melting at ~1720
C, followed by fiberization, which is a
combination of extrusion and attenuation. Then chemical coating is done followed
by drying and packing of the manufactured fibers which are classified according to
their compositions like E-glass which is manufactured by alumino-borosilicate glass
with less than 1%w/w of alkali oxides resulting in properties like high tensile
strength (~3445 MPa) and cheaper cost; it is mostly used in reinforcing plastics.
The S-glass fiber contains amino silicate glass with the presence of higher concen-
tration of magnesium oxide which increases the tensile strength of fiber
(~4890 MPa) [49]. C-glass fibers are with high concentration of boron oxide
which results in properties like corrosion resistance, high tensile strength
(~3310 MPa), density (~2.52gm/cm3), and Young’s modulus at ~68.9GPA. The
A-glass fiber doesn’t contain boron oxide, which results in properties like density
(~2.70gm/cm3), Young’s modulus(~73.1GPa), lower thermal conductivity
(~0.05 W/m·K) [50], nonflammability, heat insulation, and good sound insulation.
Considering their overall properties, glass fibers are with polymeric materials by
forming reinforced laminates which are used in marine applications, tanks, vessels,
boat hulls, and surfboards.
Georgescu et al. have fabricated polycarbonate and polyamide, reinforced with
glass fibers where they observed a tensile strength of 40 N/mm2 and 47 N/mm2 for
loading (30 wt%) of glass fibers and 5 wt% compatibilizer. Melt flow index for the
composite was also observed where they concluded that decrease in flow occurs with
the increase in weight of the polycarbonate [51].
Streib et al. had patented work on polycarbonate and glass fiber composite in
which they observed impact strength of 29,000 and 37,000 kp cm/cm2 for 0 and 10%
of glass fibers incorporated with polycarbonate matrix, respectively [52].

Pineapple Leaf Fiber

Every year enormous amount of pineapple leaf fibers are produced, but the very
minimal amount of them is used as feedstock for the generation of the energy.
12 Polycarbonate Nanocomposites for High Impact Applications 271

Pineapple leaf fiber is a natural fiber which belongs to the Bromeliaceae family,
exhibiting a ribbonlike structure and vascular bundle system present in fibrous
cells [53]. Pineapple leaf fiber exhibits the properties such as good color stability,
high tensile strength (~413–1627 MPa), and elongation at break (3%). Considering
their properties, pineapple leaf fiber can be used for various sectors like textile,
conveyor belt cord, automotive, building and construction material, as well as the
extraction of nano-cellulose which was studied by Cherian et al., who reported a
81.75% of cellulose extraction from pineapple leaf fiber for biomedical applica-
tions. Pineapple leaf fiber is also used with a polymeric matrix to fabricate a
composite for improved mechanical properties and has also been explored with
thermosetting resin, engineering thermoplastic, natural rubber, etc., for various
mechanical applications.
Threepopnatkul et al. fabricated a composite of pineapple leaf fiber and polycar-
bonate and observed that Young’s modulus of the composite is directly proportional
to that of the weight of pineapple leaf fiber. Young’s modulus was found to be
1120 MPa for pristine polycarbonate which was augmented to 1690 MPa for
pineapple leaf fiber/polycarbonate composite, along with improvement in thermal
stability with a (20 wt%) loading [54] (Table 3).

Table 3 Effect on properties of polycarbonate by incorporation of fibers

Serial Polymeric
no. material Fibers Properties Enhancement References
1 Polycarbonate Kevlar Ballistic protection 5.7% [42]
rate (259 m/s
velocity)
Polyethylene Crystallinity 1% [44]
2 Polycarbonate Carbon Viscosity reduces [48]
fiber tensile strength (39%, 17%)
(modulus, yield)
Storage modulus Improved
3 Polycarbonate Glass Tensile strength 40 N/mm2 [51]
and polyamide fiber
Polycarbonate Impact strength Improved [52]
4 Polycarbonate Pineapple Young’s modulus 1690 MPa [54]
leaf fiber Thermal stability Improved
5 Polycarbonate Jute fiber Tensile strength 63.1 MPa [55]
Bending strength 87.15 (MPa)
Shear strength 5.26 MPa
6 Polycarbonate Bamboo Tensile strength 9.6 MPa [56]
fiber
7 Polycarbonate Flax fiber Glass transition 60
C [57]
and polylactic temperature
acid Degree of 6.87%
crystallization
272 V. D. Jadhav et al.

Nanocomposites of Polycarbonate

Graphene and Graphene Oxide

Graphene and graphene oxide are synthesized by methodologies derived by Brodie
[58], Staudenmaier, and Hummer in which oxidation reaction and two-dimensional
crystallographic nature lead to superior properties. They exhibit properties such as
high electrical conductivity (~7200 Sm1), high tensile strength (~130GPa), and
high transparency (~97%). In the view of their excellent properties, they are utilized
in various applications such as transparent conductive films, sensors, fuel cells, and
wastewater filtration [59]. Graphene is also used as magnetic materials for absorbent
for wastewater filtration. Considering two-dimensional layer structure, surface area,
and pore volume, it is also used in biomedical applications. Chaung et al. reported
that graphene can be utilized in a therapeutic modalities for cancer treatment and
drug delivery system [60], along with electronic applications such as ultra-capacitors
as well as for enhancement in the properties of the polymeric material such as
polycarbonate (Fig. 8).
Kim et al. have fabricated graphene/polycarbonate composite, in which tensile
strength was observed for 10 wt% of graphite resulting in ~80% increase and ~60%
stiffness. They also observed an increase of ~150% in the Young’s modulus by
incorporation of the 15 wt % of graphite in polycarbonate [61]. Yoonessi et al.
studied the graphene/polycarbonate composite which was fabricated by emulsion
mixing and solution blending methodology and reported a conductivity of 0.226 S/
cm for 1.1 vol% and 0.526 S/cm for 2.2 vol% loading of graphene [62]. Mahendran
et al. have fabricated a sheet of graphene oxide reinforced with polycarbonate in
which they observed that sheet exhibited excellent bacteriostatic effect against
E. coli and S. aureus; further they concluded that it can be used for the biomedical
as well as for the food packing [63].

Carbon Nanotubes
Chemistry of fullerene was developed in mid of the 1980s, by Smalley and
coworkers. Fullerene is a cage-like structure of the carbon with the hexagonal and
pentagonal faces. These are classified into two classes, i.e., single-walled carbon
nanotube and multi-walled carbon nanotubes. Single-walled nanotubes have single
sheet of graphite wrapped into the tube, which are in metallic or semiconductor

Fig. 8 Structure of graphene

12 Polycarbonate Nanocomposites for High Impact Applications 273

Table 4 Effect on properties of polycarbonate by nano-additives

Serial Polymeric
no. matrix Nano-additives Properties Enhancement References
1 Polycarbonate Graphene/ Tensile strength 80% [61–63]
graphene oxide Young’s 150%
modulus
Stiffness 60%
Electrical 0.512 S/cm
conductivity
Antibacterial Improved
properties
2 Polycarbonate Carbon Viscosity Two decades [67]
nanotubes Dielectric Seven
strength decades

which depends on their chiral angle between hexagon and tube axis [64]. Multi-
walled nanotubes are the compilation of nanotubes nested like tree trunk, which are
synthesized by using chemical vapor deposition process which gives high purity at
low cost [65]. Carbon nanotubes exhibit the superior properties such as extremely
higher elastic modulus (1TPa) [64], higher strength (10–100) times than strongest
steel, superconductivity, high stability, and light in weight which makes carbon
nanotubes an ideal material for their applications. Carbon nanotubes are widely
used in various applications such as emitters for vacuum microelectronic device,
cathode ray lighting elements, gas discharge tubes in telecom network, nanosized
electronic devices, as well as electromagnetic interference shielding. Arjmand et al.
studied polycarbonate/carbon nanotube composite, where they observed an
improved shielding with absorption and refraction and also observed higher perco-
lation thresholds, lower critical exponents, and electrical resistivity due to increased
alignment in carbon nanotubes [66].
Potschke et al. have studied rheological as well as dielectric properties for the
carbon nanotube/polycarbonate composite and contemplated melt rheology for
the storage modulus with the incorporation of carbon nanotubes leading to
increase in storage modulus as well as the viscosity for about two decades.
They observed the DC conductivity for the 1wt % loading of carbon nanotubes
at room temperature which was found to be increased for more than seven
decades [67] (Table 4).

Processing Techniques for Manufacturing Polycarbonate

Nanocomposites

The comparison of vacuum casting with existing polymer processing conventional

methodologies such as injection molding, extrusion molding, reaction injection
molding, compression molding, and resin transfer molding with their defects and
advantages is tabulated in Table 5.
 274

Table 5 Comparison of vacuum casting with conventional methodologies

Serial Processing Additives/ Mechanical
no. technique Materials polymer properties Defects Advantages References
1 Injection Polycarbonate Carbon Bending Flow and sink marks, Short cycle time, good surface [27, 61,
molding nanotubes, strength voids in product, finish 68, 69]
graphene Tensile warpage, weld lines.
strength
(~80%)
Young’s
modulus
(~150%)
Acrylonitrile Tensile yield
butadiene (25%)
styrene Improved
Izod impact
strength
2 Extrusion Polycarbonate Graphene, Tensile Central bursting, Continuous segment products, [70, 71]
molding carbon modulus extruder surging, hollow article [72]
nanotubes Tensile thickness variation,
strength diameter variation
Polyhedral Yield strength
oligomeric Yield strain
silsesquioxane Modulus
3 Reaction Polyurethane Polyester Tensile Slow in cycle time, voids Eliminated shrinkage [73],
injection strength in matrix as well as
molding (improved) product
Impact
strength and
hardness
(improved)
V. D. Jadhav et al.
 12

4 Vacuum Epoxy resin Tensile Warpage. Good dimensional and color [21]
casting strength stability, low in tooling cost,
(990.66 MPa) low shrinkage, voids-free
Ultimate product
strain
(0.0618)
Polyurethane Stiffness [14]
(32.05 N/
mm)
Ductility
Stiffness
(~11%)
Tensile
strength
(~36%)
Unsaturated Tensile [74]
polyester strength
resins (92.4 MPa)
Brinell
hardness
(14.4 kJ/m2)
5 Compression Polyester Sisal fiber Tensile Blisters, burn marks, sink Low tooling cost; does not [75]
Polycarbonate Nanocomposites for High Impact Applications

molding (30 vol%) strength marks require gate, sprue, and runner
(~ 46 MPa)
Young’s
modulus
(~1283 MPa)
(continued)
275
 276

Table 5 (continued)
Serial Processing Additives/ Mechanical
no. technique Materials polymer properties Defects Advantages References
Elongation at
break (9%)
6 Resin transfer Polyester Sisal fiber Tensile Micro voids, dry spots Capability to fabricate complex [75]
molding (30 vol%) strength geometrical shapes, color
(~51 MPa) stability in products
Young’s
modulus
(~1317 MPa)
Elongation at
break (10%)
V. D. Jadhav et al.
12 Polycarbonate Nanocomposites for High Impact Applications 277

Conclusion

In the present chapter, we have reviewed the vacuum casting and polycarbonate
as a casting material with its composites. The fundamentals of vacuum casting
include mold materials, and the role of vacuum pressure in product casting and
casting materials has also been explained. Polycarbonate has been focused due to
its versatile properties like high tensile strength, high impact resistance, tough-
ness, etc. Further, we have also reviewed the additives like calcium carbonate,
montmorillonite, fly ash, fibers like Kevlar, glass, carbon, pineapple leaf fiber,
and nano-additives such as graphene/graphene oxide and carbon nanotubes help
in enhancement of properties of polycarbonate like mechanical, rheological, and
electrical properties. The application of vacuum casted products in various
sectors like automobile, mechanical and electronics, and telecommunication
along with comparison of conventional polymer processing techniques such as
injection molding, extrusion molding, and reaction injection molding has also
been studied.

Important Websites

https://www.mcam.com/products/engineering-plastics/
https://www.dupont.com/brands/kevlar.html
http://binaniindustries.com/our-business-areas/glass-fibre/
https://www.renishaw.com/en/renishaw-vacuum-casting-technology-accelerates-
innovation-for-automatic-juicer-manufacturer-zumex%2D%2D42466
https://www.nanowerk.com/nanotechnology/introduction/introduction_to_nanotech
nology_22.php

Acknowledgment The authors would like to thank Dr. Surendra Pal, Vice-Chancellor, DIAT
(DU), Pune, and Mrs. Suranjana Mandal, Vice-Principal, MIT, Aurangabad, for constant encour-
agement and support. Mr. Prakash Gore, Mr. Ramdayal Saran, Mr. Raviprakash Magisetty, and
Mr. Jay Korde are also acknowledged for continuous technical discussions and support.

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 Part VI
Consumer Nanoproducts Based on
Bionanoceramics and Bionanocomposites
Nanoproducts Based on Shape Memory
Materials 13
Ali Nabipourchakoli and Baode Zhang

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
Shape Memory Composites, an Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Shape Memory Alloy Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Shape Memory Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Sensor Applications of Shape Memory Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Some Companies with SMP Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
Guangzhou Manborui Material Technology Co. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
Cornerstone Research Group Co. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
MedShape Co. (https://www.medshape.com) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Shape Memory Medical (https://www.shapemem.com) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Shandong Yabin Medical Technology Co. Ltd. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
(http://m.en.crossnt.com/company-374.html) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Asahi Kasei Corporation (https://www.asahi-kasei.co.jp) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Changchun Foliaplast Bio-Tech Co., Ltd. (http://foliaplast.globalchemmade.com) . . . . . . . 328
Composite Technology Development Co. Ltd. (https://www.ctd-materials.com) . . . . . . . . . . 329
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Abstract
To overcome the shortcomings of neat shape memory materials (SMMs) and to
expand the scope of its applications, researchers found that fabricating composite
materials based on SMMs is an adequate alternative method. The composite
materials are made up of two or more materials, which keep as individual
components. And composites are preferred to have all excellent physical
A. Nabipourchakoli (*)
Nuclear Science and Technology Research Institute, Tehran, Iran
e-mail: [email protected]; [email protected]
B. Zhang
Liaoning Shihua University, Fushun, Liaoning, China

© Springer Nature Singapore Pte Ltd. 2022 285

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_24
286 A. Nabipourchakoli and B. Zhang

properties of their components. For the traditional shape memory material com-
posites (SMMCs), the matrix of SMMCs keeps the shape memory effect, and the
reinforcement fillers gradually increase the physical and mechanical properties.
More interestingly, fillers can also enable SMMCs multifunctionalities in the
shape recovery process. The fillers that are made of nanomaterials and fibers
can be designed as an energy converter to trigger thermally responsive SMM
matrix. The real driver of SMMCs market is developing the utilization of shape
memory materials for medical applications. The second use of SMMCs is in the
structure of self-fixing solid, froths for structure protection. In this chapter, the
research results on SMMCs production and application of SMMCs are presented.
In addition, the global market for SMMCs is evaluated.

Keywords
Shape memory material · Shape memory effect · Poly(L-lactide) · Thermoplastic
polyurethane · Poly(ε-caprolactone) · Polymer blends · Shape memory behavior ·
Shape memory polymer · Carbon nanotubes · Shape fixity · Shape recovery ·
Nanocomposites · Nanomaterials · Shape memory material market

Abbreviations
CMF: Cellulose microfiber
CNC: Cellulose nanocrystal
CNF: Cellulose nanofiber
CNP: Cellulose nanoparticle
CNT: Carbon nanotube
EVA: Ethylene-vinyl acetate
EVA: Ether-vinyl acetate
GO: Graphene oxide
MCC: Microcrystalline cellulose
MTM: Montmorillonite (plate-shaped clay)
MWCNTs: Multiwalled carbon nanotubes
NMs: Nanomaterials
NPs: Nanoparticles
NSMs: Nanostructured materials
NPs: Nanoparticles
PEEK: Poly(ether ether ketone)
PTFE: Polytetrafluoroethylene
PCL: Poly(ε-caprolactone)
PMMA: Poly(methyl methacrylate)
POSS: Polyhedral oligomeric silsesquioxanes
PEGMA: Poly(ethylene glycol)mono-methylether-monomethacrylate
PLACL: Poly(L-lactide-co-ε-caprolactone)
rGO: Reduced graphene oxide
SMP: Shape memory polymer
SWCNTs: Single-walled carbon nanotubes
13 Nanoproducts Based on Shape Memory Materials 287

SME: Shape memory effect

TPU: Thermoplastic polyurethane

Introduction

Shape memory materials are the sort of promising upgrades-responsive materials;

they can “remember” a naturally visible (changeless) shape, be controlled and
“fixed” to an impermanent and lethargic shape under explicit states of temperature
and stress, and after that later unwind to the first, tranquil condition under warm,
electrical, or ecological direction. Many types of artificial materials can achieve
shape change under environment stimuli, including metal and nonmetal alloys,
polymers, and ceramics, although each material has its unique mechanisms and
properties. These materials were termed shape memory materials.
The multiple shape memory effect (SME) is meant for that between the pro-
grammed (temporary) shape and the permanent shape; there are one or more
intermediate stable shapes, which can be precisely controlled, during shape recovery.
The multiple SME can be achieved in any SMM even based on only one transition,
which could be the glass transition or melting/crystallization transition. Thus, at least
one intermediate shape, i.e., the triple-SME, can be easily obtained within a normal
transition temperature range of polymers by step-by-step programming at different
temperatures during cooling. From application point of view, the advantage of a
narrow temperature range between the intermediate shape and that of permanent in
the triple-SME is apparent in, for example, anti-counterfeit labels, as now it is
possible to use the intermediate shape as a kind of watermark, which cannot be
seen if overheated.
The real driver of the shape memory polymer (SMP) market is developing the
utilization of SMP for shrewd medication conveyance in human services, orthopedic
props, orthodontic embeds and supports, catheters, cardiovascular stents, and so
forth. The second principal use of SMP is in the structure of self-fixing solid, froths
for structure protection, window sealants, and so forth. The relatively low estima-
tions of SMP, when contrasted with different assets, are a burden for the polymer,
which can be changed by reinforcing SMP with extra materials, like Kevlar and
fiberglass.
A typical market driver among the contrastingly looked at reports for the market
is growing use of shape memory and, generally, low firmness esteems individually.
Aside from these, the components like stringent guideline about the use of synthetic
concoctions and monomers to make mechanical applications item, for example,
savvy sedate conveyance framework and inserts, or automotive and transportation,
and so forth, are expected to influence the worldwide SMP market.
As of late, these polymers are being utilized particularly for deployable segments
and structures in aviation. The real applications incorporate supports, pivots, blasts,
optical reflectors, transforming skins, and receiving wires. In addition, there are
numerous licenses recorded by driving polymer chameleon makers in connection to
SMPs applications, for example, intravascular conveyance framework, gripper,
288 A. Nabipourchakoli and B. Zhang

tunable automotive sections, and hood/situate get together vehicles. Acrylic-based

SMP materials have likewise been a work in progress for quite a long while and are
being utilized for a wide scope of uses. This segment represented an offer of near
10% of the general market in 2018. The automotive business uses SMP-based
actuators and programmed gags for motors during the assembling and get together
of vehicles. The item is additionally utilized as a defensive spread for automotive
sequential construction systems and damping material. In the aviation part, SMP is
used for the utilization of optical reflectors, receiving wires, brackets, transforming
skins, blasts, pivots, and so on. SMPs are significantly utilized in the deployable
structures and parts in the aviation segment.
Europe market will be a key region in the SMP market. This is because of the
rising interest in innovative work in the aeronautic trade. The region spends around
10% of its complete aviation turnover in R&D exercises. A portion of the significant
activities bolstered by the European Commission for creating airplane business
incorporates.

Shape Memory Composites, an Overview

To overcome the shortcomings of pure shape memory materials and to expand the scope
of applications, researchers found that fabricating composite materials is a good method.
The composite materials are made up of two or more materials, which keep as individual
components. And composites are preferred to have all excellent physical properties of
their components. For the traditional SMPCs, the matrix of SMPs keeps the shape
memory effect, and the reinforcement fillers gradually increase the mechanical proper-
ties. More interestingly, fillers can also enable SMPCs multifunctionalities in the shape
recovery process. The fillers can be designed as an energy converter to trigger thermally
responsive SMP matrix, such as joule heat generators, radiofrequency absorbers, or
infrared radiation absorbers. The self-healing fillers can also be used to heal cracks in
SMP matrix. In addition to SMPCs with SMP matrix, the elastomer-based composites
filled by SMP fibers also show unique properties. For example, SMP fibers in elastomer
matrix can be used to induce the strain mismatch and therefore fold the plate sheet to a
3D structure. Both excellent mechanical properties and multifunctionalities can be
achieved in SMPCs [1–4].

Shape Memory Alloy Nanocomposites

The fine reinforcement of shape memory alloy (SMA) can make the composites
strengthened without losing their pseudoplasticity and shape memory property
[5, 6]. Thus, CNT-reinforced TiNi composites can be expected with excellent
properties. The integration of SMAs into composite structures has resulted in
many benefits, which include actuation, vibration control, damping, sensing, and
self-healing. This discrepancy between academic research and commercial interest is
largely associated with the material complexity that includes strong
13 Nanoproducts Based on Shape Memory Materials 289

thermomechanical coupling, large inelastic deformations, and variable thermoelastic

properties. Nonetheless, as SMAs are becoming increasingly accepted in engineer-
ing applications, a similar trend for SMA composites is expected in aerospace,
automotive, and energy conversion and storage-related applications. In an effort to
aid in this endeavor, a comprehensive overview of advances with regard to SMA
composites and devices utilizing them is pursued [7, 8].
Cai et al. synthesized carbon nanotube (CNT)-reinforced TiNi matrix composites
by spark plasma sintering (SPS) employing elemental powders [9]. The results show
that the thermoelastic martensitic transformation behaviors could be observed from
the samples that sintered above 800
C even with a short sintering time (5 min), and
the transformation temperatures gradually increased with increasing sintering tem-
perature because of more Ti-rich TiNi phase formation. Although decreasing the
sintering temperature and time to 700
C and 5 min could not protect defective
MWCNTs from reacting with Ti, still-perfect MWCNTs remained in the specimens
sintered at 900
C. This method is expected to supply a basis for preparing
CNT-reinforced TiNi composites [10].

Shape Memory Polymer Nanocomposites

A SMP is reinforced mainly to increase the driving force of the recovery process and
to provide better carrying capacity, which correspond to a high elastic modulus and a
general elastic modulus, respectively. In general, the reinforcement filler improves
these two indicators at the same time [11, 12, 13, 3, 14].
Nabipour Chakoli et al. have reported the data from comprehensive thermo-
mechanical and shape memory tests of poly(L-lactide-co-ε-caprolactone)
(PLACL), a biodegradable SMP, that is reinforced with pristine and functionalized
MWCNTs [15], and the main conclusions are as follows:

(1) The strain fixity (Rf) of the composites almost keeps a stable value with the
increase of the filler content at low initial strain deformation. At high initial strain
deformations, the addition of MWCNT-g-PLACLs increases the strain fixity of
the composites; however, the addition of pMWCNTs has no significant effect on
the strain fixity of the composites.
(2) The addition of pMWCNTs decreases the strain recovery of the composites.
When the MWCNT-g-PLACLs content is less than 2 wt%, the strain recovery
initially decreases and then increases with the increase of the MWCNT-g-
PLACLs content. With further increasing MWCNT-g-PLACLs content up to
3 wt%, the strain recovery decreases again.
(3) The recovery stress of the composites increases gradually with increasing the
amount of both kinds of reinforcing fillers. The maximum recovery stress can be
obtained at the MWCNTs-g-PLACLs content of 2 wt% and the pMWCNTs
content of 1 wt%, respectively. After that, with further increasing the reinforcing
filler content, the recovery stress of the composites decreases. The addition of
290 A. Nabipourchakoli and B. Zhang

MWCNTs is beneficial to store the internal elastic energy during stretching and
fixing, which leads to the improvement of recovery stress.
(4) The strain fixity, strain recovery, and recovery stress of the PLACL (80% LA + 20%
CL) and its composites decrease slightly after degradation in PBS at 37
C.

Miaudet et al. [16] achieved the very high recovery stress of CNTs/polyvinyl
alcohol SMPCs. The maximal stress generated by a CNTs/polyvinyl alcohol fiber
reached 150 MPa which is two orders of magnitude higher than that of neat SMPs.
The CNT/polyvinyl alcohol fiber was prepared using a special coagulation spinning
technique. Surfactant-stabilized CNTs were injected in the co-flowing stream of the
coagulating polyvinyl alcohol solution which enabled an extremely high content of
CNTs to be incorporated into the polyvinyl alcohol fiber.
Zhang et al. [17], using abundant surface hydroxyl of silica, initiated epsilon-
caprolactone on the particles. Uniform SiO2/PCL macroparticles were formed. After
cross-linking of SiO2/PCL by 4,40 -methylenediphenyl diisocyanate, the SiO2/SMP
was prepared. Compared to traditional silica-based filler-filled SMPs, the SiO2/SMP
exhibited excellent mechanical strength, high strain, and good shape memory prop-
erties due to the introduction of SiO2 as a cross-linking agent. Xu et al. [18] heat
treated a nanofabric-type clay attapulgite at 850
C to reinforce shape memory
polyurethane (SMPU). The mechanical properties and SME of the nanocomposites
were remarkably improved using the nanofabric-type clay attapulgite [19, 20].
Celite, which is primarily composed of silica and alumina, has surface hydroxyl
groups. It can be coupled with SMPU chains. Park et al. [21] prepared celite/SMPU
with celite acting as a cross-linking agent. The celite improved the shape memory
performance and mechanical properties of SMPUs. Lee et al. [22] functionalized
silicas with allyl isocyanate groups and made waterborne silica/polyurethane nano-
composites using UV. It was demonstrated that the functionalized silica particles had
the function of both reinforcing fillers and stress relaxation retarders.
Heat treatment of CNT/SMP composites can remarkably improve the composites
conductivity as reported by Cho et al. [23] and Fei et al. [24]. Fei et al. prepared
CNTs/poly(methyl methacrylate-co-butyl acrylate) by ultrasound-assisted in situ
polymerization. The composites were subjected to a simple heating and cooling
process. The mechanism of the increased electrical conductivity was tentatively
ascribed as follows: in the original composite, there may be some internal residual
stresses or strains in the interface between polymer and CNTs as a result of thermal
expansion mismatch and curing shrinkage; after the post-thermal treatment, the
interface contact area between the polymer matrix and CNTs may increase, and
the thickness of the interfacial polymer may decrease. The two effects reduce the
tunneling resistance and thus significantly enhance the electrical conductivity.
To construct physical conductive channels in SMPs, Yu et al. [25] and Leng et al.
[26] aligned Ni powders and CNTs, respectively, in CB/SMP composites using
magnetic field or electrical field. It was reported that compared with the samples
with randomly distributed conductive fillers, the electrical resistivity was reduced by
over 100 times. Instead of Ni powders, filamentary nickel nanostrands with high
aspect ratios can further improve the electrical conductivity of the composite. Lu
13 Nanoproducts Based on Shape Memory Materials 291

et al. [27] filled filamentary nickel nanostrands and CNTs into shape memory epoxy.
The aligned high aspect ratios fillers further facilitated the actuation of the SMP
nanocomposite even though a low filler volume content and low electrical voltage
were used.
Polyhedral oligomeric silsesquioxane (POSS) is a good filler for biodegrade
SMPs [28]. Jeon et al. [29] studied the shape memory properties of norbornyl-
POSS copolymers having either cyclohexyl corner groups or cyclopentyl corner
groups. The POSS composites showed two stages of strain recovery, a fast strain-
recovery process related to the polynorbornene relaxation in the norbornyl matrix
and a second slow strain-recovery process which was assumed to be related to the
POSS-rich domains. This two-stage shape recovery is like the triple SME of SMPs.
Berllin et al. [30] developed a triple-SMP by copolymerization of poly(ethylene
glycol)mono-methylether-monomethacrylate (PEGMA) with poly(caprolactone)
dimethacrylate. The polymer had crystalline poly(caprolactone) domains and crys-
talline polyethylene glycol domains, which act as the two switching phases. Then
Kumar et al. [31] filled the triple-SMP with silica-coated nano-iron(III) oxide
particles. With the stepwise increases of the magnetic field strength from H ¼ 14.6
and 29.4 kA/m, triple-shape memory behavior was observed. Paderni et al. [32]
prepared a triple-shape memory-grafted polymer network containing crystallizable
poly(ethylene glycol) side chains and poly(caprolactone) cross-links network. The
polymer has two well-separated melting transitions. Then silica-coated nano-iron
(III) oxide particles were filled into the polymer; and the MSME by noncontact
activation in a stepwise increasing alternating magnetic field was achieved.
Gold nanoparticles between 60 and 200 nm in size have a strong absorption of
light especially infrared light. Heating of focused light can be absorbed by the gold
nanoparticles to increase the temperature of gold nanoparticles/SMP composites
locally to trigger the spatially controlled SME. Zhang et al. [33] demonstrated the
spatially controllable shape recovery of the gold nanoparticle-filled SMP using
focused laser light. Surface-functionalized gold nanoparticles are loaded in semi-
crystalline shape memory poly(ε-caprolactone) macromolecules. The branched
oligo(ε-caprolactone) was cross-linked with hexamethylene diisocyanate. The
shape recovery by the localized photothermal effect of gold particles can be con-
trolled by the intensity of light which determines the amount of heat generated by the
gold nanoparticles. Once the light is turned off, the heating caused by the light is off.
Therefore, the shape recovery can be stopped at any stage [33].
He et al. [34] fabricated a multi-composite SMP consisting of a Fe3O4/SMP
region and a CNT/SMP region separated by a pure SMP region. Upon remote
actuation using two different magnetic fields of different radiofrequencies, the
triple-region composite was capable of controlled two-step shape recovery. The
Fe3O4/SMP and CNT/SMP regions have different radiofrequency absorptions.
When the deformed composite sample is in 13.56 MHz RF field, only the CNT/SMP
region is heated. This leads to the recovery of only the CNT/SMP region. Upon
being subjected to subsequent 296 kHz RF field, the Fe3O4/SMP region is selec-
tively heated leading to the recovery of the Fe3O4/SMP region. Finally, the pure
SMP region recovers in an oven.
292 A. Nabipourchakoli and B. Zhang

In some researches, the thermomechanical properties of PLLA nanocomposites

reinforced with functionalized multiwalled carbon nanotubes (MWCNTs-g-PLLAs)
were determined. For functionalization, PLLA chains were grafted from the surface
of MWCNTs. Then, func. MWCNTs/PLLA composite is prepared by solution
casting. The results show that the MWCNT-g-PLLAs were dispersed in PLLA
matrix adequately. Increasing the weight percentage of MWCNT-g-PLLAs up to
2 wt% led to gradual enhancement of the mechanical properties of nanocomposite.
The thermal analysis also revealed the func. MWCNTs increase the melting point
and the glass transition temperature of nanocomposite. Also, the DMA results show
that incrementing the concentrations of func. MWCNTs is also accompanied with
increasing Young’s modulus and the transition temperature of PLLA. The chain
stiffness in amorphous phase of PLLA can also increase due to the van der Walls
force and the homogeneous dispersion of func. MWCNTs. In addition, the crystal-
linity of PLLA could be increased due to func. MWCNTs as heterogeneous nucle-
ation points [35].
There are many researches on reinforcing the PLACL using nanomaterials. As an
example PLACLs reinforced with well-dispersed multiwalled carbon nanotubes
(MWCNTs) were prepared using functionalized MWCNT by in situ polymerization.
The surface functionalization of MWCNTs can effectively improve the dispersion
and adhesion of MWCNTs in PLACL, and hence, it will have a significant effect on
the physical, thermomechanical, and degradation properties of MWCNT/PLACL
nanocomposites [36].
Nabipour Chakoli et al. have reported the data from comprehensive thermo-
mechanical and shape memory tests of poly(L-lactide-co-ε-caprolactone)
(PLACL), a biodegradable SMP, that is reinforced with pristine and functionalized
MWCNTs [15], and the main conclusions are as follows:

(1) The strain fixity (Rf) of the composites almost keeps a stable value with the
increase of the filler content at low initial strain deformation. At high initial strain
deformations, the addition of MWCNT-g-PLACLs increases the strain fixity of
the composites; however, the addition of pMWCNTs has no significant effect on
the strain fixity of the composites.
(2) The addition of pMWCNTs decreases the strain recovery of the composites.
When the MWCNT-g-PLACLs content is less than 2 wt%, the strain recovery
initially decreases and then increases with the increase of the MWCNT-g-
PLACLs content. With further increasing MWCNT-g-PLACLs content up to
3 wt%, the strain recovery decreases again.
(3) The recovery stress of the composites increases gradually with increasing the
amount of both kinds of reinforcing fillers. The maximum recovery stress can be
obtained at the MWCNTs-g-PLACLs content of 2 wt% and the pMWCNTs
content of 1 wt%, respectively. After that, with further increasing the reinforcing
filler content, the recovery stress of the composites decreases. The addition of
MWCNTs is beneficial to store the internal elastic energy during stretching and
fixing, which leads to the improvement of recovery stress.
13 Nanoproducts Based on Shape Memory Materials 293

(4) The strain fixity, strain recovery, and recovery stress of the PLACL (80%
LA + 20%CL) and its composites decrease slightly after degradation in PBS at
37
C.

Zhou et al. discussed the key issues in optimization of the shape memory
performance, temperature memory effect, and multiple SME. It is concluded that
most shape memory phenomena are intrinsic features of polymeric materials, and
based on these basic working mechanisms, it can be enabled the SME in materials,
design a new shape memory material with the required shape memory function, and
optimize the shape memory performance (Fig. 1) [37].
Electroactive shape memory is influenced by the electrical conductivity of the
material resulting in joule heating, whereas the thermal conductivity of the nano-
composite governs the thermally stimulated SME [38].
Karabudak et al. research group grows TiO2 coatings with nano-Ag-doped and
micro-arc oxidation technique on NiTi shape memory alloy. The XRD results
showed that there were only TiO2 crystal phases (anatase and rutile) on the coating.
The results showed that a clean and dense oxide layer was grown on the surface
successfully. The surface of nano-Ag-doped TiO2-coated samples appears to be
smoother than the surface of the coatings without Ag. The corrosion tests of the
coated and uncoated samples were carried out in three different environments
(simulated body fluid, synthetic saliva, and cola) at 37
C which is a human body
temperature. The corrosion tests showed that the corrosion resistance of TiO2-coated
and nano-Ag-doped TiO2-coated samples was much higher than the corrosion
resistance of the NiTi substrate. Seven different bacteria (S. aureus,
L. monocytogenes, Bacillus subtilis, Salmonella enteritidis, Yersinia enterocolitica,
E. coli, P. aeruginosa) which have the human pathogen feature were used in the
antibacterial susceptibility tests. The process was conducted based on the disk
diffusion method to test the susceptibility of bacterial strains on the selected coated
and uncoated samples, and antimicrobial activity was evaluated in the nano-Ag-
doped TiO2-coated material; P. aeruginosa, Y. enterocolitica, and E. coli (zone

Fig. 1 The heating responsive SME in 3D-printed poly(lactic acid) (PLA) spring [37]
294 A. Nabipourchakoli and B. Zhang

diameter of 8–14 mm) were found to be moderately susceptible; S. aureus, L. mono-

cytogenes, B. subtilis, and S. enteritidis (zone diameters of 8–14 mm) were found to
be resistant. The antimicrobial activity of the coating material NiTi was found to be
sensitive for all antibacterial tests. According to the TiO2-coated material results,
S. aureus, P. aeruginosa, L. monocytogenes, and E. coli were found to be moderately
sensitive and Y. enterocolitica, S. enteritidis, and B. subtilis were found to be
resistant [39, 40].
Wu et al. applied shape memory polymers (SMPs) into digital light processing
(DLP) technology to realize four-dimensional (4D) printing. However, there is still a
great lack of shape memory-photosensitive resins suitable for DLP. They designed
novel acrylate-based photosensitive resins for DLP and prepared to fabricate SMP
parts with tert-butyl acrylate/1,6-hexanediol diacrylate (tBA/HDDA) networks. The
developed SMP with 10 wt% cross-linker can withstand 16 consecutive cycles and
retain extremely high shape recovery ratio of 100% even after 14 cycles, the one with
20 wt% cross-linker possesses the best shape fixity ratio of over 96%, and the storage
modulus can reach up to 1.48  10 3 MPa with 50 wt% cross-linker. Furthermore,
these 4D-printed SMPs only spend 7–13 s in the 180
shape recovery, indicating a
good shape recovery rate as shown in Fig. 2. This work confirms that the designed
SMPs have potential applications in many areas due to their excellent shape memory
performance and provides valuable guidance for the shape memory properties
optimization of other SMPs [41].
Abdullah et al. reinforced shape memory polyurethane (SMPU) with multi-
walled carbon nanotubes (MWNTs) which were fabricated with through mixing
and injection molding with the purpose to improve the shape memory properties
of the polymer at low filler content. Variables such as shape fixity and recovery
have been measured to evaluate the effect of nanotube fillers on the shape
memory behavior of the prepared composites. Thermomechanical tests were

Fig. 2 Preparation and shape memory effect of acrylate-based photosensitive resins for digital light
processing [41]
13 Nanoproducts Based on Shape Memory Materials 295

performed and the shape fixity and shape recovery rate were analyzed. Additions
of nanotube fillers increase the relative shape fixity of the polymer nano-
composites, while the experimental results demonstrate that the presences of
nanotube fillers reduce the shape recovery rate. The shape recovery of the
polymer nanocomposites was decreased due to the limited movement of polymer
chains by the MWCNTs [42].
Zhang et al. prepared the graphene oxide-reinforced poly(L-lactide-co-ε-
caprolactone) (GO/PLACL) nanocomposites. They used molecular dynamics to study
the shape memory effect and mechanical properties of GO/PLACL to understand the
microscopic mechanism. Two models containing dispersed graphene oxide were
constructed. It is shown that the addition of graphene oxide causes the glass transition
temperature of material to rise because of limitation on polymer activity. The uniaxial
tensile properties of the composites were studied. The results exhibited that strength of
composites depends on the interface state of the polymer and graphene oxide. The
strength of the composite with covalent bond is much higher than that of another without
the covalent bond between graphene oxide and poly(L-lactide-co-ε-caprolactone) gen-
erated. Stress-softening effect was observed in the cross-linked composite in the glass
state. Their uniaxial tension thermodynamic cycles were carried out to consider the
shape memory effect of the composites. It is shown that graphene oxide-reinforced
composites with different interactions exhibit fair shape memory effect in the direction
of paralleling graphene oxide surface. In terms of the direction perpendicular to
graphene oxide sheet, the fixed ratios of the composites decrease slightly about
1.64%–3.63%, and the recovery ratios of the composites with the covalent bond are
higher than others about 3.22%–12.93%[43].
In their research, Tsujimoto et al. deal with the synthesis of plant oil-based shape
memory materials from epoxidized soybean oil (ESO) and polycaprolactone (PCL).
PolyESO/PCLs were synthesized by an acid-catalyzed curing in the presence of
PCL. During the reaction, PCL scarcely reacted with ESO, and the crystallinity of
the PCL component decreased to form a semi-interpenetrating network structure.
The incorporation of the PCL components improved the maximum stress and strain
at break of ESO-based network polymer. The polyESO/PCL was gradually degraded
by Pseudomonas cepacia lipase. Furthermore, the polyESO/PCLs exhibited excel-
lent shape memory properties, and the strain fixity depended on the feed ratio of ESO
and PCL. Figure 3 shows that the shape memory recovery behaviors were repeatedly
practicable. The resulting materials are expected to contribute to the development of
biodegradable intelligent materials. These striking results provide a new strategy for
designing novel biodegradable smart materials [44].
Shape recovery in a commercial ether-vinyl acetate copolymer (EVA) was system-
atically characterized by Xu et al. The influences of the programming temperature and
maximum uniaxial tension strain on the shape fixity ratio and the shape recovery ratio
were investigated quantitatively. In addition to excellent SME, high elasticity and high
creep were observed at around room temperature (with the EVA in the glassy state). The
underlying mechanisms for the different shape recovery phenomena (i.e., creep and the
SME) are discussed. Two potential applications utilizing the shape recovery property
and high elasticity of this EVA are presented [45].
296 A. Nabipourchakoli and B. Zhang

Fig. 3 Molecular structure and shape memory test of poly epoxidized soybean oil/polyca-
prolactone [44]

Tsujimoto et al. developed a bio-based SMP with dynamically cross-linked

network structure from trans-1,4-polyisoprene (TPI) derived from Eucommia
ulmoides Oliver. Grafting of maleic anhydride onto TPI was performed in
1,2-dichlorobenzene, and the subsequent hydrolysis gave maleatedtrans-1,4-poly-
isoprene (MTPI). Increasing trend of the grafted maleic moiety was observed with
increasing the concentration of maleic anhydride in the grafting reaction. With
increase in maleic content, the glass transition temperature (Tg) of the resulting
polymer increased, whereas the crystallinity decreased. The maximum stress of the
MTPI with carboxylates was larger than that of the protonated MTPI. Above the
melting temperature, Young’s modulus of MTPI with carboxylates was higher than
that of neat TPI and the protonated MTPI, due to dynamically cross-linked network
structure. Figure 4 presents the scheme of cross-linking and shape memory test of
sample composite. Furthermore, the MTPI with 1% carboxylate content exhibited
excellent shape memory recovery properties, exploiting the combination of the
physical cross-linking and the melting of the crystal. The resulting materials are
expected to contribute to the development of bio-based intelligent materials [46].
A novel type of covalently cross-linked semicrystalline polymer with shape
memory and biocompatibility properties was prepared from alkoxysilane-terminated
poly(ε-caprolactone) (PCL) by sol-gel process that allowed the generation of silica-
like cross-linking points. A fine-tuning of the cross-linking density and thermal
properties (melting temperature) of the materials was obtained by controlling the
molecular weight of the PCL precursor (and thus the molecular structure of the
resulting network) and the curing conditions. The shape memory behavior was
investigated with bending tests. Recovery times of less than 1 second were observed
in water depending on the temperature, and a linear correlation of the recovery time
with cross-linking density and molecular weight of PCL network precursor was
observed [32].
13 Nanoproducts Based on Shape Memory Materials 297

Fig. 4 Schematic representation of dynamic cross-linking and shape memory test of sample [46]

In their research, Baldi et al. have explored the shape memory capabilities of a novel
type of covalently cross-linked semicrystalline polymers, prepared by exploiting the
mild sol-gel chemistry, starting from alkoxysilane-terminated poly(ε-caprolactone)
(PCL), and using silica-based domains as cross-link points. By adopting PCL precursors
with different molecular weights, semicrystalline networks with well-defined cross-link
densities and with different crystallization and melting temperatures were obtained.
Besides a satisfying one-way shape memory behavior, the materials have displayed a
significant two-way shape memory response, undergoing a reversible elongation-
contraction process between two distinguished strain levels when subjected to a constant
load and cyclically heated/cooled on a temperature region spanning from below the
crystallization temperature to above the melting temperature as shown in Fig. 5. The
applied load and the cross-link density are revealed as key parameters to obtain tailored
actuations. Concurrent wide-angle X-ray diffraction (WAXD) and DSC analyses allo-
wed to ascribe the effect to a structural evolution process occurring during melting and
crystallization [47].
Tsujimoto et al., in their research, deal with the synthesis of plant oil-based shape
memory materials from epoxidized soybean oil (ESO) and polycaprolactone (PCL).
PolyESO/PCLs were synthesized by an acid-catalyzed curing in the presence of
PCL. During the reaction, PCL scarcely reacted with ESO, and the crystallinity of
the PCL component decreased to form a semi-interpenetrating network structure as
shown in Fig. 6. The incorporation of the PCL components improved the maxi-
mum stress and strain at break of ESO-based network polymer. The polyESO/PCL
was gradually degraded by Pseudomonas cepacia lipase. Furthermore, the polyESO/
PCLs exhibited excellent shape memory properties, and the strain fixity depended on
the feed ratio of ESO and PCL. The shape memory recovery behaviors were
repeatedly practicable. The resulting materials are expected to contribute to the
development of biodegradable intelligent materials [44].
The influence of extreme conditions such as high pressure and high temperature
on shape memory function of polymers has received little attention. In this study, the
shape memory properties of poly(ε-caprolactone) (PCL)-based nanocomposites with
nanocrystalline cellulose (NCC) as fillers are investigated via recrystallization at a
298 A. Nabipourchakoli and B. Zhang

Fig. 5 The strain of composite under the fixed stress and the schematic representation for strain of
composite under fixed stress [47]

Fig. 6 Schematic representation of composite accompanying with a composite sample shape

memory test [37]

high temperature under a high-pressure environment by Wang et al. The results

exhibit that when the mass ratio of NCC was maintained constant, both the crystal
properties and melting temperatures of the nanocomposites decreased with increas-
ing pressure. Furthermore, the shape memory fixity ratios of the recrystallized
nanocomposites remained more than 90% due to the fact that the chemical cross-
linking structure and the recovery ratios kept increasing with the increase in pres-
sure. The mechanism of the improvement of the shape memory function was further
13 Nanoproducts Based on Shape Memory Materials 299

High
Pressure
140°C, 1 h
Cooling

The state of atmospheric pressure The state of high pressure

PCL crystalline domain PCL amorphous domain

NCC Cross-linking point

Fig. 7 Schematic representation of molecular scale of composite under pressure [48]

analyzed, and the result demonstrates that the pressure has a significant influence on
the crystal properties of PCL polymers during their recrystallization; subsequently
the shape recovery ratio is improved since more molecular chains participate in the
shape recovery process (Fig. 7) [48].
Shape memory surfaces with on-demand, tunable nanopatterns are developed to
observe time-dependent changes in cell alignment using temperature-responsive
poly(ε-caprolactone) (PCL) films. Temporary grooved nanopatterns are easily pro-
grammed on the films and triggered to transition quickly to permanent surface
patterns by the application of body heat. Figure 8 elucidates the scheme of cross-
linking and shape memory test of sample composite. A time-dependent cytoskeleton
remodeling is also observed under biologically relevant conditions [49].
Thermally responsive shape memory polymers have promising applications in
many fields, especially in biomedical areas. In the Jing et al. research, a simple method
was purposed to prepare thermoplastic polyurethane (TPU)/poly(-caprolactone) (PCL)
blends that possess shape memory attributes. TPU and PCL were melt compounded
via a twin-screw extruder and injection molded at various ratios. Multiple test methods
were used to characterize their shape memory properties and reveal the underlying
mechanism. The blends containing 25% TPU and 75% PCL possessed the best shape
memory properties as indicated by a 98% shape-fixing ratio and 90% shape recovery
ratio. This was attributed to the hybrid crystalline and amorphous regions of PCL and
TPU. It was also found that PCL and TPU had good miscibility and that the PCL
domain in TPU25% had higher crystallinity than neat PCL. The crystalline region in
TPU25% could deform and maintain its temporary shape when stretched, which
contributed to its high shape-fixing attribute, while the rubbery TPU region assisted
in the recovery of the sample upon heating by releasing the deformation energy stored.
Moreover, the TPU25% string prepared could knot itself in a hot water bath, indicating
300 A. Nabipourchakoli and B. Zhang

O O

=
O C O C CH= CH2 PCL macromonomer
n

Cross-linking

Programming of Recovery of the

temporal pattern Body heat permanent pattern

Fig. 8 The schematic representation of cross-linking and shape recovery of film using body heat
[49]

a potential for suture applications. Lastly, the 3T3 fibroblast cells cultured on the
TPU/PCL blends showed high viability and active substrate-cell interactions [50].
Blending commercial homopolymers represents a low cost and an easy scalable
process to extend the use of the pristine homopolymers to an industrial level.
Actually, the processing of blends by extrusion is the usual solution followed in
the industry. However, commonly polymer blends are immiscible, provoking phase
separation, which can be in the macro-, micro-, or nanoscale, depending on the
polymers as well as on the processing conditions, affecting the final properties of the
blends. Therefore, this chapter aims to study the shape memory behavior in biode-
gradable blends based on poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) in
different concentrations. A completely thermal and mechanical characterization of
the blends was performed, correlating the results with the observed morphology. In
addition, two different biodegradation studies were performed in order to correlate
the effect of each homopolymer with the degradation behavior of the biodegradable
blends [51].
Kim et al. synthesized a series of electroactive shape memory polyurethane
(SMPU) nanocomposites from poly(tetramethylene ether) glycol (PTMG),
4,4-methylenebis(phenyl isocyanate) (MDI), and 1,3-butandiol (1,3-BD) with the
13 Nanoproducts Based on Shape Memory Materials 301

addition of various amounts of thermally reduced graphenes (TRG) which were

chemically modified with allyl isocyanate (iTRG). The effects of iTRG on electro-
active shape recovery behaviors as well as the conventional direct heat-actuated
SMPU material have been studied in terms of morphological, thermal, mechanical,
electrical properties and thermomechanical cyclic behavior. It was found that sig-
nificant increases in electrical conductivity and temperature were obtained high
iTRG contents (>2%) to electrically actuate the nanocomposite, along with large
increases in glass transition temperature (Tg) and initial modulus with a dramatic
drop in elongation at break [52].
Bio-based polyester (BE) was synthesized through polycondensation using the
plant-derived resources as the starting materials. Vapor-grown carbon nanofiber
(VGCF) was then incorporated into BE to prepare BE/VGCF composites by simple
melting blending. The uniform dispersion of VGCF and fairly strong interfacial
adhesion between BE and VGCF led to a significant improvement in the mechanical
properties of the composites. Besides, the incorporation of VGCF successfully
converted the insulating BE into electrically conductive composites with a percola-
tion threshold of 2.5 vol.%. The composites showed excellent electroactive shape
memory properties, which reached a shape recovery ratio of 97% within 90 s with a
direct current voltage of 20 V. The combination of the significantly improved
mechanical properties and excellent electroactive shape memory performance of
BE/VGCF composites opens up the new opportunity for the electroactive actuator
materials in a sustainable manner [53].
Plasmonic nanoparticles can confine light in nanoscale and locally heat the surround-
ing. Here the titanium nitride (TiN) nanoparticles were used as broadband plasmonic
light absorbers and synthesized a highly photoresponsive hybrid cross-linked polymer
from SMP poly(ε-caprolactone) (PCL). The TiN-PCL hybrid is responsive to sunlight,
and the threshold irradiance was among the lowest when compared with other photo-
responsive shape memory polymers studied previously. Sunlight heating with TiN NPs
can be applied to other heat-responsive smart polymers, thereby contributing to energy-
saving smart polymers research for a sustainable society [54] (Fig. 9).
In the present work, the development of a polycaprolactone-based toughened
shape memory polyurethane biocomposite promoted by in situ incorporation of
chitosan flakes has been demonstrated. The chitosan flakes were homogeneously
present in the polymer matrix in the form of nanoflakes, as confirmed by the electron
microscopic analysis, and probably developed a cross-linked node that promoted
toughness (a > 500% elongation at break) and led to a ~ 130% increment in ultimate
tensile strength, as analyzed using a universal testing machine. During a tensile pull,
X-ray analysis revealed the development of crystallites, which resulted from a stress-
induced crystallization process that may retain the shape and melting of the crystal-
lites stimulating shape recovery (with a ~ 100% shape recovery ratio), even after
permanent deformation. The biodegradable polyurethane biocomposite also demon-
strates relatively high thermal stability (Tmax at ~360
C) as shown in Fig. 10. The
prepared material possesses a unique shape memory behavior, even after permanent
deformation up to a > 500% strain, which may have great potential in several
biomedical applications [55].
302 A. Nabipourchakoli and B. Zhang

Fig. 9 The shape memory test of composite [54]

Fig. 10 Demonstration of the shape memory effect in the PCL-PU-chitosan biocomposite in a dry
condition and the shape memory ability of the prepared random shaped chitosan polyurethane
composite for grip application (temporary shape at room temperature using tensile force; recovered
shape in water (wet condition) at 50
C within 5 s). Shape memory behavior of the polyurethane
chitosan biocomposite after tensile tension [55]

In research of Molavi et al., a novel thermally actuated triple-SMP (triple-SMP)

based on poly(L-lactide) (PLA)/poly(ε-caprolactone) (PCL)/graphene nanoplatelets
(GNPs) nanocomposite was prepared by facile solution mixing method, and the
design of which was based on two well-separated melting temperatures. In order to
improve the dispersion of GNPs in the matrix, functionalization reactions were
carried out on the GNPs surface. Functionalization was confirmed by various
techniques including FTIR, Raman, and TGA. TEM micrographs revealed an
exfoliated morphology for the functionalized GNPs (FGNPs) and a homogeneous
dispersion in the matrix. The crystallinity behavior of nanocomposites was investi-
gated by DSC and variable temperature XRD (VT-XRD) analysis, and an increase in
crystallinity was observed. Dynamic mechanical analysis (DMA) showed that the
presence of FGNPs improves the fixity and recovery ratios because of increase in
13 Nanoproducts Based on Shape Memory Materials 303

crystallinity and thermal conductivity. The best shape memory behavior was
obtained for PLA50/PCL50/FGNP 1.5 nanocomposite [56].
Rapidly electroactive thermoplastic polyurethane (TPU)/polylactide (PLA) shape
memory polymer (SMP) blends via phase morphology control and incorporation of
conductive multiwalled carbon nanotubes (MWCNTs) were achieved by simple and
efficient melt blending in this work. Binary TPU/PLA blends with various compo-
sition ratios were firstly prepared, and the effect of phase morphology on shape
memory behavior was studied. The optimum shape memory behavior was observed
for TPU50/PLA50 blends with co-continuous phase morphology. Then a small
number of MWCNTs were selectively incorporated into TPU phase of TPU50/
PLA50 and TPU60/PLA40 blends to realize electroactive shape memory effect.
Figure 11 shows the effect of MWCNTs on electrical conductivity of nano-
composite. The formation of double percolation network imparted TPU/PLA/
MWCNT conductive polymer composites with high electrical conductivities in
low percolation thresholds, thus realizing rapidly electroactive shape memory
behaviors. Additionally, the mechanical properties of TPU/PLA blends (50/50,
60/40) can be enhanced by the addition of MWCNTs even at high temperature.
Therefore, our work provides a simple way to fabricate polymer blends with rapid
electroactive shape memory performances, good mechanical properties, as well as
good processing capability but low cost [57].
In this work of Iregui et al., poly(ε-caprolactone) (PCL)/diglycidyl ether of
bisphenol A (DGEBA) blends were electrospun, and the obtained mats were UV
cured to achieve shape memory properties. In the majority of studies, when blends
with different compositions are electrospun, the process variables such as voltage or
flow rate are fixed independently of the composition, and consequently the quality of
the fibers is not optimized in all of the range studied. In the present work, using the
design of experiments methodology, flow rate and voltage required to obtain a stable
process were evaluated as responses in addition to the fiber diameter and shape
memory properties. The results showed that the solution concentration and amount
of PCL played an important role in the voltage and flow rate. For the shape memory
properties, excellent values were achieved, and no composition dependence was

Fig. 11 The effect of MWCNTs concentration on electrical conductivity of nanocomposites [57]

304 A. Nabipourchakoli and B. Zhang

Fig. 12 Photographs of the manual shape memory test showing (a) the initial longitude, (b) the
programming shape, (c) the fixed shape, and (d) the recovered sample [58]

observed. In the case of fiber diameter, similar results to previous works were
observed [58] (Fig. 12).
In the case of integration, flexible composite skins can be applied over a shape
memory foam core obtaining composite sandwich that can be shaped to change its
stiffness or to reduce its volume. After the application of a given stimulus (generally
by heating), the initial shape can be recovered. Future applications for this class of
materials are self-deployable structures for space systems (such as actuators of solar
sails or smart aerodynamic structures). In research of Santo et al., two new SMC self-
deployable structures were prototyped: a composite cross and a composite frame
containing a thin aluminum sheet as shown in Figs. 13 and 14. The former structure
represents a possible deploying configuration for a structural sheet, whereas the latter
is a conceptual study of a solar sail. The experimental results are very promising,
showing that such structures can successfully self-deploy following the desired
design constraints without noticeable damages. Figure 15 represents the shape
memory test of prepared composites during shape recovery [59].
Near-term and future spacecraft and satellites will require large ultralightweight
structures and components that must be efficiently packaged for launch and reliably
deployed on orbit. A new material technology called elastic memory composite
(EMC) materials shows promise in meeting these needs. The EMC polymer matrix
13 Nanoproducts Based on Shape Memory Materials 305

Fig. 13 Shape memory test for prototypes of composite with a composite fame [59]

Fig. 14 Memory and recovery stage for the SMC cross composite [59]

materials enable a fully cured composite structure or component to be deformed or

folded for efficient packaging into a spacecraft or launch vehicle and then regain its
original shape with no degradation or loss in mechanical or physical properties. A
component using EMC materials is fabricated in its deployed, on-orbit shape using
conventional composite manufacturing processes by Tupper et al. Then by heating
the material and applying force, this fully cured composite material can be folded or
deformed for packaging. When cooled, it will retain the package shape indefinitely.
When reheated the structure will regain its original shape with little or no external
force. This packaging/deployment cycle is reversible as shown in Fig. 16 [60].
306 A. Nabipourchakoli and B. Zhang

Fig. 15 Details of the shape memory test of the SMC frame [59]

Fig. 16 Demonstration of fully cured elastic memory composite material [60]

In their recent research, Ferreira et al. studied the effect of reduced graphene oxide
(rGO) on the thermally induced shape memory properties of poly(lactic acid) (PLA).
The rGO was incorporated within PLA at various contents (0.1–1.0 mass%) by melt
extrusion. X-ray diffraction showed that PLA/rGO nanocomposites presented
decreased crystallinity compared to PLA alone. Differential scanning calorimetry
revealed that rGO particles favored the formation of more imperfect PLA crystals.
13 Nanoproducts Based on Shape Memory Materials 307

Results from thermogravimetric analyses showed that the PLA/rGO composites

presented slightly improved thermal stability. Time-domain nuclear magnetic reso-
nance indicated increased molecular mobility for PLA/rGO nanocomposites in
relation to PLA. Dynamic mechanical analysis results showed that Tg ¼ 62.9
C
for PLA and that this value was reduced for the composites, reaching 54.2
C when
the rGO content was 1.0 mass%. The storage moduli (E0 ) were reduced with the
increase in rGO content, with a 44% decrease for the composition with 1.0 mass% of
rGO. However, above 65
C the E0 values increased substantially, which suggested
the role of graphene to fix the heat-relaxed molecules of PLA. For the composites,
the thermally induced shape memory data revealed an increase in the maximum
strain (εm), reaching 39% and 51% for the composites with the incorporation of rGO
at 0.5 and 1.0 mass% content, respectively. The effect of rGO particles on enhancing
the shape memory properties of PLA was confirmed by the increases in the recovery
rates (Rr) observed for the composites [61].
The effect of the inclusion of nano-hydroxyapatite (nano-HAp) and the porous
structure on the shape memory behavior of poly(D,L-lactide) (PDLLA) composites
was investigated by Jia et al. Porous, thermal-responsive shape memory composites,
PDLLA/nano-HAp, were prepared by a newly developed polymer coagulation,
particulate leaching, and cold compression molding technique. The inclusion of
nano-HAp to PDLLA led to a higher shape memory transition temperature,
improved mechanical strength, and larger recovery force as compared with the
neat PDLLA. The nanocomposite with 10 wt% of nano-HAp exhibited the best
shape fixity and recoverability with the shortest recovery time. Further increase in
the filler content of nano-HAp would reduce the recovery force and prolong the
recovery time due to restriction in the movement of the amorphous PDLLA chain
segments. The analysis results provide important information for designing biomed-
ical devices using this novel type of bioabsorbable SMP composite [62].
Du et al. investigated the shape memory properties of hydroxyapatite-graft-poly
(D,L-lactide) (HA-g-PDLLA) nanocomposites. Hybrid nanocomposites with vari-
ous HA proportions (5, 10, 15, and 25 wt%) were prepared via in situ grafting
polymerization. It is found that the nanocomposites exhibit various shape memory
(SM) performances with different HA loadings. Excellent shape memory properties
were found for HA-g-PDLLA nanocomposites with 15 wt% inorganic HA pro-
portions, observed through a well-established four-step SM programming cycle
method. However, at low HA loading (including pure PDLLA), the samples expe-
rienced a severe relaxation process, which caused a plastic, irreversible deformation
of the sample and resulted in a poor SM recovery ratio. In addition, the shape
memory behaviors of HA25-g-PDLLA nanocomposites and HA25/PDLLA blends
were compared. Due to the serious relaxation process caused by the weak interaction
forces of hydrogen bonding between HA and PDLLA, the HA25/PDLLA blends
had much worse shape recovery ability than the HA25-g-PDLLA nanocomposites
[62, 63]. The schematic representation of nanocomposite and its shape recovery test
is presented in Fig. 17.
The significance of SMP composites (SMPCs) has been analyzed in terms of four
aspects: reinforcement, innovation and improvement of driving methods, the
308 A. Nabipourchakoli and B. Zhang

Fig. 17 Shape recovery test of prepared nanocomposite [63]

creation of specific deformations, and the creation of multifunctional materials. Mu

et al. introduce the constitutive theory of SMPs and the post-buckling analysis of
SMPCs. Afterward, they introduce the extensive applications of SMPCs in the fields
of aerospace, biomedical equipment, self-finishing, deformable mandrels, and the
4D printing of active origami structures, demonstrating their ability to undergo
active driving and deformation, their adaptiveness, their ease of transport, and
their rapid production capacity, which fully demonstrate the unique advantages of
SMPs in solving application problems. Finally, the advantages and disadvantages of
SMPCs in applications are summarized, and the prospects for new SMPCs and new
SMPC structures are described.
Sung et al. studied the loading of the surface-modified carbon nanotube in the PU/
PLA polymer blends. For this purpose, polymer blend nanocomposites based on
thermoplastic polyurethane (PU) elastomer, polylactide (PLA), and surface-modified
carbon nanotubes were prepared via simple melt-mixing process and investigated for
its mechanical, dynamic mechanical, and electroactive shape memory properties.
Loading of the surface-modified carbon nanotube resulted in the significant
improvement on the mechanical properties such as tensile strength, when compared
to the pure and pristine CNT-loaded polymer blends. Dynamic mechanical analysis
showed that the glass transition temperature (Tg) of the PU/PLA blend slightly
increases on loading of pristine CNT and this effect is more pronounced on loading
surface-modified CNTs. Thermal and electrical properties of the polymer blend
composites increase significantly on loading pristine or surface-modified CNTs.
Finally, shape memory studies of the PU/PLA/modified CNT composites exhibit a
remarkable recoverability of its shape at lower applied dc voltages, when compared
to pure or pristine CNT-loaded system as presented in Fig. 18 [64].
In the present research of Urquijo et al., melt-mixed poly(lactic acid) (PLA)/poly
(butylene adipate-co-terephthalate) (PBAT) 80/20 and 60/40 blends were modified
with different CNT contents. Unfilled compositions were immiscible and combined
good stiffness (Young’s modulus>2000 MPa), deformability (elongation at
break>150%), and, in the case of the 60/40 composition, notched impact strength
13 Nanoproducts Based on Shape Memory Materials 309

Fig. 18 The shape recovery of composites with pristine and modified MWCNTs accompanying
the schematic representation of molecular structure of composites [64]

higher than 100 J/m. The morphology of the unfilled 80/20 composition showed
nano-sized, spherical PBAT particles finely dispersed within the PLA matrix, while
the 60/40 composition showed an almost co-continuous morphology. In the case of
the nanocomposites (NCs), the CNTs located in the minor PBAT phase because of
their greater compatibility, producing larger, elongated PBAT domains more char-
acteristic of co-continuous morphology. In addition, the CNTs created percolated
networks, and as a result, the NCs showed increased conductivity at CNT contents
equal and higher than ≈1.5 wt% as shown in Fig. 19. Although Young’s modulus did
not increase significantly in the NCs and the yield strength decreased upon the
addition of CNTs, the high deformability of the unfilled blends maintained up to
150% in all the compositions, and, in the case of the 60/40 blend, the impact strength
increased up to 250 J/m, i.e., 20 times higher than that of pure PLA [65].
Highly flexible, conductive, and two-way reversible shape memory polyurethane
nanocomposites were prepared with the in situ synthesized method, containing
different graphene nanosheet contents ranging from 1.0 to 8.0 wt% by Jiu et al.
The dispersion of the nanocomposites in the polymer was monitored by scanning
electron microscopy, and thermal properties, mechanical properties, electrical prop-
erties, and shape memory properties were comparatively investigated. The results
showed that the nanocomposite was more stable when the content of graphene is
2 wt% in the cross-linked network structure. In comparison to pristine polyurethane,
the graphene-cross-linked polyurethane composite exhibited better thermostability,
breaking stress, and exceptional elongation at break. The resulting composite
exhibited 93% shape fixity, 95% shape recovery of 2.0% loading, and fast electro-
active shape recovery rate. Moreover, the polymers also showed good reversible
two-way shape memory behaviors; thus it could be a promising material for the
fabrication of graphene-based actuating devices [66].
To use shape memory materials based on poly(lactic acid) (PLA) for medical
applications is essential to tune their transition temperature (Ttrans) near to the
human body temperature. In their research, Sonseca et al. studied the combination
of lactic acid oligomer (OLA), acting as a plasticizer, together with chitosan-
310 A. Nabipourchakoli and B. Zhang

Fig. 19 The conductivity of composites vs. the concentration of CNTs in composite [65]

mediated silver nanoparticles (AgCH-NPs) to create PLA matrices to obtain func-

tional shape memory polymers for potential medical applications. PLA/OLA nano-
composites containing different amounts of AgCH-NPs were obtained and profusely
characterized relating their structure with their antimicrobial and shape memory
performances. Nanocomposites exhibited shape memory responses at the tempera-
ture of interest (near physiological one), as well as excellent shape memory
responses, shorter recovery times, and higher recovery ratios (over 100%) when
compared to neat materials. Moreover, antibacterial activity tests confirmed biocidal
activity; therefore, these functional polymer nanocomposites with shape memory,
degradability, and biocidal activity show great potential for soft actuation applica-
tions in the medical field [67].
Shape memory polymers are required to recover fast (seconds to minutes); many
applications, particularly in the medical field, would benefit from a slow recovery
(days to weeks). In this work, Bartolo et al. exploit the broad glass transition range of
photo-cured poly(D,L-lactide) dimethacrylate networks to obtain recovery times of
up to 2 weeks, at 11
C below the peak glass transition temperature of 58
C.
Recovery times decreased considerably for higher recovery temperatures, down to
10 min at 55
C. A large spread in glass transition values (53.3–61.0
C) was
observed between samples, indicating poor reproducibility in sample preparation
and, hence, in predicting shape recovery kinetics for individual samples. Further-
more, a staged recovery was observed with different parts of the samples recovering
13 Nanoproducts Based on Shape Memory Materials 311

Fig. 20 Results from printing test parts: (a) top view of the printed slab with a cross section of
15  7.5 mm2 and 1.5  1.5 mm2 rectangular straight pores; (b) top plane view under the
microscope; (c) side view under the microscope showing the decreased pore size in the overexposed
bottom layers; (d) magnification of picture (c) showing the voxel pattern; the black square
represents one 50  50 μm2 pixel; (e) top view of the gyroid geometry scaffold print test. The
part covers an area of 5  10 mm2 containing 3  6 gyroid unit cells with a period of 1.6 mm [68]

at different times. The ability to prepare complex structures using digital light
processing stereolithography 3D printing from these polymers was confirmed as
shown in Fig. 20. To the best of our knowledge, this work provides the first
experimental evidence of prolonged recovery of shape memory polymers [68].
Nowadays, 4D-printed materials are an emerging field of research because the
physical structure of these novel materials responds to environmental changes. 3D
printing techniques have been employed to print a base material with shape memory
properties. Geometrical deformations can be observed once an external stimulus
triggers the shape memory effect (SME) integrated into the material. The plasticizing
effect is a well-known phenomenon where the microscopic polymer chain move-
ments have been altered and reflected in different shape memory behavior. It has
been suggested that a 4D material with localized actuation behavior can be fabricated
by utilizing functionally graded layers made from different degrees of plasticizing.
Sun et al. demonstrated that a novel 4D material can be fabricated from material
extraction continuous printing technique with different loadings of poly(ethylene
glycol) (PEG) plasticizer, achieving localized thermal recovery. The schematic
representation of shape memory test of composite is presented in Fig. 21. The results
indicate that a plasticized functional layer is an effective technique for creating next-
generation 4D materials [69].
An arc-shape configuration was printed to demonstrate the 4D thermal recovery
ability of the fabricated sample (Fig. 22a). Detailed dimensions of the printed model
can be found in the Supplementary Materials. The samples needed to be pro-
grammed into a temporary shape before 4D recovery could take place. This was
done by compressing the arc-like component at 50
C to prevent any possible brittle
failure. The compressed sample was then cooled back to room temperature prior to
312 A. Nabipourchakoli and B. Zhang

Fig. 21 Schematic of shape memory mechanism of arc-like 4D-printed PLA sample [69]

Fig. 22 4D-printed PLA arc (a) and flattened temporary shape (b) [69]

removal of the applied stress for shape fixing. The temporary shape training outcome
is presented (Fig. 22b). No visible cracks or delamination was observed after the
training process. After shape fixing, a heat gun was utilized above the component to
initiate 4D thermal recovery. Videos were taken to visualize thermal recovery, while
IR thermal videos were taken to measure the instantaneous temperature [69].
13 Nanoproducts Based on Shape Memory Materials 313

Sensor Applications of Shape Memory Materials

The SME has added one more dimension to potentially widen the application field of
SMPs, since it is possible to utilize this feature to design a smart polymeric system to
react automatically to the change of the surrounding environment in a passive
manner. However, the number of successfully developed SMP products is still rather
limited in the commercial market. A couple of commercial products relevant to
sensor applications are listed here. The materials used in these applications do have
the potential to be used in sensor applications as well [70, 71, 72].
Figure 23 presents a commercial anti-counterfeit SMP label (from Guangzhou
Manborui Material Technology Co., Ltd., Guangzhou, China) before and after
heating in 65
C oven for 2 minutes to get the embossed feature recovered. 3D
surface scanning using a Taylor scanner reveals that the embossed feature, which
indicates authentic in Chinese, is about 0.1 mm in height, which is about the same
magnitude as that of the surface feature in standard bank coins and can be clearly
identified via tactile sensation by fingers [66].
Shape memory polymeric splints are mostly made of poly(ε-caprolactone) (PCL)
type of polymers with/without cross-linking. After heating for softening, they can be
programmed at body temperature for fitting. After fitting, they become hard and stiff
to provide strong support.
Contrary to the memory foam, soft and elastic SMP foam is able to simulta-
neously achieve comfort fitting and provide enough support without compromising
in elasticity. Hence, a piece of insole made of such a type of SMP foam (mostly using
either ethylene-vinyl acetate (EVA) or PU) is able to maintain the shape of the foot

Fig. 23 Typical anti-counterfeit shape memory polymer (SMP) label (0.16 mm thick) available in
the market (from Guangzhou Manborui Material Technology Co., Ltd.). (a) Top, before heating
(as received); bottom, after heating in an oven at 65
C for 2 minutes. (b) 3D surface scanning result
(using Taylor scanner), which reveals that the surface feature after heating for shape recovery is
about 100 μm in height [66]
314 A. Nabipourchakoli and B. Zhang

Fig. 24 Shape memory ethylene-vinyl alcohol (EVA) insole. Top, after heating and stepping on,
foot shape is captured after cooling back to room temperature; bottom, after heating for shape
recovery (I). EVA heat shrink tube. The right end is heated for shape recovery (II). Commercial heat
shrink label. (a) Original; (b) after heating (placed between printing transparency and tape during
heating); (c) after heating (placed between two steel plates fixed by two clips); (d) after heating
(freestanding) (III) [73]

after stepping on it for a while during cooling for personalization (Fig. 24 I, top
piece). The foot impression can be fully removed after heating for reuse [73].
Probably the top two most successful commercial SMP products at present are
heat shrink tubes for protection of cables/wires and heat shrink films (membranes)
for label and packaging. Although different types of polymers are used, mostly they
are cross-linked via irradiation. In Fig. 24 II, the right end of a piece of heat shrink
tube, which is made of cross-linked EVA, is heated to over 80
C, which is above its
Tg, so that this part shrinks remarkably. Fig. 24 III(a) is a piece of commercial heat
shrink label (with screen-printed protruding oil on one side of its surface), and
Fig. 24 III(b–d) present the shapes of the labels after heating under three different
restrained conditions, from freestanding to restrained between two rigid plates
clipped together. After heating for shrinkage of the label, strip wrinkles are formed
in the area coated with protruding oil due to buckling. Consequently, if the label is
heated for free recovery [i.e., without any restraint as in Fig. 24 III(d)], instability in
the form of a combination of local buckling (wrinkling) and global buckling
resulted.
13 Nanoproducts Based on Shape Memory Materials 315

According to the previous definition, the SME is meant for nonreversible,

one-time activation. Although the SME cycle can be repeated after reprogramming,
if the programming process is practically not easy without causing any damage or
misalignment, etc., sensors based on SMPs have the combined advantages of having
high reliability/security and being non-repeatability/nonreusable.
An extremely important issue in any real engineering application is the cost-
effectiveness of a product. The cost (including both material cost and processing
cost) of some abovementioned successful commercial products, such as heat shrink
tube, EVA/PU foam, and PCL splint, has been widely accepted by the market, since
the functions that those products provide are well worth their values. However, for a
new application field, for instance, in anti-counterfeit labels, the competitors are
other materials and technologies, which are mostly well-developed/well-established
and of low price, new unique functions must be identified to justify the high price in
using SMP-based alternatives. From application point of view, film and thin sheet
should be more convenient in many sensor applications. A piece of SMP film/sheet
may be programmed in the in-plane direction (load applied in the length/width
direction) or out-of-plane direction (load applied in the thickness direction) [73, 74].
In order to provide the same feature height of 0.1 mm as in most of coins (refer to
Fig. 5), so that it could feel by fingers, the thickness of Manborui’s anti-counterfeit
SMP label is 0.16 mm, which is far thicker than most commercial anti-counterfeit
labels in the market. The typical thickness of hologram label is 40 μm, while the
typical thickness of void paper is 100 μm. In-plane programming may be done for any
thickness of film/sheet. However, to reduce the material cost, thinner film is preferred
in most of the cases. On the other hand, for out-of-plane programming, it is necessary
to consider both the cost of material and processing (mostly programming via impres-
sion). In the case of utilizing the structural coloring effect via nano-imprinting,
although it is possible to minimize the thickness of SMP to reduce the material cost,
the mold is actually the most expensive part. An ordinary mold produced by CNC
machining or even 3D printing is much cheaper and well-suitable for tactual sensation
by finger touching. Thus, the SMP film must have enough thickness in order to be stiff
enough to maintain the surface feature upon finger touching.
Heat shrink films and tubes are commercially available with different activation
temperatures and mechanical properties. Typical polymers used are polyethylene (PE),
multilayer co-extruded polyolefin shrink film (POF), oriented polystyrene (OPS), PET,
polyvinyl chloride (PVC) for heat shrink films, and radiation-cross-linked EVA for
heat shrink tubes. Biaxially oriented PET (BOPET) is the typical substrate material for
hologram stickers. The technique to fabricate heat shrink films/tubes with zero
Poisson’s ratio upon heating for shape recovery has been widely applied.
To prevent tampering, for instance, heating to remove a piece of hologram label
or void paper without causing any damage to the label/paper, the anti-heat transfer
function should be integrated into the original label/paper to have, for example, self-
destroy function upon heating. Since the heating-responsive SME is an intrinsic
property of most polymers, it should be able to easily integrate this effect into
currently used polymers in anti-counterfeit applications to enhance the reliability
of security. In Fig. 25, a very sharp blade is used to cut lines atop a piece of
316 A. Nabipourchakoli and B. Zhang

Fig. 25 Cracking in hologram sticker upon heating. (a) Original label, in which no apparent crack
can be observed and the color appears vivid; (b) after heating by hair dryer, cracks are apparent and
the color turns dull; (c) removal at high temperatures results in tearing of the label [66]

Fig. 26 Anti-heat transfer quick response (QR) code. Left, modified label; right, without modifi-
cation which is always readable. (a) Before heating, both are quickly readable by smartphone; (b)
after heating, the left is unreadable or takes much longer time to read, while the right is still quickly
readable as before [26]

commercial hologram sticker. These lines are not easily visible by naked eyes
(Fig. 25a). After heating using a hair dryer, these lines open wider, so that it could
easily see and thus the label is damaged and the original vivid color turns dull, most
likely due to heating-induced surface recovery (Fig. 25b). These precut lines serve as
a way to prevent removal of the label at both low and high temperatures, which is
able to effectively prevent heating and then the subsequent removal of the anti-
counterfeit labels (Fig. 25c). This approach can also be integrated into conventional
void paper to prevent tampering at high temperatures.
Due to the fast readability and greater storage capacity, quick response (QR) code
has become a very popular way right now in product tracking, item identification,
time tracking, document management, etc. The same heating-then-cracking concept
shown in Fig. 25 can be applied to result in anti-heat transfer QR code for improved
security as well. As demonstrated in Fig. 26a, before heating, both QR labels with
and without modification can be easily identified by a smartphone with QR code
scanning function. After heating, a small line crack appears on the upper left corner
of the modified label (Fig. 26b). Depending on the exact software used to read the
QR code, some take longer time to read the code, while some just cannot recognize
the code anymore. Of course, with further modification (e.g., with more precut
cracks and larger programming strain), it could make the QR code completely
unreadable after heating.
13 Nanoproducts Based on Shape Memory Materials 317

Stripe interference between two layers with patterns printed atop (Moiré pattern)
is another possible application using SMP to produce the moving effect during
heating-induced shape recovery. Three examples are illustrated in Fig. 27. In
Fig. 27a, upon step-by-step heating, the top layer, which is transparent, moves up

Fig. 27 Moving Moiré pattern based on the shape memory effect (SME) upon gradual heating. (a)
Vertical shifting of the top layer upon gradual heating; (b) rotating of the top layer upon gradual
heating; (c) vertical shrinking of the top layer upon gradual heating [66]
318 A. Nabipourchakoli and B. Zhang

gradually, while in Fig. 27b, upon heating, the top transparent layer rotates slightly.
Figure 27c is different from above two cases, as the top layer shrinks upon heating. A
closer look reveals that there is a fixed relationship between the number of black
bands and the actual strain due to shrinkage. Hence, after calibration, this phenom-
enon may be used in strip-shaped temperature sensors to monitor the maximum
heating temperature.
Figure 28 demonstrates two possible ways to integrate the heat shrink function
with QR code and barcode, respectively, to add in anti-heat transfer function into the
original codes. As shown, after heating, both codes become readable and indicate
void when scanned to show that both labels have been tampered by heating.
The SME in polymeric materials is able to provide not only visible (to see) but
also tactile (to feel) change after shape recovery. The latter function is lacking in
most of the current anti-counterfeit labels, except the shape memory label in Fig. 5,
in which a special polymer with a Tg around 60
C is used. The unique tactual
sensation enhances the competitiveness of SMP products and distinguishes them
with the products based on other technologies. By selecting a right commercially
available engineering polymer, instead of using a newly developed special SMP, it
could not only dramatically lower down the cost but also produce anti-counterfeit
shape memory labels with the required activation temperature.
To increase the difficulty in replication, it might be designed in such a way that
upon heating, the pattern of a special microprotrusion array on one side of a plastic
film disappears, so that the underneath printed pattern on the other side loses the 3D
effect. In Fig. 29a, the microlens array is produced atop a piece of pre-compressed
optical polymer film using laser through a microlens for heating of the required
locations only. Such a microlens array effect has been applied to realize 3D with
naked eyes. The underneath image is specially designed to have more than one
picture integrated together (e.g., in Fig. 29b). Through this microlens array, from
different viewing angles, it can be seen different individual images (e.g., elephant or
tiger in Fig. 13b). If the surface becomes smooth upon heating, the image appears as
a mixture of elephant and tiger. The difficulty to perfectly match the image on one
side to the microlens array on the other side is a big technical challenge, if anyone
attempts to reproduce the 3D effect in a cost-effective way. Customized feature,

Fig. 28 Anti-heat transfer quick response (QR) code (a) and barcode (b). (a) Left, before heating
(unreadable); right, after heating (readable to show void). (b) Left three, before heating
(unreadable); right, after heating (readable to show void) [66]
13 Nanoproducts Based on Shape Memory Materials 319

Fig. 29 Array of protrusive microlens which disappears upon heating (a), and without microlens
array, the image is a combination of tiger and elephant (b) [67]

which appears upon heating, may be produced by 3D printing as an additional

security measure.
A highly interesting feature of PCL is that it is able to crystallize/harden at around
body temperature after being heated to over its melting temperature, which is about
60
C. Furthermore, at around body temperature to room temperature (about 20
C),
the crystallization process takes a few minutes to finish. This feature provides us with
abundant time for programming to achieve comfort fitting in those applications,
where direct contact with the human body is required [75], such as commercial shape
memory splints to fix fractured bone or to stop snoring (e.g., myTAP™ from Airway
Management, USA). After cross-linking or blending with other polymers to result in
SMHs (in which PCL works as small inclusions), both high shape fixity ratio and
high shape recovery ratio could be achieved and in the meantime maintain the
abovementioned special features of PCL that are particularly suitable for direct-
body-contact-fitting. As demonstrated in Fig. 30, the material can be heated to above
its melting temperature, and then our 3D fingerprint can be inscribed on the material
at room temperature or around body temperature via a single gentle impressing of the
finger on the surface of the material. The fingerprint can be fully removed by
reheating. The cross section presented in Fig. 30c reveals that the fluctuation in the
depth of our fingerprint (adult) is about 70 μm.
The phenomenon for the formation of protrusions upon heating can be utilized as
a temperature sensor as well. In Fig. 31, the height of a protrusion increases
remarkably when it is heated to over a critical temperature, which might be tailored
by programming, so that the silver epoxy adhesive atop of the protrusion fractures.
Consequently, the electrical circuit, in which the silver epoxy adhesive is part of the
circuit, shuts down. Since the glass transition in most polymers is sensitive to the
equivalent time-temperature effect, melting transition could be a better choice in
such applications. Furthermore, based on the concept of shape memory hybrid
(SMH), other non-polymeric materials, such as metals, could be used as the
320 A. Nabipourchakoli and B. Zhang

Fig. 30 3D fingerprint (2% cross-linked poly(ε-caprolactone) (PCL)). (a) Top view of 3D scanning
result. (a1) After finger impression; (a2) after heating, the fingerprint disappears. (b) 3D fingerprint.
(c) A-A section of fingerprint

Fig. 31 3D surface scanning results of ethyl-vinyl alcohol (EVA) after programming and coating
with silver epoxy adhesive (a) and after heating for shape recovery (b). The height of the EVA
protrusion increases from 0.48 mm to 1.6 mm after heating

transition part to achieve a narrower transition temperature range and less sensitivity
to the equivalent time-temperature effect [76, 77].
In uniaxial stretching of many polymers at low temperatures, necking and
propagation can be observed. After this process of programming, PCL may change
from opaque (for thick piece) or translucent (for thin piece) to transparent due to
stress-induced crystallization. After subsequent heating, PCL becomes opaque or
translucent again. This phenomenon (transition from opaque/translucent to transpar-
ent upon severe straining and upon subsequent heating from transparent back to
opaque/translucent) may be utilized for anti-counterfeit applications, so that once
heated, the feature behind these polymers becomes invisible (thick piece)
[78]. While this transition phenomenon is limited to some specific polymers, the
stress whitening effect (even silver streaks) is commonly observed in many poly-
mers. Folding a piece of write-on transparency film, which is PVC based, results in a
white line, which can be removed by heating to above its Tg (about 60
C). If
examined under a microscope, it can be seen many micro lines within the white line,
13 Nanoproducts Based on Shape Memory Materials 321

and even the structural coloring effect can also be observed. Most of these lines
disappear after heating, and so is the structural coloring effect. The diameter of the
fibers produced via electro-spinning can reach submicron scale. Even the bulky
polymer itself is transparent; the very thin mat produced by electro-spinning could
be fully opaque and even in shiny silver color. Upon heating, such a mat made of, for
instance, abovementioned PCL or TPU 265A becomes almost transparent [79].
PET is a popular engineering polymer used in a wide range of applications, such
as substrate of RFID, printing transparency film, heat shrink film, optical lens (such
as lenticular lens and Fresnel lens), etc. Its Tg is typically around 70
C. The heating-
responsive SME of a commercial 75-line-per-inch (LPI) PET lenticular lens sheet,
which is placed atop a piece of paper with printed regular line pattern, is demon-
strated in Fig. 32. In Fig. 32a, it can be seen regular parallel lines atop the original
sheet. After heating and compression to flatten the lens, the lines observed in Fig. 32
a largely disappear (Fig. 32b). Heating to over 80
C again results in the return of the
same parallel lines (Fig. 32c) as in Fig. 16a. The underlying mechanism behind this
is the heating-responsive SME in the lenticular sheet and the Moiré effect.
A Rockwell Hardness Tester DXT-3 is used to make an indent on a piece of
Fresnel lens at room temperature. A spherical head is used for impression with a
maximum load of 15 Kg. Figure 33a is 3D scanning result after indentation. In
Fig. 33b, the cross sections along the dashed line indicated in Fig. 33a are compared
for three occasions, namely, after indentation, upon heating to 60
C, and then 80
C.
It can be concluded that unlike the abovementioned lenticular lens, in which the
shape of the lens is permanent, the profile of this Fresnel lens is most likely produced
by hot embossing at around 80
C. Thus, upon heating, not only the indent but also
the original feature of Fresnel lens disappears.
Flexibility is highly in demand in many types of nonrigid sensors, such as stick
type of labels, in order to avoid the problem of easy fracture, which is indeed a major
problem in the SMP label. Rubberlike polymeric SMHs are made of silicone mixed
with an EVA-based melting glue at high temperatures and then adding in agent for

Fig. 32 The shape memory effect (SME) in a 75-line-per-inch (LPI) PET lenticular lens sheet
placed atop a piece of paper with printed regular line pattern. (a) Original lenticular lens sheet; (b)
after compressing of lenticular lens sheet at high temperatures; (c) after heating of lenticular lens
sheet for shape recovery
322 A. Nabipourchakoli and B. Zhang

a b 100
Original
50

Depth in micron
60°C
0
80°C
–50

–100

–150
0 0.5 1 1.5 2 2.5 3
X-axis in mm

Fig. 33 The shape memory effect (SME) in a commercial Fresnel lens. (a) Surface profile of
Fresnel lens after indentation. Dashed line indicating the cross section to be analyzed in (b); (b)
cross sections of Fresnel lens after indentation and upon heating to 60 and 80
C, respectively

Fig. 34 Designed mold (a), ethyl-vinyl alcohol (EVA) plate after impression (b), and (c) heating
temperature vs. number of recovered parallel lines relationships in three labels prepared using
different processing parameters (different programming temperature and different compressive
force)

curing. A perfect combination of super-elasticity, which is tunable, and excellent

heating-responsive SME enables labels made of such SMHs not only flexible for
bending and twisting but also stretchable for significant elongation.
In Fig. 34a, b, a mold with one single protrusion (variable triangle cross section)
atop is used to impress on a piece of EVA plate with pre-marked parallel lines atop.
Upon gradual heating, shape recovery starts from one end and moves toward the
other, and thus, more and more lines become straight again. As such, the shape
recovery progress, which is related to the highest heating temperature, can be
revealed directly by counting the number of recovered parallel lines within the
indented area. Figure 34c presents typical experimental results of three such labels
programmed using different processing parameters (different programming temper-
ature and different compression force). It is obvious that by means of increasing the
density of the parallel lines, better heating temperature estimation is expected.
So far, all abovementioned applications are based on the heating-responsive
SME. As water is easily accessible, various reversible water-activated anti-
13 Nanoproducts Based on Shape Memory Materials 323

counterfeit labels have been in the market for some years. On the other hand, cost-
effective wetting sensors, such as labels to indicate whether a particular item has
been wetted by water and then dried back, are also useful.
Different materials are used in dental treatments, such as plaque removal, caries
treatment, aesthetic interventions, teeth reconstruction, and implants. Indeed, dental
material could be made from diverse sources, from metal alloys to SMPs. The
advantage to using polymers in dental materials is their high biocompatibility and
durability in implants as well as in restoration procedures, among others. Further-
more, SMPs have been used to avoid the biofilm formation during the caries or root
canal treatment as well as in implants. Branched SMPs are replacing the metallic
wires in orthodontic treatments. Indeed, the advantage of using SMPs instead of
metal alloys is that the SMPs do not release metallic ions, which could cause chronic
diseases. Moreover, most parts of the SMP degradation sub-products present high
biocompatibility. Additionally, the nanocomposites made with SMPs could be
applied as platforms for multi-applications, such as sustained release, roots fillers,
and biofilms preventative agents, among others [80].

Some Companies with SMP Products

Guangzhou Manborui Material Technology Co.

(https://manborui.en.ec21.com)
Manborui is the exclusive SMP security label producer, which combines
research, design, production, and sales. Manborui has experience in the SMP
development field and produces shape memory polymers which activate at
low/medium temperature. Manborui has in-depth knowledge about the
FDA-approved SMP material for medical grade standard. An exclusive label film
made from SMP has been developed and supplied for security label printing, which
can store embossed logo/text shape information in the synthetic-paperlike film and
release these information when exposed to 65
C heat in just seconds. As the
producer and supplier of SMP, Manborui’s SMP products for security label printing
include SMP label film, SMP label stock, and also security labels, security seal.
A SMP label film, specially developed for security label printing, supplied in rolls or
sheets, with covert and embossed pattern message hidden inside the label film, on
which any of label designs can be printed-transferred to unique security labels
(Fig. 35).
The label film is applicable for high-quality security labels, security tags, security
seal, security tickets, and security coupon (Fig. 36).

Cornerstone Research Group Co.

(http://www.crgrp.com)
324 A. Nabipourchakoli and B. Zhang

Fig. 35 Manborui’s SMP

security label film. Weight of
label film, 200gram/m2;
thickness of film, 0.18 mm;
color and finish, white (also
available in transparent);
activation temperature, 65
C;
activation is irreversible SMP
rolls; width, 300 mm; core
diameter, 75 mm

Fig. 36 Sample application of SMP label film for security label

Cornerstone Research Group’s new rapid-release, shape memory fastening tech-

nology uses the unique properties of Veriflex ®, a SMP material. At a specific
temperature, this material changes from a rigid state to an elastic state and then
returns to a rigid “memorized” state again. Cornerstone Research Group proposes a
novel reusable mandrel system utilizing SMP. This technology leverages CRG’s
previous R&D from both commercial and governmental programs. In Phase I, CRG
will develop a lab-scale prototype SMP mandrel system. The SMP mandrel will
offer the Air Force a solution to the current composite fabrication and repair issues.
Our goal is to provide a single mandrel system design that will allow quick transition
to multiple desired mandrel shapes, maintain structural rigidity through filament-
winding conditions, and then offer a simple and rapid extraction process. The
13 Nanoproducts Based on Shape Memory Materials 325

proposed mandrel system would function similarly to a rubber inflatable mandrel

during insertion and removal; however it would offer structural rigidity like current
melt-out and breakout systems during fabrication. This type of mandrel system can
only be offered by using a material capable of sharp, controllable, transitioning
properties. CRG’s shape memory materials possess these unique property traits.
CRG will begin to develop designs and calculate the forces the tooling will experi-
ence during the composite fabrication at a lab scale to demonstrate feasibility for
Phase II scale-up. The part will contain design aspects that will demonstrate the SMP
mandrel system capabilities.

MedShape Co. (https://www.medshape.com)

MedShape’s team of engineers and scientists have a proven track record in under-
standing and developing SMPs. Though other researchers have developed numerous
formulations of SMPs, MedShape was the first company to have FDA-cleared and
commercialized medical devices manufactured from shape memory polymers. Their
proprietary PEEK Altera ® biomedical polymer allows devices to enter the target
surgical site in a compact geometry and then be mechanically triggered to deploy
into the optimal geometry for maximum fixation inside bone (Fig. 37).
PEEK Altera offers many clinical advantages over regular PEEK such as
increased deformability without compromising the material strength and toughness,
less invasive insertion approach, and reduced force requirements to deploy. Devices
manufactured from PEEK Altera are biocompatible, biostable, radiolucent, and MRI
safe.

Shape Memory Medical (https://www.shapemem.com)

Shape Memory Medical is a California-based medical device company. The team

has extensive experience with the SMP technology and the commercialization of
medical devices and continues to develop and innovate new therapeutic solutions
using SMP technology. Shape Memory Medical is dedicated to developing innova-
tive therapeutic solutions for peripheral vascular, cardiovascular, and neurovascular
markets. Shape Memory Medical is a medical device company to introduce an
FDA-cleared medical device utilizing SMP technology to a vascular market.
The TrelliX Embolic Coil includes a novel SMP porous embolic scaffold, which
offers significant advantages in neurovascular and peripheral vascular embolization.
The IMPEDE Embolization Plug is indicated to obstruct or reduce the rate of blood
flow in the peripheral vasculature. The IMPEDE Embolization Plug comprises a
shape memory polymer plug and an anchor coil. The porous embolic scaffold
supports the rapid formation of small interconnected clots throughout its structure.
The biocompatible and non-inflammatory polymer promotes rapid conversion to
organized thrombus, followed by collagen deposition without chronic active inflam-
mation, which leads to a stable occlusion.‡ The anchor coil offers stability in higher-
326 A. Nabipourchakoli and B. Zhang

Fig. 37 PEEK Altera the product of MedShape Co.

flow locations, and IMPEDE may be used in combination with IMPEDE-FX to

minimize artifact in a single vessel. Vascular plugs predictably and effectively fill
space in a short time, generally leading to shorter procedure times and less radiation
exposure. Each IMPEDE Embolization Plug offers a high embolic material volume
and inherent 100% packing density. Packing density has been shown to be an
important factor in avoiding recanalization. The SMP portion of the device has no
artifact, which facilitates follow-up imaging (Fig. 38).

Shandong Yabin Medical Technology Co. Ltd.

(http://m.en.crossnt.com/company-374.html)

Shandong Yabin Medical Technology Co., Ltd., established in 2015, is a high-tech

enterprise located in Shandong province. Depending on its patented technology, the
13 Nanoproducts Based on Shape Memory Materials 327

Fig. 38 IMPEDE indication, a medical device used to treat bleeding abnormalities by deliberately
blocking blood flow

company designs, produces, and sells series of products such as functional

low-temperature thermoplastic splint sheets, splinting precuts, and radiotherapy
fixation masks. With a professional design team, a series of advanced automation
equipment, and an innovative marketing team. A sample product of the company is
Orthopedic fracture thermoplastic splint for finger/Thermoplastic (Fig. 39).
The material is able to be softened and modeled under relatively low temperature.
Under normal room temperature, the functional positioning membrane is in solid
state and firm texture. Under the temperature of 60–70 degrees, the material is able to
be activated in 2–3 minutes which will be soft and plastic. The positioning mem-
brane is light, permeable, strong, and with high plasticity. It also has the advantages
of good penetrability of X-ray, nontoxic, odorless, and biodegradable. By adding
nano-antibacterial and far-infrared material, with the function of anti-bacteria and
improve microcirculation.

Asahi Kasei Corporation (https://www.asahi-kasei.co.jp)

The Asahi Kasei Group is a diversified manufacturer centered on chemistry. The

history of the Asahi Kasei Group is rooted in Japan’s first ammonia production by
chemical synthesis, using hydroelectric power, which formed the basis for our
synthetic chemicals and chemical fibers businesses. Asahi Kasei Group now con-
tributes to life and living for people around the world through our operations in the
three business sectors of material consisting of fibers, chemicals, and electronics;
homes consisting of homes and construction materials; and health care consisting of
pharmaceuticals, medical devices, and acute critical care. The products, technolo-
gies, and services of the Asahi Kasei Group can create new value that helps society
overcome current challenges by contributing to a clean environment, to clean energy,
and to longevity with health, comfort, and peace of mind. One of the Asahi Kasei
Group products is SMP resin, resin composition and the shape memorizing molded
328 A. Nabipourchakoli and B. Zhang

Fig. 39 Orthopedic fracture

thermoplastic splint for finger/
Thermoplastic, applicable in
orthopedics, rehabilitation,
surgery, burn

product. The Shape-Retaining Doll Hair was developed for pretend-play dolls. It
offers easy hairstyling for enjoyment (Fig. 40).

Changchun Foliaplast Bio-Tech Co., Ltd. (http://foliaplast.

globalchemmade.com)

Changchun Foliaplast Bio-Tech Co., Ltd., established on 2015, which is a modern-

ized technological company mainly focuses on biomedical materials and high-end
medical equipment. The company mainly dedicated in the industrialization imple-
mentation of “The Fourth-Generation Biomedical Materials,” polylactic acid, poly
(L-lactide-co-glycolide), poly(ε-caprolactone), and so on in the medical field, which
includes the following: plastic filling injection “Sculptra,” bioabsorbable intrabony
fixers (nail, board, bar, pin, and so on), bioabsorbable cannulae implantation in the
surgery, bioabsorbable surgical suture, bioabsorbable hemostatic clip, bioabsorbable
ophthalmology filler, bioabsorbable dentistry filler, drug sustained-release packing
materials, and new type biological tissue engineering devices.
Medical grade biodegradable and bioabsorbable PCL raw material.
Poly(ε-caprolactone) has excellent biocompatibility, shape memory, biodegradabil-
ity, etc. It is widely used in various fields. PCL is soft and easy to process. It can be
used as tissue engineering scaffolds. PCL has low degradation rate and high crys-
tallinity. Its degradation can be divided into two stages in the body. The first stage is
that the molecular weight of PCL declines, but no deformation and weightlessness.
The second stage is the molecular weight of PCLs to a certain value, which is
followed by the weight loss, gradually uptake and excreting by the body.
13 Nanoproducts Based on Shape Memory Materials 329

Fig. 40 Shape-Retaining Doll Hair

Composite Technology Development Co. Ltd. (https://www.ctd-

materials.com)

Composite Technology Development, Inc. (CTD) specializes in developing state-of-

the-art materials and products for extreme conditions and demanding applications.
CTD Engineered Materials Portfolio has over 20 commercial resin systems. CTD
specializes in developing boom deployers, composite booms, solar arrays, and SMP
composite hinges. The folded configuration of self-deployable structure after heating
and stress-induced deformation is presented in Fig. 41 [76].

EndoShape Inc.

EndoShape is a venture-backed company seeking to improve embolization procedures

for patients and physicians through the application of advanced polymer technology
and unique device design. Neurovascular and peripheral vascular embolic coils were
fabricated using a novel, photopolymerized SMP (EndoShape Inc., Boulder, CO)
330 A. Nabipourchakoli and B. Zhang

Fig. 41 Shape memory recovery process of self-deployable structure. Resin from Composite
Technology Development, Inc. [81]

specifically formulated to provide radiographic and MRI visibility while minimizing

MRI artifacts. Control SMP coils were prepared using a standard formulation of tert-
butyl acrylate and poly(ethylene glycol) dimethacrylate [82].

Lubrizol Advanced Materials Co. (https://www.lubrizol.com)

The thermoplastic polyurethane (TPU)-based SMP Estane is the SMP-based product

of the company. The ESTANE ® TPU (thermoplastic polyurethane) product line
consists of polyester, polyether, and specialty polymer compounds. It is a soft,
flexible innovative material for custom and complex 3D-printed designs.

Nanoshel LLC

Nanoshel LLC is a Wilmington, Delaware-based nanotechnology company special-

izing in the commercialization of wide range of nanoparticles and innovative
materials. SMP resin (potting), shape memory resin solution (coating), and SMP
pellet PMM (injection, extrusion) are the Nanoshel products.

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 Part VII
Consumer Nanoproducts Based on
Biocompatible Nanopolymers
Bionanoceramic
and Bionanocomposite-Based 14
Nanoproducts: Concepts, Processing,
and Applications

Tanvir Arfin

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
Plant Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Alginate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Animal Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Chitin and Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Gelatin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Protein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Multiwalled Carbon Nanotube . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Polystyrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Polyamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Polyaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Polyvinyl Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Carrageenan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Applications of Bionanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Ceramic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Nanoceramic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Preparation of Nanoceramic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Another Preparation Methods of Nanoceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Calcium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350

T. Arfin (*)
Environmental Materials Division, CSIR-National Environmental Engineering Research Institute
(CSIR-NEERI), Nagpur, India
Hyderabad Zonal Centre, CSIR-National Environmental Engineering Research Institute (CSIR-
NEERI), Hyderabad, Telangana, India

© Springer Nature Singapore Pte Ltd. 2022 337

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_27
338 T. Arfin

Abstract
The application of nanomaterials in various scientific and research field has
driven progress and development. It has scientifically proved unique opportuni-
ties for future advancement due to distinctive features, namely, chemical inertness
and comfortable design. Mechanical alloying is a processing technique that is
simple, convenient, and sophisticated, and it has persuaded researchers due to
underlying features. The material is nanoscale filler and acquires various attri-
butes, namely, high surface area, strong interaction, and low loadings. As per the
recent studies, it is observed that nanocomposite is renewable and eco-friendly
and casting is minimum and is applied widely. They also reply to issues like
challenging energy, pollution, as well as the environment. The possible combi-
nation of engineered nanomaterial with flexible polymers provides a critical
opportunity for instantly creating and adequately developing the novel valuable
material filled with enhanced properties and is a crucial comparison to the
material used in the starting phase. In the current book chapter, the highlight is
substantially done on applying the material, new conclusion, and future
perspective.

Keywords
Biocompatibiliy · Polymer matrix · Nanofiller · Bionanocomposites ·
Bionanoceramics

Introduction

The composites are typically comprised of two or more than two essential compo-
nents which, after properly joining, naturally possess various unique properties
either by physical or chemical means. The biocomposites are the necessary material
composed of natural and non-biodegradable polymer [5]. Various academic
researchers have given the modern concept and valuable information about
biocomposites. The bionanocomposite is the distinct class of nanocomposite, includ-
ing the naturally attained synthetic biofunctional polymer where the size of nano-
scopic species is between 1–100 nm, which is responsible for influencing the
continuous activity of the composite system [7]. These composites possess various
innovative and multifunctional features, namely, biodegradability, antimicrobial
activity, and biocompatibility [40, 73]. The distinct parts of such nanomaterial
present an extraordinary combination of the polymer with deep concentration,
leading to produce the desired products [26]. The efficient and ubiquitous applica-
tions enable the bionanocomposite to yield nanomaterial in the polymer systems
[8]. From the initial stage of the nanocomposite, a prominent scientist has been
working effortlessly in this field due to the attainment of nanohybrid as the func-
tional and structural materials [17]. Along with various critical aspects, the
bionanocomposite also shows biodegradability and biocompatibility [59]. However,
the bionanocomposite has been instantly recognized as an exciting field because it
14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 339

gets synthesized and fabricated easily and in the same way as conventional polymer
composites [43].
To adequately develop pollution-free quality, the critical component of
bionanocomposites should be altered, which can aid in cleaning the environment,
and it can be even degraded [64]. In conclusion, it is observed that individual
nanocomposite constituent contains beneficial features [41]. On the consistent
basis of precise nature, the effective method for adequately preparing key compo-
nents, practical application of various bionanocomposite is different from the stan-
dard form of the nanocomposite [55]. During 2004, the academic studies on
bionanocomposite showed that they mostly used silica nanoparticles and rubber,
but since 1941, such materials were reinforced.
The bionanocomposites were adequately prepared by naturally making use of
polymer matrices which could instantly naturally degrade as inevitable by-product,
namely, H2O, gases, and biomass. The end products are then absorbed and elimi-
nated. The biodegradation process is natural. Elementary derivatives are mineralized
and then again distributed by the active system’s predictable cycle. The polymer
matrix is a source of the biological carrier, and it breaks down as it satisfactorily
completes its key objective through the metabolic process of hydrolysis or chain
scission. From 1990 to 1992, the term biodegradable was unknown, and the concept
was not clear, which created a raft in cleaning about the deceitful and misleading
environment. It finally carefully brought about the procurement of precisely defining
it with all the standard test protocol and the suitable methods [44].
The functional features and more enhanced capability were typically observed in
the bionanocomposite materials (BMs). It was applied in nanosensing for properly
packing materials, nanocoating, and self-cleaning uses. At present, such materials
are not up to the mark to compete with or replacing petroleum yield plastics because
BM is not vital to be used in water and it wets easily finally and it spoils the food.
The BM is not capable enough to be employed in a moist environment. Therefore,
there was a need to enhance BM either by selecting a suitable polymer or by practical
processing techniques, and they should also be cost-effective. The other most
important aspect that should be adequately considered is that the food items should
be safe in the respective packaging material and gently free from possible contam-
ination. On the gradual incorporation of recent innovative technology, including
antimicrobial activity, research is willingly undertaken to develop nanocomposite
with minimum toxic effects, and they should also be eco-friendly as well.
Clay represents a suitable option properly as it can improve the polymer biodeg-
radation tremendously by uniquely combining the biopolymer like cellulose
[10, 71].

Resources

Renewable resources (RRs) are precious in the current scenario. They possess
ubiquitous features providing various component of feasibility and enhancing the
significance of polymeric materials [56]. RR remains the vegetable species or noble
340 T. Arfin

animals that get economically exploited without the practical use of endangered
species, and some biological activities can renew it. On the specific application of
RR, the country’s economic growth increases, familiarly most of the developing
countries where the biomass, as well as agricultural resources, are abundant and are
generating the critical properties of self-sufficiency.

Plant Resources

Plant resources (PRs) such as abundant seeds, fruit, and flower are synthesized from
a private collection of distinct species in the localized form, posing inadequate tropic
importance for the potential consumers. PR’s unique composition in possible terms
of excellent quality is lignin, and cellulose and the species-particular components
traditionally include steroids and rubber.

Alginate

Alginates comprise structural components in the concerned family of Phaeophyceae,

and it is not found in the plant of land [72]. The prominent member of Phaeophyceae,
brown seaweeds, is naturally found in marine water where the water content
represents 90% along with polysaccharides. They possess various features such as
cost-effective, safe, non-toxic, and biocompatible, processed quickly into gel
[29]. They can absorb water to a large extent, and they can be used as a slimming
material in the paper and textile industry.

Cellulose

Cellulose is resistant to strong alkali with 17.5 wt%. It undergoes hydrolysis’s

creative process at the acidic condition for water-soluble sugars [27]. Cotton fibre
and wood are the primary raw material for synthesizing cellulose bioplastics
[32]. There are various distinct classes of cellulose-like cellulose nanocrystal [48],
bacterial cellulose [49], nanofibrillated cellulose [51], and ethyl cellulose [12, 18, 19,
60, 62]. The cellulose exhibits safe dispersibility properties once it is appropriately
used [63]. At present various potential applications of cellulose are being observed,
so large amounts of cellulosic waste material are adequately prepared from industrial
and agricultural behaviour [9].

Animal Resources

For PR, all the traditional technologies are unused, so animal resources (ARs) are
implemented where wool, animal fats, and leather are monographed. These local
resources are correctly used to progressively improve the quality aspect as such
resources’ profitable employment was not objected.
14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 341

Chitin and Chitosan

Chitin ranks second in the polysaccharide that is available within a similar organism.
The unique structure of chitin and cellulose is the same, but it is instantly found that
the producing organism is different for both chitin and cellulose [3]. It has a
microfibrillar arrangement where the fibrils are embedded in a protein matrix with
a diameter ranging between 2.5 and 2.8 nm [61]. There is precisely some funda-
mental limitation for chitin being traditionally used as flocculant, and it generally
works at a limited pH [20]. Chitin deacetylation is responsible for adequately
obtaining chitosan. It naturally occurs in incredible abundance within the marine
shellfish as biocompatible [2].

Gelatin

Gelatin consists precisely of a distinct type of key protein composed of 19 essential

amino acids. It is derived from bodily tissue and is appreciated from an early age, but
it was operated for the first time as glue in 600 BC [47]. The primary gelation source
is naturally bovine hides, pigskin, and cattle bones. It proves an extraordinary ability
to produce a film. The manufacture of gelatin became industrialized, and now the
application of this protein is gaining interaction as well.

Starch

Indeed in this typical day, the possible use of starch is the same as earlier, where 60%
of it is correctly employed for food purposes and 40% as industrial applications
[65]. The leading chemist carefully studying carbohydrates has merely invented
various valuable items, sufficiently establishing starch use [57]. Starch is fixed as
bioplastic directly as it possesses diverse aspects like it is water-soluble and articles
developed get swell up. It is deformed when brought in direct contact with the
moisture, finally limiting the excessive use it [28].

Protein

Responsible proteins are typically the most critical and experiment friendly mac-
romolecules with the specific residue of long-chain amino acid, commonly called
polypeptide [42]. The name is understandable about its importance and its suit-
ability as it is fundamentally concerned about the physiological methods
[13]. Since all the specific proteins are typically composed of amino acids, they
naturally possess varied features and function. The academic studies and extensive
research for adequately developing adequate protein composite will open the way
of future perspective, enabling to enhance the fundamental properties positively
[52, 53].
342 T. Arfin

Multiwalled Carbon Nanotube

Multiwalled carbon nanotubes (MWCNTs) consist of various graphite layers

instantly surrounded and gently folded on each other as stable form [50]. The simple
carbon nanotubes (CNTs) show insoluble behaviour in the polar solvent because of
the continuous availability of the hydrophobic surface. It is not adequate to
functionalize the polished surface of CNT, enabling it to be soluble in an aqueous
solution. It acts as biocompatible and least toxic in practical application
[4]. MWCNTs progressively increase the polymer matrix’s thermal conductivity
and are responsible for the economic advancement of considerable strength and
dispersibility of the composite.

Polystyrene

Polystyrene consists precisely of aromatic polymers made by the styrene monomers,

and the creative process of manufacturing is cost-effective and minimum [39]. It
possesses various features as it acts as an excellent matrix binder exhibiting crystal-
line structure [21]. It is cell-dependent on continuous dual staining where apoptosis
traditionally dominates cell death [58]. It indeed possesses extraordinary features,
namely, dielectric [16], impedance [34], electrical double-layer capacitance [35], DC
electrical conductivity [14], ionic transport effect [36], irreversible thermodynamics
[25], enthalpy [23], potential [24], charge density [22], entropy [11], antibacterial
activity [1], cell viability [66], etc.

Polyamide

The main commodity polymer is an aliphatic polyamide called nylons. There are
properly various distinct types of nylon like nylon-6, nylon-12, nylon-46, nylon-66,
and nylon-612 [15]. At present, the prime focus is adjusted on bio-based polyamide
thermoplastics developed either partly or wholly from renewable resources [37]. For
efficiently producing the polyamides, monomers synthesized by castor oil get
fermented. The particular synthetic pattern for obtaining polyamides is similar to
the other synthetic polyamide, and hence a considerable number of commercial
products are forwarded in the market.

Polyaniline

For the last 10 years, a conducting polymer, polyaniline (PANI), obtains a highly
studied substance [33]. It exists in a different form with varied physical as well as
chemical features [38]. PANI is tough to be processed when putting in a comparative
study with other conventional polymers. The manufacturing process of PANI is
unusual because of the rigid skeleton framework since it is referred to as a high
14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 343

conjugation level [68]. From the other perspective, it is carefully observed that PANI
is correctly applied in essential medicine and modern biotechnology, but yet its
biocompatibility data is minimal. The primary reason behind such a situation is
proper to the reaction of intermediates and monomer, which obtain aromatic amines,
and it is also harmful.

Polyvinyl Alcohol

Polyvinyl alcohol (PVA) consists of a synthetic and water-soluble polymer, typically

exhibiting various outstanding features, namely, biocompatibility, excellent trans-
parency, and biodegradability [31]. It is recognized as a commercially available
product derived as a combined production cycle in the petrochemical industry. It
cannot be manufactured through monomer’s direct polymerization process since the
vinyl alcohol gets converted rapidly as an enol form of acetaldehyde. This possible
mechanism is due to the thermodynamic aspect, naturally limiting the kinetic control
[45]. Very few valuable information is there on biodegradation-mediated PVA
economically driven by beneficial microorganisms except responsible bacteria.
The first report on PVA biodegradability based on Fusarium lini-specific activity
is phytopathogenic mycete.

Carrageenan

In the year 1837, carrageenans were first extracted from seaweeds. The extraction
process was carried correctly from the prominent Rhodophyceae family [6]. The
sulphate groups present in carrageenan were anionically delivering the chemical
reactivity. The brief explanation of the carrageenan extraction mechanism is under
secret by modern manufacture on a trade basis. Figure 1 exhibits various steps
occurring at the time of carrageenan extraction in the form of a flow chart.

Fig. 1 Flowchart diagram for the extraction of refined carrageenan from seaweeds
344 T. Arfin

Fig. 2. Various types of applications of bionanocomposite

Applications of Bionanocomposites

The bionanocomposites have undoubtedly gained considerable interest, and it is

brought up as important material in the technological era. Such necessary material’s
unique performance has positively enhanced in direct comparison to others in
possible term of considerable flexibility, cost-effectiveness, and so on. It has
shown a large extent of application as well. Figure 2 exhibits the applications of
bionanocomposites.

Ceramic

Ceramic is the main topic of interest for 100 years because of various features like
stiffness, hardness, and chemical stability. Recent innovative development has been
generated in the growth of ceramic by a unique application and applying military
technology, arising interest for health safety and environmental advancement.
Ceramics are divided into two parts, traditional and conventional ceramic comprised
of clay and clay-based material assembling the synthetic raw material with func-
tional and structural features.
Most of the compound has both covalent and ionic bonding. The salient features
of materials are dependent on dominant bonding approaches. Clay is considered
ubiquitous raw material for fulfilling a higher-temperature ceramic category. The
properties of ceramics are controlled through the crystal structure and composition of
14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 345

the significant constituent and by the behaviour and quantity of accessory mineral
available. The mineral of clay can comprise a layer or chain structure. The proper
ratio of layer structure is 1:1 and 2:1. Figure 3 describes the classification of the clay
mineral.

Nanoceramic

Nanoceramic has an interest in the past few years because of its properties such as
extraordinary processing and bioactivity. It can be easily manufactured as it has
ordinarily required porosity, proper size, as well as shape. The nanoceramic is
naturally of four particular categories based on unique structure – zero-dimensional,
one-dimensional, two-dimensional, and three-dimensional structural. The
bioceramic has the macro- and nanomaterial which is not regular for the past few
years. It is operated in applications such as teeth and bone. Figure 4 exhibits various
progressively extent nanoparticle ceramics.

Fig. 3 Different types of classification of the clay mineral

Fig. 4 Different types of applied ceramic nanoparticles

346 T. Arfin

Fig. 5 Applications of nanoparticle ceramic

The nanoceramics, namely, titanium oxide (TiO2), alumina (Al2O3), hydroxyap-

atite (HA), zirconia (ZrO2), and silica (SiO2), are instantly made from synthetic
pathways for merely enhancing the physiochemical features to deduct the toxicity.
Figure 5 reasonably relates to the applied nanoparticle ceramic and its application.

Preparation of Nanoceramic

Figure 6 typically indicates the various methods of manufacturing nanoceramics.

Such innovative approaches efficiently generate different types of nanoceramic,
showing varied shapes, unique composition, and valuable properties.
14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 347

Fig. 6 Various process of development of nanoceramics

Another Preparation Methods of Nanoceramics

Figure 7 summarizes another distinct method of extensive preparation for

nanoceramics.

Calcium

Calcium is the leading element of our considerable body and is vital for the proper
functioning of specific muscles, prominent bones, and immune cells in the develop-
ing organism. Figure 8 shows the various forms of calcium phosphate present in
large amounts in the controlled environment.
Hydroxyapatite (HAP), calcium phosphate, is uniquely an inorganic component
present in all mammal teeth and bone. Bones are made up of collagen molecules and
apatite. The physico-chemical features are carefully formulated as per the synthetic
HAP crystals for continuous optimization of the biomedical uses. Calcium phos-
phate serves as the carrying agents for novel agents, namely, drug and antigens,
which are employed for treating cancer. It is claimed as a delivery device for
antibiotics. Reports suggest that HAP can be combined with various chemical agents
for influencing the therapeutic effect [69].
The calcium carbonate nanoparticle is present in substantial quality within the
environment in the various sources as eggshells and bones. There are different merits
of CaCO3, such as cheaper, biocompatibility, and so on. It is traditionally employed
during functional protein and drug delivery.
TiO2 is another distinct class of ceramic profitably employed for drug delivery to
consider varied types of specific diseases. It is highly applicable in pharmacology
and, at present, for photodynamic therapy due to photo-oxidation. The possible TiO2
toxicity naturally decreases when it is instantly brought in direct contact to the
necessary material, namely, HAP.
Alumina ceramic represents a highly engaged ceramic material that is advanced
and demanding. It has different features, like heat resistance and highly stable. It is
claimed in the biomedical application.
348 T. Arfin

Fig. 7 Different types of preparation methods of nanoceramics

14 Bionanoceramic and Bionanocomposite-Based Nanoproducts: Concepts,. . . 349

Fig. 8 Various types of

calcium in nature

Glioma is a tumour occurring in the central nervous system (CNS) spinal cord and
active brain. Valuable TiO2-PEG material proved to be entirely influenced by the
malignant glioma treatment [75].
Zirconia is a typical ceramic demonstrating extraordinarily significant and ade-
quate biomedical aspects like medical tools and implements. It is concerned for
orthopaedics in synthesizing hip head prostheses. The studies carried on it clear that
there is no severe effect of zirconia insertion to the muscle and bone. But some of the
official reports are present on the comparative study of this elaborate system, and it
amply confirms future needs in specific term of extensive exploration.
Boron nitride nanotubes are used correctly in the proper form of transducers due
to their extraordinary feature that is chemical and thermal stability. The studies
carried out infer about the exploration in the respective field of CNP and putting
forward the medical and biological application.
SiO2 remains the signature product in the research field and is profitably
employed in drug delivering. Mesoporous silica nanoparticles synthesized through
the polymerizing silica in the availability of surfactants have different features. It is
readily available; volume and surface area; ligand gets attached to the silica surface.
It enhances the targetability and biocompatibility. Such nanoparticle can store and
release the drugs to the target site, completely working as a controller.

Conclusion

They are naturally going to be the succinctly summarized from different types of
bionanoceramics and bionanocomposite are already advanced as well as they are
favourably reviewed [46, 54, 74]. All such materials are unique due to the
350 T. Arfin

availability of new chemical, physical, and biological features and are highly capable
of applying [67, 70]. On the addition of nanofillers and nanocoating, the material is
altered for modifying the surface features [30]. As per the considerable variation,
corresponding physical and functional components also get changed and used in
various applications. Varied approaches are present for synthesizing the valuable
material, where every effective method possesses its possible advantages and then
shows its beneficial effect on unique properties [20, 52, 53]. At present, they have
gathered lots of interest as per the scientific and industrial culture. Communities are
posing extraordinary applications in terms of eco-friendly, recyclable, cost-effective,
and energy approaches. It creates harmony and balance between nature and human
invention. The critical point to be instantly noticed is that advancement in the
nanostructured composite will finally revolutionize the modern era of nanotechnol-
ogy. Hence, it could be the main concerning topic for multidimensional research in
the future.

Acknowledgments Authors acknowledge the Knowledge Resource Centre, CSIR-NEERI (CSIR-

NEERI/KRC/2020/SEP/EMD/2), for their support.

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C1CC10659G
 Part VIII
Consumer Nanoproducts Based on Graphene
and Graphene Nanocomposite
Graphene Nanocomposite-Based
Nanoproducts for Renewable Energy 15
Application

Seyyed Mojtaba Mousavi, Seyyed Alireza Hashemi, Chin Wei Lai,

and Gity Behbudi

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Graphene Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Battery-Powered Vehicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Solar Cell Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Fuel Cell Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369

Abstract
One of the significant challenges of the world is the solution of renewable energy
critical and increasing sources. Therefore, the use of renewable energy materials
operates one crucial resolution for this challenge. In recent years, solar cell,
battery, fuel cell, and energy storage technology is widely investigated as one
of the most considerable processes. Graphene nanocomposites are critically
presented as a significant solution to world renewable energy difficulties and
challenges. On the other hand, graphene-based materials and their composites
because of owning the large specific surface areas, hydrophobic properties, etc.

S. M. Mousavi
Department of Chemical Engineering, National Taiwan University of Science and Technology,
Taipei, Taiwan
S. A. Hashemi
Nanomaterials and Polymer Nanocomposites Laboratory, School of Engineering, University of
British Columbia, Kelowna, Canada
C. W. Lai (*)
Nanotechnology and Catalysis Research Center, University of Malaya, Kuala Lumpur, Malaysia
e-mail: [email protected]
G. Behbudi
Department of Chemical Engineering, University of Mohaghegh Ardabili, Ardabil, Iran

© Springer Nature Singapore Pte Ltd. 2022 357

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_31
358 S. M. Mousavi et al.

have a potential impact in a broad range of fields, including nanoproducts. Hence,

in this chapter, after a brief introduction of graphene, renewable energy, more
detailed information is followed on new approach processes. Eventually, the
graphene-based composite for strategic renewable energy has been described.

Keywords
Graphene · Composite · Nanocomposite · Renewable energies

Introduction

Renewable energy technology has expanded considerably, and the reason for utiliz-
ing renewable energy has mainly been to deplete nonrenewable energy supplies,
contributing to climate change and global warming. Nonetheless, as opposed to
nonrenewable energy technologies, yields for certain technologies of renewable
energy are already commercially unpermanent. To dominate this, graphene nano-
technology seeks applications to increase their efficiencies in some of those tech-
nologies. There have been several positive developments and breakthroughs, and
this chapter aims to put some of these successes to light. Just four sustainable energy
areas will be addressed in this chapter: fuel cell technology, battery technology,
energy storage products, and solar panel technology. Nanotechnology has found use
in a broad variety of fields like renewables. Carbon-based nanoparticles demonstrate
enhanced properties compared with nanomaterials from certain components of the
periodic table [1]. In recent decades, fast world economic expansion and increment
in the growth of the population have increased energy consumption. Renewable
energy is one of the most important current issues that are vital for human expansion
that has become an issue of national security [2]. One of the main concerns in the
modern world is the issue of environmental problems and decreased fossil fuels it
also bounded their reserves that affect the world economy and led to the develop-
ment of environmentally friendly systems and the creation of clean and sustainable
renewable energy sources [3]. For this purpose, energy storage device technology
has been developed, and a great of research has been done in the field. Moreover, the
ever-increasing demand for electric vehicles and their fast expansions cause and
create demand for energy storage technologies with a high amount of power and
energy density and renewable energy systems. Amid different energy storage
strategies, electrochemical energy storage (EES) devices have made tremendous
progress with the best properties, including high efficiency and flexibility [4]. There-
fore graphene may be a suitable exceptional candidate for an electron-conducting
additive in lithium-ion battery cathodes. Because of the fairly recent developments in
graphene science, especially by A. Geim et K. Novoselov [5], who in 2010 won a
Nobel Prize in Physics for pioneering work on the two-dimensional substance
structure [6], a special concern is the possibility of utilizing graphene in energy
processing and storage devices [7]. It is attributed to many special characteristics of
the materials, including such strong load carrier mobility (20 m2 V1 s1) [8], the large
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 359

theoretical surface area of about 2630 m2 g1 [9], and a wide electrochemical window
[10]. With respect to energy production and storage applications, graphene was
primarily researched for use in fuel cells [11], solar cells [12], supercapacitors
[13], lithium-ion batteries (as an additive to both anode [14] and cathode [15]),
and lithium-air batteries [16].

Graphene Nanoparticles

GO is a single sheet form of graphite [17] and defined as a two-dimensional

(2D) sheet, extremely slight, consisting of sp2 carbon particles in a honeycomb
organization with various appealing features such as remarkable mechanical resis-
tance [18], electrical conductivity [19], nuclear obstacle prospects [20] integrating
with high-density materials [21], and other uncommon features. As necessities are,
endless specialists place graphene in polymers all together that they may design
polymer-related nanocomposites [22]. Anyway, the perfect graphene business has
wind up being mentioning considering jumbled base-up association [23], low
dissolvability [24], and course of action-related agglomeration in light of van der
Waals interchanges [25]. It is indispensable that the blends, which are substantially
similar graphite or elective carbon sources, may be mixed with graphite using
methods for the top-down approach to obtain various perfect graphene benefits.
Additionally, the surface is inundated with functionalized oxygen bundles by these
blends. The graphite oxidation in protonated solvents promotes oxide in graphite,
which contains a couple of graphene oxide (GO) stacked layers. GO recognizes a
graphene-like hexagonal carbon structure and contains a hydroxyl (– Generous),
carbonyl (C ¼ O), carboxylic destructive (– COOH), alkoxy (C – O – C), and further
utilitarian sets focused on oxygen [26, 27]. Other than their mix ease, these oxygen-
ated segments speak to a vast number of focal points over graphene-like higher
dissolvability [28], similarly as the opportunities for surface functionalization, e.g.,
with octadecylamine, planning for their application in nanocomposite materials.
Also, GO may be managed by methods for various procedures for the synthesization
of decreased graphene oxide (rGO) in order to constrain oxygen sets and get
incorporates closer to those of faultless graphene [29]. Starting late, another
graphene subordinate class has been given, which is known as graphene quantum
dots (GQDs), being on an essential level graphene sheets of <100 nm inside their flat
estimation and abusing the graphene remarkable edge impacts. Graphene forms
(GO, rGO, GQDs) are used as fillers in polymer-based nanocomposite materials
that indicate their extraordinary material properties and disappear from cross-
sectional polymers [30], which prompts different applications. Graphene forms
and derivatives are shown in Fig. 1.
The GO mix could significantly be isolated into two boss parts: base-up systems
in which critical carbon particles are used for advance perfect graphene and “top-
down” techniques in which layers of graphene backups are obtained as of a carbon
source, mostly graphite [31]. Base-up mix (like substance seethe explanation,
360 S. M. Mousavi et al.

chemically active edes

a b

Single-Layer Graphene Multi-Layer Graphene

hydrophobic sp2 bond
graphenic domains
c d

GO rGO
unchrged, polar groups
charged hydrophllic groups (OH, -O-) on the basal plane

e f

GOQD rGQD

Fig. 1 Graphene forms and derivatives: (a) single-layer graphene, (b) multilayer graphene, (c) GO,
(e). GOQD, (d) rGO, (f) rGQD [33]

epitaxial enhancement for silicon carbide wafers, and so on) does not streamline on
time and faces adaptability challenges [32].
Therefore, the obsession upon top-down techniques, which from the outset make
GO just as rGO, is progressively broad for the affirmation of graphene subordinates
only for application in nanocomposite materials. The fundamental GO amalgam-
ation will, by and large, be credited toward Brodie [26], Hummers/modified Hum-
mers [34], Staudenmaier, and Offerman [35]. All of these individuals have gotten
graphite oxide by techniques for the graphite oxidation using various systems.
Hummers and Offerman have balanced the two standard frameworks for extra
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 361

Fig. 2 Improved system for synthesizing GO without poisonous gases as an essential material for
biomedical applications [36]

prosperity by utilizing KMnO4 as an oxidizer (instead of KClO3, building up the

toxic ClO2 gas) and extending sodium nitrate (convey nitric destructive in situ
instead of by nitric destructive as a dissolvable). Because of the more vital prosperity
and quantifiability of Hummers’ procedure, the one is commonly used (or, in the
majority of cases, to a limited extent changed) to make GO (Fig. 2).

Battery-Powered Vehicles

Graphene has the ability to emit lithium ions compared to bulk graphite due to its
open pores. In fact, graphene enables Li ions to travel to all layers of the underlying
graphene and resulting in high energy densities. This results in a continuous steady
anode capacity of approximately 156 mAh g1 over more than 1000 load/discharge
cycles, or a density of power that is nearly 10 kW kg1 anode 1 [18]. Hassoun et al.
used a Li-ion battery that was made of lithium iron phosphate cathode and copper
with graphene nanoflakes anode. Battery technical specifications consist of operat-
ing in 80 charging/discharge cycles and nominal power of 165 mAh g1 or in other
words energy density of roughly 190 Wh kg1. The energy efficiency obtained was
higher than the current Li-ion batteries which could be used by w25%e60%
[37]. The material can also be used to produce supercapacitors and other freshly
crafted items, for storage of electrochemical resources. Alsharaeh et al. [22]
succeeded in developing a method that silver nanoparticles depositing onto rGO
sheets to generate graphene oxide reduced in hole (HRGO). This method continues
to work to remove the silver nanoparticles done with nitric acid. This was done by
irradiating with microwaves to create a robust 3D porous coating for use in Li-ion
362 S. M. Mousavi et al.

Table 1 Materials of lithium-ion battery cathode consist of graphene

Proposed
material Preparation of graphite oxide Reduction of GO Refs
LiFePO4 Hummers method [31, 33]
LiFePO4 Commercially available graphene flakes its [38]
conductivity e 105 S m1
LiFePO4 Vacuum-promulgated with low-temperature – [39]
approach
LiMn1-x Modified Hummers method Chemical (ascorbic [40]
FexPO4 acid)
LiMn2O4 Modified Hummers method Chemical (hydrazine [41]
monohydrate)
LiMn2O4 Modified Hummers method Thermal [29]

batteries as an anode. HRGO-based battery displayed extreme cycling stability of

over 100 load/discharge cycles and a fair load/discharge efficiency of 423 mAh g1
at 100 mAg1. It demonstrates good electrochemical reaction and cyclic output with
a high reversible potential of approximately 400 mAh g1, maintained for up to
100 load/discharge cycles [22]. An ultrasonic method to be used as lithium-sulfur
(Li-S) battery cathode, a 3-D hierarchical graphene sheet sulphur/carbon composite
(C/GSS) was formed. Since the batteries have greater overload capacity, they have
low weight and toxicity, sulfur is of low cost, and therefore Li-S battery is a good
alternative to Li-ion batteries. The composite cathode demonstrated greater electro-
chemical efficiency. The battery gained good charging/discharge cycle stability for
up to 80 cycles and increased performance, after 120 charging/discharge cycles,
retaining power of 561 mAh g1 with 48% retaining power, which implies that the
composite is a popular rechargeable battery product [25] (Table 1).

Supercapacitors

The supercapacitors have considerably higher power densities than traditional

dielectric condensers and demonstrate quick charging and long cycle life discharge
rates and inadequate energy densities for fuel cells and batteries. Because of their
extraordinary physical and chemical properties, carbon-based materials such as
CNTs [42], activated carbon, and graphene were commonly used in supercapacitors
with double-layer electrochemicals. Different carbon products as electrodes for the
supercapacitor have been shown in Fig. 3. Activated carbon owns huge surface area.
Nevertheless, electrolyte ions cannot reach many of the micropores. Usually, CNTs
form bundles that limit their surface area. Electrolyte ions may only reach the
outermost surface. During the drying cycle, graphene nanosheets can presumably
aggregate via van der Waals interactions. Electrolyte ions would have trouble
accessing microscopic pores, chiefly for more abundant ions such as an organic
electrolyte or a high charge rate. CNTs can be used as a spacer between the
nanosheets of graphene to provide the electrolyte ions with rapid diffusion pathways.
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 363

Fig. 3 Assessment of different carbon products as electrodes for the supercapacitor. (a) Activated
carbon. (b) CNT bundles. (c) Pristine graphene. (d) Graphene-CNT composite [43]

Electrical conduction may be improved for the electrons. The CNTs often act as
binders to tie the nanosheets intact to avoid the disintegration of the graphene
structure of graphene in electrolyte.
By bridging the graphene sheets and decorating a typical capacitive performance,
the CNTs will significantly reduce the electrode’s electrical resistance to the
interlayer. Also, the CNTs can serve as a graphene interlayer spacer, to hold away
from restacking relative to each individual, allowing available electrolyte ions. The
electrolyte ions can readily penetrate the inner portion of the electrodes with the
spacer device, and thus higher electrochemically active products can be used
(Fig. 4d). However, CNTs may also be used as binders, to connect the graphene
sheets and to facilitate the adhesion of electrodes to the modern collector [44]. The
graphene-CNT hybrid-based materials are also particularly suitable for processing
electrode items in EDLCs. Chen et al. developed and synthesized a hierarchical
graphene (G) 3D structure using CNTs due to a transparent and green hydrothermal
route between the graphene sheets. The materials of the 3D hierarchical structure
were then used for the production of supercapacitor devices as active electrode
materials (Fig. 4a), and high potential strength of 318 F g1 was converted into
graphene-weight materials with an energy density of 11.1 W h kg1. The influence
of graphene on supercapacitor performance concerning weight ratio CNT has been
studied carefully (Fig. 4b, c). First, the maximum overall graphene output is derived
from the 1:1 ratio of the G/CNT mixture, providing an unacceptable 318 F g1
power, which is 64% of the theoretical value of the graphene. Indeed, the green
364 S. M. Mousavi et al.

Fig. 4 (a) Supercapacitor architecture basing mainly on the 3D G/CNT combination. (b) G/CNT
supercapacitor output hybrid, with weight ratios of one of a kind. (c) Strong particular graphene
capacitance of various G-to-CNT ratios in hybrid materials. (d) Schematic diagram of three-
component hybrid device configuration with CNT load spacer [45]

mechanical power of graphene declines and rises with the strain ratio of G to CNTs.
The schematic image in Fig. 4d shows that the restacking of graphene will deteri-
orate as the ratio of G to CNTs decreases. It may have a horrible influence on the
graphene fabric’s effective surface area, thus reducing graphene’s effective contri-
bution to the entire electrode traveling fabric (G/CNT hybrid).

Solar Cell Technology

Just two factors able to be designed for better performance as graphene can be used
in solar cell production. These factors are able to show the number of graphene
layers present in the device and the effect of doping with metallic and nonmetallic
elements. Graphene film is used to make color-sensitive solar cells. In fact, graphene
is used as an electrode [41]. However, the findings obtained leave space for devel-
opment, and this was given by changing the graphene film properties. Nanographene
dispersed at the nanoscale as a building unit. The changed film reveals more
significant connections to the substrate surface. Organic solar cells produced utiliz-
ing films consist of these with clarity of w85%, and they succeeded in this case
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 365

[29]. Graphene can be a good alternative to ITO to increase the durability of organic
solar cells. In the case of solar cells, one electrode should allow electrons to transfer
out, and the rest of electrode should allow electrons to pass [46]. Manufactured a
solar cell that was dye-sensitized, that used a 3D like the vespiary engineered
graphene electrode materials can replace expensive platinum. These GSs have a
conversion capacity of 7.8% from solar energy to electricity. Counter electrodes,
which were tantamount to modern solar cells and used platinum, had a power
conversion of 8% of solar energy into electricity [41]. Manufactured monolayer
graphene added a colloidal antireflective surface to the head of the graphene sheet
and in the following monolayer graphene located on silicon solar cells. They
reported an improvement in power conversion capacity from about 10% to about
14.5%. One of the benefits of colloidal coating is that it reduces the reflection of solar
radiation from solar cells, which increases efficiency of solar cell [47]. Solar cells
perform better by removing electrons while the sun is out that is heated by photons to
provide the necessary electricity. This is how solar cells produce voltage and
eventually energy [48]. When it begins to rain, the sun’s strength diminishes, and
the solar cells’ output is small, such that the system becomes negligible. Researchers
have now discovered a way to overcome this small to no light challenge. Tang et al.
[49] G-based materials have very applications and have been utilized in many layers
of PSC, which consist of ALs, TCEs, and IFLs. The most relevant findings are listed
in Table 2.
Schematic illustration of graphene and its derivatives for solar cells applications
is shown in Fig. 5.

Fuel Cell Technology

Fuel cells can provide clean energy from primary sources. Fuel cells are devices that
use hydrogen along with oxygen to generate electricity and heat. This technology
has very applications which include transportation, biosensors, food industry, micro-
grids, backup power, portable applications, and global energy systems [57]. The
most important types of fuel cells include solid oxide fuel cell (SOFC), molten
carbonate fuel cell (MCFC), alkaline fuel cells (AFCs), polymeric electrolyte mem-
brane fuel cells (PEMFCs), phosphoric acid fuel cell (PAFC), direct methanol fuel
cells (DMFC), and graphene-based fuel cells [58].
In SOFC, the electrolyte which is used is a solid oxide ion conductor. The
electrolyte should contain adequate ionic conductivity of O2- ions. Electrolytes
must operate at low operating temperatures, and for this purpose, thin electrolyte
films are used in porous electrodes. SOFC is divided into planar designs and tubular.
Both types of SOFC include one or several single cells per single layer or a single
tube [59]. Tubular cells such as macro-tubular and micro-tubular have diameter
>15 mm and diameter <5 mm, respectively. In general tubular SOFCs diameter is
more than a few millimeters and can produce by extrusion or co-extrusion of the
anode or the cathode. Planar designs formed from cumulative layers of ceramic or
366 S. M. Mousavi et al.

Table 2 Specifications of PSCs according to G with polymer nanocomposites

PCE Jsc VOC
Composite Device structure (%) FF (mA_cm2) (V) Ref
GO – PSS GO. PET – PEDOT – 1.10 0.52 2.75 0.71 [49]
PEDOT Al. F8T2. C60. PSS
ZnO (EC – G) ZnO(G). ITO – P3HT – 3.9 0.73 7.73 0.63 [50]
EC. Ag. MoO3. PC61BM
G – PSS – FLGs. ITO: PSS – PEDOT. 3.7 0.55 9.44 0.58 [51]
PEDOT P3HT. PCBM. Al. Ca
PRGO: th: NA 7.24 0.64 14.78 0.76 [50]
PTB7
EG.PSS- EG. PEDOT – PTB7. PSS 4.23 0.56 6.53 0.707 [52]
PEDOT -PC71BM. Al. Ba
Au.G. PSS – ZnO. ITO. PCBM – P3HT. 2.7 0.43 10.58 0.59 [53]
PEDOT PSs – PEDOT. G.Au
G – P3OT PEDOT. ITO – P3OT. PSS – 1.4 0.37 4.2 0.92 [54]
G. Al. LiF
Grafted GO: PEDOT. ITO – P3HT. G: PSS 0.61 0.41 3.5 0.43 [55]
P3HT –Al. C60
G: PMMA PMMA. PET: G. PEDOT. 3.3 0.45 8.88 0.83 [52]
MoO3 – PSS. PC70BM –
PCDTBT. Al. Ca
MW: f: P3HT PEDOT. ITO – P3HT. PSS: f: 1.05 0.32 4.7 0.67 [56]
SPFG: CNTs SPFG: MWCNTs. Al. LiF

metal-ceramic. In planar designs, to increase the power, a single fuel cell can
assemble into a stack [60].
MCFC is one of the fuel cells that operate at a high temperature at about 600–
650  C. This feature causes to form more power production efficiency and also the
reactions of electrodes accomplished with high speed, and therefore, platinum
(Pt) catalyst with high cost is not needed, and carbon monoxide is not produced.
MCFC uses the city gas and also sewage gases, which is an advantage for MCFC.
MCFC technology reduces the release of CO2 into the air [61].
AFC is one of the most developed fuel cell technologies and with this fuel cell,
going to the moon took place. AFC has a high amount of efficiency among the fuel
cells and usually utilizes very pure gases. The alkaline media electrolytes
containing OH- used in AFCs have high speed in the oxygen reduction kinetics.
Reduced oxygen ions at the cathode can move to the anode and form OH-
ions [62].
PEMFC technology’s cost for using on a large scale is too high, but they have
some advantages among the other fuel cells. This type of fuel cell is based on Nafion
polymer or other similar polymer membranes as the electrolyte. Electrodes using
PEMMC must be porous to have enough space to emit gases. Also, the electors must
have a high surface area of the platinum catalyst usually used. PEMFC operates at a
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 367

Fig. 5 Schematic illustration of graphene and its derivatives for solar cells applications [39]

high amount of energy density and low temperature and can produce electricity at
high fuel efficiency. PEMFCs have the smallest size, lightweight, high durability,
and high energy efficiency and resist shock and vibration. PEMFC does not produce
CO or NOx [63].
PAFCs are the first generation of fuel cells. PAFC operates at temperatures of
about 170–210  C.
PAFCs are fuel cells that contain porous carbon electrode consisting of a platinum
catalyst. The electrolyte is based on phosphoric acid (H3PO4) with high concentra-
tion. Due to its acidic properties, they can tolerate corrosive environments. Also,
PAFCs have endurance against carbon monoxide concentration. In this type of fuel
cell, pure hydrogen gas or hydrogen-rich gas is the primary fuel to power
production [64].
DMFC is a kind of fuel cell that produces electricity based on reduced oxygen and
oxidized methanol. Methanol solution is a reducer agent that has the ability to pass
the anode flow field. During the oxidation reaction, carbon dioxide is generated, and
it is removed via methanol solution. This type of cell fuel can stores more accessible;
there is no need for the presence of humidification and has a simple design. DMFC
consists of perfluorosulfonic acid (PFSA) located between an anode and a cathode.
368 S. M. Mousavi et al.

Fig. 6 Effect of graphene-based membrane on PEMFC [67]

Catalyst material on the anode side contains Pt-Ru and Pt on carbon, on the cathode
side [65].
The electrochemical properties of graphene include large electrochemically active
surface area, which leads to its potential use in electrochemical devices. Also,
graphene sheets have the ability to hold TiO2 as semiconductor particles or hold
nanoparticles caused to the development and growth of applications of electro-
catalysts for fuel cells. Graphene-based materials, because of playing a catalytic
role in oxygen reduction reactions (ORRs), can be used as catalysts for cathodes of
proton exchange membrane fuel cell (PEMFC). Graphene derivatives have many
applications in fuel cell technology, such as proton-conducting electrolyte mem-
branes, bipolar plates, and electrodes additives. Graphene is used as an electrically
conductive electrode in fuel cells. In other words, graphene can be added to cathode
and anode for oxidation reaction and ORRs of fuel cells [66].
Figure 6 shows effect of graphene-based membrane on PEMFC. As shown
without graphene-based membrane, fuel cell has low efficiency, and by locating
graphene-based membrane, fuel cell performance increases.
Cao et al. used polyethylene oxide (PEO) with GO electrolyte membrane for
low-temperature operation about 60  C of polymer fuel cells. GO’s content was
0.5 wt%. This membrane had high conductivity compared with only PEMs. Both
PEO and GO were hydrophilic and had very high potential for ion-conducting
composite membranes for fuel cells. COOH groups that existed on the GO could
release the proton, which became GO to be an appropriate candidate for proton
exchange membranes. SEM images showed that PEO with GO membrane formed
from condensed composite material. XRD results showed that the d-spacing reflec-
tion of the matrix consists of GO in PEO from 11 to 4.5 . Tensile results showed
that tensile strength, Young’s modulus, and fracture elongation of PEO with GO
15 Graphene Nanocomposite-Based Nanoproducts for Renewable Energy Application 369

membrane were 52.22 MPa, 3.21 GPa, and 5%, respectively. DC electronic resis-
tance was higher than 20 M [68].
Wang et al. used the orderly sandwich-shaped GO with Nafion composite for
DMFC. GO nanosheets were put on the surface of Nafion by using 1,4-phenyl
diamine hydrochloride (PDHC) in the role of cross-linker. The permeability of the
methanol in the composite membrane was lower than Nafion alone. Eighty layers of
GO nanosheets were put on the surface of Nafion, and this composite membrane
showed 6.7  108 cm2 s1 at 30  C. The selectivity of the composite membranes
was five times higher than the Nafion alone. The endurance time test showed that the
composite membranes in Fenton’s reagent were ten times longer than that of Nafion
alone [69].

Conclusion

In renewable energy, which is also a reversible energy, its source of production is

replaceable. Graphene has been widely used for renewable energy due to its unique
electrical, thermal, large specific surface areas, and hydrophobic properties. Espe-
cially graphene nanocomposites due to the incorporation of extraordinary properties
at the nanoscale, such as increasing the specific surface area and reactivity, are an
essential solution to solve renewable energy problems and challenges. The renew-
able energy applications of graphene nanocomposite materials have applications in
battery-powered vehicles, supercapacitors, solar cells, and fuel cells. This review has
discussed the properties and applications of graphene derivatives and their effect on
the performance of battery-powered vehicles, supercapacitors, solar cells, and fuel
cells.

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Graphene Nanocomposite-Based
Nanoproducts 16
Susanta Bera, Atanu Naskar, Hasmat Khan, and Sunirmal Jana

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
Preparation, Properties, and Importance of Graphene Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . 376
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
Graphene Nanocomposite-Based Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Bio-based Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Sustainable Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
Electronic Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
Optical Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
Environmental Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
Present Challenges and Future Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396

Abstract
Depending upon nanotechnology and nanomaterials, nanoproducts have created
a rapidly growing consumer markets. As per current database, approximately
4400 nanoproducts are available in global markets, and major nanoproducts are
being made from various metals like Ag, Ti, Zn, and Au; metal oxides such as
TiO2, ZnO, and Fe2O3; carbonaceous materials; polymers; and silica in their
nanoscale dimension (1–100 nm). Among these, carbon nanotubes (CNTs),
fullerenes, and graphene-based nanomaterials are found to be advantageous in

S. Bera · A. Naskar · H. Khan · S. Jana (*)

Specialty Glass Technology Division, CSIR-Central Glass and Ceramic Research Institute, Kolkata,
West Bengal, India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 373

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_33
374 S. Bera et al.

their functional properties including electrical conductivity and mechanical and

thermal stability. Graphene is one of the promising materials for making nano-
composites suitable for manufacturing various nanoproducts toward different
applications. An up-to-date information on graphene-based nanoproducts for
applications in different fields is scatterly available in literature but not in a single
report which is certainly needed to realize their advancements at a glance. Hence,
this chapter mainly covers synthetic strategies, properties, and applications of
graphene nanocomposite-based nanoproducts with an emphasis on
bio-nanoproducts, sustainable nanoproducts, electronic nanodevices, sensors,
optical nanodevices, and the nanoproducts for environmental remediation.
Finally, the present challenges and future prospect of the nanoproducts are
discussed briefly.

Keywords
Nanomaterials · Graphene · Graphene nanocomposites · Nanoproducts ·
Graphene nanocomposite based nanoproducts

Introduction

Nanoscience and nanotechnology have significantly progressed worldwide for most

all of the sectors [1–3]. Depending upon the nanotechnology and nanomaterials,
nanoproducts have created a rapidly growing consumer markets. As per current
database from https://nanodb.dk/, approximately 4400 nanoproducts are available in
the global markets, and major nanoproducts are being made from various metals like
Ag, Ti, Zn, and Au; metal oxides such as TiO2, ZnO, and Fe2O3; carbonaceous
materials; polymers; and silica in their nanoscale dimension (1–100 nm) [4, 5]. It is
worthy to note that the term nanoproducts is generally used to define the properties
and applications of nanomaterials as consumer products, whereas a nanodevice
means the product of nanotechnology.
According to principal dimension of underlying nanostructures in nano-
materials, the nanoproducts can be categorized into (i) one-dimensional (1D),
(ii) two-dimensional (2D), and (iii) three-dimensional (3D) [6]. Various nano-
materials such as metals, metal oxides, polymers, and nanoscale carbonaceous
materials such as carbon, carbon nanotubes (CNTs), fullerenes, and graphene are
found to be advantageous in their properties including electrical conductivity and
mechanical and thermal stability along with their flexibility toward the develop-
ment of nanoproducts [7–9]. However, graphene is one of the promising precur-
sor materials for making carbonaceous nanocomposites owing to their large-scale
availability, large specific surface area, high electrical and thermal conductivity,
and outstanding mechanical properties, suitable for manufacturing various nano-
products [10, 11]. It is important to note that graphene and its compounds under
an umbrella of chemically modified graphene (CMG) materials like graphene
oxide (GO), reduced graphene oxide (rGO), highly reduced graphene (HrGO),
16 Graphene Nanocomposite-Based Nanoproducts 375

chemically converted graphene (CCG), and in different forms (Fig. 1) with

mechanically stable structures with porous frameworks are commonly called
graphene that can be synthesized from pristine graphite or from CMG materials.
Upon further modification or hybridization with other metals, metal oxides, or
polymers, even with biomolecules like proteins, their functional properties can be
advanced, and most of these are highly promising for large-scale industrial
application. In this regard, novel physicochemical properties of CMG always
attract researchers greatly for their huge possibility to tune properties after
hybridization with the materials forming functional nanocomposites for a wide
range of applications [12–17].
This chapter mainly covers synthetic strategies, properties, and applications of
nanoproducts derived from graphene nanocomposites with an emphasis highlighted
on bio-nanoproducts, sustainable nanoproducts, electronic nanodevices, nano-
sensors, optical nanodevices, and environmental nanoremediation aspects. Finally,
the challenges and future prospect of the graphene nanocomposite-based nano-
products are discussed briefly.

Fig. 1 Mechanically stable graphene-based nanomaterials

376 S. Bera et al.

Preparation, Properties, and Importance of Graphene

Nanocomposites

Preparation

Graphene can be produced by different synthetic methods such as chemical vapor

deposition (CVD), mechanical exfoliation, and solution phase reduction of graphene
oxide (GO) [18]. In this regard, CVD and mechanical exfoliation offer thin film
graphene formation for fabrication of electronic gas- or bio-sensor devices. Espe-
cially, CVD technique can develop high-quality graphene films. However, the
synthesis of graphene oxide from graphite by Hummer’s method or modified
Hummer’s method and followed by liquid phase reduction for conversion of GO
owning hydroxyl, carboxyl, and epoxy groups to reduced/highly reduced graphene
oxide (HrGO/rGO) is found to be cost-effective and facile method [19]. This
reduction improves the properties especially electrical conductivity of GO. There
are several types of reduction processes such as chemical, thermal, and UV light-
assisted reduction. However, heteroatom doping and functionalization/hybridization
of metals, metal oxides, and organic polymers in nano-dimension through a
non-covalent approach toward formation of graphene nanocomposites can further
advance the properties [20, 21]. In this regard, several non-covalent interactions such
as van der Waals forces, H-bonding and π-π, and electrostatic and hydrophobic
interactions exist between graphene nanosheets and other components of the nano-
composites. On the other hand, covalent modification can also be achieved through
the reaction of hydroxyl and epoxy sites or oxidizing the reactive site in GO by
selecting proper functionalizing agents, which introduce a sp3 carbon in the
graphene lattice. However, the surface functionalization by addition of nucleophilic
molecules can be regarded one of the best methods for the synthesis of bulk quantity
of the nanocomposite materials. Preparation strategies of graphene nanocomposite-
based nanoproducts for different applications are given in Table 1 and also sche-
matically illustrated in Fig. 2. In addition, the modifications can enhance the
functional properties of nanocomposites especially at abundant active sites of
graphene assemblies, and these are believed to be promising for the fabrication of
graphene nanocomposite-based nanoproducts (discussed in the next sections).

Properties

Mechanical Property
Graphene possesses low bending rigidity that generally allows graphene structure to
be bent, curved, and folded easily. The bending or flexural rigidity (D) of a material
like graphene can be determined from D ¼ E t3/[12(1ν2)], where E, t, and ν are
Young modulus, thickness, and Poisson’s ratio of the material, respectively [22]. It is
worthy to note that a few layer graphene has already been investigated experimen-
tally with atomic force microscopy indentation technique. In this technique, the
values of Young’s modulus and fracture strength of defect-free graphene are 1.0 TPa
16 Graphene Nanocomposite-Based Nanoproducts 377

Table 1 Preparation strategies and applications of graphene nanocomposite-based nanoproducts

System Preparation strategy Application References
Graphene-Ag-ZnO Low-temperature solution Antibacterial [29]
process (LTSP)
Graphene-Ag-ZnO LTSP Food packaging [30]
Graphene and multi- Solution process Fertilizers [36]
walled CNTs
Graphene oxide Solution process Pesticides [39]
-copper selenide
Graphene-based Modified Hummer’s Supercapacitor [42]
materials method
Graphene-Si Ultra-sonication/solution Li-ion battery (Anode) [46]
process
rGO-Iron fluoride Reverse micelle method Na-ion battery (Cathode) [47]
Graphene oxide and Modified Hummer’s Hydrogen storage [50]
rGO method
Graphene co-doped Hydrothermal reaction Perovskite solar cells [53]
with N/S method
MoS2/graphene In situ hydrothermal route Electrocatalyst for [55]
hydrogen evolution
Graphene doped with Solution process and Electrocatalyst [57]
FeCoNiOx/N pyrolysis
rGO-branched Solid-state reduction Photocatalyst [58]
alkylamine process
Graphene- ZnO LTSP Photocatalyst [14]
rGO-polyaniline-Au Solution process Biosensor [64]
Graphene-polyaniline- LTSP Gas sensor [66]
SnO2
Graphene ZnO LTSP Adsorbent [73]

and 130 GPa, respectively. Adopting similar technique, the measured mean elastic
modulus of chemically modified graphene (CMG) by reduction of GO using hydro-
gen plasma is 0.25 TPa [23], whereas the elastic modulus and fracture strength of
paper-like GO are 32 GPa and 120 MPa, respectively. Liu et al. [24] also
proposed that both Young’s modulus and intrinsic strength are decreased monoton-
ically due to breaking of sp2 carbon network and lowering of energetic stability in
ordered and amorphous graphene oxide. This breaking of sp2 carbon network also
may result in generation of defects or dislocations that can lower energetic stability
of ordered structure of graphene which certainly impact the graphene nano-
composites. In this respect, a great devotion has been paid by many researchers to
elucidate the properties to find out their potential applications. Moreover, the change
in shape driven by bending, curving, and folding of graphene nanomaterials can
more easily be achieved compared to other bulk nanomaterials. It is seen that
relatively much lower energy is required for changing the shape of 2D to 3D
counterparts of graphene nanocomposites in stimuli-responsive materials under
mild conditions. It is a significantly important standpoint for low-powered actuated
378 S. Bera et al.

Fig. 2 Schematic illustration of possible methods for preparation of graphene nanocomposite

based nanoproducts for various applications

devices. This promising mechanical property can be achieved in graphene

nanocomposite-based nanoproducts.
16 Graphene Nanocomposite-Based Nanoproducts 379

Electrical Property
Graphene is a zero band gap material. It also possesses high room temperature
electrical conductivity (106 s.cm1). However, the synthesized GO from graphite
shows a degradation in conductivity [10]. During the synthesis of GO, the generated
hydrophilic oxygen containing functional (OCF) groups within the conjugated sp2
network of graphite results in a collective disruption of basal plane of graphene
sheets. This spoils the electrical properties of GO. In this respect, enhancement in
electrical conductivity of GO sheets is possible by reduction of OCF groups.
Moreover, introduction of optimum content of conducting polymer to chemically
modified graphene (CMG) can also increase the electrical conductivity of the
materials. This can provide an efficient way to tune the conductivity of graphene
nanocomposite-based nanoproducts.
It is noteworthy that low-dimensional graphene nanocomposites offer efficient
mass and thermal transport than that of their bulk counterparts. The performance of
devices derived from the nanoproducts is strongly dependent upon the capacitance
and conductivity of graphene. On the other hand, a high capacitance and conduc-
tivity of graphene sheets allow accumulation and fast transfer of charges that provide
a rapid device response. It is known that the graphene sheets are electrically and
thermally active materials. Upon application of an external potential, it delivers heat
to other components that lead to an asymmetrical thermal expansion between
graphene and other components of a nanocomposite resulting in the bending of
structure in the materials. In this respect, the performance of a device can be
controlled by changing the frequency and duration of the applied voltage. On the
other hand, the restacking of graphene sheets that result in decrease of surface area
and intercalation of nanoparticles within graphene sheets of a nanocomposite-based
nanoproduct can diminish the performance of a fabricated device [25]. However, the
inherent functional properties of the nanoproducts such as light weight, large surface
to volume ratio, and low surface defects can enable high device performance.

Thermal Properties
Thermal properties (such as thermal conductivity, thermal expansion) are the broad
subject under physical property of a material when heat is passed through it. On the
other hand, thermal conductivity (κ) is an important thermal property that relates to
phonon transport in a material. Due to change in temperature, the tendency to vary its
area, shape, and volume is grossly called thermal expansion of a material which is
divided into linear, superficial (related to area), and cubical/volume expansions.
These thermal properties are found to be changed significantly when the size of a
material structure reaches to nano-dimension. Depending upon temperature, there
are two types of conductions that can occur in a material: one is diffusion at high
temperature and another is ballistic conduction at sufficiently low temperature.
Equilibrium molecular dynamics (MD) simulations reveal that thermal conductivity
of defect-free graphene changes with temperature, T (κ / 1/T) [10, 26]. According to
Boltzmann equation, it is predicted that κ depends upon the width of graphene nano-
ribbons (GNRs) and the roughness of graphene edges [27]. In this respect,
380 S. Bera et al.

non-equilibrium MD simulations demonstrate that κ is dependent on length, L, of

GNRs, i.e., κ / Lβ, where β is found to vary from 0.3 to 0.5 at room temperature. On
the other hand, suspended monolayer graphene can exhibit thermal conductivity of
~6000 Wm1 K1 which is significantly higher than graphitic carbon at room
temperature [26]. These thermal characteristics may also be expected in the nano-
products derived from graphene nanocomposites.

Biocompatibility
Graphene/graphene nanocomposites as bionanoproducts should be biocompatible
for human use. Many researchers have already carried out numerous studies to
examine some preliminary steps of biocompatibility of these nanocomposites
[13, 19]. In this regard, a lot of research works also support that graphene is a
biocompatible material on which the living cells can well adhere and proliferate.
However, its compound, GO is highly toxic that may create toxicity to living cells
due to generation of reactive oxygen species (ROS) from abundant OCF groups in
GO. On the other hand, due to the presence of less number of OCF groups, CCG or
rGO/highly reduced GO (HrGO) can exhibit lower toxic effect compared to
GO. Generally, graphene/graphene composites or other particles in nano-dimension
are toxic, but their toxicity can be mitigated through its surface modification or
hybridization with rGO. For instance, rGO can tag/hybridize with highly toxic
nanoparticles such as CdSe and ZnS quantum dots (QDs) [28] to mitigate their
cytotoxicity. It was seen that these nanocomposites are internalized into so-called
targeted tumor cells showing bright fluorescence of the QDs through absorption of
NIR radiation on rGO. The absorbed radiation converts into heat causing simulta-
neous cell death in addition to the fluorescence reduction. As a whole, the nano-
composite can able tumor imaging and photothermal therapy for in situ monitoring
of cancer cells.

Graphene Nanocomposite-Based Nanoproducts

In recent times, the nanotechnology-based consumer nanoproducts of graphene

nanocomposite are increasing gradually. In this respect, the exciting advanced
functional properties and/or characteristics such as nanoscale constituent, nano-
scopic interaction, and large interfacial area of the nanocomposites are playing key
roles in making these consumer nanoproducts. In the next subsections, some
graphene nanocomposite-based nanoproducts for different applications (Table 1)
are discussed.

Bio-based Nanoproducts

Among the nanomaterials including but not limited to nanometals (Ag, Ti, Zn, Au),
nano metal oxides (TiO2, Fe2O3, ZnO), carbonaceous nanomaterials (CNTs, fuller-
enes, graphene), and nano silica are mainly found to be used for making different
16 Graphene Nanocomposite-Based Nanoproducts 381

types nanoproducts for various areas of applications as antimicrobials, food pack-

aging materials, fertilizers, and pesticides. In the next subsections, the uses of
graphene nanomaterials/nanocomposites specifically for bio-based applications are
discussed.

Antimicrobials
Based upon numerous studies that had already been done worldwide, it is no doubt
that graphene or graphene-based nanomaterials as nanoproducts (Fig. 2) have
excellent antibacterial activity [29, 30] through multimodal approaches of graphene
that involve both physical and chemical modes. These approaches are significantly
different (unidirectional, contact mode) than commercially available antibiotics.
Perhaps, the approaches are interesting toward an allied biomedical research because
bacteria can get less chance to resist against a graphene nanomaterial-based nano-
product. It is to be noted that due to the presence of sharp edges of graphene, it can
induce direct damage to bacteria membrane [29, 30]. Other physical damage of
bacteria includes photo-thermal ablation, wrapping, etc. Among the chemical
approach, building of oxidative stress by charge transfer and generation of reactive
oxygen species (ROS) of graphene/graphene nanocomposites are well-known facts
to exhibit antibacterial property of the nanoproducts.
It is worthy to note that with respect to graphene-based nanoproducts, Nano-
Graphene Inc., USA, have already announced the launch of their new “Dr. Nano”
antibacterial coating [31] for their business on “Graphene CA.” Moreover, a patent
already filed on Graphene Handwashing Liquid is also revealed, that is, the appli-
cation of graphene nanomaterial as consumer product [32]. In addition, several
research works for preclinical investigations are going on toward commercialization
of the products as antibiotics for bacterial infections. On the other hand, actual
application of the nanoproduct in wound management is also confirmed by various
research groups including Sun et al. [33].

Food Packaging
In the field of nanoscience and food science, food packaging [30] is a rapidly
growing subject. Nowadays, consumers are more aware and conscious about single
use of plastics due to their detrimental effects especially on food-related application.
Thus, it is easy to understand the pressure felt within the supply chain to eradicate/
mitigate these detrimental effects while maintaining a high standard of quality of
products. For this reason, there is a changing trend found in packaging of food
industry which serves by following several criteria of without compromise on food
protection and freshness standard of foods that must be maintained with the help of
waterproof packaging and prevention toward deterioration of foods [30]. In this
regard, many researchers are trying to find out desirable and cost-effective alterna-
tive food packaging than the use of plastics as packaging materials (Fig. 3) with
improved properties of antimicrobial activity, UV blocking, and breathability. Gel-
atin is widely considered as one of the alternatives to plastics. However, the material
is prone to bacterial attack, highly moisture sensitive, and breakable. It is important
to note that incorporation of graphene oxide into a polymer matrix can make possible
382 S. Bera et al.

Fig. 3 Antibacterial graphene nanocomposite-based nanoproducts for food packaging: (a) vege-
table, (b) meat, and (c) beverage

to improve all these undesirable properties [34]. In addition, it can enhance thermal and
light stability as an environmentally benign material due to its biodegradable property.
Recently, Tetra Pak (Headquarters, Pully, Switzerland) has joined European Commis-
sion Graphene Flagship Project to evaluate future applications of graphene nano-
materials in food and beverage manufacturing as an exclusive representative in food
packaging industry [35]. Moreover, Goh et al. [34] showed a combination of polylactic
acid (PLA) and a biopolymer as an alternative to plastics with rGO creating a sandwich
film structure that can offer high mechanical strength, semi-visible transparency, and
flexibility as well as impermeable property to most of the gases.

Fertilizers
To improve agriculture production, graphene nanomaterials/nanocomposites as
nanoproducts have also shown their application as fertilizers or plant growth regu-
lators [36]. These nanomaterials have been applied as nutrient nanocarriers because
these can act as ecofriendly and sustainable materials. Moreover, the reduction in
fertigation compounds is also possible with the use of nanomaterials which are most
vital for the development of next-generation fertilizers. In addition, there are several
advantages to use graphene nanomaterials for fertilizers toward increasing plant
growth and productivity such as seed germination enhancement, seed growth incre-
ment, biochemical content improvement, shoot and root length raising, photosyn-
thesis rate enhancement, defense system improvement, etc. [36]. Beside the
advantages, soil structure maintenance with slow release of nutrients and improved
water and nutrient retention capacity with balanced soil pH can also be achieved by
the use of the nanomaterials. However, there are some aspects such as ROSs and
phytotoxicity of these nanomaterials. In this respect, further studies are needed
toward sustainable crop production.
It is now known that the basic advantage of the nanomaterials is their high
surface-to-volume ratio that makes them ideal for nutrient carriers in agricultural
sector. According to Pandey et al. [36], graphene and CNTs showed an increased
seed germination rate in sorghum and switchgrass. It was also seen that after
16 Graphene Nanocomposite-Based Nanoproducts 383

incorporation of graphene, biomass in switchgrass increased by 28% at 200 ppm. In

another work done by Hao et al. [37], the generation of several phytohormones
including indole acetic acid, gibberellic acid, and brassinosteroid considerably
increased by fullerene C60 reduced graphene oxide and MWCNTs. These carbona-
ceous materials generally helped in plant growth. On the other hand, Anjum et al.
[38] evaluated the effect of graphene oxide on Vicia faba L. at 100–1600 ppm
concentration, and they found an increased activity of glutathione peroxidase,
glutathione sulfotransferase, and glutathione reductase enzyme in the presence of
GO. It is worthy to note that glutathione through metabolic processes such as
biosynthesis, redox homeostasis, and detoxification can play an important role in
plant growth. Also, several reports are available related to phytotoxicity, size
reduction, number of leaves, and ROSs after the treatment of graphene oxide
[38]. In brief, the effect of graphene/GO concentration has a direct effect on plant
growth, but further research is required to use graphene-based fertilizers for sustain-
able agricultural production.

Pesticides
Pesticides are extensively useful and considered to be the most effective weapon for
agriculture to boost the productivity and protect crops from pests in agricultural
sector. However, an ever increasing demand of foods due to increase in human
population results in intensive and repeated use of these pesticides with constant
increment of the dosages. Except few pesticides which reach their targets, others
pose great risk to the environment with development of insect resistance and residual
entity on non-targeted organisms. Therefore, researchers have tried to develop
advanced multifunctional formulation technologies to solve the problems such as
combined use of current pesticides with other materials. In this scenario, the com-
bination of nanomaterials such as graphene with pesticides termed as “nano-
pesticides” has attracted significant interest in recent times. In this regard, Sharma
et al. [39] reported GO decorated with copper selenide that can hold 40% (w/w) of
pesticide. Moreover, it can remain as a reservoir without any significant loss in leaf,
resulting in the improvement in Pieris rapae larval mortality by more than 35%.
Also, the work performed by Tong et al. [40] showed that polydopamine coated GO
can serve as a pesticide carrier for controlled release of pesticide to prevent the
pesticide loss. Furthermore, Wang et al. [41] reported that the combination of GO
with pesticides can result in highly potent synergistic insecticidal activity. Also,
graphene oxide can synergistically be used with three types of pesticides, such as
pyridaben (Pyr), chlorpyrifos (Chl), and beta-cyfluthrin (Cyf), against economically
important spider mites toward enhancement in activity of the pesticides.

Sustainable Nanoproducts

Sustainable technologies for producing nanoproducts represent a pillar of modern

society. With increasing the demand of nanoproducts can trigger an interest toward
development of sustainable new nanomaterials for modern applications. In this
respect, graphene nanocomposites are found to be highly efficient nanomaterials
384 S. Bera et al.

as sustainable nanoproducts especially for applications in energy storage (Fig. 4) and

conversion (Fig. 5) devices. These are discussed in the next subsections.

Energy Storage

Supercapacitors
Supercapacitors are different from regular capacitors, and these can store tremendous
amounts of energy. Compared to batteries, they have a longer cycle life, simple
charging circuit, and no memory effect, and more importantly, they are much safer
[42, 43]. The main reason of their operational safety and comparatively long life
cycle is the storage of physical energy rather than chemical energy. Also, they can
tolerate much more charge-discharge cycle compared to batteries [43]. Nowadays,
graphene nanocomposite-based supercapacitors as nanoproducts have attracted sig-
nificant attention due to their high power storage capacity and high-energy density

Fig. 4 Graphene nanocomposite-based energy nanoproducts

Fig. 5 Graphene nanocomposite-based nanoproducts for energy conversion

16 Graphene Nanocomposite-Based Nanoproducts 385

[43]. Generally, supercapacitors store energy by two different means – (a) electrical
double layer (EDL) capacitance and (b) pseudocapacitance. Currently, graphene or
carbon-based materials with a high surface area are used as electrode material in
EDL capacitors in which the capacitance arises from the charge and accumulated at
electrode/electrolyte interface [42, 43]. In case of pseudocapacitors, the conducting
polymers or metal oxides are used as electrode material, which undergoes Faradic
mechanism to store the charges. In this regard, graphene is an outstanding electrode
material with carbon atoms in a single-layer graphene sheet arranged in 2D hexag-
onal lattice of sp2 hybridization [43]. Most importantly, it has recently been found
that graphene has intrinsic capacitance of 21 μF/cm2, which is the highest EDL
capacitance value for all the reported carbon-based nanomaterials [43]. For fabrica-
tion of supercapacitor electrodes with graphene nanomaterials, different structures
such as 1D fibers, 2D films, and 3D foams as well as freestanding films and
hydrogels can be used [42], and several reports are found on graphene
nanomaterial-based nanoproducts for fabrication of supercapacitor electrode.
Graphene nanomaterials are the ideal materials to be used for fabrication of super-
capacitor (EDL) electrode due to its very high capacitance value (up to 550 F/g)
[42]. Moreover, the major surfaces of graphene sheets are mainly covered with
exterior surfaces that are easily accessible by electrolyte. These supercapacitors
can exhibit excellent capacitance performance with greater significance in scientific
and technological fields recently being studied by some researchers.

Batteries
With the development of graphene nanomaterials/graphene nanocomposites, the
electrode materials for both conventional battery and their prospective alternatives
are significantly improved. It is seen that graphene-based batteries are durable,
lightweight, and suitable for high-capacity energy storage and have very short time
for charging the batteries [44]. In case of lithium ion batteries, power density, and
energy, rate capability, cyclability, temperature dependence, safety, and, of course,
the production costs are found as controlling parameters. It is worthy to note that
carbon-based additives or conductive polymers are often used as cathode materials
of Li-ion batteries to improve electrochemical properties [44]. A trace amount of
graphene in a conductive network can also able to form long-range electron pathway.
Thus, to enhance the electrochemical performance, it is used as conductive additive
in Li-ion batteries. Pore structure and nitrogen doping in graphene sheets can provide
strong polysulfide adsorption ability in lithium-sulfur battery. In this regard, Song
et al. [45] reported highly crumpled nitrogen-doped graphene sheets having ultra-
high pore volume (5.4 cm3/g) for lithium-sulfur battery application. They achieved a
capacity of 1000 mAh/g with exceptional cycling stability. Recently, Palumbo et al. [46]
developed graphene-silicon heterostructure as an anode material for Li-ion batteries.
They achieved very high capacity of ~2300 mAh/g with high Coulombic efficiency
(99%) at a current density of 350 mA/g. It is to be noted that long-term cycle stability
at high current rates is considered to be the most desired characteristic of Li-ion
batteries. Instead of anode materials, Zhang et al. [47] also reported mesoporous
reduced graphene oxide-iron fluoride as a cathode material for high-performance
386 S. Bera et al.

Na-ion batteries. Considering the above discussion, graphene nanomaterials/nano-

composites as nanoproduct-based anodes and cathodes can fulfill the desired char-
acteristics of batteries.

Fuel Storage
Demand of clean energy from renewable energy resources is increasing rapidly to
reduce the dependency on conventional fossil fuels. It is to be noted that hydrogen
storage can be regarded as one of the alternative energy resources as it is a clean
resource and can possess high-energy density [48]. There are several roots available
to generate and store hydrogen. However, it is still a challenge to store hydrogen
efficiently. In this respect, due to high surface area available for adsorption, graphene
is considered as one of the potential candidates for hydrogen storage. In graphene
nanomaterials/nanocomposites as sustainable nanoproducts, three mechanisms of
hydrogen sorption are possible. These are (i) physisorption (van der Waals interac-
tions), (ii) chemisorption (chemical reaction between graphene and hydrogen
atoms), and (iii) electrochemical sorption (interfacial accumulation of ions or organic
substances). Moreover, certain transition metals coupled with graphene can improve
hydrogen storage capacity of the materials. Graphene-based hydrogen storage sys-
tems can avoid irreversible chemisorption problem. Based on density functional
theory, it is theoretically calculated that an interlayer gap of 6 Å is optimum for
lowering the bonding energy of hydrogen with graphene at ambient conditions
[49]. In this regard, Rajaura et al. [50] reported the factors that depend upon the
hydrogen storage properties of graphene. The binding energy and hydrogen adsorp-
tion capacity of graphene can be tuned by various microstructuring of graphene
along with coupling with different additives. The hydrogen storage capacity of
graphene nanomaterial-based systems also depends on environmental conditions
like humidity. It has also been proved that heteroatom-doped graphene coupled
with metal can improve hydrogen uptake of the material. Thus, research on graphene
nanomaterial-/nanocomposite-based nanoproducts for hydrogen storage application
can leave major scope for potential commercialization of the products.

Energy Conversion

Fuel Cells
Due to very high-energy densities, fuel cells have attracted significant attention. In
addition, low pollutant emission ability of fuel cells is one of the major factors that
are necessary for portable electronics, electric vehicles, and other related energy
applications. In fuel cells, electrode materials mainly determine the cell performance.
Thus, the fabrication of electrocatalytically active catalysts with high activity, low
cost, and good stability is highly required in fuel cell technologies. In this regard,
graphene is regarded as an efficient candidate in fuel cells for oxygen reduction,
oxygen evolution, and alcohol oxidation reactions due to its high surface area and
excellent electrical properties. The catalytic activity of graphene nanomaterials
deteriorates because of very high degree of chemical inertness and less affinity to
anchor other nanoparticles like Pd, Pt, Fe2O3, and Co3O4 [51]. However, GO has
16 Graphene Nanocomposite-Based Nanoproducts 387

OCFSs at its surface or edges which significantly improve the interfacial activity
between graphene electrode and electrolyte. These OCFs facilitate to anchor metal/
metal oxides with GO toward improving catalytic activity. Moreover, heteroatom
doping in graphene can be performed to obtain efficient Pt-free electrocatalysts for
oxygen reduction application [51]. It is found that the electrocatalytic activities of
heteroatom-doped graphene is significantly higher compared to Pt/undoped
graphene and commercial Pt/C catalysts.

Solar Cells
It is a major concern to the materials scientists for improving the efficiency of solar
cells that are highly required for commercialization. Nowadays, graphene-based
solar cells have attracted significant interest due to its improved efficiency. It is to
be noted that the principle of graphene-based solar cells is similar to silicon-based
solar cells in which some of the components are replaced by graphene nanomaterials.
To improve the efficiency, a lot of research had already been performed on graphene
and its doping effect. In this context, dye-sensitized solar cells (DSSCs) are the
foremost third-generation photovoltaic devices due to its high efficiency and rela-
tively low production cost. It is worthy to note that graphene can be used as a key
material against the challenge of developing Pt-free counter electrodes in DSSC due
to its outstanding conductivity, high electrocatalytic activity, and excellent mechan-
ical flexibility. Kaniyoor et al. reported charge transfer resistance, 11.7 Ω cm2 of
thermally exfoliated graphene [52]. This value is close to charge transfer resistance
of Pt (6.5 Ω cm2). The graphene nanomaterial-based DSSCs showed an efficiency of
2.8%, whereas the same for Pt-based DSSCs was 3.4%. It is important to note that
the efficiency of the DSSCs is lower compared to Pt-based DSSCs. However, the
low production cost of the DSSCs due to replacement of Pt metal increases its
possibility toward commercialization. In addition, graphene quantum dots can play a
leading role in the development of high efficiency solar cells. Especially, these
effectively separate photogenerated charge carriers and transfer of photoelectrons
to the electrode due to their high mobility ~10,000 cm2/Vs. In this regard, Chen et al.
[53] reported highly efficient perovskite solar cells by incorporating N or S as
co-dopant in graphene quantum dots. In brief, there is bright future possibility to
fabricate high efficiency solar cells from graphene nanomaterials as sustainable
nanoproducts.

Water Splitting
Due to increasing human population, conventional fossil fuels like coal, naturally
occurring petroleum products, and crude oils are unable to fulfill the world’s energy
demands. Therefore, it is very much important to replace the conventional fossil
fuels by renewable energy sources for sustainable development especially in energy
sector globally. Among all the renewable energy sources such as wave, wind, solar,
biomass etc., the solar energy source shows the highest theoretical potential
(~1.2  105 TW) [54]. Thus, the main focus of energy research is to be given
upon the conversion of solar energy into other energies. In this regard, photocatalytic
and photoelectrochemical (PEC) approaches for water splitting are considered to be
388 S. Bera et al.

efficient and cost-effective techniques where solar energy is converted into chemical
energy in the form of H2 fuel. However, there are some key parameters such as low
light absorption, rapid charge recombination, and instability of semiconductor
materials during the photocatalytic process that limits solar-to-H2 efficiency
resulting in restriction of the utilization of large-scale industrial application of this
process. In this scenario, graphene nanomaterials/nanocomposites as nanoproducts
are suitable candidates for photoelectrochemical and photocatalytic hydrogen gen-
eration by water splitting. These materials can act as electron acceptor and trans-
porter, co-catalyst, and photocatalyst as well as photosensitizer during the PEC
hydrogen generation reaction [55]. Graphene also possesses high work function
value (4.42 eV) that can efficiently suppress the recombination rate of photo-
generated charges, resulting in enhancement in hydrogen production rate. Yan
et al. [56] demonstrated a van der Waals heterojunction formed between 0D
graphene quantum dots (GQDs) and 2D pristine graphene sheets, prepared via
ultrasonication of graphite powder by using GQDs as intercalation surfactant for
highly efficient photoelectrochemical catalyst toward generation of hydrogen fuel
via water splitting reaction. Moreover, functionalized graphene with nanometals and
metal hydroxides, sulfides, selenides, phosphides, nitrides, carbides, etc. also has
significant role in electrochemical water splitting for generation of O2 and H2 [55]. In
addition, Jiang et al. [57] synthesized a functional material that contains one core and
dual shells. In this functional nanocomposite material, a thin layer of spinel oxides
was used to cover the alloyed FeCoNi core and encapsulated in nitrogen-doped
graphene layers (FeCoNiOx@NG). They demonstrated that the oxygen reduction
reaction activity and stability of the material can be comparable to that of 10% Pt/C,
whereas the performance of oxygen evolution reaction is comparable to that of
Ir-black. Besides electrocatalysts, Karim et al. [58] synthesized rGO-branched
alkylamine photocatalysts by a facile solid-state reduction process for photocatalytic
water splitting toward hydrogen generation as clean and sustainable energy.

Electronic Nanoproducts

Piezoelectric Generators
Mechanical energy is converted into electrical signal in piezoelectric materials. It is
the most versatile phenomenon to produce small-scale electronic devices from
surrounding environment [59]. It is to be noted that nanogenerators can be
constructed by different design principles, among which deformation is found to
be one of the important principles for piezoelectric materials. Several research works
on inorganic and organic based nanomaterials such as lead zirconate titanate, lead
magnesium niobate-lead titanate, barium titanate, and polyvinylidene fluoride have
widely been performed for development of ferroelectric nanogenerators [59]. Higher
piezoelectric characteristics can be obtained in these inorganic materials due to their
brittle and rigid nature that can facilitate the durability of the device. It has already
been reported that 2D piezoelectric materials including MoS2 are found to be
significant candidates in this field due to their higher piezoelectric coefficients,
16 Graphene Nanocomposite-Based Nanoproducts 389

Fig. 6 (a) Change in polarization of graphene by applying stress. (b) Schematic of graphene-based
nanoproduct for application in transistor device

sustainability, thermodynamic reversibility, and larger strain values (10%) com-

pared to their 3D counterparts. It is worthy to note that graphene is the most
renowned 2D material having inversion symmetry points. Therefore, it is not an
intrinsically piezoelectric material. However, it is possible to use graphene as a
piezoelectric material by bending graphene (Fig. 6a), making graphene as
inversion-asymmetric. The heterostructures (combining/hybridizing graphene with
other materials) or applying external fields can also generate piezoelectricity. Based
on the density functional theory calculation, it is reported that piezoelectricity can be
induced in graphene with piezoelectric constants up to e ¼ 1 C/m2 by prebending
graphene sheet. This value is comparable with standard piezoelectric materials
[59]. It is also to be noted that inversion symmetry in graphene is destroyed by
bending which produces a dipole moment in out-of-plane direction. Thus, an
electrical response can be generated based on mechanical deformation.

Transistors
Graphene is a good candidate for the use in electro-mechanical devices due to its
special mechanical, electronic, and thermal properties as well as high conductivity
and superior strength [60]. Also, graphene has the capability to reduce dissipated
heat in electronic device. Due to heat conductive property of graphene, it can
significantly be used in advanced electronics. Recently, several research works
focused on fabrication and utilization of graphene-based electronic devices espe-
cially graphene field effect transistors (Fig. 6b). So, depending upon thermal and
electrical properties of graphene, it is possible for potential application in electronic
devices. It is also reported that graphene sheets are well known with advanced
mechanical property. Thus, it can help for specialized and novel applications in the
field of electronics. In this regard, Sadeghzadeh et al. [61] studied the effects of
temperature, geometry, and mechanical properties of graphene-based transistors and
diodes with the help of molecular dynamics. The researchers also showed that the
modulus of elasticity in graphene transistor increases with increasing width of
390 S. Bera et al.

transistor. Moreover, graphene nanoribbon-based heterostructures synthesized via

bottom-up method have excellent electronic properties for high-performance field-
effect transistors and ultralow power devices such as tunneling field-effect transis-
tors. In addition, Llinas et al. [60] reported the fabrication of short-channel devices
from armchair graphene nanoribbons for field-effect transistor application.

Integrated Circuits
Graphene can be regarded as an ideal candidate for development of future integrated
circuits because it has a unique combination of ultrahigh electron mobility and
cut-off frequency. Nowadays, there are several techniques available in literature on
designing of graphene-based radio-frequency and digital circuits [62, 63]. Also,
numerous techniques have been proposed for designing graphene inverters in
which p-type field effect transistors are mostly used. By selectively n-type doping
in graphene sheets within micro- or nanoscale range, it is also possible to design
graphene circuits. In this regard, Al-Mumen et al. [63] demonstrated a complemen-
tary metal-SU8-graphene method to construct both p-type and n-type graphene field-
effect transistors on a single substrate to develop a monolithically integrated digital
circuit. They also showed the feasibility of this method to design an integrated
graphene inverter circuit.

Sensors

It is known that graphene, owing to its numerous functional properties, is a prom-

ising 2D material in many applications especially biosensors and gas sensors that can
be operated by electronic and electrochemical processes (Fig. 7a, b). The properties
including high surface area, conductivity, optical properties, and carrier density of
graphene make it ideal for designing the sensors. In recent time, some consumer
nanoproducts including some wearable bisosensor, diagnostic chips, etc. are
available [64].

Biosensors
The ability to detect wide range of biomolecules such as glucose, proteins, and DNA
has made graphene/graphene nanocomposite-based nanoproduct a perfect material
for application in biosensors. In this respect, the graphene with its high charge carrier
mobility enables an efficient transfer of electrons from a biomolecule that can result
in an electrical response of graphene sheet. This is important for biosensor applica-
tion that has been assessed by a number of research groups [64]. Also, several
detection methods have been employed for detection of biomolecules. However, the
electrochemical detection is mostly used one for its simplicity, rapid detection, and
good sensitivity toward application in life sciences and medicines.
It is worthy to note that graphene/graphene nanocomposite-based biosensor
nanoproducts are already found in market and currently being used by consumers.
These nanoproducts are mainly from Biolin Scientific [64] and Nanomedical Diag-
nostics [64]. In November 2016, Biolin Scientific with ICN2 Nanobioelectronics and
16 Graphene Nanocomposite-Based Nanoproducts 391

Fig. 7 (a) Graphene nanocomposite-based nanoproducts for application in sensors: (a) electronic
sensor, (b) electrochemical sensor, (c) photodetector, and (d) separator

Biosensors Group used graphene oxide (GO) for application in biosensor to their list
of nanoproducts. This Q-Sense GO sensor (the company Q-Sense, now it is a part of
Biolin Scientific) can enable to study interactions of GO with various analytes. This
application may open new avenues for diagnostics and also environmental monitor-
ing. Furthermore, the graphene-based biosensor nanoproduct named AGILE R100
by Nanomedical Diagnostics, launched in December 2016, allows real-time detec-
tion of small molecules – with no lower size limit. Other advantages of this biosensor
are portability, faster sample processing, greater accuracy, and cost effectiveness.
Also, one US-based company, Graphene Frontier, announced the development and
manufacturing of graphene functionalized GFET sensors in August 2014. They
claimed that their developed sensors are highly sensitive and can be used to
efficiently diagnose many diseases [65]. Moreover, researchers at Iowa State Uni-
versity and Northwestern University have jointly developed a graphene-based sensor
which can detect histamine down to 3.41 ppm level [65]. It is worthy to note that in
addition to its allergenic potential, histamine is also an indicator of spoiled fish and
meat. In edible portion of fish, FDA guideline for histamine is 50 ppm. Therefore,
392 S. Bera et al.

this sensor is suitable to track food freshness and safety. It is also observed that
European Union-funded MULTIMAL Research Project [65] developed a kit com-
prising graphene which can quickly identify malaria parasites from saliva sample
without using any lab equipment. The nanoproduct as biosensor for disease detec-
tion has also been reported by Archer Materials. Now, the company is progressing
for the use of their products by consumers [65]. Very recently, another revolutionary
attempt has been taken by Korean researchers to develop graphene-incorporated
field effect transistor-based biosensor to detect SARS-CoV-2 in nasopharyngeal
swabs of COVID-19 patients in less than 1 min time [65]. Similarly, Grolltex, in
collaboration with Sanford Burnham Prebys Medical Discovery Institute, is in a
process to develop this type sensor for COVID-19 detection platform [65].

Gas Sensors
Widespread research efforts are significantly focusing on development of nano-
products of graphene-based ultrasensitive gas sensors to detect harmful gas mole-
cules in extremely low concentrations for their applications in different industries
like oil, gas, and petrochemical industries. The researchers proved that these sensors
have the ability to detect different types of small molecules in gaseous state and also
some volatile organic compounds (VOCs) [66]. It is important to note that the exact
sensing mechanism to detect the molecules differs from sensor to sensor, but most of
the mechanisms function via adsorption phenomenon. These sensors can able to
detect gas molecules such as hydrogen, H2O, CO, NH3, NO2, Cl2, ethanol, I2, and O2
at ppb level [66].

Other Sensors
Apart from consumer nanoproducts related to biosensors, other sensors based on
graphene materials are also available in the market or these are still under active
research to come to the market. In this regard, Paragraf, a UK-based sensor
company in collaboration with CERN, the European Organization for Nuclear
Research, is closely working to make a graphene sensor with negligible planar
Hall effect [67]. The University of Sussex has developed a graphene-based sensor
that can stretch up to 80 times higher strain than the strain gauges currently
available in the market [65]. These sensors can tremendously help to monitor
structural integrity of buildings and bridges. On the other hand, graphene-
enhanced color-changing flexible photonic crystals have been used to develop a
sensor that can warn about earthquake [65]. Bosch and Max-Planck Institute in
June 2015 manufactured a graphene-based magnetic sensor which is 100 times
more sensitive than an equivalent silicon device [65]. In September 2014, a
German company AMO in collaboration with Alcatel Lucent Bell Labs developed
possibly the world’s fastest graphene-based photodetector [65]. Cambridge
Research Center of Nokia in November 2013 also developed a graphene-based
humidity sensor with high response and recovery time in addition to the charac-
teristics of incredibly fast, thin, transparent, and flexible [65]. In April 2018,
Uttarakhand Residential University, RI Instruments, and Innovationin, India, has
16 Graphene Nanocomposite-Based Nanoproducts 393

reported to develop a graphene-based technology which can be used to prevent

drunk driving. It is worthy to note that as per Motor Vehicles Act in India, the
driver will not allow to start a vehicle in case of his/her blood alcohol content
more than 0.03% per 100 ml of blood [65].

Optical Nanoproducts

Photodetectors
In photodetector (PD), optical signal is converted into electrical signal. Generally,
PDs are the basic building blocks of an optoelectronic device (Fig. 7c). In this regard,
graphene is found to be a promising material for optoelectronics and photonics due
to its several advantages compared to other materials [68]. Several prototype opto-
electronic devices such as optical modulators, transparent electrodes, photovoltaic
modules, ultra-fast lasers, and plasmonic devices have been designed by using
graphene. A significant effort has also been devoted for the fabrication of
graphene-based PDs. Single-layer graphene (SLG) is capable to generate charge
carrier by light absorption over a wide range of wavelength. Moreover, it is found
that SLG exhibits several distinct characteristics such as ultrafast carrier dynamics,
wavelength-independent absorption, tunable optical properties, high mobility, and
the capability of electromagnetic energy confinement in exceptionally small volumes
[68]. It is also important to note that SLG is an atomically thin material, and it is able
to absorb about 2.3% of the incident light. This interesting property of SLG
facilitates the fabrication of flexible and transparent optoelectronic devices. Gener-
ally, metal-graphene-metal (MGM) configuration is found to be exploited in
SLG-based PDs where SLG channel is used to contact between sources and drain
electrodes in PDs. Several PDs can operate in telecom wavelengths (low-loss
wavelength range, 1260–1625 nm). It is also seen that PDs can be designed from
hybrid MGM with silicon waveguide.

Polarizers
Due to extraordinary electronic transport property, graphene has attracted significant
interest in the field of nanoelectronics [69]. It is noteworthy that the photonic
(optical) properties of graphene are also found to be equally remarkable. The fine
structure constant of graphene defines its universal optical conductance, and it is
independent of frequency over a wide range. Due to zero bandgap, graphene is
capable to detect high-bandwidth of light. It can be used as saturable absorber in
ultrafast laser and also for broadband telecommunications. Moreover, it is possible to
fabricate photonic circuits with ultrathin optical elements using graphene owing to
its two-dimensional structure. It is also very much important to manage light
modulation by polarization to minimize error and signal fading in coherent optic
communications, optical gyroscopes, and interferometric sensors [69]. Graphene
may also be utilized for routing, creation, modulation, or detection of light in these
circuits/devices.
394 S. Bera et al.

Separators

Separation by membranes is a widespread phenomenon in scientific community. A

membrane can be described as a thin permeable barrier which allows certain
molecules or ions to pass through it according to their characteristics such as pore
diameter, permeability coefficient, charge, and solubility level. Several nano-
materials such as nano-silica (SiO2), metal organic framework compounds, carbon
nanotubes, aquaporins, zeolites, and graphene show excellent performance as mem-
brane materials. The development of membranes to generate separators requires
materials with high strength, non-toxic smooth surfaces and channels and also
materials that will be able to trap other substances. In this regard, graphene-based
nanomaterials are perfectly suitable to satisfy these required criteria. These are
internationally used for seawater desalination (Fig. 7d). Some essential parameters
of graphene-based membranes are pressure, concentration difference, and electricity.
By using pressure-driven membranes, Cohen-Tanugi et al. [70] demonstrated mono-
layer nanoporous graphene membrane that can successfully remove salts from water.
However, a few membranes are also observed as electric-driven membranes with
promising performance due to their stability in addition to their effective water-
retention ability. In addition, monolayer graphene can also restrict to pass a very
small gaseous molecule including helium. It is also to be noted that owing to high
surface porosity in nanoporous graphene, it can efficiently allow gas flow to selec-
tively pass through the membrane. Hence, it is a potential membrane material.

Environmental Remediation

With growing population, the global demand of fresh water increases. Basically,
suspended solids and bacteria contaminate water that results in change of odor and
color of water. The polluted water contains hazardous/toxic organic molecules such
as dyes, dioxins, phenols, pesticides, and petroleum products, which are generally
discharged from textile, printing, plastic, fertilizers, leather, paper, cosmetic, and
other processing industries. Thus, the decontamination of water is highly needed,
and it is possible through adsorption, photocatalytic degradation, and adsorption
followed by photocatalytic degradation of the water-soluble pollutants by porous
graphene nanomaterials as nanoproducts.

Adsorption
To date, several adsorption materials have been used to remove various toxic
components from waste water. Most commonly used adsorbents are activated
carbons, clay/clay-based minerals, silica gel, synthetic zeolites, and silica-based
adsorbents. For environmental remediation, graphene nanomaterials as nano-
products are known to be promising and cost-effective materials that can be used
as adsorbents to remove hazardous contaminants including heavy metal ions,
organic compounds, and gaseous molecules especially from aquatic environment.
In this regard, to remove the metal ions, Sui et al. [71] synthesized low-cost
16 Graphene Nanocomposite-Based Nanoproducts 395

CNT-graphene nanocomposite aerogels which uptake a number of heavy metal ions

like Cu(II), Ag(II), Pb(II), and Hg(II). On the other hand, the adsorption by using
magnetic graphene nanocomposites is a highly acceptable method because it not
only enhances the adsorption process but also allows easy separation in a batch
adsorption. Thus, the nanocomposites can act as recyclable adsorbents. Wang et al.
[72] synthesized graphene-magnetite nano-hybrid for removal of fuchsine dye from
water. They showed 99% sorption capacity within 30 min (89.4 mg g1). This
sorption followed Langmuir and pseudo second-order reaction models. Moreover,
the material has also been used to uptake other dyes including Congo red, methylene
blue, and pararosaniline. The adsorption of organic dye followed by photo-
degradation (further details are given in the next section) by photoactive graphene
nanocomposites is an effective strategy for their recyclability. In this regard, our
group [73] synthesized hierarchical hollow ZnO-graphene nanocomposite by solu-
tion process, and we used the material as an effective reusable adsorbent for
rhodamine B dye via photodegradation process.

Pollutant Degradation
In photodegradation process, a semiconductor (as photocatalyst) is irradiated mostly by
UV or visible light of higher energy compared to the band-gap of a semiconductor,
forming photogenerated electrons and holes on the semiconductor surface. The photo-
generated charge carriers in semiconductors take part in oxidation-reduction processes
toward the degradation of organic pollutants including various organic dyes. However,
instead of pristine semiconductors, graphene hybridized semiconductors such as TiO2-
graphene, ZnO-graphene, CdS-graphene, SnO2-graphene, etc. are found to be used as
efficient photocatalysts for degradation of organic pollutants [73–75]. It is seen that an
enhanced performance of graphene-based photocatalysts can attribute owing to their
large surface area with excellent conductivity toward efficient charge transport property.
For example, TiO2-graphene nanocomposite showed an enhanced catalytic efficiency
compared to pristine TiO2 in degradation of methylene blue [74, 75]. On the other hand,
nanostructured graphene nanocomposites with high surface area can be more advanta-
geous, and these are also promising for photocatalytic organic dye decomposition. In
this regard, our group [14, 73] synthesized hierarchical hollow and core-shell structured
ZnO-graphene microspheres for photocatalytic RhB degradation. The hollow
microsphere-based nanocomposites showed highly efficient photocatalytic activity and
recyclability compared to their solid microsphere counterparts. It also showed effective-
ness for removal of other organic pollutants such as methyl orange and phenol. An
added advantage of these graphene-based photocatalysts as nanoproducts may be their
ease of synthesis.

Present Challenges and Future Prospect

Graphene nanocomposite-based nanoproducts exhibit immense possibility for enor-

mous applications in diversified fields. Several nanoproducts are currently being
available in global markets. However, the production of high-quality products in a
396 S. Bera et al.

simple and scalable process creates bottleneck that need to be surpassed. In this
respect, establishment of chemical/physical interactions of graphene with other
components of nanocomposites can overcome a number of challenges toward
technological development of numerous nanoproducts for their widespread applica-
tions. Also, nanoengineering is mostly needed for each system toward determining
the structure that related to functional properties of graphene nanocomposite mate-
rials. This certainly deserves more detailed research toward understanding for
fundamental aspect and also for the technical advancement of the nanoproducts.
Although there are enormous attentions that already paid for development of various
nanobioproducts, further improvement in stability, biocompatibility, and toxicity of
the products is of immense importance. With the advancement of nanotechnology
for producing nanoproducts, the consumers are required to learn about health, safety,
and environmental effects of nanotechnology. It is also to be noted that in many
commercial manufacturing processes, there may have unknown sources for contam-
inant generation which changes the properties of the products. On the other hand,
graphene nanocomposite-based nanoelectronics with excellent physical and chem-
ical properties can deserve as flexible and stretchable nanoelectrical devices in very
near future. In addition, environmental remediation can be overcome by pilot scale
production of graphene nanocomposite-based nanoproducts. Hence, it is expected
that the current and forthcoming rapid research/investigations/activities continuing
worldwide upon graphene nanocomposite-based nanoproducts will lead to gift more
and more new nanoproducts with vastly improved quality compared to presently
available nanoproducts for wide range of applications.

Conclusion

Nanoproducts have created a rapidly growing consumer markets. In this respect,

graphene nanocomposite-based nanoproducts as bio-nanoproducts, sustainable
nanoproducts, electronic nanodevices, sensors, optical nanodevices, and so on are
found to be highly promising. Although there are several challenges, industrial-scale
production of these nanoproducts by robust, cost-effective, and environment-
friendly processes can greatly impact on the quality of life.

Acknowledgment One of the authors (HK) thankfully acknowledges CSIR, Government of India,
for providing financial support to his doctoral research.

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Novel Graphene-Based Nanocomposites-
Based Nanoproducts 17
Srinivasarao Yaragalla, Bhavitha K. B., and Sabu Thomas

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
Applications of Nanoproducts of 3DGPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Nano Products in Energy Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Nano Products in Conducting Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
Nano Products in Sensitive Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
Nano Products in Environmental Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
Conclusions, Challenges, and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413

Abstract
The incorporation of graphene into various polymers results in porous three-
dimensional networks that have received significant attention in the last two
decades for their multiple applications in multiple sectors, including electronic,
oil separation, and energy storage, to name a few. Such network structures have
been designed through various chemical routes with superior mechanical and
electrical properties, which significantly augmented the scope of research in
graphene polymer nanocomposites. Intricate interfacial synergistic interactions
among graphene and polymers and hierarchical porous connections in graphene
can harness the porous three-dimensional graphene polymer composites’

S. Yaragalla (*)
Istituto Italiano di Tecnologia, Smart Materials Group, Genova, Italy
B. K. B.
International and Inter-University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi
University, Kottayam, Kerala, India
Department of Physics, St Teresas’s College, Ernakulam, Kerala, India
S. Thomas (*)
International and Inter-University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi
University, Kottayam, Kerala, India
e-mail: [email protected]; [email protected]

© Springer Nature Singapore Pte Ltd. 2022 401

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_34
402 S. Yaragalla et al.

functionality. This chapter covers the potential applications of nanoproducts of

such composites, including energy storage, conducting composites, sensing,
environment protection, etc. Moreover, challenges and future perspectives asso-
ciated with these composites are highlighted at the end of the chapter.

Keywords
Graphene · Porous structure · Polymer nanocomposites · Applications ·
Nanoproducts

Introduction

Graphene is a single-layer form of graphite that comprises a hexagonal arrange-

ment of carbon atoms in a two-dimensional honeycomb structure. Each carbon
atom has sp2 hybridization leaving a pure Pz π electron that is delocalized
through adjacent π bonding orbitals. This significantly causes the high electrical
properties of graphene, and even at room temperature, it can show significant
conductance of electricity [1–3]. Moreover, it has grabbed great attention from
the scientific community as well as industry due to its unique mechanical,
thermal, and optical properties [4–6] as it could be used as efficient nano
reinforcement in polymer nanocomposites [7–14]. It also possesses a large
surface area and high aspect ratio, which lifts its usage as a promising nanofiller
for fabricating polymer composites [15]. Its versatile applications have been
utilized for manufacturing three-dimensional (3D) networks like aerogels,
sponges, and foams through synthetic manifold routes. Chemical vapor deposi-
tion (CVD), chemical modifications of graphene, self-assembly of graphene
structures, and in situ unzipping of carbon nanotubes are the most employed
methods to create such networks [16–20]. Different types of ions and molecules
could quickly diffuse through these three-dimensional graphene networks
(3DGNs), as they possess hierarchical interconnected porous structures.
The 3DGNs bring back other essential properties of pristine graphene and
intrinsic surface though the small extent of restacking of graphene sheets
which is complicated to obtain maximum functionalities as in case of polymeric
systems for various practical applications including catalysis, separation, and
sensing [21–24].
Constructing the three-dimensional graphene-polymer networks (3DGPNs)
through reinforcing graphene into various polymers has been increasing over the
past decade due to their versatile applications in multiple sectors [25–28]. Moreover,
it would help to understand the chemical interactions and self-assembly associated
with graphene and polymers. Many significant efforts have been dedicated to
developing 3DGPNs with various synthetic chemical methods, which create differ-
ent structures, morphologies, and properties to meet the challenging applications. In
this review, recent advances of 3DGPN nanoproducts have been discussed, and the
future perspectives and opportunities associated with them are highlighted.
17 Novel Graphene-Based Nanocomposites-Based Nanoproducts 403

Applications of Nanoproducts of 3DGPNs

Combining the features of 3D porous graphene with specific functionalities of

various polymers, 3DGPNs can show promising applications in the sectors of energy
storage, conducting composites, sensing, and environment [26–28].

Nano Products in Energy Storage

Due to its long cycle life, high power density, and high rate capability, super-
capacitors are renowned as indispensable devices for storing electrochemical energy.
They have attracted immense interest from material scientists from the past two
decades [29]. The supercapacitors’ energy storage mechanism originated from
adsorption phenomena, oxidation, and reduction reaction at the surface. They
generally store the energy through either fast redox reactions at the surface (pseudo-
capacitors) or ion adsorption at the electrolyte and electrode’s interjection, which can
be seen as electric double layer capacitors (EDLCs).
Due to fast ion and mass transfer, highly interconnected pore networks, large
surface area, and low density, 3D graphene macrostructures have become exten-
sively used materials as electrodes for designing EDLCs [30–32]. It is important
to note that significant theoretical capacitance could be exerted by poly pyrrole
(PPy) and polyaniline (PANI), which is much higher than carbon materials that
have been employed to fabricate pseudocapacitors owing to their super redox
reactions and easy preparation. Nevertheless, their swelling and shrinkage nature
during the charge–discharge cycles lead to poor cyclic stability, which limits
their practical applications [33]. Therefore, the inclusion of conducting materials
(pseudocapacitive) into 3D porous graphene polymer structures resulting in a
hybrid system has an additional advantage for improving energy storage
capacity.
In situ chemical polymerization or electropolymerization of monomer in the
presence of 3DGFs could be employed to fabricate 3D graphene/conducting poly-
mer composites [34, 35]. The inclusion of nano polymer structures (nanowires,
nanorods, and nanotubes) in the electrode results in improving the absorption of
electrolyte ions, which further mitigates the ion diffusion distance, thus can improve
the cyclic stability of the device [36, 37]. For instance, PANI nanocones (vertically
aligned) decorated with a 3D graphene structure results in a specific capacitance of
751.3 F g
1 in 1 M HClO4 @ current density 1.0 A g
1; importantly, it retained
93.2% of initial capacitance after completion of 1000 charging-discharging cycles
[38]. Hollow structured (micro/nano) materials, known as another class of materials,
can be employed for energy-related applications. Significant improvement in spe-
cific surface area and high electroactive regions with short diffusion lengths could be
created through designing such structures with 3DGPCs for better charge and ion
transport [39, 40]. In a report, fabrication of PANI/graphene hollow structures with
graphene oxide and polyaniline was done via electrochemical reduction of graphene
oxide (GO) [39]. The resulting three-dimensional structure provided conductive
 404

a b 2000 20
Electrochemical Oxidative
300 s 1800 s
polymerization polymerization 3600 s PANi-GF
1500 15

Inkjet
1000 10

Polyaniline coated Polyaniline filled

3D graphene foam graphene foam
graphene foam 500 5

Areal capacitance (mF/cm2)

Volumetric capacitance (F/cm3)

c 0 0
0 5 10 15 20 25
Current density (mA/cm2)
II

d 100
flexible SC device
GH GH-PANI
I
VIII ref.37
GO III

IV
nanosheets freestanding 10
GH-PANI/GP ref.41
ref.40 ref.38
VII
ref.39
GO GH-PANI Hl solution
Energy density (Wh Kg-1)

ink V ink VI
1
100 1000 10000
paper substrate GH-PANI/GOP bubbles Power density (W kg-1)

Fig. 1 (continued)
S. Yaragalla et al.
17 Novel Graphene-Based Nanocomposites-Based Nanoproducts 405

networks, which significantly enhanced the cyclic performance of the fabricated

device or product (supercapacitor) with the specific capacitance of 614 F g
1.
3D graphene foams fabricated by a CVD method have a low intrinsic electro-
chemical activity limiting their capacitive performance. The macro-sized pores (size
in the range of several hundreds of micrometers) can facilitate electrolyte transfer;
however, they do not contribute to the areal capacitance. Nonetheless, the 3DGF
offers excellent electric conductivity and porosity on which conducting polymers
can be decorated for various electrochemical applications [41]. The problem asso-
ciated with electrodepositing polymers on 3DGFs is that coating a thin layer of
conducting polymers on graphene’s surface, which provides small areal capacitance.
Therefore, it is essential to cover the macro-sized pores with smaller pores of
pseudocapacitive materials to enhance its areal capacitance. To achieve this,
bicontinuous macroporous graphene foam composed of few-layered graphene sheets
was fabricated by Chan-Park’s group [42]. The fabrication procedure is summarized
in Fig. 1a, b. The PANI thin layer has been coated on the surface of 3DGF through
electrodeposition, which is an essential step in converting a hydrophobic surface to a
hydrophilic one and filling with the mesoporous PANI network into the macroporous
graphene foam. The 3D graphene/PANI network exhibits a large areal capacitance of
over 1700 mF cm
2 with high porosity when used as an electrode for super-
capacitors. The ultrahigh areal capacitance could be originated from the hybrid
effect of the highly pseudocapacitive PANI nanostructure and good conductive
graphene backbone.
Wearable supercapacitors with flexibility and lightweight have grabbed much
attention in the area of energy storage applications because of their potentiality in
developing devices such as portable electronic, mobile phones, flexible displays, and
electronic papers [43]. For developing flexible supercapacitors, the binder-free
electrode is required with robust mechanical strength and large capacitance. For
example, a report revealed asymmetric flexible supercapacitor’s fabrication with the
support of free-standing three-dimensional reduced graphene oxide 3D rGO/PANI
foams as both electrodes [44]. Due to high electrochemical performance and the 3D
rGO/PANI composites’ aligned porous structure, the symmetric device @1 M
H2SO4 electrolyte showed a specific capacitance of 790 F g
1 and a maximum
power density and energy density of 98 kW kg
1 and 17.6 W h kg
1, respectively.
Besides, the device performed an excellent cycle life with an 80% capacitance
retention after finishing charging-discharging (5000 cycles). In another report,
flexible supercapacitor (solid-state) had been developed by Chi et al. by employing
two pieces of high-performance binder-free nanohybrid graphene paper
(GP) electrode with the help of using poly (vinyl alcohol) PVA/H3PO4 electrolyte

Fig. 1 (a) Summarizing the preparation procedure of PANI-filled 3DGN via electrodeposition and
inkjet techniques. (b) Areal capacitances of PANI-coated 3DGN foam with different deposition
times and PANI-filled 3DGN foam (c) Schematic illustration of the fabrication process of 3D
rGO/PANI/GP. (d) Ragone plots of the SC device compared with data in other literature.
(Reproduced from Ref. [46]. Copyright 2020 American Chemical Society)
406 S. Yaragalla et al.

[45] (see Fig. 1c, d). The fabricated flexible supercapacitor (all-solid-state) exhibited
significant mechanical flexibility, remarkable cycling performance, and high energy
density of 24 Wh kg
1 at a power density of 400 W kg
1.

Nano Products in Conducting Applications

Reinforcing with conducting fillers into insulating polymers could improve the elec-
trical conductivity of resulting composites where the presence of interconnected
networks of conductive fillers is essential. 3DGNs could be directly employed as a
filler (integrated graphene) instead of incorporating reduced graphene oxide (rGO) into
the polymer matrix; agglomeration/aggregation of rGO be restricted such that efficient
conductive paths could be created significantly at very lower concentrations. Cur-
rently, self-assembly of exfoliation and reduction of graphene oxide (GO) is the most
extensively used method for producing 3DGNs [47, 48]. For example, Fan et al. had
first prepared 3D rGO/ polymethyl methacrylate (PMMA) composite by utilizing
PMMA into the pores of the 3DGNs, resulting in inhomogeneous dispersion of
few-layer rGO sheets with interconnected structures in the PMMA matrix [49]. The
3D rGO/PMMA composites exhibited significant increases in thermal conductivity
(0.35–0.70 W/m K) and electrical conductivity (0.160–0.859 S m
1) graphene from
0.67 to 2.50 vol % as compared with pure PMMA.
Interestingly, exceptional anisotropic structure of 3D rGO/epoxy (EP) composites
(see Fig. 2) with 113% improvement in toughness and 67% enhancement in conduc-
tivity has been reported by infiltrating 3D rGO. Nevertheless, two shortcomings are
associated with 3D rGO composites, which limited their applications: one is easy
agglomeration in the polymer matrix and another relates to the structural defects. The
CVD method, which is being used to make graphene with intact structure and higher
conductivity, makes it an attractive nanofiller for application in conductive composites.
For instance, 3D graphene/polydimethylsiloxane (PDMS) composites were fabricated
by Chen et al. through infiltration of PDMS into CVD-grown 3D graphene foam
[50]. Interestingly, the PDMS matrix’s introduction did not alter the 3DGN networks
due to the electrical conductivity of 3DGNs that showed nearly no change after
treatment with PDMS. As such, a very high electrical conductivity of 10 S cm
1
was exhibited by the prepared 3DGN/PDMS composites at an ultralow graphene
loading of 0.22 vol %. This result was almost six orders of magnitude higher than
that of chemically fabricated graphene-based composites, revealing significant advan-
tages of 3DGFs in polymer composites for efficient electrical applications.
However, minute defects caused by the residues and dopants are common for
CVD graphene, resulting in deteriorating properties. Favorably, when this graphene
is incorporated into poly (3,4-ethylene dioxythiophene) polystyrene sulfonate
(PEDOT: PSS) system, this works as both supporting layer [51] and dopant so that
these two problems could be solved. Thus, the composites produced with the
combination of PEDOT: PSS with CVD graphene would show a better electrical
performance. The 3D composite exhibited a very high electrical conductivity in the
order of ~24 S cm
1. The prepared 3D rGO/polymer conducting composites can be
 17

3.2
f (a) Parallel to alignment
HI, 120°C Freeze drying
Transverse to alignment
3.0
24 h 48 h
2.8
GO Graphene Hydrogel Graphene Aerogel

2.6

2.4

Flexural modulus (GPa)

2.2
0.0 0.5 1.0 1.5
Graphene content (wt%)

Parallel to alignment
e Transverse to alignment
g 105
101 (b)
10-1 100
10-3
0.25 95
10-5
0.20
10-7 0.15 90
0.10
Novel Graphene-Based Nanocomposites-Based Nanoproducts

10-9
0.05 85
10-11 0.00 Disconnections
0.0 0.5 1.0 1.5
Flexural Strength (MPa)

10-13 80
0.0 0.5 1.0 1.5 0.0 0.5 1.0 1.5

Electrical Conductivity (S/cm)

Graphene content (wt%) Graphene content (wt%)

Fig. 2 (a) Schematic illustration of the fabrication process of 3D rGO and SEM images of 3D rGO prepared using GO dispersions at different concentrations of
(b) 0.5, (c) 1.5, and (d) 2.0 mg mL
1. (e) Electrical conductivity of 3D rGO/EP composites in the direction parallel to the alignment and transverse to it. (f)
Flexural modulus and (g) strength of 3D rGO/EP composites. (Reproduced from Ref. 46. Copyright 2020 American Chemical Society)
407
408 S. Yaragalla et al.

used successfully as a sensing device to detect various polar organic solvents.

The sensing mechanism of such devices originates from the swelling behavior of
the polymer. Electrical conduction paths inside the composites are reduced by the
penetration of organic solvents, leading to an increase in the composite material’s
resistance. For example, a report based on the 3D graphene/PDMS conducting
composite can sense various polar organic solvents based on the swelling response
of PDMS [52], and the degree of its swelling is related to the polarity of the solvents.
Moreover, these three-dimensional graphene polymer composites can also be used
as a strain sensor to monitor buildings such as dams and high-speed railways. For
example, a study based on poly (ethylene terephthalate) (PET) with a double-layer
3DGNs/PDMS composite has been reported for sensing applications [53], where
PET as a thin layer was applied to improve the sensitivity of 3 DGN/PDMS system.
It is important to note that the three-dimensional double-layer 3DGN/PDMS
PET
composite showed relative variation in electrical resistance sixfolds higher than that
of single-layer 3DGN/PDMS system, which suggests that 3DGN/PDMS
PET
could be successfully utilized as a strain sensor.

Nano Products in Sensitive Detection

Recent investigations suggested that 3DGPCs could exhibit superior sensing per-
formance. They can be extensively used as electrochemical detection sensors due to
their strong and selective adsorption of the target ions or molecules and porous
microstructure [54, 55]. Wang et al. had developed an electrode based on 3D
rGO/PPy for sensing Hg2+ ions in an aqueous solution, which proved high selectiv-
ity and sensitivity [56]. The sensing mechanism is that Hg2+ ions can selectively
coordinate with the nitrogen atoms of the pyrrole units of PPy. The prepared
electrode can sense as low as 0.03 nM (30 ppt), and it was very much lower than
drinking water (guideline value of 2 ppb) based on the World Health Organization.
In another report, the 3D rGO/PANI system was used as the sensitive layer [57] of a
DNA adsorbent for sensing Hg2+. Amino-group-rich 3D rGO/PANI showed high
affinity toward the T-rich DNA strands, which prefer to bind with Hg+2 to form
T
Hg+2
T coordination (See Fig. 3). Thus, 3D rGO/PANI nanocomposite could
be utilized as an efficient electrochemical biosensor as it showed high sensitivity and
selectivity toward Hg+2 within a concentration range from 0.1 to 100 nM. Biolog-
ical treatment or modification of three-dimensional porous graphene is indispensable
in creating highly sensitive biosensors, which are essential in biotechnology. For
example, a 3D graphene/CHI enzymatic biosensor was fabricated for identifying
glucose concentration with an extensive linear range (5.0μM to 19.8 mM in the
phosphate buffer solution) through a one-step electrochemical deposition of CHI on
the free-standing 3D graphene electrode [58]. This biosensor exhibited rapid
response utilizing reaching the 95% steady-state response within 8 s and a low
detection limit (1.2μM). Tan’s group fabricated porous chitosan/vacuum-stripped
graphene/polypyrrole (CHI/VSG/PPy) scaffold for utilizing as a flexible sensor
(electrochemical) for detecting the dopamine levels. The fabricated CHI/VSG/PPy
17 Novel Graphene-Based Nanocomposites-Based Nanoproducts 409

Fig. 3 (a) Schematic illustration of the detection of Hg2+ ions using the DNA biosensor based on
3D rGO/PANI composite. (b) Rct change in the presence of 10μM of other metal ions and 0.1μM
Hg2+ ions. (c) Reusability of EIS-based Hg2+ sensor challenged with 100 nM Hg2+ ions and washed
with 50 mM cysteine. (Reproduced with permission from Ref. 46. Copyright 2020 American
Chemical Society)

composite electrode exhibited high sensitivity (632.1μA mM
1 cm
2) on a broader

range (0.1–200μM), with low detection efficiency (19.4 nM, S/N ¼ 3) and proved as
a good sensor for testing the human serum samples.

Nano Products in Environmental Protection

Recycling oil leakage effectively is a challenging task because of frequency transport

and the use of oil. Many methods have been proposed and applied to rectify this
issue, e.g., chemical cleanup via in situ burning, mechanical recycling, biodegrada-
tion, etc. In the past, recycling of the leaked oil was done using some absorbent
410 S. Yaragalla et al.

materials, including carbon aerogels, polymer sponge, and carbon nanotube (CNT)
sponge. In general, the criteria for separation of oil/water using ideal porous materials
are as follows: (i) be suitable for corrosive environments, (ii) environmental friendli-
ness and low cost, (iii) efficient cleanup of oil spills in the case of the oil spreading with
high speed, and (iv) low cost and environmental friendliness. Three-dimensional
(3D) graphene has received much attention in this regard due to its high porosity,
hydrophobicity, high specific surface area, and low density.
Meanwhile, the hybrid effect of 3D graphene and low surface energy of polymer
is required to the opposite wettability to water and separate oil from water. For
instance, superoleophobic and superhydrophobic graphene/PVDF aerogels were
fabricated by Li et al. through self-assembly and solvothermal reduction via the organic
molecule cross-linking method. The prepared sponges efficiently absorbed the sur-
rounding oil when they were immersed in the oil layer [59]. Simultaneously, excellent
absorption capacities ranging from 20 to 70 g g
1 were showed by the sponges for
various kinds of organic solvents and oils. Another report is revealed based on the
dip-coating method with melamine sponge decorated with hydrophobic graphene with
superior hydrophobic and oleophobic properties [60]. High rough surface sponge with
a porous structure and hydrophobic nature of graphene could render the absorption
capacities over a range from 54 to 165 times their original weight.
3DGPCs show a high absorption capacity of organic solvents and oils due to their
intrinsic hydrophobicity and large specific surface area, combined with the poly-
mers’ functionality. For instance, 3D rGO/PPy foams fabricated by a hydrothermal
method possess highly delocalized π electrons that may interact with other conju-
gated π systems of nonpolar molecules [61]. In particular, π
π stacking interactions
exist in the case of aromatic molecules like toluene and benzene. These nonpolar
molecules can easily couple with the conjugated hydrocarbons of diesel and kero-
sene within the 3D rGO/PPy composites through van der Waals forces. Thus, both
the sorption rate and sorption capacities of 3D rGO/PPy are very high for organic
solvent (>35 g g
1) and oil (>100 g g
1). Nevertheless, such composite materials
absorbed oils and water, which decline the efficiency and separation selectivity.
Superoleophilic and superhydrophobic 3DGPNs, such as 3D rGO/ poly-
dimethylsiloxane (PDMS) and 3D rGO/polyvinylidene, have been fabricated [62]
to absorb oil from water while repelling water completely. Combined hybrid feature
of the polymers’ low surface energy and micro/nanoscale structures of graphene in
3DGPN aerogels exhibited high adsorption capacity of organic solvents, oils, and
excellent water repellency. Such materials were regarded as the ideal material for the
separation of oil and organic solvents from water. Besides, they can be easily
recyclable through squeezing or heating. Nevertheless, the heating process is rela-
tively intricate for the especially adsorbent materials when the associated solvents
possess high boiling points. Contrary, those elastic adsorbent materials could be
opposed by the squeezing method, while three-dimensional graphene-associated
materials are prone to damage irreversibly upon the mechanical stress. Therefore,
it is mandatory to fabricate 3D graphene materials with high flexibility with the
strength to act as adsorbent materials (elastic) to separate oil from the water. To
validate this, a report is revealed based on 3D rGO/polyurethane (PU) foams via self-
17 Novel Graphene-Based Nanocomposites-Based Nanoproducts 411

assembly of graphene oxide sheets [63]. This composite showed a unique structure
that maintained graphene foams’ physical properties and effectively bears the
mechanical load upon mechanical stress. Thus, results in 3D rGO/PU foams showed
superior hydrophobicity with significant cycling stability. Moreover, it has been
noticed that reinforcing cross-linked polymers into 3D-reduced graphene oxide
(rGO) aerogels significantly reduces the fragile nature of those 3D rGO aerogels.
For example, incorporation of cross-linkable poly (acrylic acid) (XPAA) with 3D
rGO resulted in >99.6% porosity of the system which can reversibly support up to
10,000 times their weight with full recovery of their original quantity (volume)
[64]. The average absorption capacities for six different oils such as gasoline, diesel,
motor oil, pump oil, olive oil, and sesame oil were estimated to be around 120 g g
1
(See Fig. 4). Smart surface modification of adsorbent materials is appealing because
the external stimuli’s simple operation could enable the removal and recovery of oil
from the aqueous media. The adsorption and desorption process could be easily

Fig. 4 (a) Morphology of the 3D rGO/XPAA aerogels. (b) SEM images of 3D rGO/XPAA
aerogels. (c) Digital images showing the compressibility of the 3D rGO/XPAA aerogels during
the 10th compression/release cycle. (d) Demonstration of oil absorption using gasoline as the
absorbed solvent from t ¼ 0 to t ¼ 35 s. (e) Absorption capacities for various oils expressed as
gram oil per gram aerogel. (Reproduced from Ref. 46. Copyright 2020 American Chemical Society)
412 S. Yaragalla et al.

harnessed by external stimuli, including heating, electricity, and pH [65, 66]. Out of
which, the pH-responsive method is most fascinating due to it could easily regulate
the surface property between hydrophilic and hydrophobic and thus rapidly reverse
the adsorption and desorption process in a short period of time. For instance, Zhu
et al. had fabricated a composite based on a smart surface of 3D graphene foam
(GF) by attaching an amphiphilic block of polyhexadecyl acrylate copolymer
(P2VP-b-PHA) and poly(2-vinylpyridine) on the surface of graphene foam [67]. In
this process, graphene foam was functionalized with another block copolymer
(P2VP-b-PHA) through a quaternization and silanization process. The as-prepared
3D composite foam could significantly absorb oil or organic solvents from the
aqueous media due to the superoleophobic and superoleophobic surface at different
medium pH levels. Besides, the as-prepared 3D composite foam showed superior
absorption capacity (approximately 196 times its weight). Removing various heavy
metal ions and industrial dyes from industrial wastewater has become a complex
challenge for industrialists and researchers. Graphene oxide offers significant
adsorption efficiency concerning various water contaminants. Nevertheless, the
centrifugation process of adsorbed GO could suppress its applications in the purifi-
cation of wastewater. The 3D GO/polymer composites comprise of interconnected
3D porous networks and extensive specific surface area so that such materials can
easily pass heavy metal ions/dye molecules. For example, a report is revealed based
on 3D graphene aerogel (amine-functionalized) prepared through the interaction
between polyethylenimine (PEI) and GO sheets with high amine density [68]. It
exhibited a too high adsorption capacity (800 mg g
1), and the 3D GO/PEI showed
significant adsorption capacity for formaldehyde and carbon dioxide (11.2 wt % at
1.0 bar and 273 K). Anionic polyacrylamide (APAM) is a widely used polymer that
is a low-cost and effective flocculant to treat municipal and industrial and wastewater
[69]. The incorporation of GO into APAM could beneficial for practical environ-
mental protection applications as the 3D GO/APAM hybrid material can be success-
fully utilized to separate fuchsin from aqueous solutions [69]. The synergistic effect
of the 3D GO/APAM with the porous structure and the adsorbents’ functional groups
led to improve the adsorption capacity. These materials are very competitive to the
carbon nanotube-based polymer composites for environmental applications [70–72].

Conclusions, Challenges, and Perspectives

In summary, the excellent performance of three-dimensional graphene polymer

network (3DGPN)-based nanoproducts exhibited a promising series of applications,
including energy storage, conducting polymer composites, sensing, and environ-
ment protection concerning wastewater treatment. Several challenges still need to be
addressed, although the exciting applications of 3DGPNs as nanoproducts are
reported. The development of eco-friendly, reliable, and easy fabrication methods
with low cost needs to be investigated for finding efficient applications of such
3DGPNs. Research related to 3DGPNs remains at its starting stage compared to
other three-dimensional graphene-based composites, including a 3D metal oxide or
17 Novel Graphene-Based Nanocomposites-Based Nanoproducts 413

three-dimensional carbon nanotube (3D-CNT). Ongoing rapid progress regarding

this field convinces us that 3DGPNs will be versatile materials that would find
efficient applications for various fields. In-depth understanding and investigations
regarding graphene (2D macromolecule) self-assembly with different polymers are
indispensable for fabricating intelligent 3DGPNs for smart applications (sensing,
energy storage, etc.). Besides, the interfaces of polymers and graphene in the
3DGPNs are still unclear. It requires thorough analysis to understand deeply for
designing materials that would regulate the structure-property relationship.
Furthermore, 3DGNs can be introduced reasonably with multifunctional poly-
mers for exploring the various technological applications of the resulting three-
dimensional graphene-based polymer networks (3DGPNs). A concurrent exhibition
of flexibility, compressibility, stretchability, and self-repairing of the multifunctional
3DGPNs has not been understood clearly but is highly needed for nanowearable
smart electronic products. Besides, diverse morphologies of 3DGPNs, including
single- and double-phase interpenetrating networks, are beneficial for developing
electrochemical devices. Considering the various functionalities of 3DGPNs that are
achieved from combining interdisciplinary areas including material science, physics,
chemistry, and biology, we assure that 3DGPNs could open up a variety of oppor-
tunities toward technological applications in diverse areas in the near future.

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organic solvents recovery. Adv Funct Mater 25:597–605. https://doi.org/10.1002/adfm.
201403864
68. Liang J, Cai Z, Li L et al (2014) Scalable and facile preparation of graphene aerogel for air
purification. RSC Adv. https://doi.org/10.1039/c3ra45147j
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69. Yang X, Li Y, Du Q et al (2015) Highly effective removal of basic fuchsin from aqueous
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doi.org/10.1016/j.jcis.2015.04.042
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Graphene-Based Nanoproducts:
Applications and the Vast Vision 18
for the Future

Sukanchan Palit and Chaudhery Mustansar Hussain

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
The Aim and Objective of This Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
What Do You Mean by Graphene-Based Nanoproducts? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
What Do You Mean by Nanomaterials and Engineered Nanomaterials? . . . . . . . . . . . . . . . . . . . . . . 422
Climate Change and Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
The Vast Doctrine of Environmental Sustainability and the Vision for the Future . . . . . . . . . . . . 423
Recent Scientific Advances in the Field of Application of Graphene-Based Nanoproducts . . . 424
Recent Scientific Advancements in the Field of Environmental Protection and Water
and Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
Nanomaterials and the Vast World of Environmental Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Drinking Water Crisis, Heavy Metal and Arsenic Groundwater Remediation,
and the Visionary Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Sustainable Resource Management and the Domain of Nanotechnology . . . . . . . . . . . . . . . . . . . . . 431
Future Research Trends in the Field of Environmental Engineering and Chemical Process
Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
Futuristic Vision and Futuristic Flow of Scientific Thoughts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
Conclusion, Summary, and Environmental Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434

Abstract
Civilization, science, and engineering are today in the avenues of new scientific
vision and regeneration. Rapid industrialization, mass manufacturing, and loss of
ecological diversity have urged the scientific research community to gear forward
towards newer scientific innovations and scientific instinct. Nanotechnology,

S. Palit
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Post-Office-Bidholi via Premnagar, Dehradun, Uttarakhand, India
C. M. Hussain (*)
Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, USA
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 419

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_36
420 S. Palit and C. M. Hussain

nanomaterials, and engineered nanomaterials are today the marvels of science and
engineering. Today, science and technology are huge colossus with a definite
purpose of its own. The authors deeply discussed the application of graphene-
based nanoproducts in diverse areas of science such as environmental engineer-
ing, chemical engineering, and nanotechnology. Today, environmental engineer-
ing disasters are destroying the human habitat. The global status of the
environment is absolutely grave. Graphene-based nanoproducts are the chal-
lenges of human civilization and human scientific progress. The areas of mem-
brane science and distillation are the other hallmarks of this research expertise.
Conventional and nonconventional environmental engineering techniques are
also the areas of deep scientific introspection. Today, graphene-based nano-
products and other nanomaterials are in the path of newer scientific regeneration
and scientific and engineering vision. The authors elucidate in deep details the
domain of environmental sustainability and environmental protection and the
recent advances in these fields. A new world of knowledge prowess and scientific
dimension will surely emerge in the field of environmental remediation and
nanotechnology if researchers, scientists, engineers, and policymakers take active
and positive steps in the mitigation of climate change and environmental
degradation.

Keywords
Graphene · Nanomaterials · Engineered Nanomaterials · Water · Wastewater ·
Vision · Arsenic · Heavy metals

Introduction

Human mankind today stands in the midst of deep scientific forbearance and
scientific ingenuity. Nanotechnology is a revolutionary area of science and engi-
neering. Rapid industrialization, global population growth, and large-scale mass
manufacturing are veritably destroying the scientific landscape and the scientific
fabric. Loss of ecosystems and loss of biodiversity are terribly a matter of immense
scientific and engineering concern. Thus the need of a detailed treatise on conven-
tional and nonconventional environmental engineering techniques such as
advanced oxidation processes, membrane separation techniques, and desalination.
A wide scientific introspection in the application of graphene-based nanoproducts
and other nanomaterials are the other hallmarks of this treatise. Human civiliza-
tion’s immense scientific stance, the world of scientific ingenuity, and the scientific
forbearance will eventually open new doors of innovation and instinct in the field
of nanotechnology. Today, human suffering and health effects are immense due to
heavy metal and arsenic groundwater and drinking water contamination.
Bangladesh and the state of West Bengal, India, are in the throes of world’s largest
environmental engineering disaster that is arsenic drinking water contamination
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 421

and thus the need of applications of graphene-based nanoproducts as well as other

nanomaterials and engineered nanomaterials in environmental remediation, water
and wastewater treatment. The authors deeply discuss these scientific and engi-
neering issues with scientific grit and scientific determination. Graphene-based
nanoproducts have immense applications in diverse areas of science and engineer-
ing. Global environmental challenges and loss of ecological biodiversity are urging
scientists and engineers around the world to gear forward towards new innovations
and newer discoveries. Environmental engineering curriculum in universities
around the world needs to be revamped and reorganized with the surge in research
and development initiatives in the field of drinking water and industrial wastewater
treatment. A new epoch in the field of nanotechnology and material science will
surely usher in with the immense efforts of scientific girth and scientific
provenance.

The Aim and Objective of This Study

Global water crisis and global warming are today destroying the global scientific and
engineering firmament. Engineering vision and scientific verve and motivation in the
field of graphene applications are changing the face of human scientific progress and
academic rigor. Graphenes, fullerenes, carbon nanotubes, and other nanomaterials
and engineered nanomaterials are today the needs of human civilization and have
diverse applications in every branch of scientific endeavor. Scientific alacrity and
scientific validation in the field of graphene-based nanoproducts applications will
eventually open new windows of futuristic vision and future flow of scientific
thoughts. Pure water scarcity and proper sanitation are confronting immensely the
vast world of public health engineering and thus the need of applications of
nanomaterials in the field of drinking water and industrial wastewater treatment.
This areas will be dealt with vision in this treatise. Graphene-based nanoproducts
have applications in renewable energy and energy sustainability. This is also one of
the cornerstones of this well researched treatise. Scientific discernment and deep
scientific revelation in the field of nanomaterials and engineered applications will
surely be an eye-opener towards the greater vistas of learning and academic rigor in
nanotechnology, chemical engineering, and environmental engineering. The vision
of this study is to target the scientific and engineering needs of graphene-based
nanoproducts. Sustainability whether it is social, economic, energy, or environmen-
tal are the scientific imperatives of humankind today. In the similar vein, circular
economy and sustainable resource management will be true visionary towards a
newer era in the field of science and technology globally. Blue economy or resources
from ocean are the other sides of the visionary coin. A deep scientific and engineer-
ing introspection into the unknown world of graphene-based nanoproducts applica-
tions in circular economy will surely enhance the world of scientific understanding
and scientific intellect in decades to come.
422 S. Palit and C. M. Hussain

What Do You Mean by Graphene-Based Nanoproducts?

Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a

two-dimensional honeycomb lattice. Each atom in a graphene sheet is connected to
its three nearest neighbors by a sigma bond and contributes one electron to a
conduction band that extends over the whole sheet. This is the same type of bonding
seen in carbon nanotubes and polycyclic aromatic hydrocarbons and partially in
fullerenes and glassy carbon. A newer scientific ingenuity, profundity, and engineer-
ing vision are the needs of graphene and other nanomaterials science today. Scien-
tists have vastly theorized about graphene for decades. It has been unknowingly
produced in small quantities for centuries, through the use of pencils and other
similar applications of graphite. It was originally observed in electron microscopes
in 1962 but only studied while supported on metal surfaces. This material was later
discovered, isolated, and characterized in 2004 by Andre Geim and Konstantin
Novoselov at the University of Manchester, who were awarded the Nobel Prize for
Physics in 2010 for their groundbreaking research on the material and thus started a
new journey of scientific vision in the field of nanomaterials. The global market for
graphene was nine million dollars in 2012 [1, 2]. Most of the demand for research
and development forays were in the areas of semiconductor, electronics, electric
batteries, and composites. Mankind’s vast scientific prowess and positive intellect in
the field of graphenes and other engineered nanomaterials will surely transform the
scientific barriers and subsequently scientific frontiers [1, 2].

What Do You Mean by Nanomaterials and Engineered

Nanomaterials?

Nanotechnology, nanomaterials, and engineered nanomaterials are paving the way

towards a newer visionary era. The major applications of nanomaterials are in the
areas of water purification science and environmental remediation science. The
success of civilization and science lies in the domain of nanotechnology today.
Nanomaterials can be defined as materials, possessing, at minimum, one external
dimension measuring 1–100 nm [1, 2]. The definition given by the European
Commission states that the particle size of at least half of the particles in the number
size distribution must measure 100 nm or below. Nanomaterial examples are tita-
nium dioxide, silver, synthetic amorphous silica, iron oxide, azo pigments, and
phthalocyanine pigments. Engineered nanomaterials are chemical substances or
materials that are engineered with particle sizes between 1 and 100 nm in at least
one dimension . It is well established that engineered nanomaterials derive many
functional advantages and engineering vision from their unique physical and chem-
ical properties. The vision, redeeming and profundity of the science of nanomaterials
today needs to be revitalized with the ever-growing concerns for sustainability such
as social, economic, energy, or environmental. Sustainability, sustainable resource
management, and nanotechnology are today aligned with each other. Circular
economy, waste minimization, and the concept of zero-waste tools are the scientific
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 423

vision of today. The authors in this chapter clearly validates the engineering issues in
the field of waste reduction and nanotechnology. Successive scientific generations
will surely be emboldened if humankind, science, and engineering move towards a
right direction in global research and development initiatives [1, 2].

Climate Change and Sustainability

Environmental sustainability and climate change mitigation are in today’s scientific

world linked to each other. The world today stands shattered at the ever-growing
crisis of heavy metal and arsenic groundwater contamination in many developing
and developed nations around the world. Humankind’s scientific progeny and the
scientific destiny of environmental or green sustainability will eventually lead
science and technology towards newer scientific frontiers. Climate change today is
a veritable burden of human scientific progress. The situation in developing nations
in South Asia is absolutely gruesome and disastrous and thus a deep need of an
introspection in the science of sustainability. Here also comes the importance of
United Nations Sustainable Development Goals which reiterates the concepts of
water purification, drinking water security, proper sanitation, food security, educa-
tion, and successful human habitat. If sustainable development is not envisioned or
implemented in human society, the nation’s economic growth and progress gets
stunted. Today, circular economy and sustainable resource management are aligned
to each other. These are the novel areas of sound research and development initia-
tives in environmental engineering and water purification. Thus in the similar vision,
scientific prowess, engineering, and technological vision will surely enhance human-
kind’s scientific hope, scientific girth and determination.

The Vast Doctrine of Environmental Sustainability and the Vision

for the Future

The vast and varied doctrine of environmental sustainability and water remediation
needs to be effectively reenvisioned and nurtured as civilization moves forward. The
status of water, clean energy, and human habitat is highly catastrophic as mankind
treads forward. The visionary definition of “sustainability” by Dr. Gro Harlem
Brundtland, former Prime Minister of Norway, needs to be rethought and revamped
as civilization confronts immense environmental and energy issues. Climate change
and sustainability are today in the vistas of new innovation and newer scientific
ingenuity. A sound concept of circular economy and zero-waste tools will surely
usher in a new field in environmental management, sustainable resource manage-
ment, and nanotechnology. The vision for the future in the field of graphenes or other
nanomaterials and their diverse applications will veritably lead a long, effective, and
visionary way towards sustainability. The other areas of scientific endeavor which
needs deep scientific and engineering introspection are water resource engineering,
integrated water resource management, and integrated urban water management.
424 S. Palit and C. M. Hussain

Without water resource engineering and environmental engineering, mankind will

plunge into a great disaster. Thus humankind’s vision, revelation, and scientific
redemption will be highly enhanced if research and development initiatives in
environmental pollution control moves towards a visionary paradigm.

Recent Scientific Advances in the Field of Application

of Graphene-Based Nanoproducts

Graphene and other nanomaterials are the wonders of science today. Engineering
science and technology in the global scientific fabric are reenergizing futuristic
vision and future flow of scientific thoughts. In this section, the authors deeply
elucidate the application of graphene-based nanoproducts in different areas of
science and technology.
Kemp et al. (2013) [3] deeply elucidate environmental applications using
graphene composites and the wide vision of water remediation and gas adsorption.
This review deals with wide-ranging environmental studies of graphene-based
materials on the adsorption of hazardous materials and photocatalytic degradation
of pollutants for water remediation and water pollution control and the
physisorption, chemisorption, reactive adsorption, and separation for gas storage.
The vast environmental and biological toxicity of graphene, which is an important
issue if graphene composites are to be veritably applied in environmental remedia-
tion, are also vastly addressed [3]. Environmental pollution and industrial pollution
by both water-soluble toxic pollutants as well as noxious greenhouse gases are an
ever-growing concern worldwide. Human suffering and human scientific progress
are at a state of disaster as heavy metal contamination of drinking water confronts
and challenges the vast scientific firmament. At the recent Rio + 20 conference, these
issues have been thrust into spotlight again. Additionally, recent studies have shown
that another issue affecting environmental integrity is the unpredicted effects certain
pollutants are having on the global environment [3]. A newer visionary era in the
field of water remediation and graphene nanocomposites will eventually usher in a
newer genre and newer scientific validation. A strong scientific validation in nano-
materials applications is the utmost need of the hour. The authors discussed in
minute details the water remediation by adsorption, adsorption by ionic pollutants,
water remediation by photocatalysts, gas adsorption and gas phase separation,
reactive gas adsorption, and environmental and biological toxicity of graphene.
The discovery of graphene is rightly regarded as a milestone in the field of material
science and composite science as can be seen from the worldwide attention the
material has received in the fields of electronic engineering, organo electronics,
photonics, supercapacitors, and biosensing to name a few [3]. A remarkable era in
the field of graphene-based nanoproducts is slowly emerging. Research and devel-
opment show that single layer, multilayer, and functionalized graphene sheets, as
well as other graphene-based architectures offer a wide range of benefits, opportu-
nities, and scientific challenges. The high stability, large surface area, and environ-
mentally friendly nature of graphenes make it a remarkable and potential candidate
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 425

for environmental applications such as water remediation, toxic gas sensors, and
acidic gas capture, and these areas are demonstrated in this article. Human society
needs to be revamped as regards scientific vision of nanotechnology applications.
Thus the authors with immense scientific judgment detail these scientific and
engineering issues [3].
Perraeault et al. (2015) [4] deeply discussed with scientific and engineering
insight environmental applications of graphene-based nanomaterials. Graphene-
based nanomaterials and nanoproducts are today transforming the vast global envi-
ronmental engineering firmament. The vision of environmental engineering science,
the scientific needs of human society, and the scientific truth of United Nations
Sustainable Development Goals will embolden research acumen and scientific
foresight in nanotechnology applications [4]. Nanoscience and nanotechnology are
today linked with the vast world of environmental protection. Nano-remediation
science is today in the path of newer scientific regeneration. The twenty-first century
has been termed with vision and scientific prowess as the century of environment
[4]. With ever-growing population, rapid industrialization and urbanization, inten-
sification of agricultural activities, contamination of air, soils and aquatic soils, and
global climate change are becoming a definite and purposeful focus of political and
scientific attention. A new scientific and engineering generation in nano-remediation
is slowly emerging with vision, cogent insight, and purpose. Today, there are
technologies to mitigate associated health and environmental impacts of nano-
material applications. The authors discussed in minute details the concepts and
properties of graphenes, graphene materials for contaminant adsorption, and
graphene-based photocatalytic materials for water contamination. Graphene in mem-
brane and desalination technologies will be an eye-opener towards a newer scientific
and engineering genre and a deep scientific profundity. Antimicrobial applications of
graphene-based materials are other pillars of this treatise [4]. Graphene-based
electrodes for environmental sensing are the other targets of this well researched
treatise. The outlook of this research endeavor is bright and far-reaching. During the
past decade, significant progress has been envisioned in understanding how
graphene and graphene-based materials can be veritably used to address environ-
mental engineering challenges. The world of science and engineering of graphenes
are today the marvels and needs to be revisited and revamped as civilization and
humankind moves forward. Graphene remains an unique material with properties
that could lead potentially to remarkable and significant scientific understanding and
discernment in numerous environmental applications. Due to ultrahigh surface area
materials, this two-dimensional material thought to be impossible 80 years ago is
now providing global scientific and engineering solutions in the progress and
advancements in science and humanity [4].
Gong et al. (2011) [5] deeply discussed with cogent insight graphene and its
synthesis, characterization, properties, and applications. The world of nanoscience
and nanotechnology are today in the vistas of newer scientific regeneration and
vision. In this book, the authors discussed in details the synthesis and characteriza-
tion of graphenes, nucleation, and vertical growth of nano-graphene sheets, synthesis
of aqueous dispersion of graphenes, supercritical fluid processing of graphene and
426 S. Palit and C. M. Hussain

graphene oxide, and the vast areas of applications of graphene [5]. Electronic
transport properties of few-layer graphene materials and large-scale graphene by
chemical vapor deposition are the other hallmarks of this treatise. The global success
of nanotechnology and graphene applications in diverse areas of science and engi-
neering will be a veritable eye-opener towards a new visionary domain of environ-
mental engineering science and chemical process engineering. Graphene discovered
in 2004 by A.K. Geim and K.S. Novoselov is an excellent electronic material and is a
promising candidate for the post-silicon age. It has immense potential in the elec-
tronic device community, for example, field effect transistor, transparent electrode,
etc. Research on graphenes is a rapidly developing field with vastly new concepts
and applications emerging at an incredible rate and thus the need of research pursuit
in the positive way in diverse applications of graphene-based nanoproducts [5].
Bharech et al. (2015) [6] elucidated and described in minute details in a review on
the properties and applications of graphene. Scientific vision, deep scientific under-
standing, and engineering prowess and acumen are the ultimate needs of the hour
[6]. Since the advent of automobile and aerospace industry, research and develop-
ment globally of materials with better properties has been the keen interest of
researchers, students, scientists, and engineers. This is a decade of “future mate-
rials.” One such material is graphene. Graphene is a two-dimensional atomic scale
hexagonally packed allotrope of carbon. The authors in this treatise deeply discussed
in details the forms of graphene, few later graphene and multilayer graphene,
graphene oxide, reduced graphene oxide, and production techniques. Production
techniques involve mechanical exfoliation, chemically derived graphene from
graphite oxide, and the vast applications of chemical vapor deposition [6]. Applica-
tion areas involve ultracapacitors with better performance than batteries, low-cost
water desalination, integrated circuits, and corrosion-resistant coating. Civilization,
science, and technology are moving fast from one visionary paradigm over another.
Graphene is a very promising material for new types of systems, circuits, and devices
where diverse functionalities can be combined into a single material. In today’s
scientific endeavor, highly critical issues with the extensive use of graphene in
electronics are integrated with mass manufacturing and industrialization. The
authors deeply stress on these fundamental engineering issues and the scientific
vision behind it [6].
The state of the art in research areas of graphene-based nanomaterials are today in
the path of deep scientific acuity and scientific perseverance. Man’s vision and
mankind’s scientific ingenuity are today the needs of the hour. In this treatise, the
authors deeply tread on the success of civilization and science in human progress.

Recent Scientific Advancements in the Field of Environmental

Protection and Water and Wastewater Treatment

Technology management and rapid industrialization are the absolute needs of the
hour. Integrated water resource management and integrated urban quality manage-
ment are moving towards positive directions of scientific girth and divination. Today,
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 427

the world stands devastated and degraded with the growing concerns of loss of
ecological biodiversity, environmental disasters, and mass scale environmental
degradation. A newer scientific genre and scientific profundity will surely emerge
in the distant future.
Abdelbasir et al. (2019) [7] discussed with vision, insight, and far-sightedness
nanomaterials for industrial wastewater treatment. Industrial and domestic waste-
water is an universal environmental issue. Recalcitrant organic pollutants, heavy
metals, and non-disintegrating materials are a burden to science and human
mankind today [7]. Presently removing these pollutants from industrial wastewater
in an effective way has become a challenging and monstrous issue. Thus civiliza-
tion’s scientific prowess and ingenuity are at the crossroads of scientific barriers
and scientific travails. Nations around the world are in the process of serious
scientific contemplation [7]. This review highlights the use of nanomaterials for
the removal of different recalcitrant pollutants from industrial wastewater with a
special importance on metal and metal oxide nanomaterials, carbon-based nano-
materials, and nanofiber/nanocomposite membranes [7]. The redemption of sci-
ence and engineering of nanoparticles and the vast vision for the future needs to be
explored at the earliest. The goal of this article is to offer a recent overview and
references in the areas of engineered nanomaterials used for removing toxic
materials from real industrial wastewater for researchers, students, and industrial-
ists. Wastewater is produced from numerous sources as in residential areas,
commercial areas, industrial properties, agricultural lands, etc. Composition of
water differs broadly and is highly dependent on the source it is generated from.
Due to application of nanomaterials, health effects of human beings, and environ-
mental toxicity are challenging the vast scientific firmament [7]. Nanotechnology
research forays can be vastly utilized to address the many complications of water
quality to warrant environmental stability and integrated by industrial wastewater
and drinking water systems [7]. Overall, nanomaterials are materials of which the
structural elements are sized (at the least one dimension) between 1 and 100 nm. A
newer beginning in the field of nanotechnology and nanoengineering are the
moments of deep scientific truth and scientific profundity. Sustainable and effec-
tive solutions are the utmost needs of the hour. Nanomaterials possess superior
adsorption capacities, reactivity, and their remarkable mobility in solution
[7]. Numerous types of nanomaterials can successfully remove heavy metal ions,
organic pollutants, inorganic ions, and bacteria. The authors in this treatise deeply
discuss sources and compositions of industrial wastewater, industrial wastewater
treatment processes, nanomaterials for industrial wastewater treatment, carbon-
based nanoadsorbents, and the areas of retaining and reuse of nanomaterials
[7]. Critical comparisons in the field of treatment of wastewater are the other
pivots of this treatise. Nanomaterials possess a number of unique physicochemical
properties. These features make them very attractive for wastewater treatment.
They are (1) higher surface areas compared with conventional nanoparticles,
(2) capability of being functionalized with diverse chemical groups, and (3) use
as high selectivity recyclable legions for detrimental elements. Detrimental and
recalcitrant chemicals are burden to human scientific progress and scientific path.
428 S. Palit and C. M. Hussain

A deep and comprehensive thought and introspection will eventually open up

newer future recommendations in the areas of environmental pollution in years
to come [7].
Mukherjee et al. (2015) [8] discussed with scientific far-sightedness contempo-
rary environmental issues of landfill leachate and its assessments and remedies.
Scientific imagination and deep scientific destiny are today the needs of deep
comprehension and contemplation. Landfills are the primary option for waste dis-
posal all over the world of science and engineering [8]. Most of the landfills around
the globe are old and not engineered to prevent contamination of the underlying soil
and groundwater by the toxic leachate. Management of this toxic leachate presents a
deep challenging problem to the regulatory authorities [8]. Technology management
and integrated water resource management are today aligned to each other. This
article focusses on (1) leachate composition, (2) plume migration, (3) contaminant
fate, (4) leachate plume monitoring tools, (5) risk assessment techniques, and
(6) recent innovations in leachate treatment techniques. This article deeply discusses
the areas of water management and the holistic domain of groundwater management
and water resource engineering [8].
Hashim et al. (2011) [9] deeply discussed with vision and scientific conscience
remediation technologies for heavy metal-contaminated groundwater. The contam-
ination of groundwater by heavy metal, originating from natural soil sources and
anthropogenic sources, is a matter of immense concern to global health, health
issues, and public health engineering [9]. Remediation of groundwater and drinking
water are matters of highest priority in the path towards human scientific progress.
Billions of people around the world are today without clean drinking water. In this
treatise, 35 approaches for groundwater treatment are reviewed and classified into
three large categories which are chemical, biological/biochemical/biosorption, and
physicochemical categories [9]. Keeping the sustainability issues and environmental
ethics in mind, the technologies encompassing natural chemistry, bioremediation,
and biosorption are highly recommended for future scientific recommendations.
Mankind’s visionary prowess and milestones in environmental engineering tools
will widely open newer doors of global science and engineering. The authors deeply
discussed in minute details the sources, chemical property, and speciation of heavy
metals in groundwater, technologies for treatment of heavy metal-contaminated
groundwater, chemical treatment technologies, reduction by iron-based technolo-
gies, soil washing, in-situ chelate flushing, in-situ chemical fixation, and biological,
biochemical, and biosorptive treatment technologies [9]. Biosorption of heavy
metals by cellulosic materials and agricultural wastes are the other marvels of this
treatise. Biological and agricultural engineering are today in the avenues of deep
scientific regeneration and engineering vision and profundity. Environmental engi-
neering and water resource engineering curriculum needs to be revamped and
reorganized with the economic growth of a nation. Permeable reactive barriers are
wonders of science today. Environmental tools using permeable reactive barriers are
also areas of scientific and engineering introspection. Adsorption, filtration, and
absorption mechanisms are the needs of science and are the pillars of human
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 429

scientific progress. Membrane science and membrane filtration are also the corner-
stones of global water technology research pursuits. These issues are deeply vali-
dated in this treatise [9].
Saikia et al. (2019) [10] deeply discussed with scientific vision nanotechnology
for water remediation. Scarcity of fresh drinking water has escalated to be one of the
major global problem. Traditional and conventional water treatment technologies are
not adequate enough to produce safe water. Thus the needs of the science of
nanotechnology and its innovations and research directions. On that premise, the
advent of nanotechnology has given immense scope and opportunities for the
removal of heavy metals, microorganisms, and other recalcitrant pollutants
[10]. The scientific divination of environmental protection and industrial pollution
control today will pave new avenues in the field of nanotechnology applications in
human society. The use of various nanomaterials including carbon-based nano-
materials, metal and metal oxides nanomaterials were deeply focused and their
modes of operation and scientific innovation towards wastewater remediation are
discussed in details [10]. The authors discussed in minute details the current status,
adsorption onto nanomaterials, photocatalytic water treatment using nanoparticles,
disinfection of wastewater with nanomaterials, nanomembrane in water and waste-
water treatment, and the vast domain of limitations of nanoparticles used in waste-
water treatment. Environmental engineering and chemical engineering curriculum
are today in the process of newer reinventing. The challenges of health effects and
eco-toxicity of nanomaterials in human society today need to be deeply pondered
with vision, scientific might, and scientific perseverance. This treatise addresses
these intricate issues [10].
Varma (2011) [11] deeply discussed with scientific far-sightedness greener
approach of nanomaterials and their vast sustainable applications. Green chemistry
and green nanotechnology are in the forefront scientific inventions and scientific
ingenuity globally. The integration of green chemistry principles with rapidly evolv-
ing area of nanoscience and nanotechnology is a need for risk reduction [11]. Chem-
ical process safety, risk assessment, and process safety management are the
coinwords of any chemical engineering processes and environmental engineering
systems. Human scientific intellect, deep scientific perceptions, and learning out-
comes will eventually lead towards a new era in sustainability and application of
nanotechnology. The sustainable use of green synthesized nanoparticles in environ-
mental remediation applications and the utility of recyclable magnetic nanoparticles
are the other areas of deep scientific contemplation. Greener synthetic strategies and
environmental remediation are the other areas of this scientific endeavor. Research
and development forays in nanomaterials can lead to new design rules that are
eco-friendly and benign in the context of protecting human health, eco-friendly
engineering systems, and public health engineering [11].
Green synthesis of nanomaterials are the marvels of the science of nanotechnol-
ogy. Nanotechnology will open new doors of innovation and inventions as regards
environmental remediation. In this article, the author deeply reiterates these scien-
tific, engineering, sustainable, and ethical issues.
430 S. Palit and C. M. Hussain

Nanomaterials and the Vast World of Environmental Remediation

Nanotechnology is a revolutionary domain of science and technology in the global

landscape. Today is the age of fourth industrial revolution [12–16]. Water and
wastewater treatment are vastly needed in the global scenario as public health
engineering, civil, and environmental engineering are highly struggling with deep
scientific travails and barriers. Nano-remediation and bioremediation of water and
industrial wastewater treatment are the needs and marvels of engineering science.
Billions of people around the world are without pure drinking water [17–20]. A
newer age in the field of water purification science and environmental engineering
curriculum are the ultimate needs of the scientific vision. Graphenes, fullerenes, and
carbon nanotubes have applications in vast and varied areas of science and engi-
neering. A deep scientific thought in the field of water remediation and water science
and technology will revitalize man and mankind’s scientific verve, motivation, and
scientific validation. Human mankind is today in a state of immense disaster as
arsenic and heavy metal groundwater contamination veritably confronts human
society and thus the immediate need of both conventional and nonconventional
environmental engineering techniques. Apart from application of nanomaterials,
ozonation, Fenton’s treatment, electrochemical treatments, and other advanced oxi-
dation processes will veritably pave the visionary way towards effective water
purification science. The challenges, the vision, and the difficulties in environmental
engineering techniques are immense, bright, and groundbreaking. The needs of
environmental protection and industrial pollution control are today transforming
the vast scientific fabric globally. Tertiary treatment of industrial wastewater should
be the pillars of environmental engineering research endeavor. The scientific divi-
nation and the scientific willpower in global tertiary environmental engineering tools
will widely open the doors of research in the field of both nanotechnology and
environmental protection in the years to come [17–22].

Drinking Water Crisis, Heavy Metal and Arsenic Groundwater

Remediation, and the Visionary Future

Drinking water crisis and heavy metal and arsenic groundwater remediation are the
bane of human civilization and concerted efforts in its mitigation are the utmost
needs of the hour. The future of environmental engineering and chemical engi-
neering are bright and far-reaching. Billions of citizens around the world are in the
need of fresh drinking water. Man’s immediate vision and humankind’s deep
futuristic vision are today in the path of immense catastrophe as global water crisis
confronts the human scientific progress and ingenuity. Bangladesh and the neigh-
boring state of West Bengal, India, are plunged into an unending and unsolvable
environmental crisis and thus the need of conventional and nonconventional
engineering tools which includes applications of nanomaterials. Graphene-based
nanoproducts needs to be applied in nano-remediation. This crisis will be mitigated
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 431

if human scientific genre and efforts will lead a long and visionary way in true
realization of science and engineering. The true need and the true scientific
ingenuity in the field of nano-remediation, bioremediation, and biological sciences
needs to be reenvisioned as regards application of nanomaterials and engineered
nanomaterials in water remediation. Soil and sub-surface groundwater remediation
are the ultimate needs of the hour if civilization can be saved from climate change,
global warming, and loss of ecological biodiversity. Humankind’s vision and
man’s relentless efforts will thus lead an effective and visionary way in the true
path of science and engineering globally. Drinking water crisis and groundwater
remediation are today in the latent stage of research endeavor. In the similar vision,
desalination technique and membrane science are today in the path of new regen-
eration and engineering profundity. A newer challenging era in the field of nano-
materials will veritably open newer dimensions in the field of almost diverse areas
of research and development pursuits. Environmental chemistry, green chemistry,
green nanotechnology, and green technology will surely advance human scientific
and academic rigor in research and development initiatives in water science and
technology in decades to come.

Sustainable Resource Management and the Domain

of Nanotechnology

Sustainable resource management and sustainable development are two opposite

sides of the visionary coin. The domain of nanotechnology is today aligned with
diverse branches of science and technology. A deep futuristic thought and a deep
scientific comprehension will unfold the scientific intricacies and the scientific
barriers in nanotechnology applications in sustainable resource management. The
divination and redeeming of science and engineering need to be rethought as regards
application of sustainable resource management in human society. Circular economy
is a marvel of science today. Reduce, reuse, and recycle are part and parcel of circular
economy. Nanoscience and nanoengineering are today linked with mass manufactur-
ing and manufacturing engineering. A deep futuristic scientific thought in nanotech-
nology, nanomaterials, and engineered nanomaterials will surely usher in a newer era
in the field of applied sciences and global engineering sciences. The authors in this
entire treatise profoundly depicts the immediate needs of nanomaterials such as
graphene-based nano-products in environmental pollution control, renewable
energy, and health care scenario. Humankind’s global engineering vision will surely
be emboldened if nanotechnology is aligned with the world of environmental
engineering and environmental process engineering. Environmental chemical engi-
neering will thus open newer windows in global scientific initiatives if the scientific
domain takes immediate and visionary steps in the field of environmental pollution
control, industrial pollution control, and groundwater remediation. A new age in the
field of nanoscience and nanoengineering will surely usher in the vast scientific
landscape with grit and determination [21–27].
432 S. Palit and C. M. Hussain

Future Research Trends in the Field of Environmental Engineering

and Chemical Process Engineering

Research trends in the field of environmental engineering and chemical process

engineering are highly bright and visionary. Environmental management and
sustainable development are two sides of the visionary coin. Water resource
engineering and water resource management are today’s research pursuit in envi-
ronmental pollution control. Human scientific progress in the global scenario is in a
state of immense scientific and engineering catastrophe. A deep scientific contem-
plation and scientific provenance are the ultimate needs of the hour. The entire
domain of engineering sciences and applied sciences needs to be refurbished if the
world needs to mitigate climate changes and global warming. Thus the future lies
in the hands of researchers, scientists, policy-makers, and governments across the
world. In this treatise, the authors deeply pronounce the needs of environmental
engineering and chemical process engineering in the true advancements of science.
The world of graphene and other engineered nanomaterials are the scientific truth,
scientific ingenuity, and the truth of engineering science today. Water science and
technology is a branch of both environmental engineering as well as the holistic
domain of chemical process engineering. In water stressed countries around the
world, desalination and membrane science are the needs of the hour and the
moments of truth. Proper sanitation, water security, food security, energy and
environmental sustainability, education, and human habitat are the pillars of
United Nations Sustainable Development Goals. Today is a world of immense
scientific stress and vast scientific barriers. Public health engineering in developing
countries around the world needs to be restressed and revamped as science,
engineering, and civilization tread forward. Governments around the world are in
the midst of deep scientific vision as well as in scientific travails and thus the
immediate need of an effort on war-footing in water purification, drinking water,
and groundwater treatment. The vision of mankind and its knowledge prowess and
ingenuity will surely be emboldened if the scientific and engineering order globally
moves in the right direction.

Futuristic Vision and Futuristic Flow of Scientific Thoughts

Futuristic vision of nanotechnology, environmental engineering, and chemical

engineering are today in the path of vast scientific and engineering regeneration.
Man’s immense scientific ardor and challenges and humankind’s vast scientific
urge to excel will pave the way towards a newer genre in the field of nano-
remediation and nanotechnology. Futuristic flow of scientific thoughts should be
akin to the scientific intricacies in chemical engineering fundamental concepts
such as mass transfer operations and process intensification. Graphene applica-
tions in water remediation involves many chemical engineering unit operations.
18 Graphene-Based Nanoproducts: Applications and the Vast Vision for the. . . 433

These are the areas of immense and vivid scientific introspection. Today, nano-
science, nanotechnology, and chemical engineering are in the process of new
rejuvenation. Global research and development initiatives will surely be
emboldened if humankind moves faster towards ecological engineering, inte-
grated water resource management, and wastewater treatment management.
Technology management and industrial system engineering are the needs of
human society today. Thus the needs of nanotechnology industrial processes.
Process integration and process intensification in chemical engineering and
environmental engineering operations will surely open up newer dimensions of
research pursuit in decades to come. Another area of deep scientific comprehen-
sion is circular economy and thus the immediate need of the science of sustain-
able resource management. A remarkable genre and profundity will usher in if
science and civilization move towards right directions.

Conclusion, Summary, and Environmental Perspectives

Today, there is an immediate need of United Nations Sustainable Development

Goals. Integrated water resource management and industrial wastewater manage-
ment are today integrated with the science of nanotechnology. The areas of water
purification, proper sanitation, and success of human habitat are today the major
pillars of United Nations Sustainable Development Goals. The visionary definition
of “sustainability” given by Dr. Gro Harlem Brundtland, former Prime Minister of
Norway, will be eventually reenvisioned and revitalized as science, technology,
and humankind moves forward. Graphene-based nanoproducts are the marvels of
science and engineering today. It has diverse applications and is an interdisciplin-
ary area of science and technology. In this chapter, the authors dealt deeply the vast
needs and the growing challenges in nanomaterials application in water remedia-
tion. Groundwater heavy metal contamination is today a burden to human scien-
tific success and academic rigor. Here also comes the importance of nanomaterials
and engineered nanomaterials applications. The authors deeply reiterate the scien-
tific and technological issues involved in graphene applications. Energy sustain-
ability and renewable energy are coinwords of global scientific progress today. The
authors with deep scientific perspectives pronounce the immense needs of energy
and environmental sustainability in unveiling the scientific truth in the field of
graphene applications. Man’s vast and varied scientific stance and ardor and
humankind’s progress will go a long way in paving the way towards energy and
environmental sustainability today. Thus a new epoch in the field of nanotechnol-
ogy and water science and technology will evolve as civilization crosses one
frontier over another. Thus United Nations Sustainable Development Goals will
be achieved if man and mankind widely move forward towards circular economy
in the future. In this entire treatise, the authors stress these scientific issues and thus
a newer epoch is emerging.
434 S. Palit and C. M. Hussain

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Consumer Nanoproducts Based
on Graphene and Graphene 19
Nanocomposite

Tanvir Arfin

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
Graphene Nanomaterial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
Graphene Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Material Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Graphene-Based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Fabrication Techniques for Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Graphene-Nanoparticle Composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Synthesis Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Creative Processes to Modify Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Suspension/Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448

Abstract
Graphene developed as extraordinary material due to its underlying properties of
naturally possessing two-dimensional structure. In the current research, the different
chemical features have promoted high-performance devices for generating and
storing graphene energy. The specific area of graphene is increasing from electronic,
chemical utilization to biomedical application. The promising challenges in this
research study are to overcome and adequately appreciate graphene’s unique prop-
erties in various proper forms. The valuable information and adequate understanding
of graphene nanocomposite ensure the safety uses of helpful material. The scientist
has undertaken particular efforts to examine recent material to develop fundamental
physics. Chemists based on organic and material are working hard for synthesizing
T. Arfin (*)
Environmental Materials Division, CSIR-National Environmental Engineering Research Institute
(CSIR-NEERI), Nagpur, India
Hyderabad Zonal Centre, CSIR-National Environmental Engineering Research Institute
(CSIR-NEERI), Hyderabad, Telangana, India

© Springer Nature Singapore Pte Ltd. 2022 437

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_39
438 T. Arfin

the novel synthetic route toward a single layer of high quality, and engineering is
working on framing the unique device for the exploitation of extraordinary charac-
teristics of graphene. The future of graphene is prosperous due to the properties and
behavior. The current book chapter’s primary focus is on providing an inspirational
source to the consumer nanoproduct mechanism of graphene nanocomposite.

Keywords
Graphene oxide · Polymer · Nanomaterial · Nanofiller · Solution mixing

Introduction

The possible use of nanotechnology came into 1974 as coined by Prof. N.T. as a
semiconductor process in an academic conference. But in the year 1959 only, the
fundamental concept of building minute thing was properly assigned by Richard
Feynman. He attributed that the giant machine could be responsible for building up
the small device and the product governed by the atom and finally called it molecular
manufacture. Nanotechnology represents a technological field employing diverse
materials ranging between 1 nm and 100 nm known as nanomaterials [31]. The
nanoscale working permits for carefully manipulating the valuable material attaining
the unique properties that usually vary from that present in molecular level or bulk
form [17, 42]. The nanoscale is the basis of a new and beneficial application for
increased reactivity and functionality due to the more excellent surface-to-volume
ratio for enhancing the dispersion. It allows developing uneven application com-
prised of diverse aspect, namely, medicine, water purification, and so on.

Graphene Nanomaterial

The graphene nanomaterial (GM) is different from each other in various ways like
lateral dimension, surface chemistry, defect density, quality of single graphene sheet,
composition, and purity [8]. The GM is equivalent toward carbon nanotubes peculiar
from each other in a practical matter of wall number, effective diameter, considerable
length, surface chemistry, a substantial amount, complex composition, and visible
form of metal impurities [43]. Figure 1 properly reflects the essential GM and even
various characteristics the same as that of colloidal behavior.

Fig. 1 Members of the graphene nanomaterial

19 Consumer Nanoproducts Based on Graphene and Graphene Nanocomposite 439

Fig. 2 Key different aspects of an effective method for graphene synthesis

Fig. 3 Material properties of graphene nanomaterials

Graphene Production

The creative process of synthesizing graphene (G) is accurately described by the

fabrication method, precisely defining the unique properties and possible application.
Hence, in this regard, G fabrication is considered an exceptionally fascinating topic of
research. To date, it is observed that not even a sole method for synthesis of G has been
noted yielding the G that demonstrates optimum properties for the continuous applica-
tion. The elaborated array of synthesizing approaches of G comprise categories into two
processes, namely, physical and chemical method shown in Fig. 2.

Material Properties

It has become mandatory to detect that synthesizing had naturally produced single-
sheet graphene accurately. Therefore, the size and functional group attached are
necessary factors for the dispersion of polymer. Figure 3 demonstrates the various
properties of the valuable material illustrated.
The significant nanomaterial employed for the consumer is G and its
nanocomposite.

Graphene-Based Nanocomposites

Graphene-Polymer Nanocomposites
In the current nanotech developed world, the used polymer is naturally found to
traditionally play an essential task in the active sensor and energy conversion sector
440 T. Arfin

[3]. The G properties are likely to improve when submerged homogeneously in the
matrix, and the masses are used as a filler and as the interaction of polymer [65]. The
pristine graphene (PG) does not possess compatibility for the organic polymer, but
despite that, it liberates the homogeneous composite [4]. In the specific case of graphene
oxide (GO), it typically exhibits compatibility for the organic polymer [5]. G is used
correctly as a nanofiller for the different polymer like polyurethane (PU), polystyrene
(PS), polyethylene terephthalate (PET), polyaniline (PANI), polyvinylidene fluoride
(PVDF), and so on to enhance the characteristics of the polymer merely.

Polyaniline
Conducting polymer is a specialized polymer with π-conjugated electrons stretched
on the polymer backbone, and it also has a delocalized electron structure
[9, 10]. PANI is a naturally exceptional electric and conducting flexible polymer
showing obscure composition [32, 37]. PANI can be processed by in situ electro-
polymerization method. This process can offer advantages, such as less reaction time
and practical simplicity. The PANI attained through a method form a thin film. It also
showed irregular structures.

Epoxy
The epoxy resin has merely low thermal conductivity, and on introducing graphene
sheets (GS), it showed highly improved quality. On adding 1 wt% of GO to epoxy
resin, there are identical effects as that of thermal conductivity, and it is filled with
regret by 1 wt% of SWNT. GO-filled epoxy resin of 5 wt% is critically four proper
times more than clear epoxy resin [75].

Polyurethane
Liang et al. [53] produced three forms of nanocomposite by the gradual process of
solution mixing. They traditionally used isocyanate-modified graphene (ICG),
sulfonated graphene (SR), nanofiller, reduced graphene, and thermoplastic polyure-
thane (TPU) in the possible way of the matrix polymer. Even some functional groups
are also attached to prepared SG sheets.

Polystyrene
Polystyrene is a synthetic, hydrophobic, and thermoplastic substance posing a highly
globalized demand that comes after PVC [38]. It possesses various properties like
noble mixer binding ability in phosphate metal [21]. It exhibits cytotoxicity [60],
antibacterial activity [11], DC conductivity [14], transport phenomena [35], double-
layer capacitance [34], thermodynamic effect [25], dielectric [16], ionic potential
[24], charge density [22], impedance [33], enthalpy [23], entropy [9, 10], etc. Eda
and Chhowalla [49] synthesized PS/FGS composite by adequately employing the
method of solution blending. The composite shows various essential features, such
as it is efficiently semiconducting in fundamental nature and possesses precisely an
ambipolar field effect. The conductivity of the composite tends to reduce with a
decrease in temperature to approximately 50 K. It tends to increase marginally with a
reduction in temperature to some extent.
19 Consumer Nanoproducts Based on Graphene and Graphene Nanocomposite 441

Nafion
The uptake of sufficient water for GO increases with the specific content of GO in the
Nafion/GO membrane because of the hydrophilic GO. Nafion/Pt-G membrane is
barely in possible comparison to Nafion/GO. Nafion/Pt-G does not reveal enough
economic improvement at different RHs [51].

PVA
The nanocomposite dependent on the wholly exfoliated graphene nanosheet and
PVA were synthesized by establishing the facial solution’s proper use. The compos-
ite’s mechanical activity was positively enhanced by instantly adding graphene
nanosheet in the active PVA matrix.

PVDF
The PVDF/GO nanocomposite fiber with dry-jet wet spinning showed that at the
specific GO concentration of 2 wt%, the composite included significant enhance-
ment in the proper form of toughness. It simultaneously increased the tensile strength
as well as the modulus. The possible variation in the mechanical features is typically
in co-relation with trace chain conformation disparity specified on the precise
drawing. The valuable material sufficiently shows a PVDF mobile because of the
conformation irregularity, and kinks naturally tend to get nucleated PVDF chain and
GO functional group instantly. The used PVDF fiber handled naturally possesses a
conventional translation of the crystal polymorphs [52].

Poly(3,4-ethyldioxythiophene)
The new and innovative graphene hybrid material (GHM), namely, PEDOT
exhibiting water and an organic method of processing, was reliably produced. The
various aspects were observed, such as conductivity of order 0.2 S/m, the light
transmittance of more than 80% ranging between the wavelength of 400 and
1800 nm, and the thickness of films of 10 nm. The material has specific features
like vigorous and elastic behavior and retention of excellent electrical conductivity
after deformation. Such extraordinary characteristics in a unique combination with
the easy preparation and critical capability of innovative solution correctly pro-
cessing merely enabled the PEDOT graphene to sufficiently show enhanced appli-
cation, and even the combined form conductivity needed transparency, and
considerable flexibility was in demand [74].

Polyethylene
The melt compounding method was adequately employed for the dispersion of GNPs
on PET, which naturally resulted in the possible formation of PET nanocomposite
posing positively enhanced mechanical and thermal features. The PET pellet was
grounded into fine powder form to improve the interaction ability between GNP sheet
and PET chains. The distribution analysis referred to the mixing of GNP to PET, and it
received a uniform distribution of GNP in comparison to PET pellet. GNP’s orientation
scheme is incredibly efficient, and it reinforced the PET matrix showing enhanced
mechanical features. The confirmation was provided by employing the matrices [70].
442 T. Arfin

Polycarbonate
The polycarbonate-based material was reinforced by GO, and then the thin trans-
parent film made through a facile method. The notable film’s microstructure accu-
rately reflected GO’s homogeneous dispersion between nanoscale and microscale.
Agglomeration was observed at higher loaded GO that is 0.7%. The PC-GO and GO
film indicated extraordinary bacteriostatic action toward E. coli and S. aureus. The
antibacterial nature of PC-GO merely enabled it to obtain suitable material for
properly employing in the biomedical device as well as in food packing
material [54].

Starch
The possible starch application is still the same, where 60% of starch applied as food
form and 40% as an industrial application [66]. The prominent chemist scientifically
studying complex carbohydrate has properly organized various innovative products
typically based on starch and its possible uses [59]. Starch is made into bioplastic,
but it is water-soluble. The valuable material developed from starch swells up and
gets severely deformed on direct exposure to excessive moisture, limiting its prac-
tical use [27, 28]. The GO exfoliated within the TWCS economically exploits the
waxy starch retrogradation, and such action results in representing a possible
interaction between the distinct phases. The BNCs of starch and GO made through
melt properly serve as suitable for application in various fields.

Alginate
Alginate is the salt of calcium (Ca), magnesium (Mg), and sodium (Na) formed
from alginic acid attained by brown algae cell wall employed for the enzyme
immobilization [29, 72]. In 1944 alginate fibers were first pronounced by
Speakman and Chamberlain, studying wet-spinning technique [30]. GAD
hydrogels’ possible use for the potential removal of heavy metal clarifies about
double network present in GAD positively enhancing the adsorption capacity of
heavy ions. It helps in maintaining reusability after several spontaneous adsorp-
tion/desorption cycles.

Cellulose
Cellulose is naturally a biomaterial present in apparent abundance in the kindly
earth’s prepared crust. It is sufficiently prepared by rare plants, reliably producing
beneficial bacteria [6]. Nanocelluloses (NC) are synthesized through cellulose deg-
radation from aboveground biomass. Some of the nanocelluloses are cellulose
nanocrystals [45], cellulose nanofibrils [50], and bacterial cellulose [46]. Ethyl
cellulose (EC) has the same structure as present in cellulose and its continuous
derivative, but it is the few hydroxyl groups changed by the ethoxy group
[18, 19]. EC is obtained from the reaction between alkali and ethyl chloride
[63]. EC’s flexible membrane is unswellable, and it is also compatible with the
plasticizers [12, 64]. It can also be employed as a rigid form [61]. The cellulose/GO
hydrogel remains a modern platform, and it applied in designing different GO base
material. The suitable, environmentally familiar reduction process can be
19 Consumer Nanoproducts Based on Graphene and Graphene Nanocomposite 443

implemented to typically obtain highly electrical conductivity and mechanical fea-

tures within the composite.

Chitosan
Chitosan is derived from chitin deamination [1]. In 1906, von Furth and Russo
suggested standard features of chitosan [62]. There are various advantages of
nanoscale chitosan, like antibacterial behavior and minimum toxicity toward
mammalian cells [20]. Glycerol permits food interaction between complex CS
matrix and GO nanosheets. Hence, valuable CS/GO/glycerol materials are rec-
ognized as appropriate material for numerous uses needing enhanced mechanical
features [48].

Gelatin
Gelatin is typically a functional protein made from native collagen partial hydro-
lysis. In the continuous availability of dilute acids, it is present in the visible bone
and precious skin of a noble animal [44]. RGO/gel composite includes an
excellent mechanical feature, and the testing clarifies that adding RGO increases
the gelatin film’s tensile strength in moist and rigid condition. It was observed
that on adding RGO, no negative behavior on the growth of the cell was found;
hence, RGO/gel can be considered critically as suitable material posing unique
mechanical features and better cell compatibility [73].

Protein
Functional protein corresponds, respectively, to amino acids positively linked
through the amide bone [40]. Most of the body hormones obtain polypeptides [13,
41, 55]. Lectins receive a protein with a feature to recognize the residue of carbo-
hydrate [56]. The possible interaction of GO and protein is generally electrostatic
and weak. With an increase in the GO oxidation degree, there is a change in the
extent of interacting with a protein [58].

Nanotubes
MWCNTs are the modern tubes properly containing multiple shells. The size is
significant, and it works efficiently compared to SWCNT [47]. The exciting topic
at valuable present represents the notable addition of MWCNT in various useful
materials for reinforcing fibers. This is primarily because of the excellent
mechanical as well as physical features such as significant tensile strength
[2]. GO nanosheets were responsible for positively enhancing and stabilizing
the MWCNTs dispersion. When minimum GO dose was added to MWCNT, the
considerable gap between carbons nanomaterials was bridged, constituting a
conductive network. It could permit for developing of a smooth pathway for
the conduction of electron.

Polyamide
Polyamides categorized into diverse class based on the necessary arrangement and
monomer chemical nature like aromatic, cycloaliphatic, and aliphatic polyamides
444 T. Arfin

Fig. 4 Various types of fabrication technique

[36]. Polyamides consist of crystalline polymers made from the condensation reac-
tion of diamine and diacid [15]. The Cr(IV) ion’s adsorption capacity was properly
47.17 mg/g of N6.6/GO graciously according to the fundamental equations and
isotherm curves. The equilibrium data observed that Langmuir isotherm was more
capable enough [69].

Fabrication Techniques for Polymer

The different fabrication processes were given for the polymer/graphene nano-
composite. The proper selection of adequate procedures was dependent on graphene
uniform dispersion and the total intercalation of the organic polymers. Figure 4
reveals a thorough process of modern fabrication.

Graphene-Nanoparticle Composite

Graphene is properly the material posing lots of principle attraction due to its
platelike extraordinary and structure features. So it is infinitely preferable as an
attractive substrate for inorganic nanoparticle deposition. The possible disad-
vantages of graphene sheet aggregation are prevented partly by intercalating
particles in the graphene’s distinct layer. Such composites can impart function-
ality to the graphene used for different applications through the single compo-
nents’ synergistic behavior. To date, many metal compounds are composed of
graphene and derivatives of graphene, e.g., Au, Cu, ZnO, CdS, Sr2Ta2O7, and
so on.

Synthesis Approaches

Figure 5 shows the different synthesis strategies used for graphene-nanoparticle

composite.
19 Consumer Nanoproducts Based on Graphene and Graphene Nanocomposite 445

Fig. 5 Ideal various types of synthetic strategies

Creative Processes to Modify Graphene

Graphene is modified by several efficient methods, as listed in Fig. 6.

Suspension/Substrate

Figure 7 exhibits various parameters responsible for positively affecting specific cells’
effective response toward graphene-based material within the possible suspension and in
the proper form of a suitable substrate. It relates to the fact that graphene as a substrate
interaction with the cell differs from the suspension of graphene particles.

Applications

The G and G derivatives gained attention in modern science and engineering

awareness because of the varied number of potential applications. G’s invention
and discovery are considered a milestone in the field of material science and noticed.
They are profitably employed in the application, as given in Fig. 8.
446 T. Arfin

Fig. 6 Creative processes of considerable modification of graphene

Fig. 7 Schematic shows different parameters of graphene in suspension and as a supportive

substrate

Conclusion

In 2004, the G discovery by Geim and Novoselov had sufficiently illustrated the
ubiquitous features, and the G derivatives have also persuaded academic researchers
on a worldwide basis [7, 26, 39]. A surface group’s continuous availability has
provided a novel process to modern synthesis GO-based material by coordinating
19 Consumer Nanoproducts Based on Graphene and Graphene Nanocomposite 447

Fig. 8 Various types of application of graphene-based material

with other material [67]. It concluded in designing new material posing record
features [57, 68, 71]. Such technology constrained technical limitations like devel-
oping the material of required optimization and adequate efficacy. The economic
advancement in this academic field helped out for environmental safety as well as
eco-friendly maintenance. The selectivity needs to be enhanced along with acute
sensitivity for the various components. By instantly following this essential step, the
commercial sector will gain either in the practical term of the sustainable economy or
controlled environment. Therefore, the investigation technique typically needs sus-
tainable development and continuous optimization of nanocomposite at necessary
minimum costing. The developed world is waiting to look forward to green and
sustainable material to use for safety regard. Therefore, in this proper context,
modern graphene-based material merely requires lots of principal attraction, and
many more investigations are needed to fulfil the basic necessity.

Acknowledgments Authors acknowledge the Knowledge Resource Centre, CSIR-NEERI (CSIR-

NEERI/KRC/2020/SEP/EMD/1), for their support.
448 T. Arfin

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Performance of Graphene: A Brief
Literature Review on Technologies 20
for Composite Manufacturing

R. Sundarakannan, V. Arumugaprabu, S. Vigneshwaran,

P. Sivaranjana, and R. Deepak Joel Johnson

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Preparation of Graphene and Processing for Composite Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Graphene Reinforced Metal Matrix Composites and Its Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Graphene Reinforced Polymer Matrix Composites and Its Properties . . . . . . . . . . . . . . . . . . . . . . . . . 460
Graphene Reinforced Ceramic Matrix Composites and Its Properties . . . . . . . . . . . . . . . . . . . . . . . . . 462
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464

Abstract
Developing new material with improved strength is one of the challenges for the
researchers in the field of composite materials. In such a way, graphene is one of the
attractive materials recently developed and reinforced in different composites to
improve their properties. Graphene has superior properties owing to their honey-
comb lattice structure and a single layer of carbon atoms arrangement. The main
advantage of graphene is their thin layer structure and lightweight. At present,
graphene is utilized as reinforcement in the composite material production and
various properties has been discussed. The graphene-based composite materials are
suitable for various applications such as medicine, electronics, sensor, energy, solar
cell, filtration, and mechanical fields. At present, graphene reinforced materials

R. Sundarakannan · P. Sivaranjana
School of Automotive and Mechanical Engineering, Kalasalingam Academy of Research and
Education, Krishnankovil, Tamil Nadu, India
V. Arumugaprabu (*)
Department of Mechanical Engineering, School of Automotive and Mechanical Engineering,
Kalasalingam Academy of Research and Education, Krishnankovil, Tamil Nadu, India
e-mail: [email protected]
S. Vigneshwaran · R. D. J. Johnson
Department of Mechanical Engineering, Saveetha School of Engineering, Saveetha School of
Medical and Technical Sciences, Thandalam, Chennai, Tamil Nadu, India

© Springer Nature Singapore Pte Ltd. 2022 453

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_40
454 R. Sundarakannan et al.

have been largely developed and investigated. This chapter reports the recent
development in composite with graphene reinforcement, in particularly graphene
reinforcement effect in the polymer, metal, and ceramic matrixes.

Keywords
Graphene · Graphene oxide · Polymer · Metals · Ceramics

Introduction

In recent years, composite materials were developing for various application to replace
over their conventional materials owing to their good strength, less weight, the
resistance of wear, and low cost [1]. Various filler has been reinforced in ceramic,
metal, and polymer matrix such as carbon nanotubes CNT [2], Al2O3 [3], TiO2 [4],
SiC [5], and industrial waste red mud [6] to enhance on their mechanical properties.
Filler reinforced composite materials showed an increase in material properties. There
have been numerous research works that reported the properties of filled composites.
Graphene advantages and its utilization have been explored during the last
decade. The graphene consists of layer-by-layer arrangement of carbon atoms, and
it is mostly prepared from carbon-rich materials like graphite [7]. Some notable
applications of graphene materials are in energy storage devices, solar cells, nano-
electromechanical systems, transistor, memory devices, photodetector, coatings,
electronic application, polymer composites, ceramic composites, and even in metal
matrix composites. The graphene poses excellent mechanical, thermal, electrical
properties [8]. The graphene delivers tremendous mechanical properties by their
monolayer structure, given the mechanical strength of 130GPa proved it considered
as one of the strongest materials [9].
Compared to CNT filler, graphene has a higher specific surface area and are not
agglomerate easily; when reinforcing, this makes a uniform dispersion in the matrix.
Also, CNT is needed to process for modifying the surface to prepared composite.
Compared to other filler materials, graphene has less health hazard [10]. Recently,
Graphene has been found as an effective reinforcement in the composite materials [11].
Research on the graphene reinforced composites is a developing area, which is
more promising and unexploited. The ultimate intent of this review is to deliver a
comprehensive picture of the graphene reinforced composites. This review classified
and reported the graphene reinforced polymers, metals matrix, and ceramic matrix.

Preparation of Graphene and Processing for Composite

Fabrication

Mostly graphene is extracted from carbon-rich material like graphite through mod-
ified Hummers method [12]. Graphene is formed through layer-by-layer exfoliation
of graphite formed with a single layer honeycomb structure [13]. The graphite
material undergoes some chemical reaction for reducing it to graphene by the
20 Performance of Graphene: A Brief Literature Review on Technologies for. . . 455

process of modified hummer’s method [14]. Most of the authors reported this
method to produce graphene oxide. On the other hand, mechanical exfoliation
process used to produce the graphene nano-platelets. In this method, planetary
mills play a role to produce graphene from bulk graphite material [15].
Graphene can also be synthesized through chemical vapor deposition method. In
this method, graphene film was coated on a particular substrate using gas molecules at
high temperature [16]. Out of all these methods, graphene processed through chemical
reduction is more popularly used, since these methods produce graphene at large
amount and are more suitable for utilizing in the practical applications [17]. But at
present for developing composites, graphene oxides reduced through exfoliation and
chemical reduction is more preferably used and also through modified Hummers’
method [18]. For fabricating graphene composites, various methods have been
followed. Some common methods used in fabricating graphene composites with
metal, polymer, and ceramic matrixes are listed in Table 1, 2, and 3 respectively. In
composite fabrication, dispersion of graphene in the matrix is more important, since it
defines the interfacial attraction between the graphene and the matrix. Unfortunately,
graphene has high surface area and strong van der Waals forces, this made them to
attract each other and agglomerates [19]. But this can be overcome by processing the
graphene through surface modification like noncovalent and covalent bonding.

Graphene Reinforced Metal Matrix Composites and Its Properties

Reinforcement of graphene in metal matrix composites is more difficult, and it is

challenging for researchers. The preparation of metal matrix composite considers
some factors such as powder size, shape, percentage of filler. This process of
producing composite material, mainly focused on uniform distribution of matrix,
plays an important role on the metal matrix composites.
Jingyue Wang et al. [80] reported the tensile strength of graphene nanosheet
reinforced aluminium matrix composites. The tensile strength of the composites
enhanced by 62% due to graphene reinforcement in the aluminum matrix. Graphene
reinforcement develops uniform dispersion throughout the matrix. Fadavi Boostani
et al. [81] fabricated graphene encapsulated sic nanoparticles reinforced aluminum
matrix composites. The result is evident as the tensile and ductility properties were
improved by 45% and 84%, owing to the graphene reinforcement. Chi-Hoon et al.
[82] fabricated the graphene oxide reinforced aluminum matrix and analyzed the
thermal properties of the composites. Thermogravimetric test results showed that the
functional group of graphene oxide improved the thermal conductivity of the
graphene aluminum matrix significantly up to 15%. Compared to pure aluminum,
the tensile strength of the composite decreased on reinforcement, although the
elongation properties are enhanced. Wenzheng Zhai et al. [83] studied tribological
properties of multi-layer graphene (MLG) reinforced Ni3Al metal matrix compos-
ites. The graphene reinforced at different weight such as 0.5, 1.0, 1.5, and 2.0 wt. %.
The results concluded that the optimum wear rate at 1.0% of MLG reinforced metal
matrix composites. The hardness and elasticity properties significantly increased up
to 1.0% of MLG addition and after that decreased.
456 R. Sundarakannan et al.

Table 1 Processing techniques of graphene reinforced metal matrix composites

S. Graphene Matrix
No reinforcement material Fabrication method References
1 Graphene nano Aluminum Powder metallurgy Jingyue Wang et al [20],
sheets 2012
2 Graphene oxide Copper Spark plasma Jaewon Hwang et al [21]
sintering 2013
3 Single-layer Iron Laser sintering Dong Lin et al [22], 2014
graphene oxide
4 Graphene oxide Aluminum Friction stir Chi-Hoon Jeon et al [23],
processing 2014
5 Graphene Aluminum Hot extrusion Muhammad Rashad et al
nanoplatelets [24], 2014
6 Multilayer TiAl Spark plasma Zengshi Xu et al [25],
grapheme sintering 2013
7 Graphene Aluminum Hot isostatic pressing S.J. Yan,[26] 2014
nanoflakes alloy
8 Graphene oxide Aluminum Powder metallurgy Xin Gao et al [27], 2016
9 Multilayer Ni3Al Powder metallurgy WenzhengZhai et al [28],
graphene 2014
10 Graphene Copper Hot-press sintering Hongyan Yue et al, [29]
nanosheets 2016
11 Graphene Copper Microwave sintering C. Ayyappadas et al [30],
processes 2017
12 Graphene Titanium Hot isostatic pressing Zhen Cao et al [31], 2017
nanoflakes
13 Graphene Magnesium Liquid Lian-Yi Chen et al [32],
nanoplatelets alloy state ultrasonic 2012
processing
14 Graphene Magnesium Hot extrusion Xian Du et al [33], 2017
nanoplatelets processes
15 Graphene oxide Aluminum Electrostatic self- Xin Gao et al [34], 2016
assembly
16 Graphene Nickel In-situ fabrication; Jinlong Jiang et al [35],
2018
17 Graphene Aluminum Sintering process Jong-Min Ju et al [36],
2017
18 Graphene oxide Aluminum Direct electrostatic Zan Li et al [37], 2014
adsorption
19 Graphene oxide Iron Laser sintering Dong Lin et al [38], 2014
20 Multi-layer Titanium Spark plasma Y. Song et al [39], 2016
graphene sintering
20 Performance of Graphene: A Brief Literature Review on Technologies for. . . 457

Table 2 Processing techniques of graphene reinforced polymer matrix composites

S. Graphene Fabrication
No reinforcement Matrix material method References
1 Few-layered Chitosan Solution casting Hailong Fan et al
graphene method [40], 2010
sheets
2 Graphene Poly(butylene succinate) Solution-based Xin Wang et al
nanosheets processing [41], 2011
method
3 Graphene Epoxy Solution casting MinooNaebe et al
oxide method [42], 2014
4 Graphene Epoxy Cast resin Xin Wang et al
plaques [43], 2013
5 Graphene Chitosan Solution casting Yongzheng Pan
oxide method et al [44], 2011
6 Graphene Hydrogenated Carboxylated Solution- Xin Bai et al [45],
oxide Nitrile–Butadiene Rubber blending method 2010
7 Graphene Polybenzimidazole Solvent- Yan Wang et al
oxide exchange method [46], 2010
8 Graphene Polypropylene Melt-blending Pingan Song et al
[47], 2011
9 Graphene Polyethylene terephthalate Melt blending Oana M. Istrate
et al [48], 2014
10 Graphene Glycerol-plasticized pea Solution casting Rui Li et al [49],
oxide starch method. 2010
11 Graphene Poly methyl methacrylate Solvent casting Gil Gonc¸alves
oxide et al [50], 2010
12 Graphene High density polyethylene Melt M. El Achaby et al
nanosheets Mixing [51], 2013
13 Graphene Polyvinylidene fluoride Solvent casting VarrlaEswaraiah
et al [52], 2011
14 Graphene Polyethylene terephthalate Melt blending Oana M. Istrate
platelets et al [53], 2014
15 Graphene Epoxy Hot pressing Ming-Yuan Shen
nanoplatelets et al [54], 2013
16 Few-layer Polyvinyl alcohol & poly Hot compaction Barun das et al
graphene methyl methacrylate [55], 2009
17 Graphene Poly(3-hydroxybutyrate-co- Solution casting V. Sridhar et al
nanoplatelets 4-hydroxybutyrate) [56], 2012
18 Graphene Polyurethane Sol–gel method Xin Wang et al
[57], 2012
19 Graphene Polyurethane In situ Santosh
nanoplatelets polymerization. kumaryadav et al
[58], 2012
20 Graphene Polybenzimidazole In-situ Md. Wasiahmad
nanosheets polymerization et al [59], 2018
458 R. Sundarakannan et al.

Table 3 Processing techniques of graphene reinforced ceramics matrix composites

S. Graphene Matrix Fabrication
No reinforcement material method References
1 Graphene nano- Alumina Spark plasma Harshit Porwal et al [60], 2016
sheets sintering.
2 Graphene Silicon nitride Spark plasma Hanuˇs Seiner et al [61], 2015
nanofillers sintering
3 Graphene Monolithic Hot pressing Mehdi ShahediAsl et al [62],
zrb2 2014
4 Reduced Zirconia Spark plasma Jung-Hoo Shin et al [63], 2014
graphene oxide sintering
5 Graphene Calcium Selective laser CijunShuai et al [64], 2014
silicate sintering
6 Graphene flakes Zirconia Spark plasma A. Smirnov et al [65], 2019
sintering
7 Graphene oxide Alumina Sintering Lu Wang et al [66], 2019
process
8 Graphene Zirconium Spark plasma Govindaraajan et al [67], 2018
diboride sintering
9 Graphene Zrb2–sic Hot pressing Xinghong Zhang, Yumin An
nanosheet Process et al [68], 2015
10 Graphene WC-Al2O3 Hot-pressing Xiaoxiao Zhang et al [69],
platelets sintering 2019
11 Graphene oxide Zirconia Spark plasma N. W. Solís et al [70], 2017
Sintering
12 Graphene Boron carbide Hot-pressing A. Kovalčíková et al [71],
platelets 2015
13 Graphene oxide Alumina/ Tape casting Oxide et al [72], 2014
zirconia
14 Graphene oxide Zirconia Spark plasma Layersacaciorincón et al [73],
sintering 2016
15 Graphene Boron carbide Hot pressing Richard sedlák et al [74], 2017
platelet
16 Graphene Silicon Hot pressing Richard sedlák et al [75], 2017
platelet carbide
17 Graphene Alumina Rapid sintering Iftikharahmad et al [76], 2017
nanosheets route
18 Graphene Si3n4 Spark plasma Tomasz cygan et al [77], 2016
sintering
19 Few-layer Alumina Spark plasma Yuchi fan et al [78], 2012
graphene sintering
20 Graphene Alumina and Spark plasma By kylejiang et al [79], 2014
platelet zirconia sintering.

Li et al. [84] performed microstructural and tensile test analysis on the graphene
reinforced aluminum matrix composites. The graphene was reinforced aluminum
matrix at various weight percentage such that (0.5, 1, 1.5, and 2%) by hot extrusion
techniques. The tensile test reports that the graphene content beyond 1% forms
20 Performance of Graphene: A Brief Literature Review on Technologies for. . . 459

agglomeration in grain boundaries and weak bonding of the matrix. This effect
decreased the ductility and tensile strength of the composites. Composite with 0.5%
graphene significantly improved mechanical properties. Xin Gao et al. [85] studied
the mechanical properties on graphene powder reinforced copper matrix. The
mechanical properties of the prepared composites increased significantly on
graphene reinforcement. Micro hardness and tensile strength reached the maximum
at 0.3% graphene reinforcement. Furthermore, addition decreased the mechanical
properties and the elastic modulus. Zengrong et al. [86] investigated the mechanical
properties on graphene reinforced titanium matrix composites. Graphene addition
improved the hardness up to 50% when compared to unfilled composite. Also, the
modulus value significantly increased at 5% graphene reinforcement. More addition
of the reinforcement decreased the hardness value due to the formation of aggrega-
tion throughout the matrix.
Saurabh Dixit et al. [87] analyzed the multilayer graphene reinforced aluminum
metal matrix composites. The aluminum matrix ductility was increased by 33% on
the graphene addition. The graphene reinforced composites show a 45% increase in
hardness value. The ultimate tensile strength of the pure aluminum value is 84MPa,
and the graphene reinforced aluminum matrix is 147MPa. This study confirmed that
graphene reinforcement enhanced mechanical properties of aluminum composites.
Duosheng et al. [88] investigated the mechanical properties of graphene reinforce-
ment aluminum composites, and it compares with pure aluminum metal. Graphene
was reinforced at different volume fraction, such as 0.5, 1.0, 1.5, and 2.0%, and it
mixed with aluminum powder to fabricate the composite plate through vacuum hot
pressing sintering method. The compressive strength increased when increasing the
graphene weight percentage. The maximum compressive strength of 527Mpa was
noted on the 2% graphene reinforcement. After graphene reinforcement, 330% to
586% increment is noted in compressive strength compared to pure aluminum
matrix. X.N. mu et al. [89] analyzed the graphene reinforced Ti carbide matrix
composites. Composites were fabricated with 0.2% graphene with Ti carbide matrix
through the hot rolling process at varying temperatures of 823, 1023, and 1223K.
Graphene composites showed 2.5% to 12.5% times increased tensile strength than
the pure matrix. The varying temperature plays a significant role in improving the
tensile strength of the Ti graphene composites.
Xian Du et al. [90] studied the microstructure, mechanical properties of graphene
nanoplates reinforced homogenous magnesium alloy (ZK60). The hardness test
shows that the maximum hardness value of 78 on 0.1% Gnp reinforcement. The
tensile load on the composites reveals the plenty of tear edges. The pure Mg alloys
tensile and compressive was compared with 0.05% and 0.1% graphene nanoplates.
The ultimate tensile strength, tensile yield strength, and elongation values increased
with reinforcement of graphene, the maximum values for that tensile strength UTS
345, TYS 283, Mpa & elongation 17%. Maximum compressive strength is noted on
of 0.1% graphene composite (OCs 463Mpa, UYS 279 & failure strain 12%).
Hansang et al. [91] compared the 1.vol% graphene oxide reinforced aluminum
matrix composites and the pure AuMg5 alloy. The hardness of 73Gpa is recorded
on graphene added matrix and 53 Gpa on pure AuMg5 matrix. The composite
460 R. Sundarakannan et al.

modulus strength enhanced by 30% and the maximum tensile strength is 556 MPa is
noted at 1.0% graphene reinforced composite. Furthermore, graphene composite
flexural strength value is 813 Mpa, which is over four times higher than the pure
composite. Haiboluo et al. [92] analyzed the graphene oxide modified silver nano-
particles (AG-Rgo) reinforced copper matrix. The tensile strength and yield strength
were significantly increased on Ag-RGo reinforced matrix, which is 478 Mpa and
332 Mpa, respectively. The elongation is higher on the pure copper matrix and
decreased on the addition of reinforcement. The tensile strength reached at maxi-
mum on RGO composites which are 52% and 98% higher than the pure copper
material. Ankita Bisht et al. [93] investigated on the graphene nanoplatelets
reinforced aluminum matrix composites. The graphene is reinforced at different
weight percentage such as 0.05, 1, 3, and 5 wt. % and composites were fabricated
by spark plasma sintering method. At 3% and 5%, graphene reinforcement develops
agglomeration on the composites due to weak interfacial adhesion between rein-
forcement and matrix. Compared to other weight percentages, 1% of the graphene-
enhanced the tensile strength, yield strength, as well as hardness and which are
84, 54.8, and 24.1% higher than the values of pure Aluminum.

Graphene Reinforced Polymer Matrix Composites and Its

Properties

In Recent years, polymers are widely used in various applications due to their
advantages. The filled polymer composites increase the mechanical behavior
depending upon the reinforcement percentages. This filler addition forms the good
bonding between the matrix, and it creates in improving the uniform stress distribu-
tion of composites. This graphene filler effect is discussed in the polymer composites
is witnessed by various researchers.
Wenchao pang et al. [94] investigated on tribological properties of graphene
oxide (GO) reinforced polyethylene matrix, fabricated different weight percentage
of GO by hot pressing techniques. Tribological properties were investigated under
the different condition on dry, deionized water and seawater. Water absorption
studies indicated that 0.13% GO composites exhibited better water resistance prop-
erties compare to neat composites. Abrasion wear studies revealed that the addition
of the graphene oxide composites lead to decreased wear resistance. GO content
significantly improved the crystallinity of the polymer matrix, which increased the
micro hardness properties. Orebotse Joseph Botlhoko et al. [95] explained that
thermal and mechanical properties of graphene reinforced polylactide/poly-
caprolactone composites. Graphene oxide reinforced polymer matrix was fabricated
by melt mixing method. Thermally reduced graphene was used in this composite.
TGA analysis shows that at 100  C, loss of weight in composites is noted due to loss
of water molecules. The carbon content present in the composites undergoes the
weight loss of peak found at 500  C. Optimal thermal properties of graphene
composites were obtained at 700  C thermally reduced graphene reinforcement at
0.05 wt. %. Rui Sun et al. [96] analyzed the behavior of polymer composites
20 Performance of Graphene: A Brief Literature Review on Technologies for. . . 461

reinforced single-layer graphene consists of single and double vacancy structure.

Compared with single vacancy graphene, composites double vacancy was exhibited
better mechanical properties of graphene filled composites. Nitai Chandra Adak
et al. [97] reported mechanical properties of graphene oxide and woven carbon fiber
reinforced epoxy polymer matrix. Graphene nanofiller incorporated at different
weight percentages such as 0.05, 0.1, 0.2, and 0.4% and the fiber weight percentage
is maintained. Nanographene filled composites at 0.2% has a maximum tensile
strength of 336 MPa. Flexural properties of the fabricated composite significantly
increased by 34, 43, 56, and 51%, respectively, when compared to neat composites.
After 0.2% of graphene reinforcement, drastic reduction in mechanical properties is
noted. Good interlocking characteristics were observed for 0.2% epoxy graphene
carbon composites.
Suman Chhetri et al. [98] investigated on mechanical, thermal, and topography
properties of graphene included epoxy matrix composites. Tensile properties were
increased on the reinforcement of graphene. Tensile strength of 0.2% graphene filled
composites reached a maximum value of 51 MPa, thus compared to a neat epoxy
matrix, 0.2% filled composites have maximum thermal stability. Lingyun Zhang
et al. [99] fabricated polystyrene matrix reinforced graphene oxide by melt mixing
method. Graphene oxide was incorporated with various weight percentages such as
0.1, 2, and 4%. Tensile strength of composites was significantly increased by the
addition of nano filler graphene oxide. Impact strength of composite plates was
increased of the graphene addition. TEM studies revealed the good dispersion of the
graphene in polystyrene composites. Han Wang et al. [100] reported that uniform
distribution of graphene with the matrix is the key to obtain maximum tensile,
impact, and toughness strength. Thermal properties of the composites revealed
high stability of graphene at 0.3 wt. % reinforcement. MinooNaebe et al. [101]
made a comparison study between graphene reinforced epoxy matrix composites
and neat epoxy composites. It is found that 0.1% of functionalized graphene
reinforcement showed 22% increase in the tensile strength when compared with
neat composites. Topographical studies were examined for interfacial bonding,
adhesion, and dispersion of functionalized graphene matrix composites.
Cui-Cui Wang et al. [102] observed that various percentage of graphene oxide
reinforced polypropylene carbon fiber composite. Graphene was prepared by mod-
ified Hummers’ method and mixed polypropylene short carbon fiber by melt mixing
method. Mechanical tests were conducted and compared with various percentage of
graphene and carbon fiber filled composites. The tensile test reported that including
graphene and short carbon fiber significantly improved the tensile, flexural, and
impact strength. The maximum properties were observed on 0.5% graphene oxide
reinforced short carbon fiber filled composites. Differential scanning calorimeter
studies revealed that 0.5% GO/SCF composites improved thermal stability of the
polymer composites. Annie Moussemba Nzenguet et al. [103] analyzed mechanical
properties of graphene oxide reinforced bio nanocomposites films. Graphene oxide
incorporated with matrix at different weight percentage such as 0.3, 0.5, 0.7, and
1.0% composites. Graphene composites at 1% exhibited maximum strength. Barun
Das et al. [104] analyzed mechanical properties of graphene reinforced polymer
462 R. Sundarakannan et al.

matrix composites. Graphene was added at a different weight percentage to polyvi-

nyl alcohol (PVA) and polymethyl methacrylate (PMMA) matrix. The hardness and
elastic strength were significantly increased on the addition of graphene for both
fabricated specimens. Compared to PVA composites, PMMA composites showed
maximum strength.

Graphene Reinforced Ceramic Matrix Composites and Its

Properties

The Ceramics materials brittle behavior limits their use in the mechanical applica-
tion. The ceramic materials found its application in the automobile industry, elec-
tronic industry, biomedical industry, etc. In recent years, graphene is used as the
reinforcement in the ceramic composites.
Lenka Kvetkova et al. [105] compared the 1% graphene platelets reinforced
silicon nitride composites fabricated through two processes, hot isostatic pressure
method and gas sintering method. Graphene platelets composites fabricated through
the gas pressure sintering attained the lower fracture value. Pavol Hvizdo et al. [106]
conducted the tribological studies for silicon nitride ceramic matrix reinforced of
different types of graphene platelets. The ceramic composites were prepared by hot
isostatic process on 1700  C at 20MPa for 3 h sample holding time. The wear
resistance property was increased on the graphene addition. Notably, 3% composites
showed lower wear value which is 60 wt. % than the pure silicon nitrate. Ya-Fei
Chen et al. [107] fabricated the graphene nanosheets reinforced on alumina com-
posites by the addition of graphene nanosheets in different weight percentages such
as 0.1, 0.2, 0.5, and 1 through hot isostatic processing method. The prepared
composites’ bending strength and fracture strength was examined, the 0.2%
graphene nanosheet alumina composites showed the maximum strength. The frac-
ture toughness of the reinforced composite showed a 43.5% increase, when com-
pared with pure alumina matrix.
Yu Cheng et al. [108] investigated the hardness properties on graphene platelets
reinforced alumina oxide and titanium matrix composites. The graphene platelets
reinforced at weight percentages such as 0.1, 0.2, 0.4, 0.6, and 0.8%, respectively.
The prepared composites hardness and toughness properties increased at 0.2 wt. %
of graphene platelet reinforcement. This work concluded that the maximum values
observed at 0.2% graphene composites reached maximum fracture value noted at
titanium matrix composites which is 67.3% higher when compared to pure alumi-
num oxide. Cui et al. [109] studied the graphene nanoplatelets incorporated Al2O3
and Ti composites by using hot pressing sintering technique and investigating the
mechanical properties. Initially, addition of graphene nanoplatelets increased the
mechanical strength, the maximum value was observed on 0.4 wt. % composites,
after that mechanical property was decreased. When compared to the pure ceramic,
0.4 wt. % composites increased the flexural strength and fracture strength by 40.13%
and 40.78%, respectively.
20 Performance of Graphene: A Brief Literature Review on Technologies for. . . 463

Tomasz Cygan et al. [110] investigated on the graphene oxide reinforced alumina
matrix by spark plasma sintering method and reported that graphene is an effective
reinforcement material to improve the mechanical properties of ceramic composites.
Grigoriev et al. [111] reported on the graphene oxide reinforced alumina-silicon
carbide composites. The maximum mechanical properties were found on 0.5 wt. %
composites (hardness 22GPa, fracture toughness 10.6GPa, and flexural strength
904 MPa, respectively.) Thereafter, additional GO doesn’t improve the strength.
Xingzhong Guo et al. [112] prepared the silicon carbide matrix reinforced multilayer
graphene composites. The investigation reports 5% graphene composite has a
promising hardness value of 16.74 Gpa, bending strength of 265.44 MPa, and dry
co-efficient of friction of 0.22. Peter Kun et al. [113] reported that the multilayer
graphene reinforcement provides the maximum bending and elastic modulus in
ceramic composites. Jian Liu et al. [114] investigated the toughness behavior of
graphene platelets reinforced zirconia alumina composites. The ceramic composites
prepared from spark plasma sintering method are at different temperatures such as
1450, 1550, 1650, and 1750  C. Composites with 0.18% graphene platelets fabri-
cated condition at 1550  C exhibited maximum toughness strength.
Fu Liu et al. [115] analyzed the graphene oxide reinforced SiC composite
fabricated by reaction sintering method at a various weight percentage of GO (0.5,
1.0, 1.5 and 3.0). The bending strength and fracture strength were observed on the
prepared composites, and it is found that 1.5 wt. % composites showed higher
fracture strength of 3.6 MPa. The bending strength of 10% composites increased
by 58% when compared to pure SiC composite. Mehdi Mehrali et al. [116] reported
the mechanical properties of calcium silicate ceramic matrix filled with reduced
graphene oxide composites. In this work, composites are prepared at a different
weight percentage of graphene (0.25, 0.5, 0.75, 1.0, and 1.5) by the hot isostatic
process. The mechanical properties were compared with pure and the 0.5 wt. %
calcium silicate composites such that elastic modulus 52%, fracture strength 123%,
and hardness 40%. Harshit porwal et al. [117] produced the graphene reinforced
alumina nanocomposites fabricated by powder processing method at different vol-
ume percentages of graphene (0.1, 0.5, 0.8, 2, and 5). The composite with 0.8 wt. %
of graphene showed improved mechanical characteristics. A linear increase is noted
up to 0.8%, after that the mechanical strength was reduced due to improper bonding
and also due to agglomeration of graphene.

Conclusions

It can be resolved from the review that the graphene has the efficiency to enhance
and vary the composite properties, which can be used in broad applications. This is
evident from the literature which shows a significant improvement in mechanical,
electrical, and thermal characteristics. Reinforcement percentage of graphene in
matrix defines the strength of the composite material. The properties of graphene
composite mainly depend on the purity, loading ratio, dispersion with matrix,
agglomeration, and interaction of graphene with the matrix. It is identified that
464 R. Sundarakannan et al.

only limited studies explain the effect of the size distribution of graphene in the
composite material. Also, the stability of the graphene at high temperature should be
addressed in detail since various fabrication processes of the graphene is exposed to
very high temperature. Reinforcement of graphene into a polymer, metal, and
ceramic composite is still in developing stage. To optimize the processing techniques
and to achieve the utilization in the application, the graphene composite should be
studied in more details which could develop a new window to utilize graphene in
various composite applications.

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Consumer Applications of Graphene and Its
Composites 21
Ramesh K. Guduru and Anurag Ateet Gupta

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
Nanomaterials and Their Importance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
Carbonaceous Nanomaterials and Their Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
Properties of Graphene and Its Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
Processing of Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
Applications of Graphene and Graphene Market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
Graphene-Based Products and Technologies Available in the Market . . . . . . . . . . . . . . . . . . . . . . . . . 479
Electrical/Electronic/Thermal Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
Sports, Safety, and Outdoor Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
Audio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
Automobiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
Textiles/Outfits and Filtration/Membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Biotech . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Coatings, Adhesives, and Oil and Gas Industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 492
Other Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494
Future Prospects of Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498

Abstract
This chapter provides a comprehensive review of current trends in graphene-
based consumer and industrial products. Initially, the chapter focuses on classi-
fication of nanomaterials, including carbon-based nanomaterials and their prop-
erties and superiority while highlighting the role of different properties in
practical applications. Then processing of graphene is briefly discussed for its
mass production to address the growing needs of the technological trends and the

R. K. Guduru · A. A. Gupta (*)

Pandit Deendayal Petroleum University, Gandhinagar, Gujarat, India
e-mail: [email protected]; [email protected]

© Springer Nature Singapore Pte Ltd. 2022 471

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_41
472 R. K. Guduru and A. A. Gupta

consumer market. It further describes the worldwide market scenario, various

applications of graphene and graphene-based consumer products, and technolo-
gies currently available in the global markets. Finally, it concludes with a
discussion on future prospects of graphene and its composites and associated
challenges in meeting the global industrial demands.

Keywords
Graphene · Graphene-based composites · Nanomaterials · Applications ·
Consumer products · Graphene market · Graphene products · Global market ·
Future prospects

Introduction

The promising superior properties of nanomaterials over the conventional macro-

and microscale counterparts have opened up plethora of opportunities for their
practical applications in the consumer world. Among various such nanomaterials,
graphene has garnered a greater attention due to its large surface area, lightweight
(0.77 mg/m2), hardest nature (than the diamond), ultrahigh strength (~100–300 times
the strength of the steels), superior electron mobility (~100 times more to the
electron mobility in Si), and better electrical conductivity (~13 times more than the
electrical conductivity of Copper) characteristics [1]. These excellent features of
graphene seem to provide great potentials to bridge several gaps in the property
constrained arena of conventional materials and their applications. The market for
graphene-based materials has been expanding quite rapidly in many segments
including electronics, sensors, biotechnology, sports, oil and gas, radiation shielding,
and textiles [2]. Thus keeping many upcoming opportunities for graphene in mind,
here in this chapter, we initially focus on the properties of graphene and its com-
posites followed by avenues for their practical applications. Then, we will discuss
about the existing as well as upcoming consumer products of graphene-based
materials in the global markets. Finally, we will provide our insights on future
prospects of furthering their applications.

Nanomaterials and Their Importance

Nanomaterials are of organic/inorganic nature that could exist either in the form of
nanoparticles or nanolayers or nanostructured materials. The nanostructured mate-
rials usually have internal features, such as grains whose size range is within
1–100 nm, whereas the nanophase/nanoparticle materials could exist as individual
particles within the size of 1–100 nm [3, 4]. On the other hand, nanolayer materials
could exist in 2D geometry with thickness hardly in the nanoregime. Thus nano-
materials can be divided into different categories based on their dimensionality,
especially the dimension in which the size effect could be apparent on the resultant
21 Consumer Applications of Graphene and Its Composites 473

property; thus the nanomaterials are classified as 0D, 1D, 2D, and 3D materials
[5]. The zero-dimensional materials basically confine the movement of electrons in
all the three dimensions, for example, the quantum dots. In case of 1D, the electrons
are free to move only along one dimension, and they are confined in the other two
directions. The examples for such nanomaterials are nanowires, nanotubes, and
carbon nanotubes (CNTs). In 2D, such as thin layer structures, the electrons are
free to move in any two directions and are confined in the third direction. The
quantum wells and layer-structured materials, such as graphene, graphene oxide,
MoS2, and WO3, are the best examples for this class of materials. In case of 3D
nanomaterials, the electrons are free to move in all the three directions, the nano-
particles represent this class of materials [6, 7]. The nanomaterials of 0D, 1D, 2D,
and 3D can be fabricated using different chemistries, which include carbon, metals,
non-metals and their oxides, and sulfides. Figure 1 shows the classification of
nanomaterials as per their dimensions.
The nanomaterials exhibit unique and enhanced properties when compared with
the bulk materials because of their high surface area to volume ratio. They have
gained a huge importance in the science and technology as well as the consumer
markets in the twenty-first century, while the technological advances were racing
toward miniaturizing the current technologies/devices [8, 9]. At the same time, the
nanomaterials have also garnered excellent attention in terms of achieving specific
functionality and selectivity. For the past couple of decades, the scientific and
technological domains of the nanotechnology focused more on miniaturization of
the current instruments/machines/devices and sensors to greatly enhance their per-
formance in terms of speed and sensitivity while minimizing the energy consump-
tion, which are expected to impact the consumer markets to a great extent. For
example, the nanotechnology has developed mimics of human brains, biosensors for

Fig. 1 Classification of nanomaterials based on their dimensionality. (Reproduced with permission

of [5] Copyright Elsevier, 2018)
474 R. K. Guduru and A. A. Gupta

early-stage detection of the diseases at the molecular level, and nanoscale electronics
for constant monitoring of the local environment with reduced energy requirement
for their functionality [10].
The huge improvement in properties of nanomaterials is achieved through their
small feature size with large percentage of atoms on the surface or along the grain
boundaries. At the same time, the characteristics of nanomaterials are quite sensitive
to their sizes [11], which is partly due to the varying surface to volume ratio; thus a
large percentage of surface atoms brings in many size-dependent phenomena. Large
surface area of nanomaterials can be exploited for many practical/industrial appli-
cations, such as filtration processes and catalytic processing because of their
enhanced chemical reactivity [12–19]. In case of optical applications, a wide range
of nanomaterial-based optical sources (e.g., high-performance lasers and illumina-
tion sources) that consume very less energy can be fabricated. For energy storage,
large surface area facilitates in storing huge amounts of charge through double-layer
formation, for example, the graphene-based supercapacitors exhibit a large increase
in the energy storage capacity. The consumer products with varying functionalities
can be made by selecting appropriate fabrication methods while controlling their
size, shape, and composition [20]. However, assembling nanomaterials is one of the
complex processes. Various research groups and industries are working toward
developing different synthetic strategies that are economically affordable for fabri-
cation of consumer products that are not only superior to the current products but
also conserve the energy and preserve their superior characteristics for longer
lifetimes [21].

Carbonaceous Nanomaterials and Their Classification

Among various types of nanomaterials, carbon-based nanomaterials (CNMs)

have captured a great interest in the scientific and applied communities for the
past couple of decades due to their unique structures and excellent properties. The
CNMs exhibit very distinctive and superior physical and chemical properties
with the virtue of their unique ability to establish robust covalent bonds with
diverse hybridization states (sp, sp2, and sp3) that result in a wide variety of
structures, including its allotropes and nanostructures [22]. Figure 2 shows the
classification of CNMs based on their dimensionality. However, based on the
hybridization of C atoms in the covalent bond linkage, CNMs can be categorized
into two.
The first group contains sp2 hybridization with graphenic nanostructures with
densely packed hexagonal honeycomb crystal lattice (Note: They may have sp3 also,
but only at the defects and edges). The CNMs that fall under this category are
graphene, CNTs, onion-like carbon nanospheres, and carbon dots. These materials
exhibit 2D lattice structure with simple hexagons, and the simplest basic represen-
tative of this group is a single atom thick graphene sheet. The graphene sheet is also
the building block for other nanostructures, such as fullerene (0D), CNT (1D),
multilayer stacked carbon nanosheets, or graphite (2D). The complex carbon
21 Consumer Applications of Graphene and Its Composites 475

Fig. 2 Classification of CNMs based on their dimensionality. (Reproduced with permission of [22]
Copyright ACS Publications, 2018)

nanohorn structures are also made of the same building block, i.e., the graphene
sheet. On the other hand, the second group of CNMs contains both sp3 and sp2
hybridizations at various sites of the bonding. They can also possess amorphous and
graphitic regions but predominantly sp3 carbon atoms. Nanodiamond and certain
types of carbon-dot structures fall under this paradigm. The distinction of these
materials is that they are not built upon the single atom or monolayer of graphene
building block. For more details on the CNM classification and their properties, one
can refer to the review articles [22, 23].
Depending on the structures and varieties, the CNMs have attracted a great
attention in various applications ranging from filtration to catalysis, energy storage,
strength enhancement, drug delivery, and improved electrical properties. With sev-
eral advances in the nanotechnologies, the widespread role of CNMs has seen a rapid
growth in the recent past, especially after realizing the capabilities of graphene.
Among all the CNMs, the graphene took over the presidency with its unbeatable
characteristics.
476 R. K. Guduru and A. A. Gupta

Properties of Graphene and Its Derivatives

Although graphene was discovered in 1987 [24], its potentials were thoroughly
studied only in the early to late 2000s. It is usually a stable material under normal
conditions with high quality at microscopic level. Researchers [22, 23] have shown
its promising characteristics and potentials from the fundamental science as well as
technological and applied research perspectives. It is the strongest materials for its
weight [25] and exhibits highest rigidity among all the natural and engineered
materials. It also has a negative thermal coefficient of expansion [26]. It exhibits
pronounced ambipolar electric field effect with high electron mobility at room
temperature [27, 28]. The electronic structure of graphene is quite different from a
typical 3D material [29]. Unlike other materials, the Fermi level of graphene can be
controlled with the applied electric field and can be turned into n- or p-doped
accordingly [30]. One of the major advantages of graphene over other materials is
its manipulative conductivity, which can be altered using adsorbent materials like
water and other chemicals compounds with which it will get doped and result in
superior electrical conductivity, which will be higher than copper’s electrical con-
ductivity. On the other hand, the large surface area of graphene (theoretical surface
area ~ 2630 m2) is usually much higher than many materials and can be exploited in
sensing and energy storage applications as well. Graphene also exhibits intrinsic
corrugations, topological defects, and vacancies, which act as reactive sites for
sensing and functional applications [22, 23]. Graphene and its derivatives can be
adsorbed onto the surfaces through introduction of active groups. For example, the
metal interactive groups could help in adsorption of graphene onto metallic surfaces
and help develop thin films that could provide lubrication and reduce the friction in
many engineering applications, including in the oil and gas industries [31]. In
addition, graphene is a hydrophobic material, which helps in creating hydrophobic
surfaces for corrosion resistance as well as in the oil drilling operations where the
hydrophobic films could help reduce the interactive forces between the drilling tools
and the drilling fluids and prevent sticking of tools and other accidents effectively
[32]. Graphene can also be used as a filtration media for selective filtration. In
addition to the above, the other desirable properties that graphene has for membrane
and filtration applications are as follows: (a) thinner than the existing membranes
almost by 20,000 times, (b) its ideal pore size, (c) resistance to oxidation (up to
450
C), and (d) mechanical stability [32].
In addition to pure graphene, in recent years, its derivatives graphene oxide
(GO) and the graphene composites have also taken up a pivotal importance from
the practical applications point of view. Thanks to GO, for its superior functional
characteristics, hydrophilic behavior. The hydroxyl and epoxy groups of GO surface,
and carboxylic/carbonyl groups on the edges of the GO layers, make the GOD
undergo easy chemical fractioning, which opens up the possibilities for organic-
mineral hybridization [33]. In case of composites, different types of polymers and
metal oxides were added to the graphene-based sheets for developing nano-
composites with great structural and multifunctional characteristics. Interestingly,
these composites showed quite contrasting properties when compared with the
21 Consumer Applications of Graphene and Its Composites 477

regular engineered composites, which will usually follow the rule of mixtures
principle. In contrary, the graphene nanocomposites were showing entirely new
properties [34]. On top, the functionalization of graphene at the defects and surface
sites has shown to prevent aggregation of graphene flakes or sheets in the liquid
media as well as in the composites and facilitated the dispersion in the composite
matrix phases while imparting superior chemical and physical attributes.

Processing of Graphene

Different approaches have been developed to synthesize graphene nanosheets, and

they can be categorized into “top-down” and “bottom up” approaches [35]. In many
approaches, the graphite-based precursors are employed, which is basically a stack
of several graphene layers held together by weak van der Waals forces. Therefore,
preparation of graphene from graphite needs to overcome the van der Waals forces
while de-stacking the graphene sheets, and this approach is called “top-down.”
However, this approach could result in low yields, surface defects, as well as
re-agglomeration of separated graphene sheets and involves tedious procedures
[36]. On the other hand, the bottom-up approaches focus on putting the building
block units, i.e., carbon molecules together, and these are usually obtained from
alternative sources. Although, this approach may not offer the capability to produce
large surface area graphene sheets, but facilitates in large quantity production of
graphene [37]. Following are the techniques that fall under top-down approaches –
mechanical exfoliation, graphite intercalation, nanotube slicing, pyrolysis, reduction
of graphite oxide, electrochemical exfoliation, sonication, ball milling, and
radiation-based methods. On the other hand, the bottom-up approach is implemented
in the following techniques: graphene growth from melt – carbon melts, epitaxial
growth on SiC, dry ice method, and deposition-based methods. For more details on
each technique, the reader is advised to refer to the review articles [35, 38–40] on
graphene synthesis. As this chapter focuses more on graphene-based commercial
products, much emphasis has been given to scalable techniques.
Among various scalable mechanical exfoliation approaches, micromechanical
exfoliation is still the key synthesis technique for yielding high-quality graphene,
but not suitable for mass production. However, the scotch tape-assisted peel off or
exfoliation method developed by Geim and Novoselov seemed to have opened up
the gateway for large size graphene flake production up to 1 mm or so [41]. Thus, the
processing techniques developed based on exfoliation of graphite or graphene oxide
(the derivative of graphite) made it possible for large-scale production of graphene.
Prior to that, free-standing graphene was believed to be unstable, and they were
expected to scroll and buckle. The shear exfoliation of graphite reported by Keith
et al. [42] using stabilizing liquids, such as N-methyl-2-pyrrolidone, sodium cholate,
etc., and applying shear forces beyond 104 s 1 seemed to provide the capability for
mass production. This approach eliminated the use of sonication as well while
implementing less energy consuming and scalable approach. In fact, shearing rate
of 104 s 1 or more is easily achievable even using a kitchen blender. Currently,
478 R. K. Guduru and A. A. Gupta

graphene is being synthesized on industrial scale following the mechanical

approaches [43], but relying on the batch production. However, the mass production
faces lots of challenges in terms of graphene quality (defect freeness), consistency in
flake sizes and thickness, etc. On the other hand, the bottom-up approaches, like
chemical vapor deposition (CVD), facilitate in a great control of the thickness and
quality of graphene but not suitable for mass production on industrial scale, except
for producing for high-end applications, such as touch screens, LCDs, OLEDs, and
solar panels. In the scientific communities, it is believed that the graphene may not
be a material of type that follows “one size fits for all.” Depending on the processing
technique implemented, the quality of graphene and accordingly its application
arena would change.

Applications of Graphene and Graphene Market

In 2008, graphene used to cost exorbitantly high, and it was the most expensive
material in the world then. However, with advances in exfoliation techniques along
with process scale up, the prices have come down. As per literature [44], with
increasing quality the graphene cost would increase. There are some processing
techniques, such as exfoliation techniques based on intercalation and liquid turned
out to be high yield processes at lower costs. Thus, large-scale production of
graphene has dramatically increased with the advent of low-cost exfoliation
methods. The initial list of commercial producers (as of 2014) of graphene in the
global markets can be found in Ref. [44]; however, this list has grown to a large
number, and the reader should be able to find the latest list in the following reference
[2, 45, 46]. There are many companies currently selling in large quantities. For
example, the price of epitaxial graphene on SiC is around 100 $/cm2, which is mostly
dominated by the price of the substrate. The deposition of graphene on metallic
substrates by CVD technique by Hong and his team from South Korea pioneered the
synthesis of large-scale graphene films. It later triggered lots of research on practical
applications [47] with wafer sizes up to 760 millimeters (30 in) [48]. By 2017,
production of graphene-incorporated electronics started on a commercial fab line
with wafer size of 200 mm by IBM [49].
For industrial applications, lubricants and graphene-based oil additives were
developed. In the consumer segment, different sportswear, sports equipment, foot-
wear, cell phone and computer cooling systems, sanitary napkins, and as the latest
the masks for COVID-19 have been launched using graphene-based materials. Thus
industrial and consumer applications of graphene have been accelerated at a large
pace. As of 2019, the global market size for graphene was estimated to be around
USD 78.7 million, and it was expected to rise at a CAGR of 38.7% from 2020 to
2027 [2]. The increasing demand for lightweight materials with improved strength
and durability, renewable energy, and flexible material systems that offer technolog-
ical advances is expected to drive the demand for graphene and its derivative
products. The market segments targeting electrical and thermal properties, and
enhanced mechanical strength and durability, and sensors and biotechnological
applications are expected to expand the scope of graphene. Current penetration
21 Consumer Applications of Graphene and Its Composites 479

Fig. 3 Growth of graphene

and related product market in
the USA. (Adapted from Ref.
[2]. Source: www.
grandviewresearch.com)

into electronics, audio, sensors, sports, coatings, energy, and textiles is anticipated to
further broaden the market. Among different markets, the USA and China are the
leading markets for graphene-based products. The US market has grown with a large
number of collaborations among research institutions and manufacturers, and it is
one of the key exporters. Figure 3 shows the growth of market for graphene and
related products within the USA.

Graphene-Based Products and Technologies Available

in the Market

Following is an overview on commercial-based products already existing in the

current global markets based on graphene and its derivatives, and these are expected
to drastically increase in the upcoming years. All the products are categorized based
on the applications of the consumer or final applications in the market. For a detailed
overview on the consumer products that are already existing in the market as well as
upcoming, the reader is advised to refer to the references [2, 38, 50–54].

Electrical/Electronic/Thermal Applications

Due to superior electron mobility, electrical conductivity, and thermal conductivity,

graphene is being exploited in consumer segment for electrical conductor, elec-
trodes, and heatsink applications. With modification of graphene through doping, it
is being extensively utilized in electronics industry. Graphene is an excellent thermal
conductor, and many Chinese companies have commercialized several graphene-
based heating elements, embedded in wearable and other devices. Following is the
list of several products that have already been available in the consumer markets
today.
480 R. K. Guduru and A. A. Gupta

• Graphene-based conductive inks are developed by Vorbeck Materials, which are

then practically implemented in printing the electrical circuits for Siren anti-theft
packaging device by global packaging solutions provider MeadWestvaco
(MWV). This is the world’s first graphene-based product. MWV developed
fully integrated conductive circuits consisting of graphene with excellent con-
ductivity, and these are damage free even upon flexing and wrinkling. Currently,
Vorbeck Materials is also making graphene-based composites, coatings, and
graphene-enhanced batteries.
• PowerBooster, China, was also able to produce 60-inch graphene transparent
conductive films in 2012 and 7.5 m2 graphene films on copper and 3- to 20-in
single/multipoint touch panels in 2013.
• By 2013 December, Wuxi Graphene Film, China, also used graphene for touch
screen production. It completed a production line with an annual output capacity
of 5 million graphene touch-screen products by 2013 itself.
• In 2017, the Team Group, which provides memory solutions and accessories,
introduced graphene-coated copper foil in cooling applications of solid-state
drives in order to maximize the benefits of cooling via natural passive and direct
fan cooling methods for a rapid heat dissipation. The Team Group utilized this
technology in their T-FORCE gaming line products. The graphene utilized by
Team Group was produced by Nitronix following a patented technology. Inter-
estingly, this technology was demonstrated to offer excellent cooling effect even
in the closed spaces.
• Huawei and Honor both are implementing the graphene film-based cooling
systems in their advanced cell phone technologies. Honor X10, one of the
cheapest 5G phone, is utilizing a graphene-based cooling system. Similarly,
Huawei Mate 20 X, P40 flagship phone family with three different devices
Huawei P40, Huawei P40 Pro and, Huawei P40 Pro Plus are using a graphene
film-based cooling technology for heat management purposes. Huawei claims
that its Mate 20 X is the world’s first super cool phone equipped with a liquid
multidimensional cooling system that consists of vapor chamber (VC) and
graphene film, and it reportedly cools off quickly with fast heat dissipation
even under heavy loads while gaming. In another similar application, Cryorig,
which is a PC gear company, has introduced graphene film-based CPU cooling
system. Similar to other players in the market, Cryorig has used graphene-coated
heatsink for cooling. In addition, they went a step ahead and used graphene-
coated radiator fins too. These cooling systems were developed for small form
factor PCs to dissipate the heat up to 125 W. The Cryorig C7G is the smallest
cooler used in high-end processors in today’s market. The high performance
cooling systems used graphene-coated heatsinks.
• Finland-based Emberion launched a graphene-based photodetector, which can
detect the wavelengths from 400 nm to shortwave infrared ~1800 nm. This
technology replaced the use of two sensors (Silicon and InGaAs) based photo-
detector systems for a wide range detection. Furthermore, this graphene detector
was expected to reduce the cost by 30% when compared to the two sensors based
photodetector system.
21 Consumer Applications of Graphene and Its Composites 481

• Graphenest launched two graphene products using proprietary graphene produc-

tion methods. The first one was HexaShield, radiation shield made of graphene-
based coating for RF electromagnetic interference (EMI). This coating was
expected to reduce the weight and manufacturing cost when compared with the
metals and at the same time provides EMI protection for Gigahertz frequency
range.
• Graphene Security (GS), which is the subsidiary of BGT Materials that produces
graphene technologies, unveiled graphene-based LED light bulbs for the UK
market. These lights use graphene for thermal dissipation, and these will be
eventually hitting the full range of home, commercial, and street lighting
systems also.
• Graphene Security (GS), which is the subsidiary of BGT Materials that produces
graphene technologies, launched flexible and green wireless antenna solutions for
the RFID industry where graphene is used as the antenna inlays.

Sports, Safety, and Outdoor Activities

Superior strength to weight ratio and high rigidity have attracted graphene toward
mechanical and structural applications with lightweight, enhanced flexibility and
strength characteristics. Especially the composite materials of graphene incorporated
have found the way to commercialization in various sports gadgets. In another
example, graphene-added rubber seems to impart reduced wear and friction charac-
teristics while making the tires harder, which is of a great importance in the
automobiles, including Formula 1 race. The Graphene Council of North Carolina,
USA, has been suggesting replacing the carbon black filler with smaller amounts of
graphene in tires in order to achieve better life and improved frictional characteris-
tics. Below are few example list of commercialized products in the global markets.

• In 2013, HEAD introduced their new range tennis rackets (YouTek Graphene
Speed series) made of graphene composites. These rackets were made lighter,
stiffer, and stronger with incorporation of graphene. HEAD offered five different
types of rackets with price ranging from $170 to $286. Again in 2014, they
launched “Joy” another lightweight and durable graphene-based product but for
ski and especially for women. It was made of a graphene-enhanced composite
product. It has several variations in models with reasonable prices when com-
pared with the traditional skis.
• Vittoria, which is an international wheel producer, currently manufactures and
sells the bicycle wheels “Quarno” (Graphene Plus inside) with three different
editions (46, 60, and 84 mm) containing graphene-based composites. Its wheels
are made of graphene-enhanced composites. They are utilizing graphene nano-
platelets provided by Directa Plus in composites for wheel production. The
advantage of these wheels was found to lie in (a) quick heat dissipation
(15–30
C lower), an important factor in the slopes, (b) an increase in lateral
stiffness (more than 50%), and (c) reduced punctures in the tires. Thus, these
482 R. K. Guduru and A. A. Gupta

products turned out to be quite superior compared to the conventional tubes that
they have been making earlier. Similarly, Goodyear also launched graphene-
enhanced bicycle tires, Eagle F1 and Eagle F1 Supersport. The weight of these
tires was just 180 g for a 23 mm model. The Eagle F1 was an “ultra-high-
performance all-round road tire,” and the Eagle F1 Supersport tire was even
lighter. These tires were made for upper echelons of competition and better suited
for road racing, time trial, and triathlon to achieve high speeds.
• In 2019, Gratomic also launched graphene-enhanced Graphene Ultra Fuel Effi-
cient Tires (GUET). They used plasma-generated high-quality graphene in their
tire composite structures, which not only increased the strength and life span but
also reduced the weight of the tires. They have received certification for their tires
for fuel efficiency after conducting several terrain tests.
• The UK-based Dassi Bikes developed the world’s first bike made of graphene
composite. This bike frame consisted of 1% graphene in the whole body with six
layers underneath the top/surface carbon layer weighing only 750 g, which is
super lightweight compared to the conventional bike frames. They are targeting to
bring it down even further below 400 g.
• In 2014, Spain-based Catlike launched cycling helmets with “Mixino” name.
These helmets had enhanced strength and impact absorption, lightweight, dura-
bility, and improved safety after incorporating with graphene. They also launched
lightweight and durable graphene-enhanced cycling shoes with “Whisper” name,
which combined variety of cycling shoes for road/mountain/triathlon biking.
• UK’s Century Composites developed Graphex fishing rods using graphene pro-
duced by Applied Graphene Materials. These fishing rods have enhanced
strength, lightweight, and excellent durability.
• NRC, the Italian sports equipment maker, launched a new class sports sunglass
using graphene-enhanced frames, which were not only lighter and flexible but
also quite durable.
• Grays Hockey of Cambridge, a world renowned hockey stick maker, launched the
hockey sticks with graphene-incorporated composite materials. The graphene-
enhanced composite technology strengthened the hockey sticks and helped in
player’s better performance while providing lightweight, enhanced strength,
improved stiffness, and durable hockey sticks. They used the graphene nano-
platelets produced by XG Sciences in their hockey stick composites.
• In 2017, the University of Manchester and British sportswear brand Inov-8-
together launched graphene-enhanced hiking boots. They produced graphene-
enhanced G-Series shoes and hiking boots, ROCLITE 335 and ROCLITE
345 GTX, respectively. ROCLITE 335 offers increased warmth on cold days,
whereas ROCLITE 345 GTX provides waterproof GORE-TEX protection for
hiking under wet conditions. In addition, Inov-8 also launched graphene-
enhanced X-Talon G 235 in off-road footwear collection.
• ECD Lacrosse is the manufacturer of high-quality lacrosse tools/kits, along with
Global Graphene Group (G3) developed and launched graphene-enhanced
Lacrosse gear. They developed customized composites using G3’s graphene
and ECD’s polymer which resulted in reduced and increased impact resistance.
21 Consumer Applications of Graphene and Its Composites 483

These graphene-enhanced lacrosse heads showed increased stiffness, impact

strength, and without no gain in the weight.
• Australia’s First Graphene and Blue Steel together developed graphene incorpo-
rated safety work boots. They used PureGRAPH, i.e., graphene produced by First
Graphene, and incorporated it into the boots of Blue Steel’s safety capped boot
TPU soles and polyurethane foam innersoles. These boots exhibited enhanced
performance, strength, and safety to the consumers.
• In 2018, Callaway unveiled a graphene-incorporated TRUVIS Chrome Soft Golf
Ball. Graphene was added to strengthen the outer core because of which the soft
inner core deforms more upon impact, which would help in suppressing the spin
and translate more into the speed and distance traveled by the ball. Thus, the golf
world has seen dramatic changes with the arrival of graphene coatings on the golf
balls.
• McLaren, the British racing team/supercar manufacturer, has launched a new
graphene incorporated RM 50–03 Tourbillon Split Seconds Chronograph Ultra-
light McLaren F1 sports watch. It weighs hardly 40 g, and the inner mechanism
weighs only 7 g. It was made of graphene, titanium, and carbon fiber composites.
McLaren’s Applied Technologies division in collaboration with National
Graphene Institute and high-end watchmaker Richard Mille developed this light-
weight and efficient watch.
• In 2019, Billabong, the global maker of surf and snow kits (e.g., clothing and
gear), announced to launch “Furnace Graphene,” a graphene incorporated suit.
The flexible graphene lining was developed on the front and back panels,
which help in thermal retention. In their innovative design and approach, the
graphene-wrapped yarns do not allow the heat to go out and efficiently keep
the suit warm.
• Vollebak, a sports gear manufacturer, developed a graphene-enhanced jacket that
is capable of absorbing the heat and then warming up over time, while conducting
electricity, repelling the bacteria, and dissipating the human body’s excess humid-
ity. The jacket is manufactured with a two-sided material with polyure-
thane + graphene composite on one side and nylon + graphene on the other
side. They used graphene nanoplatelets for the above composites. In this jacket,
the characteristics of nylon were changed dramatically with the addition of
graphene from non-thermal conductor to a thermal conductor, imparting
completely new characteristics to its behavior.
• In 2018, Oakley and Bioracer launched a cycling G+ Graphene Aero jersey that is
enhanced using DirectaPlus’ printed G+ planar thermal circuits. This jersey is
designed to leverage the unique thermal properties of graphene to dissipate the
heat from the rider’s body. The fabrics treated with G+ planar thermal circuits are
also electrostatic and bacteriostatic, which contribute to antibacterial characteris-
tics and moisture management and have an anti-odor effect. Interestingly, the
graphene circuits placed on the outside of G+ Aero Jersey reduce the friction with
air and water and supports in top sporting performance.
• Versarien in partnership with Bromley Technologies launched graphene-
enhanced sleds, and they reported a strong performance of their products in the
484 R. K. Guduru and A. A. Gupta

International Bobsleigh and Skeleton Federation World Cup race 2016. They
incorporated graphene-enhanced carbon fiber into the skeleton sleds of Bromley.
Utilizing these sleds, the players of world cup set the fastest speed record.
• Directa Plus and Deewear (an Italy-based company) launched D-ONE, a
graphene-enhanced sportswear line that combines the design, technology, and
wear ability. It is a new-generation sportswear that offers postural compress fabric
of DirectaPlus’ Graphene Plus (G+) with the benefits superior comfort.
• Many Chinese footwear manufacturers are using graphene to develop light-
weight, self-sterilizing, and deodorizing shoes in Jinjiang City, Fujian, which is
China’s largest production center for sports shoes and footwear makers. They are
adding graphene to soles for enhanced characteristics, and they are expected to
weigh less than 100 grams.
• Cecorelax launched a memory-foam pillow that is enhanced with graphene. It is
being sold as “Graphene Memory Foam Pillow,” and it is light in weight, flexible,
and highly resistant and helps maintain the body temperatures.
• IstitutoItaliano di Tecnologia (IIT), Italy, in collaboration with a leading Italian
shoe company FADEL unveiled a new line of graphene-enhanced shoe products,
and it was patented by FADEL. This product was supposed to be providing better
thermoregulation and freshness to the feet. In this shoe product, layers of
graphene flakes were added to polyurethane for augmented heat dispersion,
resistance to moisture, and enhanced antibacterial properties. Along with these
characteristics, ventilation system was also developed for a better user
experience.
• In another collaboration, IIT – Italy with an Italian design company
Momodesign launched graphene-enhanced helmet for better distribution of
impact force and enhanced safety. These helmets were coated with graphene
and made them less susceptible to damage compared to the regular without
graphene even under high temperature conditions. The superior thermal con-
ductivity of graphene helps dissipate the heat quickly and thereby preserve the
inner materials from degradation due to the heat. In addition, it was reported to
improve thermal comfort also.
• Directa Plus along with Luxottica Group, a company that designs, manufactures,
and sells eyewear, launched a new graphene-enhanced eyewear collection of
Ray-Ban. They add graphene with a special care to facilitate equal distribution
of the material along with a special resin all over the front of the frame. They
utilized all the superior characteristics of graphene in these glasses including its
light absorption properties.

Sensors

Advanced sensors play important role in analytical and biomedical fields. Here also
graphene is likely to play pivotal role. Following are the examples of several
graphene-based products that show promising applications in the field of sensor
technology:
21 Consumer Applications of Graphene and Its Composites 485

• In November 2016, ICN2 Nanobioelectronics and Biosensors group together

developed a graphene oxide (GO)-based sensor which enabled the detection of
various analytes (measured substances) in diagnostics, safety/security, and envi-
ronmental monitoring. This sensor was offered to the market by Biolin Scientific,
a renowned Nordic instrumentation company for analytical devices.
• In December 2016, San Diego-based Nanomedical Diagnostics, a diagnostics
equipment manufacturer, started selling graphene-based sensors and the AGILE
R100 systems which are used for real-time detection of small molecules – with no
limit on lower size molecules. These graphene-based sensors were portable, less
expensive, faster, and very precise in detection and sample processing.
• US-based Graphenea launched graphene-based field effect transistors (GFETs) in
order to penetrate into the sensors market. They started with production of GFET-
S10 and GFET-S20 sensor technologies which can be used for gas sensing,
bio-sensing, chemical sensing, photodetection, and bioelectronics. These two
technologies consist of 36 individual GFETs on a one square centimeter die,
but with different layouts for different sensing applications.
• In 2017, the Chinese Wuxi Graphene developed graphene-enhanced GF1 health
smart watch. It used the chemical vapor deposition technology for developing
graphene film, which acts as the conductive element for the touch screen, which
replaced the regularly used transparent conducting oxides.

Audio

The rigid as well as flexible characteristics of graphene enabled the audio field boom
with different products ranging from headphones to earbuds and contact enhancers.
Following are some of the graphene-enhanced audio products launched in the
worldwide markets with good success.

• China-based FiiO Electronics launched FiiO F3 earphones for in-ear monitoring

purposes, and it uses graphene-enhanced diaphragm driver. The thin graphene
layer enabled the development of a flexible driver for a clean, rich, and highly
reproducing transparent high-fidelity sound.
• Zolo audio brand by Anker launched Liberty named graphene-enhanced fully
wireless earphones. These wireless earphones are sweat proof and come with AI
for smart assistance. They are also capable of producing super clear and
immersive sound with impressive treble.
• UK-based MediaDevil which manufacturers phone, laptop, and tablet accessories
has launched wood earphones with “Artisanphonics CB-01” name, which is
capable of isolating the noise. These earphones are enhanced with Versarien’s
graphene and quite thinner and more flexible than traditional earphone diaphragm
materials. These earphones are found to enhance both the treble and bass of the
audio waves.
• Mad Scientist Audio, a New Zealand-based audio company developed and started
to sell Graphene Contact Enhancers (GCE), which can be used on any metal-to-
486 R. K. Guduru and A. A. Gupta

metal contacts, such as RCA plugs, sockets, loudspeaker leads, and fuses etc.,
where the superior wear resistance, lubrication characteristics, and electrical
conductivity of graphene have been thoroughly exploited.
• Ghostek launched Rapture Wireless Headphones, which are the world’s first
headphones with graphene drivers. Rapture uses 40 mm graphene drivers for
enhanced high-density (HD) audio experience. The other features of this product
include Bluetooth 4.1 + EDR, aptX Audio Technology, soft protein leather ear
cups, a 3.5 mm audio jack input, built-in HD microphone, and an LED battery
status.
• Pioneer Corporation, a global leader in optical disc technology, developed a
graphene diaphragm-based heart rate sports earphones, called SEC-S801BT. It
is initially launched in China. The SEC-S801BT is a Bluetooth-enabled dual-
mode sports earphones that tracks the user’s heart rate and plays the music
simultaneously. The graphene diaphragm was reported to be producing superior
and accurate sound reproduction with great clarity in the mid- to high-frequency
range. These earphones also provide a wider range of frequency response
enabling the users with solid listening experience with a deep bass while still
having best-in-class middle and high frequencies.
• China-based CKCOM, a manufacturer of earbuds, launched affordable “Alien
Earbuds,” which are a high-quality alternative to expensive wireless earbuds.
These earbuds are incorporated with graphene-enhanced drivers and have a
playtime of 4.5 h with a built-in mic for hands-free calling, multi-touch button
for important gestures, and more. These graphene drivers are light in weight and
yet sturdy enough to conduct clear highs, crisp mids, and resonant bass. Most
importantly, graphene in these earbuds prevents unwanted sound distortions that
usually come with regular audio drivers. CKCOM’s wireless earbuds are the first
of their kind and offer premium features at the lowest price. They have all of the
bases covered and perfect for exercise, travel, and workouts.
• ORA, a Canada-based start-up, developed graphene-enhanced audio equipment.
It has unveiled grapheneQ a graphene oxide-based composite material. It report-
edly allows for louder drivers with a lower Q resonance, and it has been specially
designed for acoustic transducers.
• The Chinese mobile phone maker, Xiaomi, recently launched a new in-ear
headphone with “Piston 3 Pro” name, and it uses a graphene membrane for
improved sound quality. According to Xiaomi, the graphene diaphragm helps
produce more natural sounds.

Automobiles

Automobile is another important area where application of graphene is being

researched at a fast pace. Few key examples are listed as follows:

• US-based Indian Motorcycle launched graphene-based ClimaCommand Classic

Seat technology, which has a new graphene-based technology, and it aims to
21 Consumer Applications of Graphene and Its Composites 487

provide both heating and cooling to the riders/passengers. It was developed using
thermo-electric technology and provides more effective performance than the
conventional HVAC-based convection systems. The interesting benefit of this
technology is that it actually provides a surface that is cold to touch rather than
cool air that is usually provided in the HVAC systems.
• HELLA, a German-based lubricants company, launched an engine oil product
with a specially formulated graphene additive for enhanced lubrication in the
internal combustion engines. The graphene nanoplatelets manufactured by XG
Sciences in HELLA’s lubricant seemed to be helping in reducing the wear almost
by 50% and friction in the IC engines and extend their life. It was also observed to
reduce the engine vibrations and improve the power output, while enhancing the
fuel economy and ride comfort.
• Automotive giant Ford has announced to use graphene-based composites for auto
body parts starting with the Mustang and F-150. Ford is working in partnership
with Eagle Industries and XG Sciences to develop graphene-reinforced compos-
ites to reduce the weight and enhance the strength, as well as to reduce the noise.
Since 2014, Ford and its partners started testing the graphene-reinforced foam
covers for noisy components, such as fuel rails, pumps, and belt-driven pulleys,
and chain-driven gears in the front parts of the engines and observed an improve-
ment of 17% in noise reduction, 20% enhancement in the strength, and 30% more
in heat resistance.
• UK-based Perpetuus Advanced Materials launched graphene-enhanced car tires
especially with surface-engineered graphene materials. These tires are not only
lighter in weight but also stronger and dissipate the heat quickly and highly
durable. They claim to enhance the wear resistance almost by 40% over the
regular tires.
• UK-based Linney Tuning developed graphene-enhanced brake and clutch pads
with enhanced wear resistance and resistant to heat generated with quick heat
dissipation. They are using bi-layer graphene in the development of brake pads,
and these are expected to ensure quiet and clean braking performance. At the
same time, they provide high strength, low density with less resin and less fad,
and highly reliable braking performance.
• MIT and Lamborghini joined together to develop graphene-enhanced super-
capacitor electric vehicle. This car would be a fully electric, supercapacitor-
powered automobile which can be charged in minutes, and there would not be
any batteries.
• The Sixth Element, a leading graphene product manufacturer in China, along with
partner Shangdong Hengyu Technology Group, a leading Chinese tire manufac-
turer, developed graphene-incorporated tire formulations with improved perfor-
mance. Addition of graphene to the tire tread reduced the wear almost by 25%,
while its tear strength was doubled and increased the life.
• A Chinese tire company, Qingdao Sentury Tire, along with Huagao Graphene
Technology, a Chinese graphene producer, develops electrostatic tires with
graphene composites, and these are expected to perform quite superior over the
regular tires.
488 R. K. Guduru and A. A. Gupta

• Briggs Automotive Company (BAC), a Manchester company, developed a car

with graphene in its bodywork. Graphene was used in the car panels also with
enhanced strength and durability. This was one of the best example for graphene
incorporation into the automobile bodies and use of graphene composites for
enhanced durability of the car body structures.

Textiles/Outfits and Filtration/Membranes

Some of the researchers are working on developing textile fiber combining graphene
with polymers which in turn would add antibacterial, anti-static, and heat-preserving
properties to textiles made from it. This advanced graphene fiber material will be
used to make clothing, sportswear, and underwear around the world. Further, the
graphene oxide membranes are capable of forming a perfect barrier when dealing
with liquids and gasses. They can effectively separate organic solvent from water
and remove water from a gas mixture to an exceptional level. They have even been
proved to stop helium, the hardest gas to block. Following is the list of few important
example products launched in the global markets:
• UK-based Alé Cycling released Velocity G+ jersey, which is a graphene-
enhanced suit for cycling people. This shirt uses a graphene-incorporated fabric
which helps in an active interaction with the body and thereby effectively
equalizes the body temperatures while creating an ideal microclimate and keeps
the cyclists comfortable even under unpleasant weather conditions.
• UK-based planarTECH is developing a bullet proof vest in a joint venture with a
Thailand-based IDEATI. This vest is enhanced with graphene for bulletproof and
ballistic plate products for body armor. The high strength properties of graphene
are exploited in these armors. Currently, IDEATI is supplying to the Royal Thai
Army, which is certified as per National Institute of Justice (NIJ) standards.
• Shanghai Kyorene New Material Technology, a Chinese company, developed a
graphene fiber that is used to produce clothes, sportswear, and underwear prod-
ucts. Armor Guys, a US-based glove maker, uses these fibers and integrated them
with high polymer materials at room temperature to impart antibacterial,
ultraviolet-proof, anti-static, and heat preservation effects to the ordinary textile
products.
• Vorbeck Materials and Bluewater developed advanced wearable antennas for
military and defense applications. They are jointly offering robust, high-gain,
low-cost, and discrete conformal printed graphene antennas embedded in military
apparel and backpacks. These high-performance wearable antennas are of great
importance in military for tactical and commercial use featuring multiple com-
munication bands including LTE capabilities. The advantages of these wearables
include (a) increasing the existing coverage of cell phones by up to 200%;
(b) great improvement in the upload and download speeds; (c) omni-directional
coverage suing the deployment of an array of antennas; (d) supports a wide range
of frequencies from 800–3000 Mhz; (e) durable, flexible, washable,
21 Consumer Applications of Graphene and Its Composites 489

non-corrosive, and environmentally friendly; and (f) increased battery life by

reducing operating power.
• Oros Apparel is a US-based company, which manufactures thermal outerwear
using aerogel technology. They have developed gloves made from graphene-
coated aerogels, which will keep the body warmth inside the gloves and insulate
from the low outer temperatures. In these gloves, the graphene is paced between
the body and the aerogel, and the high thermal conductivity of graphene helps in
trapping the heat inside the gloves itself, instead of dissipating it out. This
technology supported a better thermal energy containment and better insulation
when compared to the aerogels without graphene.

Biotech

The versatile chemistry of graphene-based nanomaterials including the capability to

conjugate with water-soluble and water-insoluble active compounds, DNA, proteins,
cells, targeting agents, polymers, and even nanoparticles makes them a desirable
nanoplatform for future biomedical research. Few important examples are summa-
rized as below:

• UK-based planarTECH along with IDEATI has recently announced about

launching of graphene-enhanced antibacterial face masks. As the COVID-19
pandemic has taken a huge toll on the global population and the economy, there
is tremendous global demand for face masks. At the same time, the rising
pollution levels at an alarming rate demand the masks that effectively filter the
air while breathing. Thus, the planarTECH and IDEATI are planning to serve the
global communities with graphene-enhanced masks with antibacterial and pollu-
tion filtration capabilities.
• The UK-based Haydale has developed a roll-to-roll gravure printing of biosensors
with graphene due to its superior electrical conductivity and protein adherence
characteristics. Using a proprietary HDPlas™ plasma technology, Haydale devel-
oped the surface functionalized graphene inks used for gravure printing of base
biosensors on cell culture microplates.
• GrapheneCA has announced the launch of graphene-based “Dr. Nano,” which is
an anti-bacterial coating. Dr. Nano is formulated to create anti-viral environment
that would protect different surfaces for 7–10 years.
• South Korea’s iCraft in collaboration with UK’s Haydale has announced
graphene nanoplatelet incorporated cosmetic face mask sheet, which is face-
shaped and utilizes the thermal and electrical conductivity of graphene to help
the skin absorb its contents through bio-electric currents. They also filed three
patents on graphene-based cosmetic products.
• A US-based Jewel Sanitary Napkins (JSN) launched four varieties of graphene-
enhanced sanitary napkins in 2019 with a cost of 6$ per piece. The four variations
of the napkins are very light panty liners, moderate flow sanitary napkins, heavy
490 R. K. Guduru and A. A. Gupta

flow sanitary napkins, and super heavy flow sanitary napkins. These napkins are
said to maintain hygiene with high absorption and antimicrobial in characteristics.
• GNM has launched a graphene heating element-based eye mask for physical
therapy, for the fatigued eyes. These masks emit far-infrared light which is close
to the far-infrared rays emitted by human body. The graphene heating pad can
help heat the eyes and improve blood circulation and relieve the body pains also.
These masks heat up with low power (12 V/3A) in a very short period, and with
auto shut off, they provide good protection.

Coatings, Adhesives, and Oil and Gas Industries

Graphene coatings can also serve as protective coatings with superior chemical,
moisture, corrosion, UV, and fire-resistance properties. On medical devices, these
coatings would provide a biocompatible surface that is resistant to degradation. Adding
graphene to the adhesive formulation improves the mechanical performance of the
matrix resin. Moreover, graphene nanoplatelets make conductive bridges between the
silver particles thereby reducing the load of silver needed to attain conductivity.
Application of graphene in the oil and gas industry has only been popularized in
the last few years. Due to graphene’s unique chemical, structural, electrical, and
mechanical properties, it shows applicability for many areas within the oil and gas
industry. Areas of application include drilling, lubrication, desalination, anti-
corrosion coatings, cementing, oil-water separation, oil spill cleanup, and emulsion
stabilization to name a few. Important examples are summarized as follows:

• Micro Powders along with Garmor launched GraphShield 730, which is a

graphene-enhanced anticorrosion additive for powder coatings. It uses Micro
Powders’ wax composite technology and Garmor’s proprietary edge
functionalized graphene particles with high loading for corrosion resistance
applications. Graphene imparts significant corrosion resistance and reduces the
corrosion rates almost by 50%.
• Thermene launched a new graphene-based thermal paste, which is easy to use and
comes in a syringe, which can be applied using a paint brush. The curing time of
this paste is around 10 h. It is developed based on graphene-derivative products
and used in CPU and video card cooling. It offers a better performance compared
to the conventional processor cooling technologies. In fact, the second-generation
Thermene’s thermal paste product is even more efficient than the first generation
and cools almost 12
C lower than the first generation and also comes with a
lower price tag of 25% price reduction.
• Applied Graphene Materials launched graphene-incorporated thermally conduc-
tive epoxy paste adhesives for Space and Defense sectors. They are producing
two unique and novel graphene-enhanced thermally conductive adhesives AGM
TP300 and AGM TP400 with high levels of thermal conductivity (3–6 W/mK)
along with excellent mechanical, adhesive, and outgassing performance. Interest-
ingly, their densities are as low as 40% that of the competitive conductive
21 Consumer Applications of Graphene and Its Composites 491

adhesives, which makes them even lighter. These AGM TP 300/400 are highly
versatile and provide cost savings also.
• James Briggs along with Applied Graphene Materials launched graphene-based
anti-corrosive coatings under their brand Hycote, which demonstrated outstand-
ing and repeatable anti-corrosion performance for their automotive aerosol
primer.
• Sweden-based Applied Nano Surfaces (ANS) launched Tricolit GO, which is the
first graphene-enhanced low-friction coatings. ANS used the graphene supplied
by Applied Graphene Materials. Tricolit is an easy-to-apply spray coatings from
cans or in bulk. It reduces the friction and wear. Interestingly, incorporation of
graphene in these coatings enhanced their strength and abrasion resistance almost
by tenfold.
• Manchester University in collaboration with Akzo Nobel, a Netherlands paints
company, is developing anti-corrosion coatings with graphene oxide incorporated
paints for large metal structures (e.g., oil rigs, tankers and bridges, etc.).
• SAAB and GE are separately developing graphene-based anti-icing coatings to
reduce the adhesion or delay the onset of ice formation on the vehicles and
airplanes in the cold seasons.
• Graphene NanoChem has developed PlatDrill, an environmental friendly
graphene-based drilling fluid, which is also biodegradable and less toxic com-
pared to the conventional products being sold by the competitors in the same
market segment for the same or similar applications. They also produce oil and
water-based graphene-drilling additives. They have also been developing
graphene-based products for oil recovery, water treatment, and coatings for
pipes and equipment.
• Directa Plus is manufacturing a graphene-based “Graphene Plus,” an eco-friendly
and innovative adsorbent for cleaning of oil spills in the oil and gas industries.
• US-based Lockeed Martin is producing graphene-based filters for wastewater
treatment in the oil and gas industry. Their graphene-based Perforene membrane
is currently being tested by oil and gas companies for water separation from
the oils.
• In 2015, the Sixth Element Materials along with its partner Toppen Technology
developed graphene-enhanced anti-corrosion coating system, which was later
deployed to bridges and the wind mill (steel) towers across China. Their coating
is based on graphene-zinc primer, which consists of The Sixth Element’s
graphene type SE1132 and Toppens 2k-epoxy primer. They reported that addition
of 1% graphene reduced the Zn content almost from 25% to 80%, and the
corrosion protection life time was doubled. Reduction of Zn also helps reduce
the pollution and results in cost savings with increased life time.
• India-based Tata Steel developed ready-made graphene-coated stirrups, which are
being sold as TisconSuperlinks+. Tata Steel claims that the stirrup Superlink+
enhanced the corrosion resistance and supported in better bonding strength than
the regular stirrups. It has filed seven patent applications in this technology.
• Spain-based Avanzare, a nanomaterials and nanotech specialist, developed
graphene-based additives to improve the industrial-scale resins. Avanzare
492 R. K. Guduru and A. A. Gupta

introduced a graphene additive in industrial resins used for corrosion-resistant

applications in the tanks and pipes that are employed for storage and transport of
potentially explosive chemicals. The graphene-enhanced coating can also be used
to avoid explosions due to the electrostatic charges. Currently, Avanzare is
focusing on manufacturing vessels and equipment using the graphene-enhanced
resins instead of the usual metals. These resins are cheaper and lighter and have
very good corrosion resistance. This graphene-enhanced resin is already being
extensively used in the industries and is being sold by Ashland, an international
chemical manufacturing company.
• Graphene 3D Lab, a global leader in the development and manufacturing of
proprietary composites and coatings based on graphene, has unveiled a new
product called G6E-GSTMepoxy. It is a highly electrically conductive (resistivity
~0.0001 Ω cm) adhesive with the combination of graphene and silver additives. It
can be cured either at room temperature or at elevated temperatures and bonds
very well to a wide variety of substrates including metals, composites, ceramics,
and glass. The graphene filler in this adhesive contributes to enhanced electrical
conductivity and helps prevent the propagation of cracks and thereby improves
the durability and fatigue characteristics. These properties are critical when there
is bonding between dissimilar materials which are subjected to rapid fluctuations
in the temperature and exposed to thermal fatigue. Enhanced fatigue resistance of
these adhesives also augments the impact resistance and mitigates the damages
caused by any vibrations.

Energy

In the last two decades, significant research has been carried out to develop energy-
related materials to meet worldwide energy demand. Among various organic and
inorganic materials, graphene exhibits strong potential to contribute to the energy
demand in various ways. Solar cells can be manufactured using graphene to enhance
power conversion efficiency. Batteries can use graphene to improve charge–dis-
charge cycling performance and overall capacity. Graphene and its various compos-
ites can also be used in super capacitors to enhance power density and rate
performance. Broadly, the use of graphene can be classified into two main catego-
ries: energy storage devices and energy conversion devices. Graphene-based devices
can provide clean energy with theoretically zero waste emission.
Some of the important examples are highlighted as follows:

• Versarien of UK in collaboration with Warwick Manufacturing is currently

developing graphene-incorporated lithium ion batteries and supercapacitors for
enhanced storage and charge/discharge rate capabilities, where the graphene was
expected to provide enhanced electronic conductivity compared to the commonly
used conductive carbon.
• US-based Urbix unveiled new graphene-based supercapacitors with high energy
density (>75 Wh/L) and low leakage currents (<1μA/day over 30 days). The
21 Consumer Applications of Graphene and Its Composites 493

volumetric discharge energy density of these supercaps is five times higher than
the currently available technologies in the market. Their operational temperatures
range from 40
C to 70
C. Urbix is also customizing the supercaps as per the
customer requirements. These supercaps are commercially available in three form
factors: 2032 (capacitance – 2.5F), 2430 (4F), and customized sizes (capacitance
as per customer requirements).
• Skeleton Technologies launched a graphene-based engine start supercapacitor
with very high energy and power densities. It has developed a new graphene-
based engine start module called SkelStart Engine Start Module 2.0 to help power
heavy industry vehicles in the extreme conditions. The SkelStart Engine Start
Module 2.0 is available in 24 V and 12 V versions and provides the highest power
and energy densities on the market.
• In 2016, China’s Chowei Power launched graphene-enhanced “Black Gold”
VRLA series lead-acid battery. This battery uses graphene as an additive, and it
reduces the battery resistance by 52% and helps operate the battery in
low-temperature conditions also.
• A China-based Carbon Century Technology developed graphene-enhanced
Li-ion AA batteries with life cycles up to 30,000 under operational temperatures
between 45
C and 60
C, which are quite superior by several folds compared to
any of the Li-ion battery technologies existing in the market.
• Huawei unveiled a new graphene-enhanced Li-ion battery that can remain func-
tional at higher temperature up to 60
C as opposed to 50
C limit. At the same
time, they offer longer operation times and almost twice their previous batteries.
In order to improve the functional metrics of their batteries, Huawei introduced
anti-decomposition additives in the electrolyte and utilized chemically stabilized
single crystal cathodes – and graphene, where graphene helped dissipate the heat
and increase the electrical conductivity in the electrodes.
• Henrik Fisker in partnership with Nanotech Energy recently announced a
graphene-enhanced battery technology supported sports car – “EMotion” to
compete with Tesla. EMotion currently achieved a top speed of 161 mph and a
400-mile travel range using the graphene-based battery technologies. It is still in
early stages, and this is totally a sports car with a high price tag and not meant for
everyday commuting. It runs on the graphene-based battery.
• In 2016, Graphene Energy Storage Devices Corp. (GESD) developed a graphene-
based electric double-layer charge (EDLC)-based supercapacitor. These capaci-
tors are internally balanced and do not have any external circuit. Their electrodes
are very cost-effective containing nano-carbon composites made of graphene
platelets and carbon nanotubes. These supercapacitor technology exhibits good
charge – discharge characteristics along with enhanced life cycles, and it is
expected to enable new compact energy storage solutions for grid and vehicular
applications.
• Chinese mobile network carrier China Telecom unveiled a graphene-enhanced
mobile power pack with a capacity of 6000 mAh, and it recharges in a 10 min
period time. However, these battery packs have slightly lower energy density
compared to the existing ones. It comes with an aluminum enclosure to protect the
494 R. K. Guduru and A. A. Gupta

graphene materials. It is supported by USB-A and micro USB ports and QC3.0
output (5V – 3A/9V – 2A/12V – 1.5A). It can be recharged with 9V – 40V and
120 W power supplies.
• Dongxu Optoelectronic Technology recently unveiled an impressive graphene-
enhanced battery, called G-King. It was the world’s first graphene battery. This
battery has a capacity of 4800 mAh, close to the capacity of a laptop battery.
However, it charges quite fast within 13–15 min, which is almost 10–20 times
faster than the existing batteries in the market. This particular battery can last up
to 3500 charge/discharge cycles, which is again almost seven times higher than
most of the Li-Ion batteries available in the market.
• The Oxford-based start-up Zapgocharger Ltd. has unveiled a graphene-based
portable supercapacitor charger for phones and tablets. This charger utilizes a
graphene supercapacitor, and it will enable on-the-go charging of the devices. It
can store the charge up to 1500 mAh capacity.
• Skeleton Technologies developed graphene-based supercapacitor technology for
road freights. In collaboration with Adgero and Kinetic Energy Recovery Sys-
tems, it is planning to launch SkelMod 160V supercapacitor modules for
increased efficiency of the truck transport industry.

Other Technologies

• An Indian-based start-up, Log 9 Materials, incubated at the TIDES incubation

center of Indian Institute of Technology Roorkee, produced and utilized graphene
in energy and filtration technologies. It initially launched a filtration product
called PuFF, which is a graphene-based filter, used in the cigarettes to reduce
the toxic chemicals from smoking by 50% without affecting the smoker’s expe-
rience. This product is now sold with a brand name “Filtr” by a pharma company.
Recently, Log 9 also launched its Oil Sorbent Pads LSP 20.
• An Australian-based Imagine Intelligent Materials (IIM) announced commercial
installation of graphene coating for geotextiles. This installation comprised a
10,000 m2 of bidim C geotextiles, manufactured by Geofabrics Australasia, and
then it was coated with IIM’s imgne ® X3 graphene coating for the detection of
holes as small as 0.7 mm using preexisting, proven electrical testing techniques.
This technology enabled operators from risking to the leakage of toxic leachate
from the mining into the groundwater and aquifers.
• Two start-ups Graphematech and Add North 3D (Swedish company) jointly
developed novel graphene-enhanced conductive “Aros,” the 3D printing fila-
ments. This innovation is expected to open up several 3D-printing applications
related to printing of thermal management components, circuit boards, and
electromagnetic and radiofrequency shielding devices, where the printed compo-
nents and circuits will have good thermal and electrical conductivity characteris-
tics. Similarly, Graphene 3D Lab released a Graphene-HIPS 3D printing filament,
which is again incorporated with graphene. It is a distinctively engineered semi-
flexible fused deposition modeling (FDM)-based 3D Printing material and
21 Consumer Applications of Graphene and Its Composites 495

reinforced with graphene. It imparts excellent interlayer adhesion, toughness, and

superior impact resistance with enhanced mechanical and structural properties the
printed objects. Graphene-HIPS is also a temperature and weather resistant
product, and it helps print outdoor projects. Directa Plus in collaboration with
FILOALFA launched GRAFYLON 3D, a graphene-based filament for 3D print-
ing. GRAFYLON 3D is a new generation of polylactic acid-based (PLA) filament
containing the graphene made of Directa Plus. Similarly, Haydale also launched
graphene-enhanced PLA filaments for 3D printing.
• Global Graphene Group (G3) launched a G3-Fireshield Technology, which
utilizes graphene-based components in the Li-ion batteries to reduce the risks of
fire occurrences in the electric vehicles, portable electronics, and a range of other
devices. At elevated temperatures or during thermal runaway, or by mechanical or
electrical or thermal abuse, the Li-ion battery components undergo chemical
and/or structural changes and result in shorting of the cells or degradation of
the chemicals and thereby result in fires. Graphene having good thermal conduc-
tivity and stronger mechanical characteristics would help protect the batteries
from the temperature rises or the fires caused by other means of failures.
• A Chinese company called MS Technology is deploying graphene-enhanced
street lighting fixtures in Beijing, and these were reported to be 30% energy
efficient and can reach up to 140 lumens/watt (brighter than the old ones). The
exteriors of fixtures are made of composite materials, and they seemed to have
used heat dispersing materials by using graphene-incorporated heat-conducting
adhesives and chips inside the fixtures.
• A UK-based company, Exposure Lights, unveiled “Capture” a graphene-
enhanced action camera light. Capture is enclosed inside a hydrophobic or
waterproof and heat dissipating conducting graphene-enhanced polymer casing.
It comes with a provision to use standard batteries with conventional style mount
points.
• Vorbeck Materials and Reliance together announced the development of a supe-
rior graphene-incorporated hydrogenated nitrile butadiene rubber (HNBR) elas-
tomer with (a) very high strength at low deformation (high modulus) and (b) the
ability to withstand temperature up to 200
F. It has a nominal tensile strength of
3500 psi and a Shore A hardness of 88, and it is used in several industrial and
consumer applications.
• Graphene 3D Lab introduced a new and exceptional graphene-based oil absor-
bent materials. They are ultralight materials (density ~ 20 mg/cm3) and consist of
a foam structure. They can be able to hold up to 3500–8000% of their own weight
of organic solvents and oils without being affected by water. These products are
of great use in oil clean up and minimizing the damage during the oil spill
disasters. Graphene 3D lab claims that these products may also have find appli-
cations in energy storage devices/chemical catalysts/ultrasensitive sensors.
• University of New South Wales signed an agreement with a China cable com-
pany, Hangzhou Cables, to develop efficient graphene-based cables for transmis-
sion purposes for boosting 5% of electricity transmission with annual savings of
275 terawatt hours.
496 R. K. Guduru and A. A. Gupta

• Guangzou OED developed a graphene-based e-paper technology, which is

brighter and more flexible where graphene is possibly used as conducting mate-
rial very similar to the display’s touch panel.
• Interim, a Chinese company, unveiled a graphene-based flexible and bendable
smartphone OLED touch screen with a weight around 200 g.

Future Prospects of Graphene

Graphene is a versatile material and can be customized with respect to its properties
and structure, and hence it should be capable of serving almost an unlimited number
of applications. However, there are some challenges from the manufacturing point of
view, especially with its quality, consistency in the thickness and defects, etc. As
earlier predicted by different authors, the quality of graphene will very likely drive
its applications and expansion in the consumer markets, and yet that challenges still
persist. As per Todd Krauss, a chemist at the University of Rochester, it is very
difficult to predict the applications and success of graphene by scientists just based
on the research findings [55]. Thus, there is some gap between the practical world
and the research communities in terms of bridging the research findings with
practical implementations and viability aspects. At the same time, the environmental
friendliness and biocompatibility of most of the nanomaterials, including graphene,
are not yet well researched and understood. Also, the long-term impacts on the health
and environment and the recyclability issues need to be thoroughly investigated. In
fact, some worry that the curled graphene, very similar to carbon nanotubes, could be
as dangerous as the asbestos. Hence, there will be few challenges and resistance from
the safety point of view in implementation of graphene into all the practical
applications.
The current and the first wave of consumer and industrial products developed
based on graphene and its derivatives have penetrated into the markets of
smartphones, wearables, energy sector, automobiles, sports equipment, sensors,
and supercars. They have already been found to profoundly impact the human
lives. This is just the beginning of graphene world in the consumer markets. It has
great potentials to penetrate into every corner of our lives, very similar to what the
plastics and silicon-based technologies did in our lives since the last few decades.
From the consumer market point of view, graphene is yet to open the doors for
magnetic applications, computer chips, superconductors, airplanes, space industry,
construction applications, biomedical in vivo applications, and drug delivery. There
is a good possibility that the upcoming years may be called “GRAPHENE ERA” as
it roots into every product of our daily lives. As projected in Fig. 3, the graphene
market is expected to expand quite rapidly across the globe. According to Elon
Musk’s presentation on International Astronomical Congress (IAC) in Mexico, the
gigantic carbon materials including graphene for fuel storage in the spaceships with
lightweight and high strength still hold great potentials in the space industry [56].
Graphene-based batteries are also being actively researched for many commercial
applications. The improved performance and life cycle advantages when developing
21 Consumer Applications of Graphene and Its Composites 497

graphene-based batteries over traditional metal-ion batteries are well worth the
resource investment. Elon Musk’s Tesla Motors provides a famous example of
innovative companies actively pursuing graphene battery research and commercial-
ization [57]. It is believed that the real graphene battery breakthroughs will be from
graphene-lithium-ion hybrid chemistries incorporated into the cathodes of lithium-
sulfur cells. This type of technology is still years away from commercialization, and
intensive research is ongoing. The more innovative graphene battery technologies
will require significant R&D expenditures and will take many years to
commercialize.
Interestingly, graphene has also fueled the research in finding new generations of
other two-dimensional nanomaterials. On top, the practically success story of
graphene has been encouraging the efforts to find the atomically thin
two-dimensional materials of different chemistries to exploit their physical, chemi-
cal, and functional properties in different areas of emerging markets. The dedicated
websites like https://www.graphene-info.com/ have been constantly updating the
progress in the applications of graphene and its derivatives in consumer markets.
Although different products have emerged in the consumer markets, the fate of
graphene and its derivatives in biotechnology is difficult to predict at this point. Due
to extraordinary characteristics, graphene-based chemistries have been found to be
extremely promising and versatile in many fields of research and practical applica-
tions. Nevertheless, the convergence of multiple disciplines will be required for more
progress in the upcoming years. Ultimately, progress could lead to several innova-
tive multifunctional smart materials based on graphene.

Conclusions

Over the past a decade, graphene and its nanocomposites have shown promising
growth in various technologies and consumer applications. However, there are a few
key challenges that must be addressed and resolved to realize the full potentials of
graphene and its composites. These include improved synthesis methods, its quality,
affordable costs, and exploration of diverse applications. From the present review, it
is clearly evident that both graphene and graphene-based composites have demon-
strated their potentials as promising candidates in various applications. Since
graphene tops the charts with its exceptional properties, the graphene-based products
are gaining importance in various day-to-day applications. As a sequel to this,
graphene has therefore attracted worldwide attention. The intensity and number of
publications and patents arising from various countries and related subject areas
have triggered a chain reaction in the field of electronics, sports, sensors, automo-
biles, textile, biotechnology, oil and gas, energy, and other critical applications.
Expected remarkable growth in the coming years predicts an exponential boom in
graphene research and development throughout the world. Various attempts are
being made to further improve and enhance the properties of graphene-based
composites by altering the chemical structures of graphene and its derivatives
through functionalization and other advanced techniques. Due to the high diversity,
498 R. K. Guduru and A. A. Gupta

properties, and advantages of graphene, a multitude of nanocomposite-based appli-

cations have been envisioned to be practical. These multifunctional graphene com-
posites coupled with affordable cost are likely to storm the global market soon.

Recommendations
Following websites may be referred for constant updates on consumer products and
major activities related to graphene:

https://www.graphene-info.com
https://www.thegraphenecouncil.org
https://www.nga2d.com/

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Applications of Graphene and Graphene-
Based Nanocomposite for Consumer 22
Nanoproducts

Jnyanashree Darabdhara and Md. Ahmaruzzaman

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
Graphene in Touch Screen Displays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 504
Graphene in Wireless Communications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
Graphene in Sports Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
Graphene in Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
Graphene in Automobile Parts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
Graphene Nanocomposites in Packaging Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512
Graphene in Conductive Inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
Other Consumer-Based Products Using Graphene or Graphene Nanocomposites . . . . . . . . . . . . 515
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
URL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518

Abstract
Development in the field of nanoscience and nanotechnology has paved the way
for the use of nanomaterials in diverse applications ranging from industrial sector,
healthcare, electronic appliances, and cosmetics to other consumer-based prod-
ucts. Majority of the products available in the market are produced by the
application of nanoscience and nanotechnology. Graphene, the wonder material,
comprises of two-dimensional sheets of sp2-hybridized carbon atoms that are
connected to each other in a honeycomb lattice structure. Graphene is one of the
thinnest materials, and after its isolation by Andre Geim and Konstantin
Novoselov in 2004, it has gained a wide range of interest in the field of physics,
materials chemistry, and biology. Due to its high surface area and extraordinary
electrical, mechanical, and thermal properties, graphene has been able to grasp
the interest of researchers for its development in the industrial sector and also to
involve it in the manufacture of essential products for the mankind. Due to its

J. Darabdhara · M. Ahmaruzzaman (*)

Department of Chemistry, National Institute of Technology, Silchar, Assam, India

© Springer Nature Singapore Pte Ltd. 2022 501

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_87
502 J. Darabdhara and M. Ahmaruzzaman

superior physical and chemical properties, graphene finds its application in a wide
range of fields ranging from electronics, energy storage, to certain biological
applications. Until now a large number of graphene-based consumer products
have reached the markets from the laboratory benches. The use of graphene in
consumer-based products may lead to better product performance and enhance
the lifetime of the products. Considering all the unique and superior properties of
graphene and graphene-based nanocomposites, this chapter focuses on the vari-
ous advances which have been made to date on the development of products or
ideas based on graphene and graphene-based nanocomposites and keeping in
mind its application in our day-to-day lives.

Keywords
Nanotechnology · Graphene · Graphene Oxide (GO) · Consumer based
products · Nanocomposites

Introduction

Nanotechnology is an emerging branch of science that has improvised and brought

tremendous changes toward mankind. Over the years, developments in the field of
nanotechnology have resulted in numerous possibilities for their applications in the
production of consumer-based products. The term nanotechnology was first coined
by Norio Taniguchi in 1974 [1]. The physical, chemical, and biological properties of
nanomaterials vary from those of the bulk materials having same chemical compo-
sition, and these variations could be observed in terms of magnetic properties,
different electrical or optical properties, and difference in chemical or biological
activity [2]. The dispersibility and particle size distribution are some of the important
characteristics of nanoparticles which is essential for the optical appearance and taste
of many products, and hence most of the modern engineered nanoparticles find its
application in paints, self-cleaning surfaces, scratch-resistant coatings, sunscreens,
clothes protected from the UV radiation, high-performance insulation, and food
technology [3].
Among the various materials that are available in the present world, the carbon-
based materials are very prominent and perform an important role in our human
civilization. At the present scenario, our life seems to be very difficult without the
use of carbon-based materials. After the isolation of graphene in the year 2004, it is
considered as one of the most magnificent success in the area of science and
technology [4]. Graphene is a two-dimensional sheet comprising of sp2-hybridized
carbon atoms that forms an extended honeycomb network which serves as the basis
for the preparation of other important allotropes. The two-dimensional sheets of
graphene layers can be stacked to get 3D graphite, rolled to form 1D nanotubes, and
wrapped in order to obtain 0D fullerenes. Graphene has gained a wide interest in
both theoretical and experimental studies owing to its extraordinary thermal,
mechanical, and electrical properties which exist due to the long-range π conjugation
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 503

that prevails in its structure [5]. The isolation of graphene was first carried out by
Geim and coworkers, and they published a paper in the year 2004 reporting the
isolation, identification, and characterization of graphene for which they were
successful in achieving the Nobel Prize award in the year 2010. They isolated
graphene films by using mechanical exfoliation method where thin
two-dimensional layers of graphene were extracted from three-dimensional graphite
using a scotch tape and then transferred it to a substrate of silicon [6]. At present we
can obtain graphene by two main different approaches, viz., the top-down method
where we use graphite in order to obtain graphene sheets and the bottom-up method
where we use a starting material containing carbon to produce graphene sheets.
Some of the top-down approaches for the synthesis of graphene involve exfoliation
of graphite, intercalation, micromechanical exfoliation, solvent-based exfoliation,
arc discharge, and unzipping of carbon nanotubes. While chemical vapor deposition,
epitaxial growth over SiC, and carbonization are some of the bottom-up approaches
which are used for the preparation of graphene, out of the abovementioned methods,
the exfoliation method and the chemical vapor deposition are most often used for
commercial generation of graphene [7, 8].
Graphene displays remarkable properties such as high planar surface area
( 2630 m2g
1) [9]; they exhibit high mechanical strength having a Young’s modulus
of 1100 GPa [10] and high thermal conductivity of 5000 Wm
1 K
1 [11]. Graphene
displays remarkable electronic and optical properties with a high carrier mobility of
10,000 cm2V
1 s
1, high opacity of 97.7%, etc. [12–14]. Hence, it is of no doubt
that due to its remarkable properties, graphene has been able to grab the interest of
different scientists for its application in various fields involving biological applica-
tions, sensing, and as a catalyst. Graphene also finds its application in electronics
involving energy conservation and storage devices and in displays and solar
cells [15].
Graphene-based nanocomposites are mostly prepared by incorporating graphene
with metal nanoparticles [16]. With the advent of this idea, the various derivatives of
graphene sheets such as graphene oxide (GO) and reduced graphene oxide (rGO) are
used as an integral element for developing new materials [17]. Due to van der Waals
force of attraction, the graphene layers can be restacked which in turn reduces its
intrinsic properties due to which the application of graphene gets limited. However,
upon modification of the surface, using metal or metal oxide nanoparticles reduces
the π-stacking interactions that prevail between the graphene layers [18]. π-π
stacking and noncovalent bonding are the two interactions that are considered to
hold the nanoparticles over the graphene surface [19]. On the other hand, polymer
nanocomposites composed of graphene display the superior behavior of graphene;
such types of graphene-polymer composites show better electrical, thermal, and
mechanical properties as compared to the polymer alone [20, 21]. The physico-
chemical properties of graphene-polymer nanocomposites are governed by the
dispersal of the layers of graphene in the polymer matrix and also the interfacial
bonding between the polymer matrix and the graphene layers. Graphene oxide
(GO) sheets are most often used to form homogeneous composites with organic
polymers compared to the pristine graphene which is incompatible with organic
504 J. Darabdhara and M. Ahmaruzzaman

polymers and hence do not form homogeneous composites with organic polymers
[22–24]. Polymer nanocomposites containing graphene nanofillers show application
in energy storage devices, in different biological applications involving drug deliv-
ery and biosensors, and also in different photocatalytic reactions [25–28].
Considering the above aspects of graphene and graphene-based nanocomposites,
they are expected to make reformations in the manufacturing of many industrial and
consumer-based products. Graphene and graphene-based materials find numerous
potential applications in food packaging and in the touch screens of mobile phones
and laptops; it is also used in protective coatings and in high-capacity batteries. Until
now a lot of efforts have been made in the development of products which are based
on graphene. Rackets, helmets, and shoes are some of the sports-related products
which are based on graphene that have been made available [7, 29]. Here in this
chapter we will discuss the potential incorporation of graphene and graphene-based
nanocomposites in the preparation of consumer-based products while considering
their role in making our lives simpler.

Graphene in Touch Screen Displays

Touch screen serves as an intermediate between the user and the cell phones and
helps in proper control of the various operations over the device. Over the past few
years, much development has been made in the industrial manufacture of touch
screens. In fact, many companies produce millions of touch screens annually [30].
Flexible electronics are usually looked upon as an important part for use in
optoelectronics including displays and solar cells. However, such flexible electronics
are needed to be constructed over soft surface such as plastic or rubber. Owing to the
better conductivity as well as optical transparency of indium tin oxide (ITO), it is
often used for construction of transparent electrodes which serves as an important
element for optoelectronic devices. However, graphene has emerged as a potential
candidate that displays several advantages over ITO for use in transparent electrodes
because ITO has the probability to get cracked owing to its very inferior mechanical
properties. While monolayer or multilayered graphene developed by CVD shows
better optical transmittance compared to that of ITO, graphene also possesses
comparable sheet resistance with ITO owing to its high carrier mobility which is
found to be greater than 103cm2V
1 s
1 and high carrier density which is found to be
greater than 1012 for doped samples of graphene [14, 31]. Graphene developed over
flexible entity is found to be robust mechanically. Moreover, amidst other transparent
stretchable conductors, graphene carries the lowest bending radius [32]. Several
flexible optoelectronics including touch screen sensors and photovoltaic devices has
illustrated the usage of graphene as transparent electrode [33, 34].
However, there are certain limitations over the instant replacement of ITO for
transparent electrodes by graphene because graphene developed by CVD is needed
to be relocated over an absolutely flat surface. But nearly majority of the electronic
device possess interlinked multiple layered frameworks, and hence two-dimensional
tailoring of the device framework is required while using electrodes of graphene.
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 505

Fig. 1 (a) A touch screen based on graphene showing its flexible behavior [33]. (b) Picture
showing touch screen formed of graphene films established over a mobile phone (left) compared
with mobile phones containing an ITO-based touch screen (right) [35, 37]

Due to this, it was expected that the application over flat structures including touch
screens, lighting and transparent heaters will be studied first followed by the
application to flexible surface which might take some years. Although till now
many materials such as metal meshes and silver nanowires have emerged as an
alternative for ITO, they are not as much flexible compared with graphene. Graphene
shows certain conducting properties that can persist up to extension of 11% [31], and
at a bending strain of 3%, graphene also displays its original sheet resistance up to
300,000 cycles [35], while in case of silver nanowires, they undergo fracture at
strains lesser than 1% [36]. The application of graphene in touch screen technology
is shown in Fig. 1.

Graphene in Wireless Communications

Humans can communicate using frequency ranges between 20 Hz and 20 kHz.

Commercial earphones used for the human beings possess frequency ranging
between 20 Hz and 20 kHz. Ordinary speakers comprise of mechanically movable
components that produces sound waves by compression of air, while in contrast
electro-thermoacoustic (ETA) device uses a conducting film for generation of sound.
The air molecules lying near the surface of ETA device gets warmed upon transfer of
heat from the surface of the ETA device which gets heated up upon application of
signal from alternating current (AC). The warmed up air molecules then further
transfer their energy to other air molecules lying near to them, and this process
continues further which ultimately results in the generation of the sound. ETA
devices have paved the way for the design of earphones for response toward wide
range of frequency. However, there are certain criteria that have to be fulfilled in
order to achieve ETA devices exhibiting elevated performance. The first condition
involves the use of thin conductor with lower thermal capacity per unit area. Second,
there shouldn’t be any thermal leakage, and last in order to generate satisfactory
506 J. Darabdhara and M. Ahmaruzzaman

sound field, the area of the conductor must be sufficiently large. Graphene has been
formerly analyzed for application in sound emission, but most of the previous
studies applied CVD method for the growth of graphene films which is found to
be tedious in terms of growth of the film, to transfer the film, and for patterning of the
transferred film. Moreover, the van der Waals force is responsible for holding the
planar graphene layer over the substrate, and the substrate carries thermal conduc-
tivity which is sufficiently higher compared with air. Hence, due to this attachment,
the substrate experiences over 90% heat loss. Therefore, certain porous substances,
such as filter paper, anodic aluminum oxide, porous silicon oxide, etc., have to be
used for prevention of thermal leakage, but this approach requires a complicated
manufacturing process and results in a suspended graphene structure in lower
yield [38].
Tao et al. studied the development of earphones based on graphene by applying
the laser scribing method [39]. They prepared a membrane of GO by dropwise
dispersing GO upon a polyethylene terephthalate (PET) substrate which is followed
by the application of laser scribing technology to inscribe rGO in the form of a
square that wraps the GO layer. At last copper adhesive tapes were fixed upon both
the sides of the rGO layer which is then finally inserted to the case of commercially
available earphones. Figure 2 shows the various fabrication steps which are
discussed above in the development of graphene-based earphones.
The developed graphene-based earphone was used for wireless communication
system based on an ARM board. Wireless communication was established between
the mobile phone and the ARM board which was connected to the graphene-based
earphone that resulted in similar output sound from the graphene-based earphone
with that of the input sound waves.
A similar study was performed by Tian et al. from Tsinghua University where
they worked on the development of graphene-based earphones toward response for
wider frequency range covering 100 Hz to 50 kHz [38]. They developed the

Fig. 2 The various steps in the construction of graphene-based earphone [39]

22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 507

Fig. 3 Lower fluctuations observed for graphene-based earphones compared with commercial
earphones [38]

graphene-based earphone by laser scribing technique and further compared with that
of commercial earphones. They used the same audio analysis system for comparison
purpose. They used a standard microphone which was located at a distance of 1 cm
from the graphene earphone to convert the generated sound from the graphene
earphone to electrical signal. Owing to the resonance free oscillation in the graphene
earphone, it showed flat response over a wide range of frequency from 100 Hz to
50 KHz as shown in Fig. 3 and a much lower fluctuation of 10 dB, while for
commercial earphones much fluctuations were observed over the frequency range.
Further, according to their theoretical calculations, they predicted that the graphene
earphone could function up to a frequency of 1 MHz.
From the above discussion, it is clear that due to the flat frequency response by the
graphene-based earphones, they could be potentially used in various ultrasound
applications. Also the laser scribing technique could be used conveniently for the
manufacture of graphene-based electronic devices in larger scale [39].

Graphene in Sports Equipment

Science and technology seems to play an immense role in the development of a

number of equipment, especially in the field of sports; technology needs to be
implemented in various stages of sports considering from the training session of
the player to their completion stage. The main objective toward the development of
sports equipment is to make improvement in the performance of the athlete and to
minimize the chances of injury for which the sporting tools should possess anti-
508 J. Darabdhara and M. Ahmaruzzaman

fatigue property and higher strength. Nowadays with the occurrence of science and
technology in sports, graphene has emerged as a new class of material which is
considered to have a wide application in the area of sports.
The primary purpose of the rackets is to achieve better hitting strength. Frame
weight, torsional stability, and head size of the racket are some of the factors that
influence over the control of the rackets. Enhanced controlling could be achieved
when the racket weight is small, the racket head has a smaller area, and the
torsional resistance of the racket is high. However, in order to experience better
comfort in the tennis rackets, it is essentially necessary to increase the sweet zone
area of the racket, to enhance the torsion resistance of the racket, to make
improvement in the capacity of the material of the racket’s frame to show better
ability in absorption of different vibrations, and also to make changes in the weight
of the racket string. Composites of graphene carbon fiber constituting of epoxy
resin containing well-distributed graphite exhibit better strength and better elastic
modulus compared with conventional carbon fibers, and hence they tend to
improve the rigidity and strength of the tennis rackets [40]. Graphene-based tennis
racket was first made commercially by the HEAD Company in Austria in 2013.
Application of graphene was found to be quite beneficial for the rackets, it made
the shaft more strong and lightweight, also better distribution of the weight is
achieved upon the assistance of graphene, and hence a better control can be
achieved over the racket [41].
Young et al. made a microstructural investigation on the HEAD ® Youtek
Graphene Instinct Junior Tennis Racket as shown in Fig. 4 using a combination of
optical microscopy and Raman spectroscopy to study the graphene type that has
been used and its region of application in the racket [42]. According to them, the
racket frame is composed of high-strength carbon fibers in a matrix of epoxy resin as
the main structural constituents. They also predicted resin-rich regions in the racket
where the head of the racket is connected to the racket shaft. Graphite nanoplatelets
were incorporated to enhance the mechanical property of the resin-rich region which
is considered to be a weak point of the racket.
Another example of graphene in sports-based product is the development of
helmets containing graphene. A graphene-based helmet was developed by the Italian
company Momodesign upon collaboration with the Italian Institute of Technology.

Fig. 4 Graphene based racket from HEAD YouTek [42]

22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 509

Graphene was embedded on the external side of the helmet as graphene powder
consisting of graphene flakes or graphene nanoplatelets which were further mixed
into a solution and then sprayed on the outer side of the helmet. According to the
manufacturer, incorporation of graphene in the helmet offered better mechanical
protection for the helmet and also results in better dissipation of heat which ulti-
mately provided better comfort for the user [43].
However, in the similar context, efforts have been made for application of
graphene in running shoes; the use of graphene in winter running shoes could reduce
the weight of the shoes and provide better support strength. Owing to high elasticity,
high resistance against fatigue, and better adsorption characteristic of graphene
aerogel, it could secure better health of the consumer’s foot due to its ability to
absorb smell better [44]. On the other hand, a team of scientist from the University of
Manchester developed a new rubber composite comprising of graphene which was
later used in the sole of graphene-based shoes developed by the UK-based company
inov-8. According to them, the use of graphene greatly enhances the strength,
flexibility, grip, and wear resistance of the graphene-based shoes [43].

Graphene in Batteries

Over the years, owing to the rise in the demand for energy has persuaded many
countries to think for new devices or new techniques to preserve energy. Lithium ion
batteries have emerged as an energy storage device and display many advantages
such as high open circuit voltage, high longevity, less pollution, high value of energy
density, and lower discharge rates over conventional batteries. Due to the above men-
tioned behavior shown by lithium ion batteries, they find its application in many
electronic devices such as mobile phones, laptops, and other portable devices.
Common compounds of lithium such as LiCoO2, LiMn2O4, and LiFePO4 are
often used as cathode materials, while graphite, oxides of tin, and oxides of other
transition metal are most often used as anode materials in lithium ion batteries.
However, these materials possess certain drawbacks which restrict them for use in
lithium ion batteries. On the other hand, graphene, the wonder material, has emerged
as a potential alternative for electrodes to be used in battery applications. High
lithium storage capacity could be achieved in the batteries containing graphene due
to the high specific surface area of graphene. Conventional lithium ion batteries may
break down early due to swelling and shrinking of the material during insertion and
removal of lithium ions from the electrodes. However, a different scenario is
observed in case of batteries containing graphene; they can operate at lesser tem-
perature, thus enhancing the safety of the battery by lowering the resistive heating
within the electrode owing to the high conductivity of graphene [45]. Although till
today efforts have been made in the direction of improving the demerits of the
lithium ion batteries, lithium-sulfur (Li-S) and lithium-air are considered to be the
technology to be used in future generation batteries. Comparing with today’s lithium
ion batteries, Li-S batteries exhibit more potential to store the specific energy and
display longer battery lifetime for portable devices [43]. Usually in Li-S batteries the
510 J. Darabdhara and M. Ahmaruzzaman

cathode is considered to be of sulfur, while the anode is considered to be of lithium.

Oxidation of lithium to lithium ion occurs at the anode, while reduction of sulfur to
sulfur ion occurs at the cathode at the time of discharge of the Li-S battery. Li2S is
formed at the cathode upon the reaction of lithium ions with sulfur after their
migration to cathode from anode. Amalgamation of graphene to both the cathode
and anode enhances the battery performance and the rate of charge/discharge cycle.
Due to the excellent electrical conductivity, high aspect ratio, and dispersibility of
graphene, it exhibits superior behavior over conventional electrodes, thereby reduc-
ing their limitations. Because of the above nature shown by graphene, it finds
application in Li-S batteries [46].
The world’s first lightweight and ductile graphene-enhanced battery product Vor-
Power straps was launched in 2014 by the Vorbeck Materials. It is a power source
connected to the strap of an existing bag that allows charging of mobile phones. On
the other hand, a China-based technology company “Huawei” developed a new kind
of Li-ion battery by adapting newer technologies such as they added anti-
decomposition additives to the electrolyte; they used single crystal cathodes that
were stabilized chemically and also graphene in order to dissipate heat. According to
them, the new batteries could operate at higher temperature and provide more
longevity compared to previous batteries [41].

Graphene in Automobile Parts

The automobile industry has to encounter many challenges worldwide for ensuring
the safety of the passenger and to reduce the emission of gases of carbon oxides. It is
becoming essential to apply new technologies that would facilitate the manufacture
of more green and safe automobiles. Graphene has emerged as a new material which
is considered to play a crucial role in the automobile industry. Utilization of
graphene-based batteries and supercapacitors enhances the performance and
efficiency of vehicles and decreases the rate of power consumption
[47]. Graphene-reinforced polymeric composites show improvement in its perfor-
mance and properties such as tensile strength, electrical conductivity, thermal sta-
bility, thermal conductivity, and gas barrier properties. The abovementioned
properties of graphene polymer composites make it a promising candidate for use
in different important sectors including the automobile industry. The “Graphene
Flagship” project has primarily aimed for development of materials composed of
graphene for application in automobile industry. This initiative allows the use of
different graphene-based polymeric materials in various structural applications for
enhancing the safety of the vehicles which is still remaining light, Fig. 5 [48].
Professor Ahmed Elmarakbi from the University of Sunderland in England
worked in a task which was under the European Commission’s Future and Emerging
Technology Flagship and aimed at the enforcement of graphene to develop light-
weight, strong, safer, and energy-efficient vehicles that could bring changes to the
automobile sector. A bumper fabricated with graphene fiber composite was devel-
oped in which the graphene-embedded polymer material was mixed with glass or
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 511

Fig. 5 Use of graphene-based composite materials in various structural parts of an automobile [48]

carbon fibers that improves the characteristics of the bumper by making it lighter in
weight and making it more strong and tough [49]. According to Professor Jiaxing
Huang from Northwestern University, the use of graphene balls could enhance the
lubricant performance of oil in engines and therefore increase the energy efficiency
of engines by reducing friction. His team further investigated that crumpled
graphene balls in oil could act as carriers for materials and also inhibit corrosion
[50]. A UK-based company Linney Tuning studied the development of brake pads
using bilayer graphene. According to them, using graphene as an ingredient of
automotive friction results in enhanced wear resistance and increases the friction
coefficient for longer durability, thus mitigating the issue of noise while braking
[51]. Briggs Automotive Company (BAC) inspected the benefits of using graphene
composite in the body panels of cars which lead them to be the first company in the
world to unveil the graphene-paneled car in the year 2016 where they enforced
graphene-carbon fiber composite to the arches of rear wheels [47]. Following this in
the year 2017, a team of scientist from the University of Alabama used graphene and
carbon fiber for fabricating lighter weight car hood of a Chevrolet Camaro [52]. In
2014, FORD motor company cooperated with Eagle Industries and XG for testing
graphene-reinforced foam covers in different automobile parts including fuel rail,
pumps, and front engines that resulted in 17% reduction of noise, 20% increase in
mechanical properties, and 30.7% increase in heat-resistive tendency. In 2018,
FORD announced to apply graphene in different parts of their vehicles initiating
with Mustang and F-150 [47].
Mao et al. fabricated GO/styrene butadiene rubber composite which has the
potential for application in green tires [53]. In their paper, they described the
preparation of GO/SBR composite upon mixing of GO colloid with SBR latex in
the presence of butadiene-styrene-vinyl-pyridine (VPR) rubber latex in aqueous
phase. VPR prevents the agglomeration of the sheets of GO and behaves itself as
an interface-bridge between GO and SBR which thus enhances the interactions
between the GO and SBR. Their developed GO/SBR composite displayed lesser
permeability for air and low mass density and exhibited better mechanical properties
512 J. Darabdhara and M. Ahmaruzzaman

in the presence of small quantity of GO compared to the mechanical characteristics

of carbon black (CB)-SBR composites at higher percentage of CB. They mixed
silica/SBR composite with GO/SBR composite for preparation of GO-silica/SBR
that displayed higher wear resistance and reduced rolling resistance. Hence, the
developed GO-silica/SBR composite is applicable for use in green tire applications.
According to them, their work has created the possibility for the production of rubber
composites that displays enhanced performance and finds its way for application in
future engineering.
In the year 2016, a Chinese company “Qingdao Sentury” launched the develop-
ment of electrostatic tires enforcing graphene as a component upon collaboration
with another Chinese company “Huagao Graphene Technology.” However, in the
same year “Shandong Hengyu Technology” grouped with “The Sixth Element” and
unveiled their developed graphene tires with decreased wear rate and high tear
strength [41].
Hence, from the above discussion, it is clear that many countries have opted for
the use of graphene in manufacturing of different components of a car considering
from the use of graphene in body panels to the tire composites and thus making the
car more user-friendly choice for customers.

Graphene Nanocomposites in Packaging Applications

Graphene possesses high optical clarity and displays high barrier properties against
diffusion of gases which makes them effective for use in packaging industries
[54]. Impermeability toward degradative gases and opacity toward transferring
light are the two primary qualities which determine the efficacy of packaging
materials. Polyethylene, PET, and polystyrene are some of the widely used polymers
for packaging applications; while they are lighter in weight, less expensive, and
readily processable, however they possess certain limitations such as they offer easy
permeability toward gasses and are transparent. Introduction of small quantities of
nanofillers could significantly increase their barrier properties, thereby reducing the
permeability of oxygen gasses and offering easy processing of the parent polymer.
Polymer-clay nanocomposites were mostly investigated in previous studies owing to
their improved barrier properties compared to the polymer alone. However, the
hydrophilic clay surface and complications during exfoliation of clay aggregates
limit its chances of application as packaging material. On the other hand, polymer-
graphene nanocomposites have emerged as a new material for packaging applica-
tions due to its ability to overcome the limitations of graphene-clay composites by
chemical modifications of the graphene sheets for increasing the interactions within
the polymer matrix. Compton et al. described the application of graphene nanofillers
in polymer films and investigated the ability of the composite in limiting the oxygen
permeability and transmission of light [55]. As per their report, in the presence of
very low concentration of crumpled graphene nearly 0.02 vol%, significant decrease
in oxygen permeability was observed for the polystyrene-graphene composite which
displayed the similar effect as clay-polymer nanocomposites at 25–130 loading
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 513

concentration. Inhibiting the transference of light particularly those having wave-

lengths 500 nm increases the shelf lives of food products; accordingly, graphene-
polystyrene nanocomposite film at 0.02 vol% having thickness of 0.28 mm transmits
only 40% of incident light at 500 nm, and at concentrations 0.24 vol% the film
develops full opaque nature toward incident light. They further attributed that the
easily chemically adjustable and crumple nature of graphene nanosheets facilitates
the preparation of polymer-graphene nanocomposite films having lower permeabil-
ity and transparency for oxygen and incident light. The enhanced interaction occur-
ring between the polymer and graphene sheets facilitates full dispersion and is
considered to be an important factor for making polymer-graphene composites
more effective than polymer-clay composites, thus making polymer-graphene com-
posites more potent for use in packaging applications, thereby increasing the shelf
life of perishable items compared to the polymer alone.
Polylactic acid (PLA) is most often used biopolymers for packaging purposes.
However, its poor barrier properties make it less effective for use in food packaging
purposes. Application of graphene nanofillers reduces this drawback of PLA,
thereby making it a suitable candidate for packaging applications [56]. By using
both graphene and reduced graphene (rGO) oxides, Chen et al. illustrated the use of
PLA-graphene composite films in packaging applications [57]. They obtained rGO
layer upon reduction of freestanding graphene sheets with hydroiodic (HI) acid. A
PLA-graphene composite film having sandwich structure was developed which
contained films of GO or rGO in between two layers of PLA. The PLA layer served
as an outer cover protecting the inner barrier core composed of GO or rGO from
outer physical damage. The designed sandwich-shaped PLA-graphene composite
films showed enhanced barrier properties for both water vapor and oxygen gas; they
achieved 87.6% reduction in water vapor permeability, and two order reductions in
magnitude were observed for oxygen permeability. According to them, the compact
lamellar microstructure, improved hydrophobic behavior of sandwich-structured
rGO film, high lateral dimension of rGO, and reduced interlayer gap between the
layers of rGO were responsible for such decrease in observed permeability. The
PLA-graphene composite films thus carry the desired processability and barrier
properties for application in food packaging.
Besides these, graphene composites also exhibit anticorrosion behavior. Huang
et al. designed vinyl polymer-graphene nanocomposites and studied the anti-
corrosive nature of the prepared composite [58]. They developed polystyrene-
graphene-based nanocomposites by in situ polymerization approach comprising of
graphene oxide sheets modified with p-phenylenediamine/4-vinylbenzoic acid.
According to them, their study was a new investigation, while previous studies
were conducted on the design of graphene-based polyaniline (PANI) composite
against gas barrier and corrosion protection. The vinyl polymer-graphene composite
showed 25% reduction for permeability of oxygen and 60% reduction in nitrogen
permeability nearly at 2 wt% loading of modified graphene oxide. Moreover, the
designed nanocomposite also showed improved anticorrosion efficiency of 99.53%
compared to individual polystyrene which showed only 37.90% corrosion protection
tendency. According to them, exfoliated dispersion of modified graphene oxide in
514 J. Darabdhara and M. Ahmaruzzaman

the polymer matrix increases the path for diffusion of gases and is the reason behind
the reduction of gas permeability and anticorrosion behavior.
Again, graphene nanocomposites also displays antibacterial activity. Chook et al.
applied microwave irradiation method for the development of silver nanoparticles
(AgNPs) on graphene oxide sheets [59]. According to them, both AgNPs and
Ag-graphene oxide composite showed antibacterial activity toward Gram-negative
bacteria, while the antibacterial performance of Ag-graphene oxide composite was
enhanced in the presence of very low concentrations of Ag compared to the AgNPs
alone. The interaction between the graphene oxide and AgNPs facilitates the neces-
sity for the use of smaller amounts of Ag without affecting the antibacterial behavior
of the developed composite. This antibacterial behaviour of Ag-graphene oxide
nanocomposite makes it a suitable material for application in food packaging.

Graphene in Conductive Inks

At the present days, conductive inks have gained much importance in the printing
sector and are applied in many printing processes such as in inkjet printing, screen
printing, roll to roll printing, and gravure printing. Conductive inks most often find
its application in printed electronics such as in organic light-emitting diodes
(OLEDs), radio frequency identification devices, flexible displays, transistors, bat-
teries, etc. [60]. Conductive inks are generally suspensions constituting of conduc-
tive nanomaterials in a solvent system along with a stabilizer which is most often a
surfactant or a polymer; however, after deposition, the solvent has to be rapidly
evaporated instead of instantly drying at the print head of nozzles. An ideal conduc-
tive ink must be inexpensive, low viscous, and highly stable; it should remain highly
adhesive to the surface and must be easy to prepare [61]. Amongst the various
printing techniques that have utilized conductive inks for fabrication in printed
electronics, inkjet printing has been able to grab much attention owing to its easy
printing action and high repeatability; it is also economic and requires less time
compared to other printing techniques. Amongst the various conductive nano-
materials and conductive polymer inks that have been used in printed electronic
applications, gold nanoparticles (AuNPs), silver nanoparticles (AgNPs), and copper
nanoparticles (CuNPs) have received much importance due to their high electrical
conductivity; however, there are certain disadvantages of these nanoparticles that
limit their use in conductive ink [62]. Graphene is one of the most potential
candidates for use in conductive inks due to its high carrier mobility and mechanical
robustness; it is environmentally stable and requires lower charges for production
[63]. Graphene conductive inks have the capability to replace other metallic inks,
conductive polymeric inks, and other inks composed of carbon materials by reducing
the cost of production and the risk toward biological issues [62]. Huang et al. studied
the inkjet printing of single-layered and few-layered GO over different flexible
substrates; accordingly, the electrical conductivities of single-layered GO and
few-layered GO after 25 layers of printing over a polyimide (PI) substrate were
found to be 5.0  102 S/m and 9.0  102 S/m [64]. According to them, the lower
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 515

value of GO compared to the few-layered GO sample is due to the presence of large

numbers of oxygen contained in the GO samples. In the year 2017, Pei and Li used
ultrasonication method for fabrication of GO ink by dispersal of GO in mixture of
solvents in a 1:1:1 ratio of deionized water, ethanol, and ethylene glycol [65]. The
electrical conductivity of the fabricated ink after 20 layers of inkjet printing over a
PET substrate was found to be 0.497 S/m. Secor et al. in 2017 developed graphene
ink using nitrocellulose as a stabilizer. They printed the graphene films over a glass
which showed electrical conductivity of 1.0  104 S/m and 4.1  104 S/m at
temperatures 200  C and 350  C, respectively [66]. Besides this, Majee et al. used
shear-exfoliation process for the fabrication of a graphene-based ink in aqueous
medium by intercalation of bromine with the help of cellulose stabilizer soluble in
water [67]. They observed DC conductivity of 1.4  103 S/m of the successfully
inkjet-printed graphene nanoplatelet (GNP) films upon drying at 100  C which later
increased to 3  104 S/m on treating the film with an aqueous solution of iodine
before the film was allowed to dry. The as-printed GNP films showed increased
conductivity of 2.4  104 S/m at annealing temperature of 250–300  C, while it
showed further increase in its conductivity of approximately 105 S/m upon treatment
with aqueous iodine solution and at higher elevated annealing temperature. The
developed graphene ink displayed viscosity of 9–12 mPas at a concentration of
8.5 mg/ml at 30  C temperature. They used Dimatix DMP-2831 printing setup
comprising of 10 pL cartridge having a nozzle with diameter 20μm for the purpose
of inkjet printing of the developed graphene-based ink. Karim et al. developed a rGO
ink which had a viscosity value of 1.35 mPas and a surface tension value of
65 mNm
1. The developed graphene ink was later used for the purpose of printing
by using Dimatix DMP-2800 printer consisting of 10 pL drop cartridge [68]. Figure 6
shows the image of developed graphene-based ink.

Other Consumer-Based Products Using Graphene or Graphene

Nanocomposites

In addition to the abovementioned consumer-based products of graphene, till today,

there are many other products that have incorporated graphene in its body and have
already launched, or its manufacturing has been already published in various
websites or reports. In 2015, “G-Rods,” an American company, developed fishing
rods made of graphene; they fabricated the rods using carbon fiber and graphene
which showed nearly 30–50% improvement in strength compared to the rods which
are composed of 100% carbon fiber and also displayed better sensitivity and
responsive ability [69]. In the year 2016, a UK-based bike manufacturing company
“Dassi” designed a bike frame constituting of graphene whose weight was just 750 g
and further asserted that they could reduce the weight to 350 g. They fabricated the
frame with very small percentage of graphene with an epoxy resin and carbon fiber
which was used for one level layering in the frame [70]. The world’s first ever
graphene-based paints were launched in the UK in the year 2017 by “The Graphene
Company” [71]. A jacket comprising of graphene was first manufactured by the
516 J. Darabdhara and M. Ahmaruzzaman

Fig. 6 Image of a graphene-based ink (left), AFM image showing the topography of GNPs over
Si/SiO2 substrate (upper right), HR-TEM image of GNPs (bottom right) [67]

clothing manufacturing company “Vollebak” in the UK. According to them, the

manufactured jacket displays the properties of graphene by absorbing heat, thereby
keeping the body warm; the jacket shows repellent tendency toward bacteria and
also dissipates the body’s excess humidity. They made a two-sided jacket in which
one side is composed of graphene which appeared like a gun metal gray, while the
other side appeared matte black and is composed of nylon. The fabrication of
graphene with nylon changes the mechanical and chemical properties of nylon fabric
and thus makes it more conductive for heat [72]. Recently, in 2021, Lin et al.
reported the development of wearing a mask composed of graphene nanosheet-
embedded carbon (GNEC) film. The developed GNEC film-based mask was
reported to exhibit remarkable characteristics involving superhydrophobic nature
at 157.9o water contact angle, high bacterial filtration ability, and high photo-sterilize
capability [73].

Conclusion

As per report published by Ren et al., from the last 6–7 years, many commercial
organizations have concentrated on the production of graphene and graphene-based
materials [74]. However, till now there are only a very few numbers of graphene-
based products that have reached our markets. According to them, initially only a
few companies of the USA particularly “Angstron Materials,” “Vorbeck Materials,”
22 Applications of Graphene and Graphene-Based Nanocomposite for Consumer. . . 517

and “XG Sciences” were involved in the fabrication of small sheets of graphene;
however, with the passage of time, a large number of graphene companies focused
on the production of both small and large area graphene sheets. The production of
graphene materials is rapidly increasing in China producing 400 tons and
110,000 m2 of small graphene sheets and graphene films annually. Small sheets of
graphene find its application in coatings, conductive inks, and batteries, while large-
area graphene films can be applied as transparent electrodes for touch panels and
displays; it is also believed that large-area graphene films can be used for the design
of flexible and wearable devices [14, 30]. The graphene market was considered to
occupy an area of US$12 million till the year 2013. However, the rapidly increasing
demand for graphene should increase its production scale while reducing the cost,
thus resulting in the domination of the global market by graphene-enhanced prod-
ucts. According to a review written by Hamzah et al., the global growth in the
graphene market was assumed to reach up to USD 113.7 million till the year 2020,
Fig. 7 [75].
Graphene is not remained only as a topic of research in the laboratories; instead,
graphene-related product has already reached our markets from the laboratory
houses. From the discussions in this chapter, it is undeniable that graphene has
attracted a wide interest of researchers worldwide for its applications in different
sectors. The growth in the use of graphene-based materials is expected to revolu-
tionize the current manufacturing processes and open up new possibilities in the
global market for customers to increase their demand for graphene-enhanced
products.

Fig. 7 Global growth of the market revenue of graphene from the year 2014 to 2020 [75]
518 J. Darabdhara and M. Ahmaruzzaman

URL

1. Smartphones of the Future Will Use Graphene Touchscreens [Online] Available.

https://www.forbes.com/sites/jasperhamill/2014/09/26/iphones-of-the-future-
could-use-graphene-touchscreens/?sh¼eb000dc47e80.
2. Flexible Touch Screen Made with Printed Graphene [Online] Available: https://
www.technologyreview.com/2010/06/21/121632/flexible-touch-screen-made-
with-printed-graphene.
3. https://www.nanowerk.com/what_is_graphene.php.
4. ORA introduce the world’s first graphene headphones [Online] Available:
https://www.soundonsound.com/news/ora-introduce-worlds-first-graphene-
headphones.
5. HEAD developed a new tennis racket with graphene coating [Online] Available:
https://www.graphene-info.com/head-developed-new-tennis-racket-graphene-
coating.
6. Inov-8 launches new graphene-enhanced trail running shoes [Online] Available:
https://www.graphene-info.com/inov-8-launches-new-graphene-enhanced-trail-
running-shoes.
7. Graphene batteries: Introduction and Market News [Online] Available: https://
www.graphene-info.com/graphene-batteries.
8. Graphene getting the automotive industry into gear [Online] Available: https://
www.mewburn.com/news-insights/graphene-getting-the-automotive-industry-
into-gear.
9. Automotive grade graphene: the clock is ticking [Online] Available:https://
www.automotiveworld.com/articles/automotive-grade-graphene-clock-ticking/.
10. Can graphene give a glimpse into the automotive future? [Online] Available:
https://autovistagroup.com/news-and-insights/can-graphene-give-glimpse-auto
motive-future.
11. Graphene and PLA combined to create a new food-packaging film [Online]
Available: https://www.italianfoodtech.com/graphene-and-pla-combined-to-cre
ate-a-new-food-packaging-film/.
12. Graphene Ink [Online] Available: https://www.graphene-info.com/taxonomy/
term/63/all.

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 Part IX
Consumer Nanoproducts for Biomedical
Applications
Nanotechnology Applied to Personalized
3D Dressings for Diabetic Feet 23
Guillermo Tejada Jacob, Guillermo R. Castro, and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
3D Printing Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
Nanotechnology and Nanomedicine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
Combination of Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
Market and Marketing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545

Abstract
Advances in nanotechnology are showing a major impact in the manufacture of
biomaterials, electronics, and medicine. Nanotechnology based on biopolymers is
a new strategy for the diagnosis and treatment of local diseases and infections.
There is a wide range of applications for nanotechnology in the field of drug

G. Tejada Jacob (*)

Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones en Ciencia y
Tecnología de Materiales (INTEMA), Facultad de Ingeniería, Universidad Nacional de Mar del
Plata (UNMdP) y Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Mar del
Plata, Argentina
G. R. Castro
Laboratorio de Nanobiomateriales, CINDEFI, Departamento de Química, Facultad de Ciencias
Exactas, Universidad Nacional de La Plata (UNLP) -CONICET (CCT La Plata), Buenos Aires,
Argentina
V. A. Alvarez
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina

© Springer Nature Singapore Pte Ltd. 2022 525

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_45
526 G. Tejada Jacob et al.

administration because this technology has improved the delivery of drugs to

areas that were unfavorable to macromolecules, where it is targeted to specific
sites and goal oriented. There is a wide range of nanoparticulate systems like
carbon nanotubes, metallic nanoparticles, polymeric nanoparticles, and lipid
nanoparticles, among others. The development of nanoparticles loaded with
antibacterial drugs for the treatment of infections could improve the pharmaco-
logical therapy of the patient. These nanosystems should be placed on a vehicle
for the design of enhanced dressings.
Another technology that has become very relevant in the present day is 3D
bioprinting, and relevant in the field of dressings, advances have been done. 3D
bioprinting is largely performed with one of three additive manufacturing tech-
niques: inkjet printing, extrusion printing, and laser-assisted printing. All three
techniques require cells, biomolecules, and proteins to be suspended within a
biotint that can be 3D printed. The developed hydrogels based on natural,
nontoxic, biodegradable, and non-immunogenic linear polysaccharides with the
addition of antibiotics and molecules with biological activity are the challenge of
both 3D bioprinting and nanotechnology for the treatment of severe diseases or
infections and thus improve the pharmacological therapy of the patient.
Diabetic foot is an infection, ulceration, and destruction of deep tissues,
associated with loss of sensitivity to pain and peripheral vascular disease of
varying severity in the lower extremities. Foot ulcers in people with diabetes
are one of the main causes for possible amputation. In the presence of necrotic
tissue, as in the case of diabetic foot, treatment by debridement, removal of
necrotic tissue and bacterial load from the wound bed, is recommended to
decrease infection, pain, odor, and wound complications acute or chronic.
This chapter proposes the development of nanosystems loaded with antimi-
crobial drug incorporated in personalized dressings in the 3D bioprinter for
diabetic feet.

Keywords
3D bioprinter · Diabetic feet · Nanoparticles · Dressing · Antimicrobial

Introduction

In 1986 Chuck Hull invented the stereolithography apparatus (SLA). This three-
dimensional (3D) printing technique refers to a method of printing objects layer by
layer using a process in which lasers cause the chains of molecules to unite, forming
polymers [1]. Advances in technology have allowed 3D printing to use biocompat-
ible materials (3D bioprinting). Many advances were made through this technique,
and in 2003 Tom Boland of Clemson University received the first patent for a
bioprinting technique, which was based on inkjet technology [2]. The 3D technology
started to become very relevant since this decade because it is capable of using a
myriad of biocompatible compounds, natural polymers, and biotints such as
hydrogels as raw material and the growing demand for alternative manufacturing
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 527

approaches. One of the major applications expected in the future is the development
of scaffolds, tissues, and organs because of their complexity that cannot be covered
by conventional techniques.
The global size of the 3D printing market was valued at U$651 million dollar in
2019 with a forecast of U$ 1.6 million dollar for 2024. The expansion of the market
can be attributed to the potential use in biomedicine by development of high-
precision and sophisticated 3D equipment [3].

3D Printing Technology

The 3D printing technique is based on additive manufacturing which consists of layer

over layer of materials on an established surface. This procedure has enabled the
fabrication of a wide range of structurally complex reproducible structures and scaf-
folds from computerized three-dimensional model data. Additive manufacturing can
make different and many parts of various sizes from microscale to large one.
However, the precision of printed parts depends on the precision of the equipment,
method used, and the scale of printing [4]. Recently, the microfabrication of 3D
microstructures using different methods and materials has been rapidly improved. 3D
microcomponent manufacturing technology plays an important role in the develop-
ment of highly functional applications, especially in the field of biomedicine. Among
the feasible alternatives, the additive manufacturing process based on layer-by-layer
manufacturing is considered an effective way to achieve true 3D microproducts in
many devices. 3D additive micromanufacturing can be divided into three categories,
including scalable technologies, additive manufacturing that can be used in macro-
and microscale, and 3D direct writing techniques that have been developed directly
for microscale and hybrid processes [5]. Within these categories different techniques
were classified (Table 1). However, the present review is focused on four currently
applicable to 3D bioprinting. These are stereolithography; extrusion-based, laser-
assisted bioprinting; inkjet bioprinting; and nanobioprinting.

Table 1 3D additive micromanufacturing categories and methods

Categories
Methods Scalable technologies 3D direct writing techniques Hybrid processes
Stereolithography Laser chemical vapor deposition Shape deposition
modeling
Selective laser Focused ion beam Electrochemical
sintering fabrication
3D printing Aerosol jet process, laser-induced
forward transfer
Inkjet printing
processes
Fused deposition
modeling
Laminated object
manufacturing
528 G. Tejada Jacob et al.

The stereolithography (SL) process is the first commercial additive manufactur-

ing process developed by 3D Systems Inc. in 1986 (California, United State). The
process is based on layer-by-layer polymerization using ultraviolet light and photo-
sensitive resin [5]. In this SL manufacturing process, ultraviolet light is irradiated
onto the surface of the photosensitive resin in an exact three-dimensional model,
which was previously defined by designed software. Free radicals and other reactive
species are formed by ultraviolet light that excites the photoinitiator molecules,
causing the resin to polymerize and form a consistent phase of the material. SL
allows the manufacture of complex scaffolds with physiologically relevant micro-
structures. Scaffolds with defined porosity, pore size and distribution, interconnec-
tivity, and gradient have been manufactured using stereolithography [6]. The
improvement of the resin in terms of biocompatibility and biodegradation and
encapsulation of cells during processing have made stereolithography a promising
bioprinting technology in the future [7]. The difficulty of this technique is the
production of free radicals. When they are produced excessively, this causes the
phenomenon called oxidative stress. This will severely alter the cell membranes and
other macromolecular structures found in the resin [8]. Another technique is extru-
sion based which appeared in the early 2000 and is the most common and accessible
bioprinting technique. Extrusion-based printers disperse the biotin through a pneu-
matic or mechanical system [9]. One of the most important factors in the 3D
bioprinting process is the rheological behavior of the bio-ink. The bio-ink is gener-
ally made of diverse polymers and components in a sol-gel structure able to be
extruded from a syringe. During the matrix deposition, the constructs can gellify by
physical or chemical methods in a layer-by-layer procedure. One of main limitation
of this technique is the slower deposition of material because of a compromise
between the bio-ink transition from sol to gel and the speed of the extrusion. The
fusion of the layers results in controlled pore size, morphology, and interconnectiv-
ity. The main characteristic of this technique is the control of the apparent viscosity
of bio-ink since it must be low enough to be extruded and mechanically strong
filament to resists deposition of the top layer. However, there is a compromise
between filament speed deposition and environmental conditions to keep the cell
alive and physiologically active and in the case of molecules to avoid denaturation
and/or redox stress. Also, an advantage of this procedure is not necessary to
compress or change the form of the matrix evaluation for further use [10]. Viscosity
is one of the key parameters of bio-ink formulations because it affects printability
and fidelity and cell and/or molecular encapsulation efficiency. High viscosity poly-
mer solutions are not easy to flow, but the structure after printing can hold its shape
for a long time. However, request higher pressure to flow, limiting the gauge size and
the smallest print size that can be achieved (the resolution is in a similar range,
between 150μm and 600μm) [11]. These materials, thought of as biotints, will make
it possible to manufacture complex structures with high resolution, and the final
mechanical properties of the printed structure should also be sufficient to handle and
transport to the next stage [12].
The third method is laser assisted bioprinting. This technique allows high resolu-
tion deposition of materials in solid or liquid phases. Laser-based bioprinting uses a
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 529

pulsed laser source, a laser focusing tool, a laser absorbing metal tape film, and a
receptor substrate [13]. The transparent glass-like laser plate is covered with a metal
film, and the liquid biological material is deposited on the surface of the film. Under
the action of the focused laser, the film evaporates, forming a jet of liquid, which is
deposited on the substrate in the form of drops. Laser-assisted bioprinting resolution
is affected by many factors, including laser wavelength and flux (energy transferred
per unit area), taut surface, substrate wettability, air gap between tape and substrate,
and thickness and viscosity of biolayer [14].
For the last, inkjet bioprinting was the first bioprinting technology and is like
conventional 2D inkjet printing. An encapsulated hydrogel prepolymer solution is
stored in the cartridge; also 3D inkjet printing provides advantages such as the
potential to selectively form powder parts of any material that agglomerates through
a binder formulation, high scalability, and cost effectiveness. One technique is based
on the fact that the head of the thermal printhead employs a heating element that
locally raises the temperature, decreases the viscosity of the fluid, and creates a
bubble that drives the droplets through the nozzle. A piezoelectric head is used with
a material that changes shape with the application of voltage and expels the droplets
[15]. However, the main limitation of this technique is the temperature associated
with changes in the viscosity of the bubbles that can denature molecules in the
interface liquid-air or liquid-liquid, and also the shear stress must be considered in
the case of cells.
Another technique is based on the requirements of more friendly technologies for
cell and molecules without heating, where all components were placed in the
cartridge and are able to produce the transition from sol to gel at controlled rate
and established deposition speed from the nozzle.
The basic requirement of this process is its ability to deliver scaffolding materials,
cells, diverse types of molecules including drugs and growth factors, nutrients, and
other chemicals simultaneously. This technology can be applied for the development
of complex biological structures such as the living extracellular matrix or scaffold to
grow in vitro or in vivo because the components can be deposited at the right time, in
the right place, in the right amount, and in the right environment. This type of
bioprinting due to its high performance, low cost, reproducibility, and ease of use has
always been the center of attention. Particularly for the potential in cell printing,
inkjet printing has become an efficient method for delivering multiple cell types in
specific regions of the gel structure, making it very useful to dispense diverse type of
molecules and/or materials, including cells [16].
The choice of 3D bioprinting technology will depend on the size of the scaffold
structure, biomaterials, biomolecules, and the required print resolution (Fig. 1).

Materials

The 3D bioprinting process can be divided into four stages. First, an exhaustive
collection of data of 3D models can be drawn and/or obtained by means of x-rays,
computed tomography, and magnetic resonance, among others for scanning and
530 G. Tejada Jacob et al.

Fig. 1 3D bioprinting techniques

reconstruction, or directly using assisted design software. The 3D model will be

divided into 2D horizontal sectors by a specific software [17]. The obtained images
are converted into stereolithography files with a specific program. The files provide
the 3D representation of the image, and the information is prototyped by the 3D
bioprinter. The files must be processed using a slicer software (such as Cura and
Slic3r), which converts the model into layers and generates G-code files. According
to these G-code instructions, various commercially available printers place specific
volumes of required materials on successive 2D horizontal layers. There are a variety
of 3D modeling software available, free and open source software. 3D Slicer, OsiriX
(macOS application, dedicated to DICOM images), InVesalius, and FSL are used to
process computed tomography and magnetic resonance data, whereas MeshLab,
Blender, Creo, HyperMesh, SolidWorks, CATIA, and DAZ Studio are used for
design and 3D rendering [18]. This data will be processed into particles or filaments
according to different printing methods.
Second, the material selection. Materials including monomers, polymers, therapeu-
tic molecules (i.e., growth factors, proteins, drugs, etc.), cells, etc. The printable
material must be carefully selected according to the requirements of the structure,
the bioprinting method, and the application. The combination of biomaterials is called
a bio-ink and could be used to develop biodegradable devices in many cases used in
therapeutic applications and also for biotechnological application such as cell-loaded
hydrogels. Choosing proper bio-ink is crucial to ensure biocompatibility, printability,
and mechanical properties, which will be discussed in the last part of this review.
Third, the printing parameters in the 3D bioprinter must be configured correctly. Also,
in the course of bioprinting, the dynamic character of the printed device could cause
problems such as printing speed, amount of biomaterial, and biophysical parameters.
However, through the software, it is possible to make adjustments during the printing
process. Finally, the 3D structures obtained can be functionalized. The objective is to
determine the pores dispersed in the hydrogel through physical and chemical interac-
tions in order to create some natural structures able to develop in the future functions of
tissues. Today, it is clear that it is not completely realistic to perform 3D bioprinting of
fully functional organs for transplantation. However, it is a fact that it cannot be denied
that 3D bioprinting techniques have evolved considerably, and in the future these
bioprints will be within reach in biomedicine [19].
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 531

As it was mentioned before, the use of this technology involves the use of biotint
(bio-ink). The choice in biomedicine is of utmost importance since this selection
should satisfy certain material and biological requirements. The properties of the
material are mainly printability, mechanical stability, and chemical and biological
degradability. Also, for biological purposes include functionalization; biological
requirements mainly include biocompatibility, cytocompatibility, and bioactivity
[20]. Bio-inks are an essential part of bioprinting and are usually composed of
biomaterials such as hydrogels, cellular aggregates, or combinations of them. In
addition, hydrogels can be used in combination with therapeutic molecules (i.e.,
antibiotics, growth factors, prodrugs, etc.) and/or biologically active molecules (i.e.,
enzymes, antibodies, etc.). Also, the advantage of printing 3D structures at room
temperature is the lack significant effect on cell viability and predictable mechanical
reliability [21]. Due to recent advances, hydrogel based systems have become prime
candidates for many applications, as molecular or drug delivery vehicles. In 3D
bioprinting technology, hydrogels are formed by cross-linking of monomers and/or
polymer chains in aqueous media through various mechanisms (physical entangle-
ments and chemical cross-linking) (Fig. 2) [22]. Hydrogels are advantageous due to
their chemical similarity to the extracellular matrix, flexibility, rapid diffusion of
nutrients and hydrophilic metabolites, and their low dry mass content and generally
can cause reduced irritation and toxicity and a much lower level of cargo
inactivation.
When these hydrogels are mixed with cells, they can be used as encapsulating
agents to protect cells from direct damage and to provide a microenvironment for
survival and reproduction [23]. Natural hydrogels such as agarose, alginate,
chitosan, collagen, gelatin, fibrin, and hyaluronic acid (being of high molecular
weight, have high viscosity and low solubility) are used, as well as synthetic
hydrogels such as pluronic (poloxamer), polyethylene glycol, or mixtures of both.
The table below (Table 2) shows some of the types of hydrogels and their respective
applications in the field of biomedicine.
Natural hydrogels offer inherent bioactivity. However, up today, only few poly-
mers were approved by Food and Drug Administration (FDA, US) and/or by the
EMA (European Medicinal Agency, EU) for biomedical use. Compared to natural
hydrogels, synthetic hydrogels generally provide adjustable mechanical properties
but sometimes with undesirable side effects (e.g., secondary toxicity of monomers,
radical products and contaminants, etc.) [20]. Natural polymers such as gelatin and
hyaluronic acid have skeletal side chains that can be functionalized, allowing them to
interact with chemical moieties to induce crosslinking (chemical crosslinking and/or
photocrosslinking) or other biological activities [28]. In experimental research,
hydrogels are the most widely used biopolymers for cell loading because they can
be easily formulated by extrusion and/or laser-based bioprinting technologies.
Cell loaded hydrogel bio-ink formulations also use a mix of synthetic polymers
and hydrogels. However, to our best knowledge, all working 3D cell printing is still
in it’s infancy and only studied at laboratory scale. Also, 3D cell printing was
non validated by any regulatory agency (e.g., EMA, FDA) to be employed in
biomedicine and/or therapeutic purposes in humans. Blends of natural and synthetic
 532

Fig. 2 Characteristics of hydrogel

G. Tejada Jacob et al.
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 533

Table 2 Hydrogel type with its biomedical application

Hydrogel Application Reference
Alginate 3D bioprinting of articular cartilage and fibrocartilage. Cartilage [24]
tissue
Chitosan Chitosan hydrogel incorporated into a poly(ε-caprolactone) [25]
scaffold for osteogenics. Bone tissue
Collagen Collagen scaffolds as substitutes for bone or cartilage. Cartilage [26]
tissue
Gelatin Alginate/gelatin hydrogel formulations to fabricate living [27]
heterogeneous aortic valve conduits. Vascular tissue
Hyaluronic Hyaluronic acid derivatives are used as scaffold materials for bone [28]
acid and skin tissue regeneration, for treating vascular diseases
Poloxamer Pluronic 127 combined with other polymers (gelatin methacrylate) [29]
to form a hydrogel similar to the vascularization structure.
Vascular tissue
Polyethylene Polyethylene glycol hydrogel with mesenchymal cells to promote [30]
glycol bone and cartilage formation. Cartilage and bone tissue

Table 3 Advantage and disadvantage of different types of hydrogels

Advantage Disadvantage Reference
Natural Biocompatible Poor mechanical properties [32]
hydrogels Biodegradable Generally not used alone
Inherent bioactivity
Synthetic Adjustable mechanical Low cell proliferation [22]
hydrogels properties
Can be easily manipulated Cell viability depends on
by chemical modification photocrosslinking time, light
techniques intensity, and photoinitiator

polymers have been used to develop mechanically adjustable hydrogels with defined
biological activities. They provide novel strategies, including multi-material print-
ing, thinning functions, and sequential crosslinking with self-supporting structures.
For in vivo applications, biocompatibility increases the requirement that the material
can be degradable and able to interact or fuse within the extracellular matrix without
producing harmful byproducts or negative interaction with cell membrane [31].
The following table (Table 3) shows some advantages and disadvantages of the
properties of natural and synthetic hydrogels.
The main characteristics of the material are printability, mechanical properties,
degradability, and functionality. The biological requirements, when working with
cell-laden hydrogels, mainly include biocompatibility, cell compatibility, and bio-
logical activity [20]. The biocompatibility of biomaterials is the most important
prerequisite for use as a scaffold. Biomaterials have to be interacting within cells by
binding, allowing migration and other basic and fundamental cell functions. Com-
pounds involved in crosslinking hydrogels should not affect cell viability [33].
A very effective method of evaluating biocompatibility is live/dead staining,
which is generally used after 24 h to determine the cellular compatibility of the
534 G. Tejada Jacob et al.

hydrogel and the crosslinking process used with cells. A microplate reader is then
used to measure the fluorescence intensity to determine the percentage of viable cells
and to quantify the results [34].
The purpose of biocompatibility is the need for an implant material that can
coexist with endogenous tissue without causing any undesirable local or systemic
side effects on the host, and also the implanted material produces the desired
responses on the local host tissue [14].
Mechanical properties are also a key factor in the bioprinting process. Force is
the pressure required by the material to start flow. In bioprinting, this affects the
minimum required tension applied to the material before pushing the plunger.
This feature is important because the stress applied to the gel will in turn affect
the shear stress caused in the cell during printing. Soft polymers form brittle
networks when at rest. When a cutting force above the elastic limit is applied,
this network will break. When the cutting force separates, it slowly forms again.
This stress causes a delayed flow and the collapse of the gel structure. Perfor-
mance pressure also helps keep cells in the hydrogel reservoir even. Related
factors including pore connectivity, orientation, shape, size, and volume affect
the mechanical properties and structural integrity of the scaffold [23]. The
mechanical properties are also important factors for the polymers, in the cases
of regeneration of the hard tissue that depends on it. Because the scaffold needs
to withstand loads and pressures to successfully grow new fabrics, the rheolog-
ical properties of the polymer (stretch, elastic, and deformation), this measure-
ment is of great importance [35].
The amount of water in the hydrogel determines in part the velocity and diffusion
of solutes in the material. Water can bind to the gel and two major interactions can be
defined. First, the polar hydrophilic groups hydrate and the polymer network swells.
Second, the hydrophobic groups of the gel are exposed, and the water molecules
form cages, which through octagonal structures encapsulate hydrophobic waste
[36]. In hydrophilic polymers, there are many layers of water molecules interacting
with polar residues, and the continuous exchange between those water molecules is
related to the binding groups of the polymer or molecule and also to the environ-
mental physicochemical conditions.
Excess water is absorbed as free water, which fills the space, like the space formed
between the large holes and the chains. The water content on the hydrogel can be
easily determined by measuring the change in the percentage of mass between the
hydrogel and its dry form.
Another point to consider in bioprinting is the surface area. A larger and more
accessible surface area makes it easier to attach cells and tissues to the scaffold. This
is essential to restore or replace tissue or organ function, because the high surface-to-
volume ratio helps accommodate more cells [23].
It is of extreme importance when developing a product, choosing the most
appropriate technique for bioprinting, and it is also crucial to choose bio-ink forming
materials, taking into account all the aforementioned characteristics.
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 535

Applications

The 3D printing technology has demonstrated its potential in regenerative medicine,

tissue engineering, organ manufacturing, disease research, and drug delivery [37].
Tissue engineering has become a promising solution to meet the unmet needs of
tissues and organs in regenerative medicine and pharmaceutical research. Tissue
engineering uses a combination of cells, biomaterials, and bioengineering techniques
to create biological constructs that can mimic and/or enhance their corresponding
human physiological functions and activities. 3D bioprinting is considered to have
unprecedented versatility and the ability to manage cells and biological materials
through the precise control that this technology brings. As a result, it is possible to
recreate engineering constructions with precise, detailed, and even custom features
that can mimic shapes, structures, and architectures, thereby mimicking the function
of attacking tissues and organs [38].
The implanted 3D-printed tissue is expected to eventually fuse with other tissues
in the body. Therefore, the hydrogel scaffold must be degradable in vivo and/or
integrate into the extracellular matrix within the environment. In addition, the
3D-printed hydrogels must have natural and controllable degradation rate similar
to the rate of matrix growth [14]. Looking for potential applications of 3D
bioprinting in the future, the possibility of tissue replacement is one of the most
exciting prospects on the horizon [20].
The skin surface constitutes the largest sensory organ in the human body, with an
area of approximately 1.7 square meters in adults. Due to its structure, it is consid-
ered a barrier between the external environment and the interior of the human being,
which leads to being an efficient means to prevent external damage (chemical,
mechanical, and thermal injuries, radiation, or pathogens) [39]. Tissue engineering
is expected to have a high potential in the production of new skin. In this case,
creating precise and complex new tissues containing various cell types arranged in a
specific 3D mode remains a challenge. If the skin is superficially damaged, it will
usually heal on its own without causing further complications, whereas under certain
circumstances, the skin cannot regenerate, particularly when there are large or deep
burn injuries. Both direct heat (fire), irradiation, and friction can also cause burns
[40]. Split thickness autogenous skin grafts are generally used to cover wounds, but
donor sites are rare in large burns, and many scars are inevitably formed. Besides, the
topology of the wound is an additional problem in severe cases of burn and tissue
ablation.
This leads to a decrease in aesthetics and functionality. In the presence of deep
wounds, dermal substitutes are used, but insufficient vascularization can lead to
rejection of the implant, adding that these substitutes do not have hair follicles,
melanocytes, and sebaceous and sweat glands, depriving them of functions of
temperature regulation and aesthetic attractiveness. In this case, skin substitutes
that are as similar to the physiological skin as possible should be used to completely
replace the lost skin and surrounding tissue [40]. Of paramount importance is the 3D
536 G. Tejada Jacob et al.

organotypic structure of the skin equivalent, which mimics natural skin and guaran-
tees the natural interaction potential of different types of skin cells. 3D bioprinting
can achieve a distribution of various cell types. To print skin cells, the three most
common bioprinting techniques are extrusion printing, inkjet printing, and laser-
assisted bioprinting. As mentioned above, to begin the bioprinting process, it is
essential to have an image of the damaged skin, which can be obtained through hand
scanners or by more complex instruments such as x-rays, computed tomography, and
magnetic resonance imaging. In some cases the images taken from the skin damaged
area can be converted in a negative 3D picture, digitalized, and printed to the
respective scaffold. The resulting 3D structure is complementary of the wounded
area with perfect tridimensional fit.
Then, the selected biomaterials must meet the biocompatibility and biodegrad-
ability requirements, and natural biopolymers have the highest advantage in mim-
icking the matrix of natural tissues, but their mechanical properties are generally
poor. In contrast, synthetic biopolymers have greater mechanical properties.
Researchers have used composite polymers based on natural and synthetic biopoly-
mer and fillers of different origins in many works to combine the advantages of both
and overcome the limitations which is extremely important with 3D bioprinting. The
types of cells most used in current skin substitutes are keratinocytes, which are the
most important cell population in the skin as they provide the main contribution to
the skin’s barrier function [41]; fibroblasts coexist with keratinocytes and exist in the
dermal layer of natural skin, obviously used for skin substitutes. Vascularization is
another problem that can be solved to some extent by integrating endothelial cells to
promote angiogenesis and therapeutic molecules such as growth factors and colla-
gen, also some nanoparticles to induce immune response [42]. Bioprinting technol-
ogy can precisely deposit each cell type in its correct three-dimensional position,
helping to create the necessary microenvironment for cells to perform their func-
tions. This makes bioprinting a promising tool for tissue engineering. The ability to
accurately transfer biological materials (including cells, macromolecules, and
growth factors) to the desired three-dimensional location in tissue is the unique
function and greatest advantage of 3D bioprinting. It should be noted that all these
technologies have great potential for improvement and the skin is especially suitable
for improving bioprinting technology [40].
Continuing along this line of regenerative medicine, another current problem that
concerns attention in the biomedical world is cartilages and its wear. Cartilage is an
excellent living tissue that makes the synovial joints almost frictionless and protects
the subchondral bone from mechanical stress. Cartilage contains mainly proteogly-
cans, water, type II collagen, and small amounts of chondrocytes. Due to the small
number of cells and the absence of blood vessel formation, the capacity for tissue
regeneration is very limited. Cartilage bioprinting research has been focused pri-
marily on the use of chondrocytes by extrusion based 3D technique. When using
autologous chondrocytes, the main obstacle is to obtain enough cells which remains
a challenge, especially since expansion in monolayer culture causes cells to dedif-
ferentiate into a more fibroblastic phenotype [43]. In addition, complications such as
the incidence of donor sites can occur. Another type of cell is a pluripotent
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 537

population of mesenchymal stromal cells, which can be derived from a variety of

tissues, including bone marrow, adipose tissue, and muscle [44]. These cells can
differentiate into chondrocyte-like cells in the presence of specific growth factors,
but because these cells tend to become hypertrophic cartilage, they must provide
enough signals to control the fate of the mesenchymal stromal cells. Once implanted
in the body, it will lead to bone formation through the intrachondral route. Specif-
ically, in the amount of work on cartilage regeneration, the great potential that this
technology has in this type of injury can be seen.
Organ printing is a new concept in tissue engineering, expanding the applications
currently available. Cells inside 3D hydrogel could survive the bioprinting process
and could retain the potential for differentiation. Although the hydrogel itself is
mechanically weak, remodeling of the hydrogel and matrix formation in the body is
expected to provide the necessary mechanical strength in the newly formed tissue
[45]. However, the mechanisms of cell behavior, interactions, and differentiation are
extremely complex in mammals. The interaction between cells and 3D biomatrix to
develop an organ must require extensive multidisciplinary and complex studies
before use in implants.
Another field of application in tissue engineering and not the least is the
bioprinting of organs. Currently, the technologies developed and implemented for
the purpose of digitally printing human organs are microextrusion-based, inkjet-
based, and laser-based bioprinting. Many manufacturing challenges (e.g., increasing
resolution, increasing scalability, and expanding the manufacturing process window)
can be expected to directly conflict with biological challenges (e.g., feasibility cell
viability and functionality after bioprinting). Although cell differentiation, tridimen-
sional cell organization and structure associated with the integration of vascular
networks in organs are major obstacles to tissue engineering, these complex chal-
lenges have been proposed by many research groups around the world [46].
One of the most important events in recent years was, in 2019, when Noor et al.
have developed and printed the world’s first 3D vascularized engineered patch heart
using the patient’s own cells and biological materials. The adipose tissue has been
removed from the patient, and the cellular materials have been processed to form
various personalized biological connections. These biological connections that orig-
inated in the same patient have resulted in the designed patch not inducing an
immune response after transplantation. This opens the window for possible organ
replacement methods or drug testing in an appropriate anatomy [47].
Compared to traditional tissue engineering strategies, one of the main advantages
of bioprinting is its ability to affect stem cell differentiation at multiple stages of the
process. The choice of the stem cell source, the bioprinting method, the choice of
scaffolding, additives, and the specific mechanical force applied over the cells will
affect the differentiation of the stem cells into specific target tissues. Other benefits of
using own stem cells in bioprinting include their ability to induce immune tolerance
and expand once incorporated into tissue. Although each 3D bioprinting technology
exhibits specific attributes such as high resolution, low price, high security, and high
performance, it is clear that to implement more advanced applications in tissue
engineering, these processes must be combined [48].
538 G. Tejada Jacob et al.

Talking about improvements in medicine also leads us to talk about improve-

ments in the pharmaceutical industry. This technology is highly flexible and can
produce a variety of drugs with custom designs and defined release profiles, includ-
ing both slow and fast controlled release formulations and drug combinations. In this
sense, the technique to be used for the development of the vehicle for the drug is a
key parameter. In this way, for hydrophilic 3D matrices, water can easily penetrate
the entire formulation base; rapidly dispersing devices can be formulated [49]. 3D
bioprinting also shows the advantages of producing solid dispersions of amorphous
drugs within the pharmaceutical dosage form, which is particularly beneficial in
improving drug release from poorly soluble compounds, more of 70% of drug
market.
As previously mentioned, many challenges face 3D bioprinting in the biomedical
field such as repair of 3D anatomical defects, the reconstruction of complex organs
with complex 3D microstructures (e.g., liver, lymphoid organs), and scaffolds for
stem cell differentiation [50].
It is worth noting the importance of the applications that this technology has and
the extension of scientific works that exist in the world. This demonstrates the
magnitude of this technology and the future great advances of it. Finally, the ultimate
goal is not simply to design biomimetic properties but to choose and develop proper
bio-ink to be used in tissue generation that can withstand physiological loads and can
adapt to changing conditions and be able to repair themselves when injured.
In the last decades, 3D bioprinting in the field of nanomedicine has had great
relevance and great advances.

Nanotechnology and Nanomedicine

As mentioned above, many of the products developed through 3D bioprinting have

nanometric sizes, and this relationship between 3D bioprinting and nanotechnology
has taken a lot of attraction in the scientific community and even in companies.
Bioprinted three-dimensional nanomaterials have unique structural and functional
properties that can be adjusted to meet the mechanical, physiological, and therapeu-
tic needs. Therefore, it is hoped that the scaffold system used to develop drug
delivery devices and cultivate human cell lines or stem cells in tissue engineering
can control volume by improving the volume, morphology, and phase arrangement
of the material [21]. In 2004, the European Science Foundation proposed the
following definition of nanomedicine: “The field of nanomedicine is the science
and technology of diagnosing, treating and preventing disease and traumatic injury,
of relieving pain, and of preserving and improving human health, using molecular
tools and molecular knowledge of the human body” [51]. Now, talking about
nanomedicine leads us, first of all, to define nanotechnology concepts. Nanotech-
nology from physics approach is the study of things at the nanoscale, dedicated to the
study of a world so small, we can’t see it even with a light microscope, which is
about 1 to 100 nanometers (nm) in where quantum mechanics govern the interaction
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 539

between atom and molecules [52]. In nanoscale, the materials have unique charac-
teristics, which are not present in bulk.
Several factors make the properties of nanomaterials specifically different from
other materials such as chemical composition, electronic structure, relative surface
area, topology, morphology, hydrophatic profile, solubility and surface area/rough-
ness, impurities/atomic adsorptivity of surface species, history, reactive oxygen
species (ROS) O2/H2O, ability to produce ROS, structure/composition, competitive
receptor binding sites, and dispersion/aggregation which are important properties of
nanoparticles [53].

Nanomaterials

Due to the growing need to control the required molecules that exist in the human
body and the environment, nanomaterials have aroused great interest. Nanomaterials
are developing rapidly because of their potential applications in the fields of nano-
electronics, catalysis, magnetic data storage, structural components, biomaterials,
biosensors, and medicine. The engineered nanomaterials provide nanoscale size and
are compatible with biological molecules. Nanostructured materials show increased
surface to volume ratio, chemical activity, mechanical strength, electrocatalytic
properties, and enhanced diffusivity. Nanomaterials have been predicted to play an
important role toward the high performance of a biosensor [54].

Application

Nanotechnology research and development are very active globally (the world
market for nanotechnology was valued at U$ 1 billion in 2018, and by 2025 it will
reach U$ 2 billion dollar) [55].
Nanoscale technology currently has many applications in various fields, and
many scientific works and advances have been reported. In recent years, this
technology has had great advances in different areas and is used in hundreds of
products, including agriculture, cosmetics, food industry, energy, and environ-
mental remediation, among all. Nanotechnology is also being developed for its
use in the administration of medications and other biomedical applications
[56]. Nanoscale systems have been developed and studied, such as quantum
dots, metallic nanoparticles, carbon nanotubes, gold nanowires, polymeric nano-
particles, and liposomes, which will be analyzed in the following section of
applications [57]
Nanomedicine has allowed the use of nanomaterials for the diagnosis, monitor-
ing, control, prevention, and treatment of diseases. Nanomaterials tend to adsorb
biomolecules, for example, proteins and lipids, among others, when they come into
contact with biological fluids [58].
There are several nanoparticles used in molecular diagnostics: gold nanoparticles,
quantum dots, and magnetic nanoparticles among the most widely used [59]. Any of
540 G. Tejada Jacob et al.

these nanostructured systems is useful in diagnosing a disease. Early cancer diag-

nosis can effectively treat primary tumors through local therapeutic interventions.
Early detection is highly dependent on blood biomarkers. Protease activity is
associated with a variety of noncommunicable human diseases, including cancer,
inflammation, and thrombosis. Quantum dots are suitable for immunolabeling, cell
motility assays, in situ hybridization, and as live cell markers. They have an
additional feature that they can emit in the infrared and near-infrared regions,
allowing them to be used in diagnostic imaging applications and in deep cells within
tissues, since tissue absorption is minimal in this region [57].
The application of magnetic nanoparticles in health is an increasingly common
practice that is being implemented for various purposes. In particular, its use as a
target drug delivery device in tumor therapy or for hyperthermia has been widely
explored in recent decades. Hyperthermia is a good technique for treating cancer, in
which a magnetic field is used to raise the temperature of living cells above a
physiological level [60].
Biopolymer-based nanotechnology is a new strategy for diagnosing and treating
local diseases and infections. There is a wide range of applications for nanotechnol-
ogy in the field of drug delivery because this technology has improved the delivery
of drugs to areas that were not favorable to macromolecules, where it is targeted to
specific, target-oriented sites. There is a wide range of nanoparticle systems such as
carbon nanotubes, metallic nanoparticles, polymeric nanoparticles, and lipid nano-
particles, among others [57]. The development of nanoparticles loaded with active
pharmaceutical ingredients for the treatment of diseases or infections could improve
the pharmacological therapy of the patient. These nanosystems must be placed in a
vehicle for the design of improved dressings [60].
The nanosystems used to control drug release consist of different biodegrad-
able materials, such as polymers, lipids, or metals. The choice of therapy for
specific delivery needs careful consideration. As a drug delivery system, nano-
particles have many advantages compared to traditional drug delivery systems.
First, pharmacological agents can target a specific area of the human body by
adding nanoreceptors to the surface that specifically recognize and bind to the
target of the tissue and release drug molecules; this in turn makes healthy tissues
unaffected due to the cytotoxic effects of the drug. Second, drugs can protect
themselves from degradation by encapsulating them with coated nanoparticles.
The nanoparticles are extremely small, capable of penetrating through smaller
capillaries to be more easily absorbed by the affected cells. Third, the use of
biodegradable nanoparticles allows the sustained release of the drug within the
target. Therefore, nanosystems with an improved drug supply and objective
specificity lead to superior performance and improved efficacy [61].
Currently, the horizon of the scientific community is ready to study, analyze,
develop, and advance nontraditional treatments for several diseases. Conventional
treatments, which involve very long time treatments, are expensive, and many times,
for different reasons, their effectiveness is hampered by the patient, thus avoiding
adherence to therapeutic treatment.
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 541

Combination of Technologies

We have already developed and discussed the many applications of both technolo-
gies, and it led us to find many points in common. Now it remains to analyze
technological developments between 3D bioprinting and nanotechnology.
Bioprinted three-dimensional scaffolds made from nanomaterials play a vital role
in accommodating cells and guiding them to differentiate into specific tissues during
regeneration. Nanotechnology provides an opportunity to regulate the structural and
functional properties of the natural cellular microenvironment within the bioprinted
3D scaffold to enhance cell growth and function [21].
Bioprinted three-dimensional nanomaterials have unique structural and func-
tional properties that can be adjusted to meet the mechanical and physiological
needs of host tissues, which is why the scaffold system used to cultivate human
cell lines or stem cells in engineering is expected improve volume and morphology
of tissues [21].
The human bone structure is a nanocomposite material, composed of collagen,
osteopontin, and a matrix of water hydrogel and inorganic components based on soft
proteins (mainly nanocrystalline hydroxyapatite), which represent 70% of the bone
matrix [62]. The incorporation of nanomaterials such as nanocrystalline hydroxyap-
atite, tricalcium phosphate, and calcium polyphosphate is the progress of research in
3D bioprinting [63]. Due to its excellent cellular compatibility, bone conductivity,
and bioactive properties, hydroxyapatite is considered a promising bone nano-
material in 3D bioprint systems. Groups of researchers have developed a 3D
hydroxyapatite hydrogel scaffold with different pore sizes through the 3D bioprinter.
The sintered tricalcium phosphate scaffold showed an increase in compressive
strength and good microporosity that managed to increase new bone formation
in vivo compared to constructions made of convection sources [64].
Continuing with tissue regeneration, we find a reality in people of different ages
and origins: damage to the nervous system. Currently, there is no effective strategy to
improve nerve regeneration, but nevertheless, this 3D technology is a promising way
for regeneration [65]. Carbon-based nanomaterials have been extensively tested in
the regeneration of nervous tissue due to their excellent properties of electrical
conductivity, mechanical resistance, and ability to chemically modify. Unfortu-
nately, it’s actually not approved in the European Union. Furthermore, nanotechnol-
ogy in tissue engineering can easily involve the manufacture of 3D nanostructured
scaffolds to enhance tissue regeneration. Today, this combination of technologies is
in preliminary stages; many jobs and positive results are lacking in order to continue
advancing in the concrete resolution of this problem.
Unconventional treatments using nanotechnology and 3D bioprinting are focused
on chronic diseases like cancer and diabetes. Cancer is the second leading cause of
death in the Americas. In 2018, around 3.8 million cases were diagnosed and
1.4 million people died from this disease. The most commonly diagnosed types of
cancer in men are prostate cancer (21.7%), lung cancer (9.5%), and colorectal cancer
(8.0%). Among women, the most common cancers are breast cancer (25.2%), lung
542 G. Tejada Jacob et al.

cancer (8.5%), and colorectal cancer (8.2%). By implementing prevention, detec-

tion, early detection, treatment, and evidence-based opportunities to improve palli-
ative care, the burden of cancer can be reduced [66]. There are numerous scientific
works that link this bioprinting technology with cancer diseases. The in vivo micro-
environmental cancer model achieved through 3D bioprinting has become an effec-
tive tool for detecting cancer drugs and tailoring treatment plans for individual
cancer patients and is an important platform for research into the biology and cancer
pathology [67].
Also, diabetes is a chronic disease that occurs when the pancreas does not make
enough insulin or when the body cannot effectively use the insulin it does make.
Diabetes is a major public health problem and, along with cancer, treats lung and
heart diseases among the top four causes of death worldwide. Diabetic foot, in
particular, is defined as infection, ulceration, and destruction of deep tissues, asso-
ciated with loss of sensitivity to pain and peripheral vascular disease of varying
severity in the lower extremities. Foot ulcers in people with diabetes are one of the
main causes of possible amputation [68]. In the presence of necrotic tissue, as in the
case of diabetic foot, treatment by debridement, removal of necrotic tissue and
bacterial load from the wound bed, is recommended to decrease infection, pain,
odor, and complications of acute wounds or chronicles.
As we mentioned previously, the advantages of nanosystems is directionality to a
specific area of the body or site of action before adding nanoreceptors to the surface;
in addition the active pharmaceutical ingredient is protected from degradation by
being encapsulated in the system. For the treatment of people with diabetes, there
were very relevant advances, such as the use of insulin-loaded chitosan nanoparticles
that have prolonged their residence in the small intestine. This insulin released from
the nanoparticles has been able to penetrate through the paracellular pathway into the
bloodstream. Likewise, the development of microspheres for insulin production has
also been reported. They protect encapsulated insulin from enzymatic degradation
within its matrix as they act as protease inhibitors [69]. In previous sections,
applications of 3D bioprinting, more specifically in skin regeneration, were
discussed. In this sense, the utility of this technology in treating ulcerated feet of
diabetic patients has taken on great importance. Chitosan scaffolds have been
developed (through the extrusion technique) to treat wounds which promote the
regeneration of a tissue with improved functionality being beneficial for the treat-
ment of chronic dermal wounds. These scaffolds have excellent properties in terms
of biocompatibility, cytocompatibility, and toxicity. These preliminary studies in rats
gave good results to be thought in the future, to develop them in human beings,
taking into account chitosan toxicity, which depends on degree of deacetylation,
molecular weight, and concentration, among some factors [70].
The new challenge is to think, design, and develop scaffolds using bio-
polymers together with the choice of the bio-ink, with all the previously
mentioned characteristics, to select a 3D bioprinting technique, and to introduce
notions of nanomedicine, to achieve sustained release nanosystems of active
pharmaceutical ingredients for the disease (cancer, diabetes, and wound
healing, among others).
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 543

Market and Marketing

Since the great boom of 3D bioprinting in the 2000s, until today, there have been a
large number of patents and developments in different parts of the world, as well as
in nanotechnology.
Currently in the global market, there are many companies dedicated to 3D
bioprinting, among which we find Organovo Holdings, Cyfuse Biomedical, TeVido
BioDevices, OxSyBio, Osteopore, nScrypt, RegenHU, EnvisionTEC, and Oxford
Performance Materials, among others. Most of these companies are linked to
research institutions and universities dedicated to organ transplantation and regen-
eration technology [3]. Some companies focus on improving printed hardware
and/or printed materials. Others have applied bioprinting strategies for high-
throughput assays, the development of commercial tissue models, or graft wound
repair products [71]. The following table (Table 4) shows some of the different
companies and their purposes, whether they are fields of application, marketing, or
development.
It should be noted that the company, Organovo Holdings, in 2004, designed and
developed the first commercial 3D bioprinter (Bioprinter Organovo Novogen MMX)
which has extrusion-based technology that uses cellular spheres as tissue building
blocks [48]. Organovo made its first breakthrough in 2010 when it received funding
from the National Institutes of Health where the company successfully printed the
blood vessels of the cells using only human primary cells [72]. In 2014, they
launched the first liver tissue model available on the market, which is a historic
achievement because it can be considered the first 3D cell-based bioprinting product
[71]. It has also managed to carry out numerous scientific publications of great
impact in biomedicine and current patents. This biopolymer is osteoconductive and
mechanically strong, exhibiting a highly textured surface while maintaining cell
proliferation capacity without depleting metabolic demands on cells. The Food and
Drug Administration approved this biomimetic polymer for clinical use in 2013,
making it one of the first 3D-printed polymer implants approved for human use
[64]. If we want to talk about companies that combine both technologies, we find
Aether Inc. (United State), which presented its first Aether 1 bioprinter in 2016.
Today, through collaboration with researchers at the University of London and
Loughborough University, Aether is developing an ink that contains nanoparticles
and can be used as a nanosurgical tool. Depending on the user’s needs, the tool can
be used to provide pharmaceuticals and bioactive products, or as a mechanical and
structural support system.

Conclusions

3D bioprinting is increasingly seen as the technology of the future. It is still in the

early stages of its development. In this chapter we have mentioned, developed, and
discussed many aspects of this technology. We have carried out a review from initial
concepts to commercial products, analyzing the different uses of this technology and
544 G. Tejada Jacob et al.

Table 4 Major companies involved in bioprinting

3D bioprinting
companies Nationality Application
Organovo United Designs and develops functional three-dimensional human
Holdings Inc States tissues
Developed the first commercially available liver tissue
model
Cyfuse Japan 3D printing method uses needles to thread these cell
Biomedical spheres, which then fuse to form tissue
3D fabric manufacturing
TeVido United Wound healing and cosmetic surgery
BioDevices States Development of personalized 3D breast implants, from a
woman’s own cells, for reconstruction after cancer
treatment
OxSyBio England 3D bioprinting manufacturing to produce functional fabrics
Precision medicine and organ repair or replacement
RegenHU Switzerland Develop and sell their own line of hardware, software,
bio-link, and biomaterial products
Osteopore Singapore Regeneration of bone cells
Biologically active designed synthetic products for the
restoration of the human skeleton
Osteoplug is a bioresorbable implant that is used to cover
trepan burr holes in neurosurgery
nScrypt United Designs and manufactures high-precision direct digital
States manufacturing and industrial micro-dispensing equipment
with precision and flexibility
Developed the world’s first commercially available
bioprinter
EnvisionTec Germany Develops, manufactures, and sells 3D printers and
proprietary materials
Oxford United Produces 3D-printed PEKK-based products in today’s
Performance States market, including patient-specific medical implants and
Materials strong, lightweight parts for space, defense, and commercial
aircraft
Manufacture specific 3D-printed polymeric implants
Development and patenting of OsteoFab cranial prostheses

relating it to nanotechnology and its different methods. Extensive bibliographic

references on these topics were handled. 3D bioprinting has great structural com-
plexity and design flexibility as it can manufacture patient-oriented modules, stents
and equipment, and tissue models, so it has great potential to become a general
medical manufacturing technology. Nanomedicine plays a vital role in drug delivery
systems and vascular imaging. The integration of 3D bioprinting in the field of
nanomedicine will constitute an improvement in medical developments, especially
in treatments such as cancer, diabetes, and wound healing. The biggest challenge is
to develop and select excellent biological linkages (meeting the above requirements)
for bioprintable structures that can be used in medicine and healthcare. We can say
23 Nanotechnology Applied to Personalized 3D Dressings for Diabetic Feet 545

that there is clear evidence that both are innovation and production technologies of
this new era in biomedicine. They are low cost technologies that use natural or
synthetic, biodegradable polymers, all friendly to the environment and human
health.

Acknowledgments The authors acknowledge the financial support of CONICET (Consejo

Nacional de Investigaciones Científicas y Técnicas de Argentina), UNMdP (Universidad Nacional
de Mar del Plata), UNLP (Universidad Nacional de La Plata), and ANPCyT (Agencia Nacional de
Promoción de la Investigación, el Desarrollo Tecnológico y la Innovación).

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Consumer Nanoproducts for Biomedical
Applications 24
Deepa Thomas, R. Reshmy, Eapen Philip, Aravind Madhavan,
Raveendran Sindhu, Parameswaran Binod, and Ashok Pandey

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
Commonly Used Nanomaterials in Biomedical Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Carbon-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Metal-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 554
Polymeric Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
Biomedical Applications of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
Drug Delivery Vehicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Wound Dressing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565
Molecular Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 566
Theranostics (A Type of Molecular Imaging) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
Biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
Global Market of Nanomedicine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570

D. Thomas · R. Reshmy · E. Philip

Post Graduate and Research Department of Chemistry, Bishop Moore College, Mavelikara, Kerala,
India
A. Madhavan
Rajiv Gandhi Center for Biotechnology, Thiruvananthapuram, India
R. Sindhu (*) · P. Binod
Microbial Processes and Technology Division, CSIR-National Institute for Interdisciplinary,
Science and Technology (CSIR-NIIST), Thiruvananthapuram, Kerala, India
A. Pandey
Centre for Innovation and Translational Research, CSIR- Indian Institute for Toxicology Research
(CSIR-IITR), Lucknow, India

© Springer Nature Singapore Pte Ltd. 2022 549

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_47
550 D. Thomas et al.

Abstract
Nano-based consumer products are considered as major innovation in the twenty-
first century. The most profound impact of nanoparticles has been found in
biomedical field such as targeted therapy, biomedical imaging, bimolecular
sensing, and tissue engineering. The peculiar magnetic, electronic, and optical
properties of nanomaterial made it an attractive candidate for a number of
biomedical applications. Biomedical application of nanotechnology intends to
upgrade lifestyles and results in better medical treatments, especially for diseases
for which existing therapies have nasty side effects or diseases that do not
currently have any therapies.

Keywords
Nanoparticles · Nanotechnology · Biomedical · Applications · Targeted therapy

Introduction

Nano-based consumer products reflect the twenty-first century’s technological tran-

sition, offering a significant perspective on emerging and advanced technologies
covering a wide variety of biomedical and pharmaceutical applications. This field is
continually expanding by influencing human life and developing increasing excite-
ment in the science of growth, especially biotechnology and biomedical science
[1, 2]. The integrated knowledge of nanotechnology is provided by disciplines such
as physics, chemistry, engineering, biology, health science, and materials science. It
also has vast submissions in electronics and medicine in particular. Products from
nanotechnology have become increasingly significant in various fields. Over the past
decade, major advances have been made in applying nanotechnology in several
fields such as the biomedical sciences.
The impact of the nanotechnology revolution in the biomedical field brings
significant improvements to the methods used to diagnose and treat diseases. NPs
are used in various ways for the imaging, for both medical purposes and a greater
understanding of in vitro and in vivo metabolic processes. It is easy to alter the
thermal, mechanical, and catalytic properties by raising or lowering the surface area/
volume ratio, and these new properties allow nanomaterials to be applied in several
biological fields. For biological systems, the nano range particles may be suitable for
circulating in the tissues, cells, and blood stream. The effects of nanoparticles must
be controllable and predictable and with minimum cytotoxicity can achieve the
desired result. These criteria can be met through careful ligand shell tailoring,
allowing for stabilization, specific targeting, and biochemical species recognition.
Modification of a nanomaterial’s surface is possible in various ways, which can
produce materials with unique biological functionalities and properties for a specific
application and with improved solubility under physiological conditions. Moreover,
to improve biocompatibility, nanomaterials can be coated with polymers and
24 Consumer Nanoproducts for Biomedical Applications 551

bioactive molecules. Functionally modified NPs have special features which make
them suitable for image applications. Such capability of new-generation NPs in
managed drug delivery has transformed secure and convenient pharmacotherapy for
complex diseases. NPs for theranostic applications are fitted with dual ability for
diagnosis of illness and care. Drug delivery systems are a key strategy for improving
the effectiveness of the pharmacokinetics and biodistribution of pharmaceuticals.
Designed NPs were also used to enhance different vaccine distribution and
performance.
Moreover, nanomaterials are better equipped for use as drug delivery systems,
biomedical imaging devices, and tissue engineering materials and for biomolecular
sensing. Nanotechnology implementation in medical and pharmaceutical fields boosts
the disease diagnosis and treatment. By harmonizing their nature, it is possible to take
advantage of such benefits as biocompatibility and biofunctionality and make nano-
materials ideal for a variety of therapeutic and diagnostic applications.

Commonly Used Nanomaterials in Biomedical Field

Nanoscale material properties are different compared to bulk materials. Latest

advances in nanomaterials and nanotechnology can make engineering processes
more effective by lowering energy consumption and atmospheric emissions. Recent
progress in the scientific world on this subject has stimulated pharmaceutical
research activities. Nanoparticles based on carbon, metal-based nanoparticles, poly-
mer nanoparticles, solid lipid nanoparticles, and liposomes (Fig. 1) include some
nanomaterials intended for medicinal applications. Nanomaterials applications in
medical field include therapeutic and diagnostic processes for a variety of ailments
affecting various organs. Nanodimension drug delivery tools can have a huge effect
on drug production and treatment. Nanosized probes can be used to track and deliver
medicines and provide immediate feedback on the drug therapeutic efficacy.

Carbon-Based Nanoparticles

Carbon-based nanomaterials include fullerenes, graphene, nanodiamonds (ND),

carbon nanotubes (CNTs), carbon-based quantum dots (CQD), and mesoporous

Fig. 1 Common nanoparticles used for biomedical applications

552 D. Thomas et al.

carbon nanoparticles (MCNs). These carbon-based nanoparticles have promising

applications in biomedical area.

Fullerenes
Fullerenes are zero-dimensional carbon-based nanoparticles. The most studied ful-
lerene is buckminsterfullerene with a polygonal structure of 60 carbon atoms and is a
truncated icosahedron of 20 hexagons and 12 pentagons, which resembles football.
Fullerenes are characterized by the presence of large amount of free bonds which can
be utilized for tissue binding. A C60 fullerene molecule has a diameter of around
1 nm. The ability to penetrate the cell membrane, to cross the blood-brain barrier, and
to optimize the ion transport leads to the development of fullerene-based immuno-
modulators, vaccine carriers, and tissue scaffolds. Moreover, its nanodimension,
switchable structural modifications, and uniform dispersion make it suitable for
bioimaging and diagnostic applications. The neuron apoptosis inhibition property
of fullerene can be used to produce drugs in the treatment of various neurodegen-
erative disorders [3].
However, in fact fullerene is hydrophobic, and its low water solubility restricts its
biomedical applications. Research has shown that the methods to enhance its
aqueous solubility are fullerene amination, carboxylation, and hydroxylation.
Research has shown that fullerene amination, carboxylation, and hydroxylation are
the strategies to improve its aqueous solubility. Such chemically modified fullerenes
possess antibacterial, antioxidant, and photodynamic properties. Additionally,
greater biocompatibility may be achieved through these covalent reactions [4].

Graphene
Graphenes are two-dimensional layered materials structured in a hexagonal pattern
in which sp2 hybridized carbon atoms are packed in nanodimensional honeycomb
lattice. The grapheme’s unique structure and unusual optical, electrochemical, and
physical properties make it ideal for biomedical uses. Moreover its super-
paramagnetism; mechanical, thermal, and chemical characteristics; and superior
biocompatibility and conductivity are being especially benefitted in biosensing and
bioimaging applications. Furthermore, functionalized graphenes including graphene
oxide (GO), graphene quantum dots (GQD), and reduced graphene oxide (rGO)
were also useful in biomedical and bioimaging fields. It is because of their incredibly
wide surface area and ability to interact with specific molecular forms. The use of
graphene-based nanomaterials coupled with magnetic nanoparticles brings signifi-
cant opportunities in current biomedical science [5].

Nanodiamonds (ND)
ND have three-dimensional core-shell structure in which core has sp3 hybridized
diamond crystalline structure, while the surface shell consists of sp2 hybridized
graphitic structure. ND has a particle diameter ranging between 2 and 8 nm
[6]. Owing to renowned biocompatibility, large specific surface area, minimum
cytotoxicity, high adsorption ability, and chemical inertness, NDs have gained
particular attention in biomedical and pharmaceutical sector. ND surface versatility
24 Consumer Nanoproducts for Biomedical Applications 553

is responsible for its binding capacity with a variety of biomolecules including

polymers, drugs, proteins, and genes. This makes ND suitable as polymer composite
dental resin, gene carrier, photo-acoustic imaging agents, fluorescence marker, and
drug reservoir [7]. Laser-irradiated ND with a nitrogen vacancy color center is
considered to possess magnetism and fluorescence properties, making it useful for
nano-level biolabeling and bioimaging applications [8]. The ND’s energy-absorbing
ability makes it suitable for photo-sensitive drugs as a shielding agent. ND and
oxidized ND have shown antibacterial activity against Gram-negative and Gram-
positive bacteria, which may be important in preservatives and can boost pharma-
ceutical shelf life. To promote rapid wound healing and skin repair, ND-based
wound dressing has been used. Large surface area and improved mechanical prop-
erties of ND are suitable for implanted devices [9].

Carbon Quantum Dots

Carbon-based quantum dots (CQDs) are a newly developed group of carbon nano-
particles that have gained considerable attention because of their incomparable and
unique characteristics as new rivals to traditional quantum semiconductor dots. They
are zero-dimensional carbon-based nanomaterial. They possess excellent biocom-
patibility, low toxicity, and significant conductivity. They also have adjustable
fluorescence emissions properties, exceptional water solubility, and simple synthesis
procedure. Surface functional groups (such as carboxyl) of CQD play a key role in
the stability of CQDs, biocompatibility, and water solubility along with its surface
functionalization. High water solubility of CQDs makes it suitable for biological
applications. CQDs are considered the most suitable candidates for drug delivery
systems and as catalyst carriers because of attractive physiochemical specifications,
i.e., large surface area and outstanding flow efficiency. Enhancing drug selectivity
can be achieved by surface modification which boosts therapeutic drug selectivity
against cancer cells. In addition, their ability to be used as an electron donor and
receiver enabled themselves an effective choice for components of biosensors. The
peculiar optical properties, resilient stability, and astounding biocompatibility make
it suitable for bioimaging and cancer therapy applications including photodynamic
therapy, phototherapy, and chemotherapy. CQDs are used to immobilize enzymes,
resulting in the formation of CDs enzyme conjugates, which are used in vivo to
detect hazardous chemicals. The antibiotic selectivity and specificity can be
enhanced by doping it with CQD [10].

Carbon Nanotubes (CNTs)

CNTs are cylindrical-shaped, one-dimensional materials in which sp2 hybridized
carbon atoms are arranged hexagonally. Since it has unique architectural, optoelec-
tronic, mechanical, electrical, and chemical characteristics, CNTs have promising
applications as chemical sensors, field emission products, antiviral and antibacterial
agents, and catalyst carriers. The versatile material chemistry as well as the high
aspect ratio of CNTs contributes to adequate drug delivery applications. For photo-
thermal and photodynamic therapy, CNTs have special optical properties. The
exceptional versatility along with durability under mechanical stress and
554 D. Thomas et al.

biocompatibility has made it an ideal candidate for tissue engineering applications.

CNTs are classified as single-walled carbon nanotubes (SWCNTs) and multi-walled
carbon nanotubes (MWCNTs) [11]. Because of its solid nature and the high absorp-
tion strength of the inner tube, CNTs are insoluble in most solvents; this greatly
limits the use of CNTs in biosensor applications. To overcome this problem,
functionalization of the CNT is required. Surface modification includes the immo-
bilization (covalently or noncovalently) on the skeleton of the CNTs of various
functional groups. Such surface functionalization improves their biocompatibility
along with solubility, modifies cellular interaction pathways, reduces toxicity, and
makes it ideal for biomedical applications.

Mesoporous Carbon Nanoparticles (MCNs)

Inorganic mesoporous materials have gained considerable attention in the field of
biomedicine. Because of their unique characteristics, MCNs have been widely
used among various mesoporous nanoparticles. They have both mesoporous struc-
ture and carbonaceous configuration, combining all the benefits of mesoporous
nanomaterials and carbon-based materials. They have large specific surface area,
customizable pore morphologies, high pore volume, supramolecular π-π stacking
interactions, and easy-grafted surface. Furthermore, they have excellent biocom-
patibility, high load efficiency and physicochemical stability, and good adsorption
power. These unique characteristics make it suitable for drug, protein, and gene
delivery application [12]. In addition, the combinational photothermal therapy
(PTT) and chemotherapy may be accomplished to boost the clinical and therapeu-
tic impact because of the ability of MCNs to change NIR light to heat. MCNs are
suitable for biodetection and real-time imaging after integration with fluorescent
dyes or carbon dots. MCNs are strongly hydrophobic in original form. The
hydrophobic nature restricts its biomedical applications. The methods adopted to
enhance their hydrophilicity and establish functional groups were oxidation, car-
boxylation, and subsequent amination. This may enhance therapeutic effectiveness
and minimize side effects.

Metal-Based Nanoparticles

The most common inorganic nanoparticles are metal-based NPs which possess
excellent chemical and biological stability, nontoxicity, and biocompatibility. They
also possess ample therapeutic potential as antimicrobials and antiplatelet agents.
Some are magnetic in nature, holding great saturation magnetization and high
magnetic sensitivity. Such properties have found exciting applications in various
biomedical fields including drug delivery, photo ablation therapy, hyperthermia,
biosensors, and bioimaging. Because of their excellent surface plasmon resonance
properties, they are ideal markers for the optical detection of biomolecules
[13]. Metal-based NPs can be categorized as metallic NPs, bimetallic NPs, and
metal oxide NPs.
24 Consumer Nanoproducts for Biomedical Applications 555

Metallic NPs
Noble metal nanoparticles such as gold and silver have gained considerable consid-
eration for biomedical applications. Because of its chemical inertness and excellent
biocompatibility, gold has established a solid base for its widespread use in biomed-
icine. The remarkable electronic and optical properties of gold led to their use in
biosensors, bioimaging, as well as photodynamic therapy. Gold NPs have been
widely used in numerous visualization and bioimaging methods to detect chemical
and biological agents. Wide absorption range varying from ultraviolet to near-
infrared and surface-enhanced Raman scattering effect enables comprehensive uti-
lization of gold NPs in plasmonic PTT. Since the gold NPs’ surface enables the
effective binding of different biomacromolecules through chemical conjugation,
chemisorption, and electrostatic interaction, it is possible for efficacious delivery
of genetic material to the cytoplasm and cell nucleus and can act as molecular
nanoprobes [14].
Silver NPs have special physicochemical features including chemical stability,
catalytic activity, and high electrical and thermal conductivity. It has also been found
that they display antifungal, anti-inflammatory, antiparasitic, antiviral, and anti-
bacterial activity. Silver NPs were also improving traditional antibiotic’s action.
Those properties led to silver nanoparticles being used in antimicrobial, photonic,
electronic, wound dressing disinfectant, drug delivery, and cancer therapy applica-
tions. Certain applications include enhanced surface protection for indwelling cath-
eters and other body-implanted medical devices. In addition to these properties,
AgNPs also display an antiproliferative and antiangiogenic effects. Because of its
excellent substrate morphology, simple preparation, and easily accessible excitation
wavelengths in the visible range, silver NPs react pointedly to surface-enhanced
Raman spectroscopy (SERS) signals and are the favored metallic substrates for
SERS, thus being used to classify and detect a wide range of molecules including
proteins. Silver nanoparticles-based sensors have begun the development of new
diagnostic methods for early-phase disease detection and other physiological chal-
lenges. These have also been used to study the interactions for drug production
between different drugs and proteins, to create gene-based microarray samples, and
for biodetection and biolabeling. Because of their nanometer size range, they benefit
in targeted delivery and can cross blood capillaries and the blood-brain barrier and
serve as a possible candidate for new and patient-specific therapies for cancer [15].

Bimetallic NPs
Bimetallic NPs have the ability to enhance the physicochemical properties of
metallic NPs, making them attractive candidates for biomedical applications. As a
consequence of the synergetic effect between the two elements, they may exhibit a
wide range of new properties and application. Such approaches can be as varied as
the solutions to antibacterial therapies or anticancer or biological imaging, as well as
the delivery of drugs. Bimetallic NPs of noble metals are of great importance for
imaging applications. Bimetallic NPs which contain silver are most popular in
biomedical applications due to their antibacterial action. The bimetallic NPs include
556 D. Thomas et al.

NPs made from iron-cobalt (Fe-Co), iron-nickel (Fe-Ni), copper-nickel (Cu-Ni), and
iron-platinum (Fe-Pt) which have wide applications in biomedical field. Fe-Co NPs
have strong magnetic properties, including superparamagnetism, high saturation
magnetization, high coercivity, and high Curie temperature. These also possess
structural stability, resistance to oxidation, and biocompatibility: These have been
used in biomedical applications such as magnetic hyperthermia and MRI contrast
agents. Fe-Ni NPs have high Curie temperature and high saturation properties and
are primarily used as MRI contrasting agents. Cu-Ni nanoparticles exhibit strong
Curie temperatures and magnetic properties with magnetic hyperthermia as their key
use. Fe-Pt NPs have unusual chemical and magnetic properties and are ideal for the
treatment of hyperthermia and radiopharmaceutical applications. In addition, they
are good MRI contrast agents [16].

Metal Oxides NPs

Nanoparticles made of metal oxide possess a special configuration and are biocom-
patible with fascinating and peculiar characteristics, high surface area, and good
mechanical firmness. Despite this, metal oxide nanoparticles have drawn significant
interest in biomedical field such as cancer diagnosis and therapy. Iron oxide nano-
particles have been widely studied for numerous biomedical applications including
medical diagnosis and drug delivery. In addition, they have received substantial
popularity as contrast agents for magnetic resonance imaging and dietary iron
supplements. Biosensors based on iron oxide made use of its catalytic efficiency
and stability [17].
Cerium oxide NPs’ catalase, oxidase, superoxide dismutase, and peroxidase
enzymic mimetic activities have opened up a wide range of applications in nano-
biotechnology and nanomedicine, including in chemical stroke care, wound healing
potential, biological antioxidants, molecular sensing, and drug delivery. It is also
used as neuroprotective agents in spinal cord repair, to facilitate cell survival under
oxidative conditions, and to scavenge reactive molecules in the eye to avoid or
postpone degenerative retinal disorders [18].
Titanium dioxide NPs have special characteristics such as biocompatibility,
optical properties, and chemical stability and have been used in various biomedical
applications for many years. Furthermore, it has low cost, multifunctionality, and
nontoxicity. This has been used in numerous applications including photo ablation
therapy, photodynamic therapy, drug delivery, and genetic engineering. TiO2 are
commonly used as medical implant materials because of their biocompatibility with
the bone. It has been broadly used in the production of sensors for biomedical
applications due to the excellent stability of TiO2 in physiological fluids with a
high mechanical resistance. TiO2 NPs’ photocatalytic property has made it popular
for photodynamic therapy [19].
Zinc oxide is regarded as one of the safest materials for biomedical applications.
The multifunctionality, biocompatibility, and peculiar optical properties make it an
ideal tool for applications in theragnostic and bioimaging. In addition, the medical
sector has utilized its antibacterial, antitumor, antimicrobial, and antidiabetic prop-
erties. Zinc oxide NPs were also used for drug delivery applications. These are
24 Consumer Nanoproducts for Biomedical Applications 557

increasingly used in personal care products such as cosmetics and sunscreen due to
ZnO’s strong UV absorption properties [20].
Manganese-based NPs are another form of NPs which have gained huge interest
in biomedical applications. Manganese oxide NPs are used in many applications,
such as photothermal imaging, cytoprotection and disease therapy. In addition,
various biosensors based on manganese oxide have been developed, such as color-
imetric biosensors and electrochemical biosensors. MnO2 NPs are widely used as
fluorescence quenchers in fluorescence biosensors due to their strong optical absorp-
tion across the entire visible light spectrum. Manganese oxide NPs generate attention
as contrast agents. Moreover, they have been used as therapeutic agents and are also
commonly used in magnetic hyperthermia, gene therapy, chemotherapy, starvation
therapy, photodynamic therapy, immunotherapy, and numerous combination
therapies [21].
The use of silica (SiO2) NPs is expanding in biomedical applications. Its unique
surface characteristics, pore volume, biocompatibility, functionalization efficiency,
tunable particle size, low cost, and easy preparation make them a good tool for
biomolecule detection and separation, drug delivery, and biosensing. It is also used
as a contrast agent protector and as bioactive materials for tissue regeneration. They
are also used as secure and biocompatible pharmaceutical additives [22].
Copper oxide is another significant pharmaceutical metal oxide. They showed
effects in antimicrobial activity. They have also been researched for biomedical
applications such as quantitative detection of glucose.

Polymeric Nanoparticles

Due to the flexibility of change in structures of polymeric nanoparticles, therapies

based on polymeric nanoparticles display a great promise in the treatment of a broad
range of diseases. Moreover, breakthroughs in the field of polymerization chemistry
and the development of selective and effective chemical adaptation reactions have
allowed the architecture of versatile polymeric nanoparticles with specific dimen-
sions. Polymeric particles made from both natural and synthetic biocompatible and
biodegradable materials are utilized for biomedical applications including biomo-
lecular sensing, drug delivery, biological imaging, disease therapy, and tissue engi-
neering purposes. Natural polymers widely used in nanomedicine can be classified
into two main categories: one being polysaccharides and the other being proteins.
Natural polymers provide essential benefits such as biocompatibility and nontoxicity
and are affordable for use in biomedical applications. Some popular polysaccharide-
based polymers used in biomedical applications include alginate, cellulose, chitosan,
and hyaluronic acid. Proteins have benefits such as biodegradability and easiness to
modify. The most widely used protein polymers in biomedical applications are
albumin, elastin, collagen, and silk. Synthetic polymers are highly flexible, easily
controllable materials that provide advantages over natural polymers. However,
without due attention, many synthetic polymers may not be biocompatible enough
compared to natural polymers, and thus material selection is a key parameter in the
558 D. Thomas et al.

design of an effective tool for biomedical applications. Synthetic polymers comprise

an incredibly wide variety of materials, including polyesters, poly (glycolic acid),
polyamides, polylactic acids, poly (ε-caprolactone), and polyanhydrides. It is possi-
ble to regulate the polymer chemistry and the supramolecular assembly for the
development of polymeric nanoparticles with improved stability and efficacy [23] .

Solid Lipid Nanoparticles

Solid lipid nanoparticles are composed of the main stable hydrophobic lipids that are
distributed in an aqueous process of surfactant. They are particles of a nanometer
scale, ranging from 50 to 200 nm. Numerous lipids such as mono-, di-, and tri-
glycerides, waxes, fatty acids, and their combinations can be used to synthesize these
particles. Solid lipid nanoparticles are synthesized by replacing the liquid lipid of an
oil-water emulsion by a solid lipid. These materials should be stabilized by different
surfactants to form orally administrable emulsions [24]. Their main benefits include
physical stability, biocompatibility, coalescence durability, biodegradability, non-
toxicity, and avoidance of drug leakage. As an integrated drug carrier, they provide
an outstanding potential for oral delivery, pulmonary administration, parenteral
administration, gene delivery, and effective vaccine adjuvant. These particles have
been used successfully for the administration of different anticancer drugs and found
to be suitable for treating MDR cancers. In addition, they have potential applications
in cosmetics such as topical vehicles for antiaging, sunscreens, and anti-acne
actives [25].

Liposomes

Liposomes are colloidal particles based on aqueous cavity surrounded by lipid

bilayers. They are comparatively stable. Conventional liposomes have relatively
limited circulation time in the blood. Owing to the successful production of long-
circulating liposomes or stealth liposomes, the problems related to limited blood
circulation time were solved by coating with a polymer, thereby increasing the blood
circulation time. Liposomes can be classified according to the size and number of
bilayers in 3. These are small unilamellar vesicles (25–50 nm in size, surrounded by
a single lipid layer, homogeneous in nature, and with a low lipid aqueous volume),
large unilamellar vesicles (size >0.1 μm, surrounded by a single lipid layer, hetero-
geneous in nature, and with high lipid aqueous volume), multilamellar vesicles (size
>0.1 μm, composed of more than one lipid layer and possess moderate aqueous lipid
volume).
Liposomes have nontoxic, non-immunogenic, and biodegradable characteristics
and are capable of enhancing the bioavailability and therapeutic efficacy of drugs.
Furthermore, their flexibility in composition, easy size handling, high enzyme
degradation resistance, increased absorption rates in cell membranes, and alternative
surface charges make them suitable for biomedical applications. Liposomes were
24 Consumer Nanoproducts for Biomedical Applications 559

used in large biomedical applications ranging from tissue engineering strategies to

clinical diagnostics, immunoassays, array configurations, vaccine formulations,
theranostics, etc. Additionally, they have been used as a carrier to help deliver a
number of drugs such as imaging agents, genetic materials, antigens, chemotherapy
agents, and immune modulators. Liposomes can be formulated with a range of
biodegradable and biocompatible lipids and functionalized to allow tissue targeting
and intracellular delivery with various types of targeting molecules. Nanoliposomes
and liposomes possess same physical, chemical, and structural properties. Nano-
liposomes provide more surface area and have the capability to enhance solubility,
increase controlled release, enhance bioavailability, and improve precise targeting of
the bound material compared with liposomes [26]. Liposomes can be synthesized by
using natural components like soy, milk, or egg. So they can be considered as food-
grade products. Phospholipid components of liposomes possess a variety of health
benefits for humans, such as liver protection and memory improvement. In addition,
several cationic lipids, polymers, or peptides may be integrated in the liposomal
bilayers allowing the discharge of the trapped drug molecules into the cytoplasm
[27, 28].

Biomedical Applications of Nanomaterials

Nanotechnologies can be used with its high surface-to-volume ratio to form scaf-
folds and deliver drugs and growth factors to promote bone formation at the affected
site. In animal models, nanotechnologies were also used to modify the gene expres-
sion. In biomedicine, nanotechnology materials have become extremely important
and have resulted to the emergence of a hybrid science called nanobiotechnology.
Some therapeutic nanoparticles range from 10 to 100 nm, so they can flow through-
out the circulatory system and enter into the target tissues via capillaries. The
architecture of nanomaterials by regulating their surface characteristics is portrayed
as an approach for enhancing improved responses targeting a particular application.
The coming section discusses the application of nanomaterials in biomedical field
which is depicted in Fig. 2.

Drug Delivery Vehicles

Drug delivery systems (DDSs) rely on multidisciplinary approaches that bring

together pharmaceutical, polymer, chemical, and nanotechnology sciences. Using
nanotechnology in the delivery of drugs helps achieve the drug’s optimum dosage to
the target position of action and can reduce the adverse side effects of traditional
drug therapy. Nano drug delivery approach primarily focuses on overcoming the
diagnostic and therapeutic problems related to various diseases.
Carbon-based nanomaterial is exploited drug delivery applications. The config-
uration adaptability of carbon favors the formation of zero-, one-, two-, and three-
dimensional structures. It has been shown that fullerene has detrimental or protective
560 D. Thomas et al.

Fig. 2 Biomedical applications of nanoparticles

effects on biological systems which can be used for medicinal application. The
unique structure and suitable properties make it as a pioneer nanomaterial for drug
delivery applications. Studies showed that fullerenes’ scavenging ability has been
used to arbitrate adverse side effects from other chemotherapeutic agents such as
doxorubicin and also as a neuroprotective agent. Fullerene can play a significant role
in oncology by scavenging reactive species in a defensive mechanism or by causing
cellular damage and death. Recently fullerene-based nanocarrier system was also
used for the delivery of anti-inflammatory drugs such as ibuprofen [29]. Nucleic acid
delivery based on fullerene is another groundbreaking therapeutic technique that has
recently been developed in nanomedicine. In addition, fullerene’s epidermal
keratinocyte interactions and antioxidant property permitted this stunning nano-
material to be used in transdermal delivery with tremendous potential. Some studies
reported that the water-soluble fullerene derivatives can effectively cross the blood-
brain barrier and be used to deliver drugs into the central nervous system [30].
CNT is another essential nanocarbonaceous material for use in drug delivery. The
simple modification method for combining bioactive compounds and ligands,
24 Consumer Nanoproducts for Biomedical Applications 561

extremely broad surface area, chemical purity, possibility, capacity for in vivo real-
time monitoring, and free π electron availability make CNTs the ultimate drug
delivery vehicle. Several in vitro and in vivo studies demonstrated the potential of
CNT in cancer therapy [31]. Chemotherapeutic agents based on platinum are best
candidate for use in combination with CNT drug delivery because they are small,
reliable, and easily quantifiable due to the metallic core and moreover create better
cancer response when used in combination with hyperthermia. In a study, Badea
et al. portrayed the capacity of multi-walled carbon nanotubes as a carrier for
cisplatin in breast cancer therapy [32].
Graphene and functionalized graphene were also used as drug delivery carriers.
The peculiar chemical and physical properties, exceptionally large surface area, and
the availability of delocalized π electrons give graphene ultrahigh efficiency in the
loading of drugs. The potential of graphene-based carriers for the delivery of
anticancer drugs was demonstrated in vitro and in vivo by several groups [33]. In
addition, it found application in gene delivery [34].
Because of its biocompatibility, simple surface functionality, and inherent fluo-
rescence properties, CQD has already established its presence in the field of nano-
medicine as a drug/gene delivery vehicle. The efficacy of CQD as a DOX carrier and
the cytotoxic effect of DOX-loaded CQD on cancer cells were evaluated in various
in vitro and in vivo studies. The findings showed that DOX-conjugated CQD have
an enhanced cytotoxic effect against tumor cells as compared to free DOX
[35]. However, not much use is being made of the potential of CQDs as a gene
carrier.
Due to their excellent physicochemical properties and better biocompatibility,
NDs have appeared as a promising material for developing drug delivery systems
with high efficacy and low toxicity. NDs are primarily used as drug carrier in two
ways. In the first method, NDs were mounted onto a chemical substrate in the form
of thin film resulting in a 2D interaction between drug and ND. For the second kind,
NDs form hydrogels by dispersing into aqueous solution, resulting in a 3D interac-
tion between ND and product [36]. Giufa et al. utilized NDs to enhance delivery of
DOX using a convection-enhanced delivery method in a preclinical glioma model
[37]. In another study, Rafael et al. developed a ND-insulin system for the successful
delivery of insulin [38]. Furthermore, NDs were used to deliver antioxidants as they
possess highly versatile surface chemistry and favorable surface-to-mass ratio
[39]. MCN and its functionalized derivatives exhibit low toxicity and are suitable
for drug delivery applications. Numerous studies were reported in which MCN acts
as carriers for antitumor drugs like DOX. Carbon nanomaterials are presumably to
be advantageous in medicine, especially in forthcoming oncology uses. There are
several prospects for drug delivery using carbon-based nanomaterial to release a
drug directly at a specific site or to improve the cellular absorption and efficacy of
medication.
For a long time, gold NPs have been used to deliver molecules to cells. Due to
their specific dimensions, tuneable surface characteristics, and controllable drug
release, it constitutes highly attractive and favorable candidates in drug delivery
applications. It has been used primarily for providing anticancer drugs to cancer
562 D. Thomas et al.

tissue. In addition, it is used to deliver selective antibiotics, antibacterial agents,

antidiabetics, and antioxidants. The molecules are adsorbed onto the Au NPs’
surfaces, and the conjugate is then delivered into the cells as a whole. Zhou et al.
developed functionalized gold NPs for the simultaneous delivery of DOX, antican-
cer drug which is hydrophobic in nature, and diclofenac sodium, an anionic anti-
inflammatory drug [40]. Laxmi Devi et al. analyzed the potential of gemcitabine
hydrochloride-loaded colloidal gold NPs synthesized using gum acacia for the
treatment of breast cancer [41]. Peptide capped gold NPs have been shown to be a
potential delivery vehicle for the intracellular delivery of DOX.
Surface-modified gold NPs are recognized as beneficial vehicles for gene delivery
due to their small size, flexible functionalization, and nontoxicity. AuNPs can
potentially help overcome some of the gene delivery barriers, including penetration
of the cell membrane, prevention of enzymatic degradation, and successful delivery
to the intact gene nucleus. Giesen et al. have prepared fluorescent gold nanoparticles
by one pot synthesis and assessed its potential for gene delivery in glioblastoma
therapy. The in vitro results show that the NPs show better efficacy as carrier to
transport DNA in GBM cells and are able to enter three-dimensional stem cell.
Peptide capped gold NP has been developed as a vehicle of small interfering RNA
delivery for breast cancer treatment [42].
Silver NP-based drug delivery system was also designed for drug delivery
applications. Franco-Molina et al. have been exploring colloidal silver for breast
cancer treatment. Patra et al. demonstrated the potential of biosynthesized gold and
silver NPs for DOX delivery [43]. Benyettou et al. investigated the use of silver NPs
as drug delivery platform to deliver doxorubicin and alendronate efficiently to the
cervical cancer cells (HeLa) at the same time [44]. In another study, Qui et al.
developed a potential efficient drug delivery system in cancer therapy based on
camptothecin-covered silver NPs [45]. Prusty et al. have prepared nano silver
ornamented polyacrylamide/dextran nanohydrogel hybrid composites for drug
delivery [46]. Yadollahi et al. assessed the potential of one pot synthesized silver
NPs/chitosan hybrid particles for drug delivery applications [47].
Owing to their novel properties, bimetallic NPs have been identified as impor-
tant multifunctional materials for drug delivery applications. Fuchigami et al.
investigated the utility of magnetic porous Fe-Pt NPs, which are synthesized by
hydrothermal process for the targeted delivery of DOX in lung cancer cells. The
results of the in vitro study show that the drug-loaded NPs could kill about 70% of
the cancer cells [48]. Studies by Chen et al. included the use of folic acid
functionalized Fe-Pt NPs as a powerful tool for phototherapy to treat breast cancer.
They demonstrated the ability of ultrafast laser-assisted NPs for photothermal
cancer therapy [49].
Scientists have drawn attention to NPs derived from metal oxide because they are
flexible platforms for biomedical applications and therapeutic intervention. Diverse
experimental, preclinical, and clinical studies revealed the ability of ZnO NPs for
drug delivery applications. Preliminary work conducted by Yuan et al. has shown
that the use of ZnO quantum dots synthesized by chemical hydrolysis method is an
efficient drug carrier for DOX [50]. Sadhukhan et al. assessed the ability of ZnO NPs
24 Consumer Nanoproducts for Biomedical Applications 563

conjugated with phenyl boronic acid for quercetin delivery. The in vitro and in vivo
studies revealed the efficacy of the prepared NPs in clinical cancer treatment [51].
Magnetic iron oxide nanoparticles are versatile nano platforms for drug delivery
applications because they can achieve high drug loading and targeting capabilities
due to their remarkable biological and magnetic characteristics. TiO2 nanoparticles
have proven to be effective drug delivery nanocarriers. Salahuddin et al. developed
nanocomposite based on titanium dioxide and polylactic acid for the sustained
delivery of norfloxacin. The in vitro studies have revealed the antibacterial effec-
tiveness of the formulated nanocomposites. The results demonstrated that the nano-
composites could be efficient vehicles for the targeted delivery of anticancer drug
[52]. Cerium oxide NPs have immense potential to act as a carrier for drug delivery
applications due to their highly favorable characteristics. Shivani et al. formulated a
bio safe, antibacterial, and hemocompatible ceria-based nanocarrier system for
benzyl isothiocyanate delivery [53].
The incorporation of polymers into medicinal applications revolutionized the area
of drug delivery. The use of polymers in the composition of nanoparticles provides
advantages such as biodegradability and biocompatibility in drug delivery systems.
In addition, surface modification of polymeric NPs with hydrophilic polymers
reduces opsonization and provides extended circulation time. Polymers have a
vital role in the drug delivery mechanism for the treatment of different diseases
such as cardiovascular disorders, cancer, and neurodegenerative diseases. The
functionalized polymer NPs have a broad range of applications such as drug delivery
in the brain and vagina, gene therapy, vaccine delivery, cancer treatment, and much
more. Polymeric NPs deliver the medication not only to a particular location but also
at a particular pace that is beneficial in the treatment of several diseases. Numerous
sustained release pharmaceutical devices based on nano-polymers have been
reported [54]. Andrade and coworkers utilized chitosan NPs as a carrier for N-
0
-((5-nitrofuran-2-yl) methylene)-2-benzhydrazide against multidrug-resistant infec-
tion [55]. Thomas et al. developed alginate NPs and assessed its potential for the
controlled release of rifampicin and theophylline [56, 57]. In another study, Thomas
et al. utilized alginate-cellulose nanocrystal hybrid NPs for rifampicin delivery [58].
The use of solid lipid NPs as a carrier platform enables an improvement in the
therapeutic effectiveness of drugs from various therapeutic types. Solid lipid NPs
include ophthalmic disorders, cancer treatment, bacterial infections, and brain
targeting. The use of solid lipid NPs offers better pharmacokinetic properties and a
modulated release of drugs. Pandya and coworkers produced olmesartan
medoxomil-loaded solid lipid NPs by hot homogenization method. The in vitro
and in vivo study showed solid lipid NPs enhancing the bioavailability and thera-
peutic effectiveness of the drug and could act as substitute to traditional oral
preparation in hypertension therapy [59].
Different studies demonstrated the potential of liposome formulations for anti-
cancer drug delivery applications. Liposomes also have been widely used as efficient
tool for DNA and siRNA delivery. They became a successful candidate for multiple
delivery systems due to the simple route of chemical modifications, the ability to
hold different types of drugs/genes, and the ability to be delivered by different
564 D. Thomas et al.

routes. The delivery of encapsulated drug molecules to treat cancer has been
facilitated by the liposomes. It has been found that the combination of liposomes
and porous nanoparticles can promote the intracellular delivery of therapeutics for
cancer cells. Liposomes embedded in iron oxide nanoparticles were often used for
gene delivery.

Tissue Engineering

Carbon-based nanomaterial has specific electrical, mechanical, and optical proper-

ties and can provide an analogous microenvironment as an extracellular biological
matrix that offers new tissue engineering possibilities. There are a number of carbon
nanomaterials, such as GO CNTs, CQDs, ND, and their derivatives, which are
capable of serving as scaffolds for bone tissue engineering. Numerous studies
have shown their stimulating effects on cell development, low cytotoxicity, and
efficacy for efficient nutrient delivery in the scaffold microenvironment. Prakash and
coworkers developed graphene oxide-based nanocomposite for bone tissue regen-
eration [60]. In another study, Olad et al. formulated graphene oxide and its
functionalized derivative for tissue engineering applications. The in vitro investiga-
tion demonstrated their biomineralization ability and cell viability [61]. Biomimetic
fibrous scaffolds based on functionalized carbon nanotubes received much attention
for tissue engineering applications. Chitosan- and cellulose-modified CNTs were
also fabricated for bone regeneration. Martinelli et al. developed elastomeric 3D
CNT-based composites for cardiac tissue engineering and demonstrated its potential
for enhancing cardiac myocyte proliferation and functional maturation [62].
Due to the unique properties such as their high penetration potential and greater
surface area with adaptable surface properties, the use of metal NPs is widely
proven as a favored candidate for tissue engineering. Pattanashetti et al. assessed
the effect of bio inert TiO2 incorporation into polyvinyl alcohol matrix for bone
tissue engineering. Surface porosity of nano TiO2 improves tissue binding. The
study found that the addition of TiO2 increased the mechanical strength and
hydrophilicity of the scaffold [63]. In another study, as a scaffold for tissue
engineering, Augustine and coworkers reported the preparation of electrospun
polycaprolactone fabricated with ZnO NPs. They were using the ZnO NP ROS
activity to stimulate angiogenesis [64].
A wide variety of synthetic and natural polymers have been widely used as tissue
regeneration scaffolds. Biopolymers show greater biocompatibility and minimum
immunogenicity because of which they have cell binding capability. A significant
number of polymer scaffolds have been used in tissue engineering. Zhang et al.
developed a three-dimensional composite membrane of poly (ε-caprolactone),
poly (ethylene glycol), and magnetic iron oxide for skin tissue engineering
[65]. Extremely porous poly (D, L-lactide-co-glycolide) fibrous electrospun mats
with considerable surface area have been used to make scaffolds that facilitate cell
development and proliferation. Different natural as well as synthetic polymers were
electrospun with hydroxyapatite to generate artificial extracellular matrix that
24 Consumer Nanoproducts for Biomedical Applications 565

mimics the extracellular matrix of the native cartilage and is best suited for tissue
engineering applications.
Liposomes mimic cell matrix. Bioactive agent-loaded liposomes combined with
scaffolds provide various intrinsic benefits including stable and effective concentra-
tion, potential to develop spatiotemporal patterning, less toxicity, and multiple
deliveries of bioactive agents. Combination of liposomes and scaffolds is widely
used for bone, tissue, and cartilage regeneration applications. Liposome-scaffolds
have the potential to control the release pattern of incorporated bioactive agents and
enhance stem cell differentiation and can bring new developments in regenerative
medicine and tissue engineering.

Wound Dressing

Wound healing is a process whereby a forced response to different stimuli which

influence the skin is created. Hemostasis, inflammation, proliferation, and
remodeling are the four phases of wound healing process. Previous work shows
the significance of the process of inflammation in healing of wounds. Studies show
that the nature of wound dressing material has a massive effect on inflammatory
response, which can promote or inhibit regeneration of tissues. Also to reduce the
microbial infection and improve the healing process, proper selection of wound
dressing material is important. Nano scaffold dressings are a better choice for
achieving desirable properties. They provide a prodigious method for facilitating
the healing of chronic and acute wounds. They can stimulate the multiple stages of
healing process. The small-sized nanomaterials are used in nanotechnology to
deliver drugs in the wound area. Carbon-based nanomaterial such as GO, reduced
graphene, CNT, and fullerene may provide higher mechanical strength and biocom-
patibility to scaffolds used in wound healing. Numerous studies evaluated graph-
eme’s potential as a wound healing scaffold and found it suitable due to its peculiar
characteristics such as high water absorption power, antibacterial activity, and the
ability to add mechanical strength to the composites. Studies demonstrated the
antibacterial efficacy of graphene oxide NPs. Copper- and silver-immobilized car-
bon-based NPs show excellent antibacterial activity and are used as scaffold for
wound dressing applications. Vedhanayagam et al. prepared a composite of CNT-
dendrimer-collagen and assessed its potential for in vivo wound healing and found
that the presence of CNT helps to improve the mechanical strength of collage-based
scaffold [66].
Noble metal NPs such as gold and silver also have excellent wound healing
ability as they demonstrate controlled release, strong mechanical strength, and
antibacterial activity against both fungi and bacteria. These NPs show synergic
effect towards wound healing when they fabricated with polymers like cellulose,
collagen, gelatin, and chitosan. Goutham Rath and colleagues prepared a blend of
collagen and silver nanoparticles and investigated its potential for wound healing.
The antibacterial efficacy has been demonstrated by in vitro studies. The in vivo
experiments depicted its efficacy in healing wounds. The histopathological findings
566 D. Thomas et al.

concluded that the incorporation of silver NPs in collagen helps to speed up

reepithelialization and collagen development [67]. Metal oxide NPs such as silica,
cerium oxide, and zinc oxide are widely used in wound dressing. Numerous studies
have shown their ability to facilitate collagen deposition and reepithelialization, thus
improving the process of wound healing. In a study, in vitro and in vivo modeling
revealed the efficacy of silica-gold core-shell material as a wound dressing scaffold
and promotes the process of cell adhesion and wound healing [68]. In dermal wound
healing, the cerium oxide NPs showed therapeutic efficiency. In addition, the NPs
demonstrated greater penetration into the wound tissue and subsequently decreased
oxidative damage to proteins and cellular membranes.
Natural and synthetic polymer-derived nanomaterials have been found to be
suitable tools to prevent infection and wound healing applications because of their
specific biological and physicochemical features. Ferreira et al. developed a biomi-
metic scaffold for wound healing applications, based on poly (L-lactic acid), colla-
gen, PCL diol, and polyesterurethane. The cellular study showed that the proposed
scaffold reinforces the process of tissue regeneration and healing process [69]. In
another study, Panea et al. found that the antimicrobial dressing consisting of
collagen, dextran, and ZnO NPs resulted in faster wound closure and serves as a
promising biomaterial for skin regeneration applications [70]. Fabrication of
engineered nanomaterials with synthetic or natural polymers is a safer strategy for
achieving sustained therapeutic release that speeds up the healing process.
The application of liposomes to the skin offers numerous advantages. Liposomes
ensured flexibility, improved hydrophilicity, and adhesion, resulting in relatively
higher encapsulation efficiency, improved stability, and increased activity in wound
healing. Wound dressing based on liposomal hydrogel creates a barrier that success-
fully avoids wound contamination and further progression to deeper tissue infection.
The drug encapsulated within the liposomes raises the concentration of the drug
locally and reduces the concentration of systemic drugs, and hydrogels combine the
characteristics of moist wound healing with strong fluid absorption. Liposomes and
their functionalized derivatives could potentially be used as wound healing carriers.

Molecular Imaging

Molecular imaging (MI) is a technique that tracks molecular-level changes in vivo to

detect diseases at an early stage. The development of noninvasive methods for tumor
microenvironment visualization is important for tumor detection and treatment.
Large studies were devoted to the design of stimulus-responsive and intelligent
nanoprobes for imaging purpose. Using imaging techniques, a customized treatment
can be created for patients by closely observing the region affected by the disease
within the body. Contrast agents play an essential part in visualizing a target.
CNTs are being used as a probe to enhance tissue penetration in biomedical
imaging. Because of its important optical properties, CNTs are used as a contrast
agent in imagery. Functionalized CNTs were also used in various imaging tech-
niques for labeling and tracking of cells. Huth et al. reported the preparation of
24 Consumer Nanoproducts for Biomedical Applications 567

polymer-wrapped carbon nanotube complex with fluorescent property for

bioimaging applications. The photo physical measurements and in vitro biological
studies show its optical properties, cellular uptake, cytocompatibility, and intracel-
lular staining capacity [71].
Due to their excellent photoluminescence properties, CQDs have become very
significant for molecular imaging. Functionalized fluorescent CQDs are special mate-
rials for bioimaging applications. Microwave-assisted synthesis of functionalized
CQD with fluorescence property has excellent potential in bioimaging applications.
Silver NPs have been widely used for biolabeling and biodetection. Silver
NP-coated substrates are used for the visualization of intracellular proteins. Gold
NPs are a very attractive contrasting agent for in vitro and in vivo molecular imaging
techniques. It can be used as X-ray contrast agent and for single-particle tracking.
Gold NPs modified with Raman-active molecules have wide application for the
detection of DNA or proteins.
Magnetic iron oxide NPs have attracted interest in cell labeling, magnetic reso-
nance imaging, and bioimaging applications. They are capable of shortening the
relaxation time of surrounding protons due to their super paramagnetic behavior and
used for cellular and molecular imaging as contrast agents in MRI. They were
commonly used to visualize metastases in the spleen, liver, tumors, and lymph
nodes, as a blood pool agent in angiography, and to visualize inflammatory lesions
such atherosclerotic plaques. Surface-functionalized derivatives of iron oxide NPs
were utilized for in vivo imaging and as nanoprobes for understanding living cell
molecular interactions.
The intellectual combination of polymer chemistry, nanotechnology, and
bioimaging sciences has resulted in the development of polymeric NP-based
bioimaging probes with extended plasma half-lives, reduced toxicity, enhanced
target specificity, and increased stability. These probes were used for imaging tumors
and atherosclerosis. For almost all medical imaging techniques, they provide an
excellent contrast enhancement that creates the ability to examine tumor activity by
monitoring NP kinetics. They have also been used to deliver fluorescent contrast
agents. In addition, in positron emission tomography technique, they were used to
deliver radioactive tracer. Cao et al. developed fluorescent polymeric NPs with
aggregation-induced emission properties by click reaction and implemented for
cell imaging [72].
Liposomes are utilized as a carrier for contrast agents in imaging applications
such as brain imaging, cardiovascular imaging, liver imaging, tumor imaging, spleen
imaging, infection imaging, and inflammatory imaging.

Theranostics (A Type of Molecular Imaging)

Theranostics, a combination of therapy and diagnostics, is an emerging nanomedicine

paradigm formulated for molecular detection and targeted treatment. It focuses in
administering the correct dosage of the drug in the correct location at the correct time
by imaging the extent of the disease, delivering treatment, and monitoring the
568 D. Thomas et al.

effectiveness of real-time therapies. The diagnostic function of theranostic agents

indicates the nature, condition, and response of a disease to a particular treatment,
whereas the therapeutic function of the agent can be applied in many ways.
Nanoparticle-based theranostics can be promising because of their desired character-
istics such as efficacy for site-specific delivery and capacity to achieve better syner-
gistic outcomes with reduced side effects. Rapid nanotechnology advances give rise to
numerous nanomaterial including polymer conjugations, magnetic NPs, silica NPs,
dendrimers, quantum dots, and micelles. Nanotheranostics is suitable for diagnosis,
controlled drug release, and therapeutic response monitoring and is expected to play a
key role in the advancement of personalized medicine. They are widely used to treat
numerous biomedical complications such as cardiovascular diseases and pulmonary
disorder. They have gained greater prominence in oncology, where advanced tumors
can be correctly identified and effectively treated with fewer side effects. The potential
of iron oxide NPs, CQDs, gold NPs, CNT, and silica NPs as nanotheranostics
platforms has been well-established.
Iron oxide NPs, due to their potential in hyperthermia, can play a combined role
in the imaging and therapeutic applications. Because of their ability to be visualized
by MRI while their shell can be physically or chemically loaded with therapeutic
agents, they are intrinsically very suited for theranostic purposes.
The use of carbon-based QDs for biomedical application stems from their ideal
chemical and physical properties, including size-dependent stable and narrow emis-
sion spectra, wide absorption spectra, and the potential to act as scaffold for targeting
ligands and therapeutic drugs and their photostability.
Gold NPs have been extensively used for nanotheranostic application because of
their unique characteristics including stability, strong surface plasmon absorption,
and ease of modification [73]. Aromatic stacking, special physical and surface
characteristics, and the high optical absorption of CNTs in the NIR region have
made it a promising resource for theranostics. Silica NPs can also function as a
tremendous platform for theranostic applications that enables a wide range of
imaging and therapeutic agents to be easily loaded, making them a good candidate
for theranostic applications.

Biosensors

Biosensors were commonly used in the study of metal ions, small biological
molecules, and proteins. Nanostructured materials such as carbon-based nano-
particles, metal nanoparticles, and magnetic nanoparticles have been used in sensing
applications. The unique characteristics of carbon-based NPs make them suitable for
use in a variety of biosensors. Biomolecule integration with them allows for the use
of some rather hybrid systems as electrochemical biosensors. Biosensors based on
CQDs were used for the detection of inorganic ions in small molecules and biolog-
ical samples. Graphene-based biosensors were used to detect many essential bio-
molecules including DNA, dopamine, glucose, and alcohol. Biosensors based on
GO have been used as markers for tumor. CNTs have a broad specific surface area
24 Consumer Nanoproducts for Biomedical Applications 569

that enables numerous functional moieties to be immobilized and can be used to

identify a wide variety of biological species including glucose, neurotransmitters,
pathogen toxins, proteins, and DNA. CNTs have a large specific surface area which
enables the immobilization of a wide variety of functional moieties such as
biosensing receptors. It has also been used as biomarkers for cancer and for detecting
HIV in complex media.
A number of metal-based NPs were researched for potential use in biosensors.
Fe3O4/Au core-shell nanocomposite probes were designed to detect DNA point
mutation in aqueous DNA solutions. Nanosensors based on the Au/Pd NPs have
been developed for glucose detection. Au/Ag core-shell nanoparticles labeled by
monoclonal antibodies onto silica/polymer shell are a lucrative option for
immunosensor chips. Titana nano-shells with a diameter of 10–30 nm were used for
the production of bioactive coatings with adjustable permeability and dopamine and
ascorbic acid sieving functions for use in neurochemical tracking. The films were
synchronized with the nervous tissue and, in the presence of ascorbic acid, enabled
selective detection of dopamine, an essential neurotransmitter. The negative charge of
the TiO2 NPs enhanced the permeation of positively changed dopamine while
restricting the access of ascorbic acid, a negatively charged compound. TiO2 NPs is
used in neurochemical monitoring. The TiO2-polyelectrolyte assembly was harmoni-
ous with nerve cells and able to track brain activity in vivo. Cerium oxide NPs have
potential uses to track dopamine, glucose, glutamate, and hydrogen peroxide. These
systems can be utilized in neuroscience research involving neurotransmitter function
studies on diseases such as stroke, autism, Alzheimer, and Parkinson.
Biosensing applications are also possible using metal NP-polymer composites.
Nagasaki et al. showed that biotin-PEG/polyamine cadmium sulfide quantum dots
may be used to detect proteins with high sensitivity. PEGlation improved the
dispersion stability of cadmium sulfide quantum dots in this work [74]. In another
study, Phillips and coworkers utilized Au NP-poly(para-phenyleneethynylene) con-
struct for the detection of bacterial strains [75].
Liposomes are widely used in the field of biosensors. They are used for signal
marker compound encapsulation in a broad range of identifying modalities because
they have excellent carrier properties. Liposomes possess a large internal cavity for
signal marker encapsulation and a broad surface area for the conjugation of recog-
nition elements. A significant feature of their use in bioanalysis is the ability to adjust
the liposome surface structure to perform recognition functions with a large variety
of analyte forms. Liposomes are utilized for recognition in biotarget detection.
Functionalized liposome detectors provide more precise detection. Sensors based
on liposome-enzyme combination have been developed as disease biomarkers.

Global Market of Nanomedicine

As a result of massive nanotechnology studies and the realization of their applica-

tions in human health and environment, there is a wide variety of nanomaterials and
nanoproducts available in the industry. In particular, the nanomedicine industry is
570 D. Thomas et al.

dominated by nano-delivery methods of drugs, and one of the leading fields is

in vitro diagnosis. Manufacturers of biopharmaceutical and medical devices are
well aware of the potential opportunities of nanotechnology to the healthcare sector,
as evidenced by the growing partnerships between these companies and nano-
medicine start-ups. Anticancer drugs constitute one of the growing segments of
this industry. Nanotechnology applications continue to evolve rapidly, and the
overall market for new nanoproducts continues to grow, along with the degree to
which they permeate our daily lives. Governments in different countries, due to the
variety of potential industrial and military applications, have made investments in
nanotechnology research.

Conclusion and Future Perspectives

Nanoparticles and their applications in biomedicine and pharmacology have become

an important and distinct area of scientific and technological evolution over the last
decade. Nanotechnology has gained tremendous public interest owing to the broad
applications of nanomaterials in many fields of society such as medicine manufactur-
ing and public health. Nowadays, nanotechnology application is extensively used in
various fields such as molecular imaging, drug delivery, biosensing, and wound
dressing. Nanomaterials have displayed tremendous potential in developing multi-
functional nanoprobes for in vivo applications including imaging and therapy,
bearing the excellent intrinsic physical properties and flexible surface, thus increas-
ing vital particle requirements including biocompatibility, efficacy, and colloidal
stability. It is expected that nanomaterials will play an important role in the devel-
opment of advanced diagnostic and therapeutic techniques emerging in the future.

Acknowledgment Reshmy R and Raveendran Sindhu acknowledge the Department of Science

and Technology for sanctioning projects under DST WOS-B scheme. Aravind Madhavan acknowl-
edges the Department of Health Research, Ministry of Health and Family Welfare, for sanctioning a
project under Young Scientist Scheme.

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“Nanosilver”: A Versatile and
New-Generation Nanoproduct in 25
Biomedical Applications

Shikha Gulati, Sanjay Kumar, Anchita Diwan, Parinita Singh, and

Ayush Mongia

Contents
About the Chapter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
Nanosilver (NS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
Unique Properties of Nanosilver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
Antibacterial Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
Antifungal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
Antiviral Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
Anti-inflammatory Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Synthesis Methods of Nanosilver (NS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Chemical Method of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Physical Method of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
Biological Method of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
Mechanisms of Biological Interactions of Nanosilver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
Toxicology of Nanosilver (NS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
Applications of NS in the Biomedical Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
Cardiovascular Implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
Catheters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
Bone Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
Wound Dressing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591

Abstract
Nanotechnology, being a promising arena for creating innovative applications in
medicine, is advancing fast due to the immense growth achieved in other diverse
fields including mechanics, electronics, food, cosmetics, etc. To productively
bifunctionalize nanoparticles for a particular biomedical application, a broad
range of physical, chemical, and biological factors have to be taken into account.
In this context, silver in the form of nanoparticles is playing a most important role

S. Gulati (*) · S. Kumar · A. Diwan · P. Singh · A. Mongia

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 575

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_48
576 S. Gulati et al.

in the field of nanotechnology and nanomedicine due to their challenging and

unique size-dependent properties which formulate them and are advanced and
essential in a range of biomedical applications, including diagnosis, treatment,
drug delivery, medical device coating, and for personal healthcare products.
Silver nanoparticles (AgNPs), or nanosilver (NS), are clusters of silver atoms
that range in diameter from 1 to 100 nm and are primarily attracting interest as
antibacterial and antimicrobial agents for applications in medicine. Hence, nano-
silver is an emerging field of research and has been highly commercialized with a
diversity of commercially available products being used clinically. In particular,
nanosilver has already been used in everyday consumer products requiring broad-
spectrum antibiotic performance due to its massive surface area and reactivity.
Consequently, there is a need to recognize a worldwide background of nanosilver
and their products, and their manufacturers. During the past few years, various
novel synthesis methods for nanosilver production have emerged and are being
evaluated, making them superior and versatile for biomedical applications. In this
chapter, we first introduce the unique physiochemical properties of nanosilver,
such as antibacterial, antifungal, antiviral, and anti-inflammatory activity
followed by the synthesis routes of nanosilver, including physical, chemical,
and biological or green method. Further, in this chapter, we provide an overview
of some recent applications of nanosilver. Even though nanosilver has remarkable
biomedical potential, its mechanisms of biological interactions and toxicology are
also critically discussed in light of potential concerns before extensive application
in prevention, diagnosis, and treatment in the biomedical field.

Keywords
Nanosilver · Nanoparticles · Drug delivery · Silver · Biomedical applications ·
Diagnosis · Treatment

About the Chapter

This chapter provides an overview on the developments of nanosilver (NS) as a

versatile and new-generation nanoproduct in biomedical applications. NS is an
advancing arena of research and has been greatly commercialized. The integration
of NS into the medical industry is now gaining momentum to exploit the potential of
NS in infection prophylaxis. Potentially, NS also demonstrates anti-inflammatory
characteristics and speeds up wound healing. NS has its applications in medical
device coating, diagnosis, treatment, wound dressings, drug delivery, contraceptive
devices, and medical textiles due to their antibacterial, antiviral, antifungal, and anti-
inflammatory characteristics. Several diverse strategies for the synthesis of NS have
been discussed due to the intrinsic versatility of NS, such as physicochemical,
physical, chemical, and biological synthesis approaches. In supplement to the
intrinsic antimicrobial-related applications, NS has been extensively evaluated
owing to their beneficial size-related physicochemical effects exhibited in novel
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 577

electronic, catalytic, magnetic, and optical devices. Although nanosilver (NS) pos-
sesses remarkable advantages for various biomedical applications, it exhibits toxic-
ity at some concentrations and can cause some major health issues if not properly
administered. Thus, it is essential to address the biosafety of NS in human health.
This chapter discusses the advancements of nanosilver (NS) as a versatile and
new-generation nanoproduct in biomedical applications.

Introduction

Nanotechnology is among the most promising fields for generating novel biomedical
advancements. Nanotechnology has emerged as the central axis of the world’s
technological applications [48]. For the past several years, nanomaterials had a
prompt evolution, thereby pioneering new horizons in the field of scientific, indus-
trial, and technological researches [70]. However, only few nanoproducts are cur-
rently in use for biomedical purposes. Alongside gold, among the rare and precious
metals, silver metal has been extensively exploited for thousands of years, applica-
tions including ornaments, cooking wares, currency, dental alloy, photography, and
even explosives. Unadulterated silver is ideally ductile and malleable and possesses
the highest electrical and thermal conductivity as well as the lowest contact resis-
tance [47]. Among the silver’s many applications, those that utilized its disinfectant
characteristics for hygienic and medicinal impetus are time honored and noteworthy,
though the mechanism of action is not yet fully recognized. Metallic silver is
subjected to latest engineering mechanization resulting in extraordinarily novel
morphologies and properties. Silver is being engineered into minute particles
whose size is in nanometers (nm). Upon reaching nanoscale, like various other
nanomaterials and mainly owing to their extremely small size, silver particles
display remarkably unique physicochemical characteristics and biological activities.
Excellent research efforts have been accomplished owing to this field and have
yielded encouraging outcomes. As a result, the administration of engineered nano-
silver especially in the field of healthcare has been and is being fiercely explored.
Nanosilver is emerging as one of the sprightly growing product categories in the
nanotechnology domain, and it is evaluated that out of all the nanomaterials in
biomedical and healthcare area, nanosilver application has gained the elevated
degree of commercialization. Therefore, the exposure to nanosilver in our human
body is becoming highly widespread and intimate. On a nanoscale perspective,
nanosilver (NS) exhibits excellently unique physical, chemical, and biological
characteristics. Therefore, they are among the most eminent nanomaterials and
have been extensively utilized to the expanse of biomedical applications, including
diagnosis, treatment, drug delivery, medical device coating, and for personal health
care. Due to their plausible bactericidal activity, nanosilver coatings are used on
several textiles and also on certain implants. Furthermore, nanosilver particles are
being utilized for treating wounds and burns or as contraceptives and commercial-
ized as water disinfectant and room spray. Thus, nanosilver application is emerging
as more and more widespread in biotechnology, and due to increased exposure
578 S. Gulati et al.

toxicological and environmental subjects need to be raised. In stark contrast to the

consideration paid to new applications of nanosilver, few investigations provide only
limited insights into the interaction of nanosilver particle with the human morphol-
ogy after entering via dissimilar portals. With the growing applications of nanosilver
in medical environment, it is becoming crucial for a better conception of the
mechanisms of biological interactions of nanosilver and their potential toxicity.

Nanosilver (NS)

Nanosilver (NS) or nanosilver particles (NSPs) are normally present as clusters of

silver atoms at 1–100 nm in size range in diameter at least in one dimension. As the
nanoparticle decreases in size, the area-to-volume ratio of the surface of NS particles
increases adequately which leads to a prominent change in their physical, chemical,
and biological properties. For elucidation, nanosilver as well as silver NPs are
comparable and exemplify as general terms for all silver nanocrystals, nanospheres,
or colloidal NPs (Fig. 1). NS is an evolving field of investigation and has been
tremendously commercialized. They have captivated a lot of interest because of their
chemical stability, catalytic activity, localized surface plasma resonance, and high
conductivity. Silver in a short time has been known to hold antibacterial activity and
has been made to use throughout history, from Hippocrates’ early treatment of ulcers
to C.S.F. Crede’s treatment for gonococcal infections in newborns. Silver till now
was being used clinically, and NS application is emerging as a valuable instrument in

Fig. 1 Different shapes of nanosilver

25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 579

the therapeutic armory [6]. Lately, nanosilver (NS) has become of extreme impor-
tance in biomedical applications, due to their antibacterial, antifungal, antiviral, and
anti-inflammatory actions. Therefore, they have been widely utilized for diagnosis,
treatment, drug delivery, medical device coating, wound dressings, medical textiles,
and contraceptive devices.

Unique Properties of Nanosilver

Nanosilver particles exhibit remarkable physical, optical, and chemical properties

because of their dominance of quantum mechanics. These distinct characteristics are
used in biomedical imaging and sensing applications such as surface-enhanced
Raman scattering and single-step immunoassays. Hence, they are extensively uti-
lized for their antibacterial, antiviral, antifungal, and anti-inflammatory properties
(Fig. 2).

Antibacterial Properties

Studies evidently showed that silver and NS in aqueous solution release silver ions,
which are biologically active and surprisingly transmit bactericidal reaction. A
relative study of NS, silver nitrate, and silver chloride showed that NS has elevated
antibacterial potency as compared to the free silver ions [14]. This suggests that NS
has inherent antibacterial characteristics that are independent of the elution of Ag+
ion. NS amply associates with the bacterial cell walls and has been suggested that it
causes lysis [44, 68]. There has been considerable evidence that NS produces
reactive oxygen species (ROS), which might aid in both the antibacterial activity
of NS and its potential toxicity toward human beings [10]. NS has a wide-ranging

Fig. 2 Unique properties of nanosilver

580 S. Gulati et al.

antibacterial effect on a range of Gram-negative and Gram-positive bacteria and

antibiotic-resistant bacteria strains. Excluding the size and concentration, shape
influences the antimicrobial efficiency of NS as well. Sadeghi et al. studied the
antimicrobial activity of distinct nanosilver shapes, which comprise of silver nano-
plates, silver nanorods, and silver nanoparticles, on Staphylococcus aureus and
E. coli, and they found out that silver nanoplates had a remarkable antimicrobial
activity [55].
Even though the antimicrobial activity of nanosilver has been widely investi-
gated, the exact process of NS is still evasive. It has also been studied and found that
NS particles can release silver ions and associate with the thiol groups of many
essential enzymes and phosphorus-containing bases, therefore hampering some
functions in cells, such as blocking cell division and DNA replication.

Antifungal Properties

NS has proved to be a successful antifungal agent against a wide range of common

fungi. Kim et al. investigated NS antifungal characteristics on 44 strains of 6 fungal
breeds and discovered that NS can inhibit the development of Candida albicans,
Candida glabrata, Candida parapsilosis, Candida krusei, and Trichophyton
mentagrophytes effectively [33]. Jolanta et al. also investigated NS suspension,
and the assessment demonstrated the antifungal activity of nanosilver against
cladosporioides and Aspergillus niger strains where suspension was an efficient
growth inhibition factor against these fungi [50]. Nasrollahi et al. [46] observed
that NS possesses the ability to disrupt cellular membrane and inhibit their general
budding mechanism; however, the precise mechanisms of fungicidal action of NS
are still not clear. The utilization of silver nanoparticles with fungicidal properties in
fabrication materials can bring about various potential advantages, such as improv-
ing their hygienic properties, inhibiting microbial growth and maintaining their
mechanical features.

Antiviral Properties

Nanosilver (NS) has recently appeared as a novel antiviral agent against numerous
viruses and acts as an antiviral agent against HIV-1, hepatitis B virus respiratory
syncytial virus, herpes simplex virus type 1, and monkeypox virus. It has been
noticed that NS has greater antiviral activity than silver ions, because of their species
variation as they dissolve to liberate Ag0 (atomic) and Ag+ (ionic) clusters, whereas
silver salts liberate Ag+ ions only. Lara et al. found out that the anti-HIV mechanism
of action of NS is on the basis of inhibition of the initial stages of the HIV-1 cycle.
NS can attach to glycoprotein (gp)120, thus inhibiting the cluster of differentiation
(CD) 4-dependent binding, fusion, and infectivity. They behave as a powerful
antiviral agent to obstruct HIV-1 cell-free and cell-associated infection. Additionally,
they also hinder the postentry stages of the life cycle of HIV-1 [36]. Although the
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 581

process behind their viral-inhibitory action is not yet entirely understood, NS could
be considered as a broad-spectrum factor against a lot of viral strains and is not
susceptible to developing resistance.

Anti-inflammatory Properties

Nanosilver (NS) exhibits anti-inflammatory characteristics in both animal models as

well as in clinic. For instance, in a swine model with contact dermatitis induced by
topically applying 1,2-dinitrochlorobenzene, NS modified the utterance of pro-
inflammatory cytokines mutating growth factor-β and tumor necrosis factor-α.
Shin and Ye found out that nanosilver enervated nasal symptoms in allergic rhinitis
mice and hampered OVA-specific immunoglobulin E, IL-4, and interleukin-10, and
that inflammatory cell infiltration and goblet cell hyperplasia were hampered by the
nanosilver particles [59]. In a human clinical trial, wound dressing containing NS
was noticed to aid the healing of chronic leg ulcers by not only lowering bacterial
growth in the wound, but also by slowing down inflammatory response as well. NS’s
potentiality to lower the cytokine release and matrix metalloproteinases reduces
lymphocyte and mast cell infiltration, induces apoptosis in inflammatory cells [59],
and aids in their anti-inflammatory activity.

Synthesis Methods of Nanosilver (NS)

Different routes of synthesis result in varied shapes, sizes, stability, and morphology.
Nanosilver (NS) has been synthesized generally via three routes – chemical, phys-
ical, and biological (green) which are discussed below.

Chemical Method of Synthesis

The most widely used method of nanosilver synthesis is chemical reduction. The
three main constituents of this method include a silver salt, capping agents or a
stabilizer, and reductants. These are necessary to control the growth of NS (Fig. 3). A
silver salt which is widely employed in this method due to its chemical stability and
low cost in comparison to other available silver salts is silver nitrate. Citrate,
borohydride, ascorbate, and hydrogen gas are the reductants used.
A reducing agent that is strong and has a faster reduction rate to result in smaller
particles is borohydride, because it can avoid NS aggregation during its decompo-
sition and can also exhibit the role of an NS stabilizer [42]. Due to their aggregation,
it is challenging to obtain NS in high concentrations. Using a stabilizer during
synthesis is often very common. Functional groups are a component of stabilizers
such as polymers or ligands and surfactants like poly(methacrylic acid), poly-
vinylpyrrolidone, poly(methyl methacrylate), poly(ethylene glycol), and others.
Stabilizers can also include temperature-sensitive polymers such as collagen and
582 S. Gulati et al.

Reductants Ag+ Capping agent Nanosilver particle

Fig. 3 Synthesis of NS via chemical route

poly(N-isopropylacrylamide). Novel thermal switching applications can be realized

by nanosilver that is capped by those chemicals.
A two-phase water-organic system can also be employed for NS synthesis. This
method produces uniform and controllable nanoparticles. This system involves two
constituents that are separated in two phases – a reducing agent and metal precursor;
thus, the intensity of interphase transport between oil and aqueous phases controls
the rate of interaction; however, the surface of synthesized NS may get contaminated
due to high amounts of organic solvents and surfactants, and their removal is also
expensive and consumes a lot of time.

Physical Method of Synthesis

The most significant physical techniques employed for synthesizing nanosilver from
metal samples are laser ablation and evaporation/condensation. Pure nanosilver
colloids are obtained without the use of any chemical reagents via laser ablation of
metals in solution. The number of laser shots and laser fluences affects the morphol-
ogy and concentration of nanosilver. Particle size formed is larger along with high
concentration when the time duration and laser fluence are increased.
In case of the evaporation/condensation technique, NS is synthesized by
employing a furnace tube under atmospheric pressure; however, traditional furnace
tubes present several challenges, such as gaining thermal stability
requires a long duration of time along with increased consumption of energy. In a
study, nanosilver was synthesized in high concentrations by using a small ceramic
heater which consisted of a local heating area so that a favorable cooling rate could
be established for the evaporated vapor [32]. Recently, silver suspension was
generated via a novel arc-discharge method in pure water and without any stabilizers
or surfactants. Positive and negative electrodes were made by using silver wires and
were etched in pure water. During discharge, well-dispersed and stable NS were
synthesized as the surface layer of the silver wires was evaporated and condensed in
the water.
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 583

Biological Method of Synthesis

The need for environment-friendly synthesis methods is increasing in this modern

era, and biosynthesis (green synthesis) has gained significant attention with respect
to this approach. These methods employ eco-friendly agents for capping and reduc-
tion, such as peptides, protein, carbohydrate, several species of yeast, fungi and
bacteria algae, and plants. Large-scale chitosan-nanosilver (400 nm) films have been
synthesized using chitosan as a stabilizing and chelating agent via an in situ,
economical, and fascicled method; the prepared films exhibited phenomenal anti-
bacterial action against Escherichia coli and Bacillus [64].
The biosynthesis method avoids the use of toxic reagents and organic solvents as
bacteria, fungi, plants, algae, yeasts, carbohydrates, and proteins are responsible for
the production of stabilizing and reducing agent molecules. Enzymatic and non-
enzymatic reduction is involved in the possible mechanism of biosynthesis (Fig. 4).
NS can be synthesized via enzymatic reduction by nicotinamide adenine dinucleo-
tide phosphate-dependent reductase. However, the reduction rate exhibited by the
enzyme is often slow [3]. On the other hand, nonenzymatic reduction takes just a few
minutes to complete and is very rapid along with being a viable technique amid
extreme conditions, such as high temperature or pH, that enhance the pace of
synthesis [60]. This kind of reduction of silver is similar to chemical reduction,
except for the fact that plants or microorganisms are employed here as reducing and
stabilizing agents.
NS that is synthesized biologically is more stable than that which is synthesized
chemically, as this method does not involve the use of organic solvents and toxic
reagents. Therefore, NS prepared through this method retains its stability for long

Fig. 4 Biosynthesis of NS
584 S. Gulati et al.

durations. Moreover, as the multiplication of microbial cells continues, NS biosyn-

thesis under a nontoxic concentration of silver nitrate becomes possible [45]. How-
ever, this method of synthesis is also susceptible to drawbacks such as the
requirement of practicing caution in medical applications because the purification
process may lead to pathogenic bacteria that might result in contamination [61].

Mechanisms of Biological Interactions of Nanosilver

As indicated by its current clinical use, the antibacterial activity of silver is well
established in treating burns [6]. It is accepted that biologically active silver ions are
furnished by silver and NS present in aqueous solution, which can effectively exhibit
the bactericidal effect. Complete understanding of this mechanism has not yet been
realized, but observations from recent studies can somewhat explain the interactions
involved [10]. The bactericidal effect that is mediated by silver ions is via interaction
with three main components of the bacterial cell: the peptidoglycan cell wall [68]
and the plasma membrane, bacterial (cytoplasmic) DNA, and bacterial proteins [68]
(Fig. 5). On comparing silver chloride, silver nitrate, and NS, it was found that free
silver ions have lower antibacterial effectiveness than NPs [14]. This indicates that
the furnishing of Ag+ ions does not influence the intrinsic antibacterial properties
that are possessed by NS. It has been proposed that NS results in lysis upon
interaction with bacterial cell walls [68]. The potential cytotoxicity of NS toward

Fig. 5 Mechanism of the antibacterial action exhibited by silver ions

25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 585

humans and its antibacterial potency [10] both can be explained with respect to the
reactive oxygen species (ROS) that are produced by NS. By employing proteomics
via 2D electrophoresis in combination with mass spectroscopy of protein samples
from NS-treated Escherichia coli cells, efforts have been made to understand the
antibacterial mechanism of NS [38]. Upregulation of outer-membrane protein pre-
cursors (OmpF, OmpA, and OmpC) has been observed upon NS treatment [38], and
a compensatory effect is caused by these precursors to counteract the cell wall
damage mediated by both NS and silver ions. Inhibition of ATP synthesis and
disintegration of the proton motive force are caused by the disruption of the bacterial
membrane and cell wall [38].

Toxicology of Nanosilver (NS)

Although nanosilver (NS) possesses remarkable advantages for various biomedical

applications, it exhibits toxicity at some concentrations and can cause some major
health issues if not properly administered. Thus, it is essential to address the
biosafety of NS in human health. The daily quantity of silver extracted from
natural sources in water and food consumed by humans is roughly 0.4–30 μg.
Some other research performed per toxic effects of NS in biological systems such
as viruses, bacteria, and human cells has demonstrated conflicting results
[56, 66]. Usually, NS are highly effective antimicrobial agents with nontoxic
effects to healthy mammalian cells [62]. On the other hand, several in vitro studies
validated the NS toxic effects in rat hepatocytes and neuronal cells, human lung
epithelial cells, and murine stem cells. The toxicology study of nanosilver was also
performed in vivo. The research demonstrated that exposure of NS in a rat ear
model leads to mitochondrial dysfunction, following a temporary or permanent
hearing loss, depending on the inoculation dose. In fact, a low concentration of NS
was absorbed by retinal cells resulting in structural disruption, because of the
increased number of cells that endured oxidative stress. Various investigations
performed proved that the surface functionalization leading to variations in surface
charge of NS can influence translocation to various tissues, cellular uptake, and
cytotoxicity. The extent of the surface charge, as measured by the zeta potential,
can impact the number of nanoparticles and their mechanism of uptake into cells.
The evaluation of NS toxicity is a twofold procedure. First, the innate toxicity of
NS must be assessed, which arises from having the similar extents as biological
molecules (e.g., proteins and DNA, 2 nm) and therefore can directly interact to
denature proteins and enzymes, damage DNA, and produce free radicals [27]. This
is additionally confined by the toxicity of biologically active silver ions [18] and
elemental silver [17]. Investigations have demonstrated that NS is toxic to a
number of different cell lines, including C18-4 male mouse germline cells [8],
NIH3T3 mouse fibroblasts [27], BRL 3A rat liver cells [29], and THP-1 monocytes
[18]. Current evidence strongly advocates that NS is toxic via its interaction with
mitochondria [10, 27] and initiation of the apoptosis pathway [27] through the
production of ROS, causing cell death. The relationship between NS size and
586 S. Gulati et al.

inhibitory effects on mitochondria was also demonstrated. It was identified that NS

of smaller size ( 15 nm) is more toxic than NS of larger size ( 55 nm) [10]. Inves-
tigations on oral toxicity and inhalation of NS in Sprague-Dawley rats have
demonstrated that low concentrations induce toxicity only after 28 days of contact
[33]. Consequently, long-term exposure of NS in food packaging or aerosols to
humans might pose toxicity problems. No investigations have been done on the
teratogenicity of NS in human trials. Nevertheless, it has been demonstrated that
NS can alter the early premature development of zebrafish embryos in vivo
[5]. Hence, it can be concluded that NS displays a substantial level of cytotoxicity
by investigations done in vitro and in vivo. Long-term exposure is related to
increased argyria, which has been demonstrated by in vivo studies. A restricted
number of human trials have been performed [22], but the nontoxic and extensive
use of NS in vitro [5] and in vivo [57] for wound dressings in the administration of
burns has not reflected the apprehensions. Still, the evaluation of any potential NS
toxicity is essential for human trials. Precaution must be taken for the use of NS in
everyday purposes (e.g., socks, cooking ware) so that the liability of NS contact
does not exceed subtoxic levels. Moreover, the environmental effect of NS, which
percolates into the water system, must be considered to avert ecological
catastrophe.

Applications of NS in the Biomedical Field

Remarkable research has been done on NS for its use in biomedicine, with diverse
products being used clinically. Groundbreaking applications are being projected and
assessed as more knowledge of NS is disseminated throughout medicine. During a
medical intervention, implantable devices pose a threat to the reduction of hospital-
acquired infections. There are two categories of implantable intrusive devices: one,
where implantable devices are completely rooted within the body, and another,
where implantable devices are partly implanted inside the patients and are partially
exposed to the external environment. Devices such as heart valves, which are fully
implantable devices, are prone to contamination throughout the operation and entail
prophylactic antibiotic treatment for the first few days postimplantation to prevent
infection [9]. In comparison, partly implantable devices such as venous and urinary
catheters are in continuous exposure to the external environment and hence suscep-
tible to bacterial colonization. The use of such catheters is limited in clinical practice
owing to its high risk of infection. The characteristics of a novel antibacterial coating
comprise of low in vivo toxicity, prolonged activity, the capability to act against a
wide spectrum of bacteria, high levels of bactericidal and bacteriostatic activity, and
biocompatibility. Additionally, the coating should be reproducible, inexpensive, and
environmentally benign. Antibacterial coating for cardiovascular diseases must
possess hemocompatibility to prevent thrombosis [63]. Herein, we discuss several
biomedical applications of NS, ranging from cardiovascular implants to catheters
(Fig. 6) (Table 1).
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 587

Fig. 6 Various medical applications of NS

Cardiovascular Implants

In 1998, the first-ever cardiovascular medical device, a prosthetic silicone heart

valve coated with elemental silver, was designed (Silzone), encouraged by favorable
in vitro and in vivo investigations. It was designed to reduce the incidence of
endocarditis, to prevent bacterial infection on the silicone valve, and to reduce
inflammation response succeeding valve replacement and was consequently used
in a clinical trial [23]. The underlying principle behind the usage of silver was to
prevent bacterial colonization on the silicone valve, therefore reducing inflammation
of the heart. Extensive toxicological investigations of the Silzone demonstrated
encouraging biocompatibility. Nevertheless, 4 years into the trial, silver heart valves
were discontinued due to elevated rates of paravalvular leakage in patients, hyper-
sensitivity, and inhibition of normal fibroblast function [30], which led to the failure
of the trial. As a result, the usage of silver in cardiovascular device coatings has been
withdrawn. Currently, NS is being advertised as a sustainable alternative to metal
silver in providing a nontoxic and safe antibacterial coating for medical devices.
Hence, a new nanocomposite based on diamond-like carbon as a surface coating
with 4 – nm NS implanted on the matrix has been synthesized for cardiovascular
medical devices (such as heart valves and stents). It was observed that platelet
adhesion investigations have shown reduced platelet attachment to the surface of
588 S. Gulati et al.

Table 1 NS-applied biomedical products and their effects

S. no. Product Characteristic Reference
1. Silzone Cardiovascular implant – to prevent [23]
bacterial colonization and reduce
inflammation of the heart
2. Diamond-like carbon as a Cardiovascular medical devices [2]
surface coating with 4 nm antithrombogenic characteristics and
NS implanted hemocompatibility properties
3. ON-Q SilverSoakerTM Delivery of medication (e.g., local [12]
anesthetics or analgesics) per-, peri-, or
postoperatively for pain management or
for antibiotic treatment
4. Silverline Neurosurgical drain of CSF for [12]
hydrocephalus. Also can be adapted for
use as shunts. Antibacterial silver NP
coating prevents catheter-associated
infections
5. ActicoatTM Dressing for a range of wounds including [41]
burns and ulcers; prevents bacterial
infection and improves wound healing
6. NS-PMMA bone cement Antibacterial activity and low [1]
cytotoxicity
7. NS-impregnated Efficient silver ion release [20]
neurosurgical catheters
8. NS-impregnated plastic Inhibition of biofilm growth in vitro and [53]
catheter nontoxic in vivo
9. Chitosan-nanocrystalline Improved healing rates [39, 40]
silver dressing
10. NS-carbon-based Presence of antithrombogenic properties [2]
nanomaterial as surface- after being coated onto cardiovascular
coating agent medical devices

the nanocomposite, and those that did adhere were haphazardly disseminated,
signifying that the material has antithrombogenic characteristics. Besides, the sur-
face of nanocomposites demonstrated antibacterial characteristics and was studied
for hemocompatibility properties [2]. Furthermore, Ghanbari et al. [21] and Fu et al.
[19] also fabricated antibacterial multilayer films comprising of NS and examined
their antibacterial, hemodynamic, and mechanical characteristics in vitro for use in
coating of the cardiovascular implant [21].

Catheters

An extensive study has been conducted to examine NS as antibacterial materials for

coating catheters, including central venous catheters (CVC) and neurosurgical
catheters. CVCs are significant therapeutic devices for use in replacement therapy
(such as renal disease and cancer) and malnutrition [25]. They are used to provide
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 589

access for hemodynamic monitoring, fluid administration, drug-delivery pathways

[65], and nutritional support to critically ill patients. Alterations of one-dimensional
and two-dimensional NS surfaces are being investigated extensively for antibacterial
effects in clinically relevant tools [54]. Although silver is vulnerable to the rapid
oxidation process, the outstanding surface-to-volume ratio characteristically out-
weighs its oxidation process as coating interface has unrelenting Ag+ supply
[63]. The bactericidal effects are estimated to be size-dependent since the binding
capacity of NS to bacterial cells is influenced by the surface area available for
interaction [49]. ON-Q Silver Soaker™ (I-Flow Corporation, CA, USA) and
Silverline (Spiegelberg GmbH and Co. KG, Hamburg, Germany) are two commer-
cially accessible medical catheters consisting of NS to inhibit catheter-associated
infections [12]. Medical catheters can lead to serious complications as they are prone
to bacterial infection, which can quickly spread to the wound and its nearby areas.
Due to lack of toxicity and remarkable antibacterial characteristics, NS can reduce
the prevalence of bacterial infection and difficulties after surgery. Several diverse
methods have been studied for NS-impregnated polymers as antibacterial materials
to delay biofilm growth on catheters [58]. Generally, polyurethanes, already recog-
nized as plastic catheters, have been modulated with NS. Plastic catheter tubes can
readily be coated with a layer of NS to form effective antibacterial catheters [53].

Bone Cement

Each year, globally, millions of individuals are affected by complex and distinctive
bone-related pathologies, such as cancers, degenerative and genetic conditions,
infectious diseases, and fractures [16]. Regrettably, as the associated infections are
accompanied by high morbidity, the resourceful colonization and contamination of
orthopedic grafts signify foremost apprehensions in osseous-tissue replacement
approaches [11]. Bone is an active tissue that undergoes restorative and regenerative
developments through the complex and intrinsic bone-remodeling mechanism
[51]. Bone implants are generally rooted to restore or replace severe flaws that
irremediably affect osseous tissue, such as tumors, genetic malformations, or
traumas. Bone-destruction occurrences, highly inflammatory progressions, and sub-
sequent implant loss are associated with orthopedic and bone-implant-related infec-
tions [7]. Bone cement has its use in safe attachment of joint prostheses in, e.g., knee
and hip replacement surgery. Total joint replacement has infection rates as high as
1.0–4.0%. Infection rates of antibiotic-loaded bone cement have significantly
reduced to between 0.4% and 1.8%, but relying on antibiotics is adverse as bacterial
resistance develops rapidly [31]. NS has been evaluated as an antibacterial additive
to poly (methyl methacrylate) (PMMA) bone cement conjugated with different NS
ratios in vitro. It has been observed that bone cement-conjugated 1% NS entirely
prevented the proliferation of methicillin-resistant S. epidermidis, Staphylococcus
epidermidis, and methicillin-resistant S. aureus, with no major variation between the
nontoxic control group and nanosilver bone cement in qualitative and quantitative
toxicity tests. NS-PMMA has shown a reduction in the occurrence of resistance
590 S. Gulati et al.

through its complex mechanism of action and also demonstrated outstanding anti-
bacterial activity, retardation of biofilm growth, and low toxicity in vitro. NS bone
cement did not display toxicity in vivo, signifying good biocompatibility [1]. NS
also acted as an additive to ultrahigh-molecular-weight polyethylene for assembling
inserts for total joint replacement mechanisms, and it was observed that NS signif-
icantly reduced the deterioration of the polymer [43].

Wound Dressing

Wound infections signify an essential clinical challenge, with foremost impact on

patient mortality and morbidity causing prominent economic consequences [67]. Pre-
venting wound rupture and surgical-site infection is a crucial and challenging feature
in current clinical practice [15]. The structural and functional integrity of skin may be
disrupted significantly at different stages induced by chemical or physical wounds,
causing permanent damage or even death depending on the severity of the wound. The
wound-healing mechanism is a complex pathophysiological process, which includes
different phases, such as cellular proliferation, coagulation, inflammation, and matrix
and tissue remodeling [26]. Since primeval periods, silver-based compounds and
resources were used for the exceptional and effective control of distinctive infections
[24]. Due to its biological uniqueness and intrinsic physicochemical features, NS
provides an extensive variety of effective biocide activities against a remarkable
variety of Gram-negative and Gram-positive and anaerobic and aerobic, bacterial
strains. Due to the chemical inactivation of mammalian and bacterial cells, they poorly
absorb metallic silver. Hence, the ionization of silver is crucial with the aim to provide
particular antibacterial effects under physiological circumstances (including the pres-
ence of body fluids or secretions). After their dissemination inside cells, Ag+ ions
combine with enzymatic and structural proteins [34]. NS used in penetrable wound
dressings can interact with bacteria found in exudate and terminate it [69]. Concisely,
current facts reveal the following evidence concerning NS skin absorption: (i) in vitro
skin permeation by nanoparticles, and (ii) significant increase in permeation of
damaged skin [37]. Naturally available biopolymers such as chitosan and collagen
exhibit incredible potential concerning the procurement of novel and functionally
enhanced platforms for effective wound-healing approaches, when implied along
with nanotechnology applications [35]. Aquacel™(ConvaTec), Acticoat™ and
Bactigras ™ (Smith & Nephew), Tegaderm™ (3M), and PolyMem Silver™(Aspen)
are commercially available products for wound-dressing applications, biocomposites
modified with ionic silver and approved by the United States Food and Drug Admin-
istration (FDA). The use of NS as carriers also signifies a valuable approach for
delayed diabetic wound-healing procedures, as diabetic wounds may be accompanied
by several secondary infections. NS can assist diabetic patients in early wound-healing
phases, furthermore providing minor marks [41]. Considering the improved anti-
bacterial effects demonstrated by NS and the remarkable attention focused toward
their application in medical-device coatings and wound therapy, their biocompatibility
and safety characteristics must be thoroughly illuminated [52]. Huang et al. demon-
strated that nanocrystalline silver wound dressings significantly reduced the healing
25 “Nanosilver”: A Versatile and New-Generation Nanoproduct in Biomedical. . . 591

time by an average of 3.35 days and enhanced bacterial clearance from infected
wounds in comparison to silver sulfadiazine, with no hostile effects [28]. Moreover,
Chen et al. evaluated NS wound dressings and demonstrated the advantage of NS
wound dressings in reducing the healing time for superficial burn wounds, but no
change was observed in deep burn wounds, in comparison to 1% silver sulfadiazine.
This proposes that NS quickens re-epithelization, but not other segments of wound
healing connected with new tissue formation, such as proliferation and
angiogenesis [13].

Conclusion

Nanosilver (NS) is an extensively investigated nanostructure for exceptional bio-

medical applications, owing to its size-related attractive physicochemical character-
istics and biological functionality, including its high antimicrobial efficacy and
nontoxic nature. The application of NS is well reputed for various biomedical
applications such as cardiovascular implants, catheters, bone cement, wound dress-
ing, diagnosis, and pharmacological treatment. The shape, composition, and size of
NS can have significant effects on its function and potential risks to human health,
hence wide-ranging research is needed to completely understand their synthesis,
possible toxicity, and characterization. This chapter started with an overview of NS
synthesis, then its outstanding biological properties were discussed, followed by
toxicology, and then its biomedical applications were reviewed. NS possesses
outstanding biological properties, including antiviral and anti-inflammatory charac-
teristics, along with highly distinguished antibacterial properties. Intrinsic parame-
ters such as shape, size, surface charge, concentration, and colloidal state are
associated with antimicrobial properties exhibited by NS. Surface functionalization
of NS is possible as the available surface of NS allows the coordination of many
ligands. Besides their versatile antimicrobial properties, NS provides supplementary
chemical, mechanical, optical, and biological properties that suggest them for the
design, evaluation, obtaining, and clinical evaluation of performance-enhanced bio-
materials and medical tools. NS dressings are now the benchmark in the conven-
tional treatment of burns and wounds. Implantable medical tools, such as venous and
neurosurgical catheters, have greatly reduced patient infection and reliance on
antibiotic use and the associated costs. However, significant research on toxic-
related mechanisms is mandatory. The existing shortcoming of healthcare practice
and the latest experiments resulting from nanosilver-based technology highlight the
extraordinary potential of NS in biomedical applications.

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Synthesis of Biocompatible Chitosan
Nanoparticles by Some Greener Methods 26
for Drug Encapsulations

Srijita Basumallick

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
Bottlenecks of Biomedical Uses of Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
Strategies of Preparation of Water-Soluble Chitosan Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
Preparation of Water-Soluble Depolymerized Chitosan and Its Derivatives by Some Green
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
Synthesis of Chitosan Nanoparticles by Ionic Cross-Linking Using TPP . . . . . . . . . . . . . . . . . . . . . 600
Synthesis of Chitosan Nanoparticles by Ionic Cross-Linking Using
Bi-carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
Synthesis of Chitosan Nanoparticles by Reverse Micelle Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Characterization of Chitosan Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Fluorescence Properties of Chitosan Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
Various Methods of Drug Loading onto Chitosan Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Method of Formation of Ionic Complex Between Drug and CS Nanoparticles . . . . . . . . . . . 605
Method of Spray-Drying Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Method of Emulsification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Method of Micelle Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
Method of Poly-electrolyte Complex Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

Abstract
Chitosan is obtained from chitin, and it is the second most abundant biopolymer
after cellulose. Chitosan is biocompatible and biodegradable, hence an ideal
biomaterial for drug encapsulation and delivery. But chitosan is not soluble in
water which is a major bottleneck of chitosan for its biomedical applications. In
this chapter, we have discussed some greener methods of making water-soluble
chitosan nanoparticles and their drug-encapsulating behaviors. Basically, this
chapter describes depolymerization of water-insoluble larger chitosan polymers
followed by formation of compact nanostructure by cross-linking. Discussions on
S. Basumallick (*)
Department of Chemistry, Asutosh College under Calcutta University, Kolkata, India

© Springer Nature Singapore Pte Ltd. 2022 595

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_49
596 S. Basumallick

different types of cross-linking agent and nature of cross-linked chitosan nano-

particles have been presented. Recent reports on drug encapsulation by chitosan
nanoparticles, their stability at different pH, and their biomedical applications
have been highlighted. Methods of encapsulation of different types of drugs
(hydrophilic or hydrophobic) within the chitosan particles have been cited.

Keywords
Depolymerization of chitosan · Hydrothermal method · Ionic cross-linking · Drug
loading · Biomedical uses of chitosan

Introduction

During the recent past application of potential nanomaterials have been nicely
described in a series of handbooks by Hussain et al. [1–6]. In this chapter, we
shall present synthesis and biomedical applications of another important (web
references i–v) nanomaterial, chitosan. Chitosan is a polysaccharide comprised of
D-glucosamine and N-acetyl-D-glucosamine joined through a β(1 ! 4) linkage. It is
derived from the naturally occurring biopolymer chitin, the second most abundant
biopolymer in nature, the first being cellulose. The main sources of chitin are
crustacean shells, but it is also seen as a structural component of some fungal cell
walls. The structures of both chitin and chitosan are shown in Fig. 1. Chitosans
(CS) are classified by the quantity of amine groups present on the chain referred to as
either the degree of acetylation (DA) or the degree of deacetylation (DD). The amine
groups along the chitosan chain contribute to the unique and beneficial properties of
chitosan. It behaves as a cationic polyelectrolyte under neutral and acidic conditions.
Chitosan is a nontoxic biomaterial having biocompatible and biodegradable proper-
ties and it can be safely used [7–10] as a drug-encapsulating material.
Due to the presence of reactive hydroxyl and amine groups along the chain,
chitosan can be chemically modified in order to tailor its functionality. This chapter
includes some examples of chitosan derivatives with improved solubility and other
properties.

Bottlenecks of Biomedical Uses of Chitosan

In spite of presence of almost all the requirements of an ideal biomaterial, chitosan is

not widely used as a biomaterial for drug encapsulation and drug delivery. This is
owing to insolubility of chitosan at biological pH. Chitosan (CS) is soluble only in
acidic solution pH < 6.5. In acidic pH the –NH2 groups of chitosan get protonated
making it water soluble. Thus, the major challenge [10] of using chitosan in
pharmaceutical industries is to prepare water-soluble chitosan at biological pH.
Two different strategies are taken to prepare water-soluble chitosan. In one
approach hydrophilic groups are introduced to the chitosan skeleton to make it
water soluble.
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 597

CH3
CH3

O
O
OH OH
NH
NH
O O
O O
O
HO HO O
O
NH NH
OH
OH O
O
CH3

CH3

OH OH
NH2
NH2
O O
O O
O
HO HO O
O
NH2 NH
OH
OH O

CH3

Fig. 1 Structures of chitin (upper) and chitosan (lower). As shown in this image, the chitosan
would have a degree of deacetylation of 75%

The other approach is to prepare water-dispersible chitosan nanoparticles. This

chapter will primarily deal with the preparation procedure of chitosan nanoparticles
and their characterization.

Strategies of Preparation of Water-Soluble Chitosan

Nanoparticles

A great variety of methods for the synthesis of chitosan nanoparticles can be found in
literature, like ionic gelation [11, 12], synthesis with carboxymethylcellulose [13],
formulations using glutaraldehyde [14, 15], synthesis with alginate [16], and reverse
micelle method [17, 18].

Preparation of Water-Soluble Depolymerized Chitosan and Its

Derivatives by Some Green Methods

Chitosan is a natural biopolymer obtained by deacetylation of chitin. Cellulose is the

most abundant polysaccharide in nature; chitin is the second most natural polysac-
charide. Chitosan is a low-cost biodegradable, nontoxic biopolymer easily obtained
from the natural polymer chitin by deacetylation. It has high application potential as
598 S. Basumallick

a carrier of drugs through different routes, but the major bottleneck of using chitosan
in biomedical applications is its extremely poor solubility in aqueous medium at
biological pH. Therefore, it is challenging to develop an easy and cost-effective
method of preparation of water-soluble chitosan nanoparticles at biological
pH. Currently, water-soluble chitosan is prepared by forming its water-soluble
derivatives. But this conversion needs several steps and sometime uses hazardous
chemicals [19]. One of the commonly used derivatives is carboxymethyl derivative
of chitosan [20]. Other imortant derivatives are Schiff bases of chitosan. On treat-
ment of monochloroacetic acid with such Schiff bases give purely water-soluble
chitosan [21]. N-(2-Hydroxy) propyl-3-trimethylammonium chitosan chloride is
another important water-soluble derivative [22] of chitosan. Apart from these,
several urea groups are included into the chitosan derivatives with quaternary
ammonium salt giving water-soluble chitosan [23]. Another type of modification
is graft polymerization of dicyandiamide. Due to decrease in crystallization, the
solubility decreases [24]. Enzymatic hydrolysis of chitosan is another possible way
of getting water-soluble chitosan. Enzyme-catalyzed hydrolysis of chitosan pro-
duces water-soluble chitosan; here enzyme catalyst is isolated from soluble part of
jelly fig latex [25].
Apart from preparation of water-soluble derivatives of chitosan, derivatives
formed by simple conjugations are also a greener path. Another way of making
water soluble chitosan is by anchoring with small molecules/groups like
carboxymethyl group [20], N-(2-hydroxypropyl)-3-trimethylammonium [26, 27]
group, glycol [28] or with water-soluble polymer conjugation like alginate [29,
30], dextrin [31], polyglutamic acid [32], hyaluronic acid [33], sodium cellulose
sulfate [34], etc. [36]. Water soluble chitosan may be made by attaching chitosan
with long chain fatty acid like oleic acid [36] and palmatic acid [37].
But all these processes need hazardous chemical or expensive enzyme. Compared
to these, greener methods of preparation of water-soluble chitosan include
deacetylation or depolymerization.
Chitosans of well-defined degree of deacetylation (DA) and molecular weights
are commercially available, and they are soluble only in the dilute acid. To convert
this water-insoluble biopolymer to water-soluble polymer, both depolymerization
and deacetylation techniques are largely used. The common methods of depolymer-
ization are hydrolysis by acetic acid and oxidative depolymerization by H2O2 and
sodium nitrite. While degree of depolymerization is often indicated by average
molecular mass of the polymer and size of the polymer particles, the degree of
deacetylation is determined by CHN analysis or by C13NMR study. Apart from
simple depolymerization, attempts have also been made to make water-soluble
polymer nanoparticles using techniques of ionic gelation or by covalent cross-
linking method to form small nanoparticles which will be discussed later. The degree
of deacetylation plays an important role in dictating physicochemical and the cross-
linking density of the chitosan. Fully deacetylated chitosans have also been prepared
by enzymatic hydrolysis of high molecular weight chitosan.
Among depolymerization techniques the first one is use of inorganic acid like
HCl [38], H3PO4 [39], H2SO4 [40], etc. The second is depolymerization by organic
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 599

acids like acetic acid [41] or formic acid or by using oxidizing agent like H2O2 [42]or
ozone [43] or other radical generators like potassium persulfate [44]. Interestingly,
physical methods that are perfectly green in all sense, like use of X-ray [45], γ-ray
[46],microwave, or ultrasound, have been examined [47, 48].
Table 1 shows the summary of different depolymerization methods of chitosan.
Oxidative depolymerization: In oxidative depolymerization the depolymerization
as well as decolorization occurs in a single step. The by-products are often gaseous
and easily get out. Demin et al. [49] first mentioned that the initial stage of
interactions of ozone with polysaccharide is its electrophilic attack on C(1)-H
bond with the formation of labile hydro-trioxides, destruction of which results in
depolymerization of polysaccharide. Kabal’nova et al. [50] mentioned the detailed
mechanism of ozone-mediated cleavage of 1–4 glycoside bond. The formation of
aldehyde and carboxyl group was confirmed from IR data as well as potentiometric
titration.
NaNO2-mediated depolymerization: Chitosan depolymerization by NaNO2 was
done by Liu et al. [51]. NaNO2 depolymerization is hugely affected by the concen-
tration of the reactants rather than the chitosan/NaNO2 ratio. The IR spectra indi-
cated associated significant amount of de acetylation as well as decrease in hydrogen
bonding between >C¼O. . ...HN- and -C-OH. . ...HO-C. The drawback of this
procedure is that aldehyde formed undergoes imine formation by the interaction
with free NH2 group of chitosan.
H2O2-mediated depolymerization: H2O2 mediated depolymerization was
reported by several scientist [42, 52]. The depolymerization by the hydrogen perox-
ide produced carboxylic acid and reduction in 15% of NH2 groups. The mechanism
of depolymerization is more or less same as ozone mediated depolymerization and as

Table 1 Depolymerization of chitosan using different agents

Method of making water-soluble chitosan Reagents
Chemical Conjugation of Small Carboxymethyl group,
modification water soluble molecules [N-(2-hydroxypropyl)-3-
trimethylammonium], glycol
Polymer Alginate, polyglutamic acid, dextran
Long Oleic acid and N-palmitoylation
chain fatty
acid
Depolymerization Chemical Inorganic HCl,H2SO4, H3PO4
depolymerization acid
Organic CH3CO2H, formic acid
acid
Oxidizing H2O2, O3
agent
Enzymatic depolymerization Chitosinase
Radiation-mediated X-ray, γ-ray, microwave
depolymerization
Hydrothermal None
depolymerization
600 S. Basumallick

in the case of ozone mediated depolymerization FTIR shows formation of

carboxylic acid.
Comparison of the methods: Enzymatic method is best in the sense DD (degree of
depolymerization) is more controllable. But it is costly and difficult to purify
enzymes. Chemical method is better in terms of yield, but exact optimization is
needed to avoid excess by-products. Physical methods are perfectly green, but yield
is poor. NaNO2 oxidative depolymerization gives best yield [53] and fastest reaction
rate in comparison to all acid-catalyzed reactions [54]. But it forms aldehyde that
undergoes other reactions [55] unless reduced by NaBH4 just after reaction. Acetic
acid gives moderately good yield more or less similar to mineral acids and almost
100% completion without much by-product, but here reaction time is relatively
longer [56]. Inorganic acid hydrolysis gives comparatively clean depolymerization
reaction with overall yield after 6 hr. in the presence of excess of reagent being 50–
60% [57]. For H2O2- and O3-mediated depolymerization, the reaction time is less
and yield is moderate and depends on other parameters, for example, 6% H2O2 at
80  C with 30 min reaction time gives 30% yield [58]. In case of hydrothermal
depolymerization, amorphous chitosan degrades faster [59].
During target-specific drug loading onto these depolymerized chitosans, care
should be taken so that drugs are not flashed out [60] before reaching to the target.

Synthesis of Chitosan Nanoparticles by Ionic Cross-Linking

Using TPP

In this method the ionic gelation technique is applied, which is based on the principle
that at acidic conditions, the (-NH2) groups of chitosan are protonated to –NH3+ and
interact with anions, like triphosphate, creating nanoparticles [61]. Chitosan nano-
particles are easily prepared by the ionic gelation method using TPP as a cross-
linking agent. This is a simple process based on an ionic interaction between
positively charged amino groups on chitosan and the negatively charged tri-
polyphosphate ion at room temperature.
This method presents the following advantages: the nanoparticles are obtained
spontaneously under mild control conditions without involving high temperatures,
organic solvents, or sonication, and it has a surface charge which can be modulated
from high to low positive values.
Since there are different kinds of chitosan, with distinct deacetylation degrees and
molar weights, it is important to study which are the best conditions in order to
obtain the smallest nanoparticles with the appropriate superficial charge.
Neves et al. [62] have evaluated the influence of pH, ratio of chitosan/tri-poly-
phosphate (CS:TPP), and acetic acid concentration in the size and zeta potential of
the nanoparticles obtained through ionic gelation. The nanoparticles were character-
ized concerning their antimicrobial activity and morphology using transmission
electron microscopy.
It has been reported [62] that a small variation up to 5% in pH does not influence
significantly on diameter and zeta potential of chitosan nanoparticles.
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 601

It is reported [62] that the parameter that most influenced the zeta potential of the
nanoparticles was ratio of CS:TPP and its optimum condition was that at the lowest
level it should be 3:0.8. This is the main parameter because the tri-polyphosphate
anions interact with the protonated amino groups of chitosan forming nanoparticles.
It is due to the fact that with the highest level of CS:TPP (ratio 3:1), there are more
cross linkages between polymer and phosphates forming nanoparticles with smaller
hydrodynamic diameter. However, for the ratio of 3:0.8, the nanoparticles exhibited
average zeta potential greater than 33 mV, while for ratio of 3:1, the average potential
was less than 29 mV. It is known that nanoparticles with surface charge greater than
30 mV are more stable and this value is sufficient to prevent aggregation of the
particles; therefore, the ratio of CS:TPP 3:0.8 is acceptable for chitosan nanoparticle
production.
From statistical analysis these authors have shown that with 0.1 and 0.2 M of
acetic acid, the observed zeta potential and particle sizes do not vary much.
Based on these results, the parameters were fixed at pH 4.4 and acetic acid
concentration of 0.1 M and ratio CS:TPP of 3:0.8 was recommended. Under these
conditions, the average size of the chitosan nanoparticles was 69.7 nm.

Synthesis of Chitosan Nanoparticles by Ionic Cross-Linking Using

Bi-carboxylic Acids

Here, a description of the compact folded nanostructure formation of chitosan

polymer by cross-linking with bi-carboxylic acid anions has been presented. Since
chitosan is a cationic polyelectrolyte at pH < 6.5, it is best cross-linked with
phosphate ion (as discussed above). But phosphate-cross-linked chitosan nano-
structures are rigid, and therefore drug-releasing processes are hindered.
Basumallick and Santra [10] have proposed a hydrothermal method of preparation
of chitosan nanoparticles using tartaric acid as cross linker.
In this preparation, these researchers have used equal masses of low molecular
weight chitosan and L-(+) tartaric acid in a centrifuge tube followed by dissolving
the mixture in DI water under brief vortex. The chitosan particles are not dissolved
completely and formed a semifluid gel-like material. The mixture is transferred to a
Teflon taped hydrothermal container, and the hydrothermal reaction was continued at
150 C for 90 minutes followed by cooling at room temperature. The final product is a
transparent liquid at pH 2.97 (step1). The solution obtained in step 1 is then filtered
through a 0.2um filter to obtain a transparent liquid at pH 2.93 (step2). The solution
is transparent owing to the fact that chitosan is soluble in acidic pH.
After step 2, the solution is dialyzed by dialysis bag with 3.5 KDa Mwt cutoff
against DI water for 7 days to remove the excess tartaric acid; the pH of the dialyzed
clear solution is found to be 6.0 (step 3). The solution obtained in step 3 was filtered
through 0.22 μm nylon syringe filter to obtain a solution of clear chitosan nano-
particles at pH 6.5 (final step).
Chitosan nanoparticles prepared under such mild hydrothermal route have been
shown to be ionically cross-linked particles. Important difference between covalent
602 S. Basumallick

cross-linking of chitosan with bi-carboxylic acid requires more drastic preparation

conditions. It is worth mentioning that covalent cross-linking of chitosan with
bi-carboxylic acid may be done by chemical and thermal treatment. But the major
differences are seen in FTIR spectra with a new amide peak which is absent in case
of ionically bound dibasic acid. For example, in malonic acid [63], ionic cross-linked
chitosan shows a broad, strong absorption in the region of 3300–2500 cm1
resulting from superimposed –OH and –NH3 + stretching band. Peaks observed at
2823 and 2768 cm1 were due to C–H stretch, and absorption at 1723 and
1675 cm1 corresponds to the presence of asymmetric N–H (–NH3+) bend and
asymmetric –COO- stretching, respectively. Very importantly peaks observed at
1520 and 1381 cm1 were due to symmetric N–H (–NH3+) bend, and symmetric
–COO- stretching, respectively, gives indication for ionic bond [63]. Similarly peak
position are also found for chitosan ionically cross-linked with acetic acid, lactic acid
and citric acid. These peaks at 1597 and 1615 cm1 are diminished, suggesting that –
NH groups are protonated. The carboxylate band of –COO at 1556 cm1 appeared
in all chitosan acid salts. Consequently, it is reasonable to assume that there is an
ionic interaction between chitosan and acids. The intense peaks at 1550–1600 cm1
and the weak peaks near 1400 cm1 (attributed to carboxylate anion stretching,
respectively). Chitosan lactate shows a large band for –NH2 at 1630 cm1. The shift
of this vibration to higher wave numbers compared with the usual wave numbers of
the amine group proves the formation of an ionic bond between the –COO groups
of the acid and the –NH3+ groups of chitosan. The FTIR spectra of chitosan citrate
show bands at 1630 and 1400 cm1 assigned to –NH3+ and –COO, respectively. In
addition, the peaks at 1730 cm1 can be seen suggesting the presence of free –
COOH groups [64].

Synthesis of Chitosan Nanoparticles by Reverse Micelle Method

Reverse micelle method is another green method of chitosan nanoparticle synthesis

and useful for drug loading. The basic principle of reverse micelle formation is to
select a suitable solvent (here a green solvent), so that hydrophobic part of the
surfactant may dissolve but hydrophilic part may accumulate on a micro water drop
so that chitosan nanoparticles grow within this aqueous microcontainer. This method
has been applied for the preparation of chitosan nanoparticles by different workers
including Santra et al. [10] using ethyl acetate as a green non-solvent. These authors
have optimized surfactant concentration, temperature of the solution, and effect of
degree of depolymerization of chitosan. This method is safe for drug loading.

Characterization of Chitosan Nanoparticles

Like metal and metal oxide nanoparticles, the chitosan nanoparticles are best
characterized by TEM images, and a typical TEM image of chitosan nanoparticles
is shown in Fig. 2.
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 603

Fig. 2 A typical TEM image

of chitosan nanoparticles

Basumallick and Santra studied HRTEM images of their tartaric acid-cross-linked

chitosan nanoparticles; the high dark field (DF) contrast of CS-TA nanoparticles
shows that the particles are dense in their core with a semicrystalline structure having
d spacing values close to literature value of chitosan crystal parameter. The particles
are spherical of different sizes varying from 100 to 300 nm. The semicrystalline
nature with high DF contrast makes it perfect targeting agent in high-angle annular
dark field scanning transmission electron microscopy (HAADF-SEM) used to detect
NPs inside cells and elevate background.
These authors have also carried out 2D proton NMR study [10] on their nano-
particles to understand the fate of tartaric acid within the chitosan nanoparticles.

Fluorescence Properties of Chitosan Nanoparticles

Why is fluorescence of chitosan nanoparticles desirable in drug delivery system?

This is because one can tract the movement of drug-loaded chitosan nanoparticles
within biological system simply by monitoring its fluorescence images. Inherent
fluorescence of chitosan nanoparticles was first reported [65] by Haung et al. and
subsequently by Basumallick and Santra et al. [10] and explained in detail the
genesis of fluorescence exhibited by chitosan nanoparticles. These authors have
argued that main fluorophore in chitosan backbone is >C¼O group of acetylated
amine and emission peak of a mixture of chitosan tartaric acid is close to reported
value [66] of fluorescence from aliphatic poly-ketone indicating carbonyl group
plays a major role in imparting fluorescence of chitosan.
It is interesting that fluorescence spectra of chitosan nanoparticles depend on the
pH of the solution. There is always a red shift at higher pH. This has been explained
604 S. Basumallick

proposing that at low pH amide will be present in its enol form but at neutral
pH > C¼O can act as acceptor and N-H as donor to form intramolecular hydrogen
bond as in protein. This will disrupt the presence of enol form of >C¼O group of
chitosan at low pH. So at higher pH, amide may undergo J aggregation, and the
observed red shift has been explained.
In a typical >C¼O molecular orbital, HOMO is nonbonding p electron on “C”
and LUMO is a π*. Now, N lone pair interacts with π* of >C¼O resulting in
increase in the energy of π* (LUMO). As a result, HOMO-LUMO band gap
increases. Thus, at lower pH, there is an overall destabilization of excited state
with reduction of fluorescence intensity. Moreover, alpha and gamma hydrogen of
ketone help in quenching fluorescence from ketone-containing polymer [66]. Now in
the present case, gamma hydrogen is bound to an -OH group. At low pH, the –OH
group will be protonated withdrawing gamma C-H bond electron towards it. Overall,
when compared with chitosan control, the much enhancement of fluorescence might
be either due to structural change of CS polymer with more exposure of >C¼O
groups or due to short conjugation of -C¼O with N of acetyl group in nanoparticle.
The latter explains red shift as well as fluorescence enhancement with pH. In
temperature-sensitive fluorescent polymer, amide linkage plays important role.
The observed excited wavelength dependent on emission spectra as seen from
Fig. 3 indicates that the purified sample of chitosan nanoparticles is a heterogeneous
mixture of nanospheres of chitosan with different sizes as seen in the TEM picture.

Fig. 3 Fluorescence spectra of tartaric acid depolymerized chitosan at different excitation wave-
length. λex ¼ 287 nm (black), 320 nm (red), 335 nm (green), 340 nm (blue), 350 nm (cyan), 360 nm
(pink), 380 nm (yellow)
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 605

Various Methods of Drug Loading onto Chitosan Nanoparticles

Basic principles of drug loading onto chitosan nanoparticles are of much impotence
in view of their application potential in pharmaceutical industries. Obviously, this
will depend on the nature of the drugs. Drugs may be of small molecular type or they
may have larger molecular structures. Again, these drugs may be of hydrophobic,
hydrophilic, or amphiphilic types. In general drug loading technique is selected by
considering the nature of the drug. Some of the commonly used methods of drug
loading onto chitosan nanoparticles are discussed here.

Method of Formation of Ionic Complex Between Drug and CS

Nanoparticles

Because of the cationic properties of chitosan, ion complexes can be formed by

electrostatic interaction between chitosan and anionic drugs. Cheng et al. [67] prepared
chitosan nanoparticles linked with antisense oligonucleotide drug simply by mixing
the CS nanoparticles and this drug in the ratio of 2:1 M proportion. The size of the
nanoparticles was around 102.6 nm; the encapsulation efficiency was found very high.
Kim et al. [68] encapsulated retinol into chitosan nanoparticles through the
electrostatic interaction between the amine group of chitosan and the hydroxyl
group of retinol. Encapsulation into chitosan nanoparticles was shown to increase
solubility of retinol by more than 1600-fold.

Method of Spray-Drying Technique

Spray-drying method can be used as a one-step preparation of nanoparticles loaded

with drug. Grenha et al. [69] prepared mannitol microspheres containing chitosan
nanoparticles-loaded protein drug by this method.
Huang et al. [70] prepared chitosan-iron oxide nanoparticles with various
chitosan/iron oxide ratios by spray-drying. Atomic absorption spectrometry results
implied that chitosan had strong chelation with iron. Meanwhile, Fe3O4 was crys-
tallized and distributed in the chitosan matrix. These chitosan-iron oxide nano-
particles were stable in water with strong superparamagnetism.
Yamamoto et al. [71] investigated the use of chitosan capsules for colon-specific
delivery of 5-aminosalicylic acid (5-ASA) drug. The surface of the chitosan capsules
containing 5-ASA was coated with hydroxy-propyl methyl cellulose phthalate as an
enteric coating material. The experimental results demonstrated that the capsules
were able to reach the large intestine 3.5 h after oral administration.

Method of Emulsification

Tacrine, an anti-Alzheimer drug-loaded chitosan nanoparticle, was prepared by

spontaneous emulsification [72]. The particle size and zeta potential were
606 S. Basumallick

determined by scanning probe microscopy and Zetasizer, respectively. The prepared

particles showed good drug-loading capacity.
Varshosaz et al. [73] reported chitosan microspheres coated with cellulose acetate
butyrate, prepared by the emulsion-solvent evaporation technique, for delivery of
5-ASA into the colon.

Method of Micelle Formation

Doxorubicin-chitosan polymeric micelles had excellent drug-loading properties,

were suitable for targeting the liver and spleen, and significantly reduced drug
toxicity to the heart and kidney [74].

Method of Poly-electrolyte Complex Formation

Chitosan is a cationic polymer and alginate [10] is an anionic polymer; they easily
form poly-electrolyte complex. Thus, chitosan-Ca-alginate microparticles can be
loaded with 5-amino salicylic acid (-5-ASA). Recently, Jain et al. prepared hydrogel
microspheres of chitosan grafted with vinyl polymers for the controlled and targeted
drug release.

Summary

In this chapter, we have discussed the bottlenecks of biomedical uses of chitosan and
need of chitosan nanoparticles for biomedical applications. We have described three
important greener methods of obtaining chitosan nanoparticles. These are (i) ionic
gelation with TPP, (ii) ionic gelation with tartaric acid, and (iii) reverse micelle
method. We have also highlighted the need of fluorescent chitosan nanoparticles for
biomedical applications and genesis of fluorescent property of chitosan nano-
particles. Finally, we have discussed different methods of drug loading onto chitosan
nanoparticles.

Acknowledgment The author is thankful to Professor Swadesh mukul Santra of NanoScience

Technology Center of the University of Central Florida for motivating me to this research. She is
also thankful to the Principal of Asutosh college, Kolkata for academic support.

Important Web References Related to Drug Encapsulation and Delivery by Chitosan

Nanoparticles

(i) https://www.mdpi.com/1999-4923/9/4/53
(ii) https://www.jstage.jst.go.jp/article/cpb/58/11/58_11_1423/_article/-char/ja/
(iii) https://iopscience.iop.org/article/10.1088/0957-4484/18/40/405102/meta
(iv) https://www.sciencedirect.com/science/article/abs/pii/S016836590100342X
(v) https://www.sciencedirect.com/science/article/abs/pii/S0268005X16308700
26 Synthesis of Biocompatible Chitosan Nanoparticles by Some Greener Methods. . . 607

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Application of Nanoparticles in Medicine
27
May M. Eid

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
Drug Delivery and Targeting Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
Neurological Disease Control Using Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
Mechanisms of Nanoparticle Therapeutics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
Nanomaterials for Immunotherapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
The Differences in Treatment Response and Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
Nanoparticles as Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
Nanoparticles in Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
Chitosan-Encapsulated Au NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
ICG-Functionalized Au NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
Application of Nanoparticles in Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
Photodynamic Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
Interaction of X-Ray and Gamma Radiations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
Nanomedicine in Market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
Potential Hazards of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640

Abstract
Nanotechnology is the focus of much research in the last 30 years. The unique
optical, electrical, magnetic, chemical, and biological properties of materials are
approximately 10,000 times smaller than the diameter of a hair strand.
Researchers have developed methods to synthesize and characterize nano-
materials, and their preclinical utility was reported. Now the new phase of
nanomedicine is to translate these technologies to benefit patients.

M. M. Eid (*)
Spectroscopy Department, National Research Center (NRC), ElDokki, Cairo, Egypt

© Springer Nature Singapore Pte Ltd. 2022 611

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_88
612 M. M. Eid

Keywords
Nanomedicine · Drug delivery · Immunotherapy · Nanotoxicity · Targeting

Introduction

Nanomaterials are of great interest for use in biomedicine as imaging tools, photo-
therapy agents, and gene delivery carriers. In this chapter, we will try to introduce
different applications of nanoparticles in nanomedicine. The chapter includes two
main topics of nanoparticle application in therapy and diagnosis; then the chapter
will close with some examples of nanoparticles that have been authorized by the
FDA and the limitation of using nanoparticles concerning their toxicity. The first
part of this chapter is a summation of the recent works of researchers in the field of
drug delivery, and immunotherapy, whereas the second one shows nanoparticles’
usage in sensing and imaging.

Drug Delivery and Targeting Therapy

Recently, targeting has gained great concentricity in biological research. The vascu-
lar biology of the normal tissue has a regular structure compared to the irregular
branched and disorganized, high vascular density, increased vascular permeability,
and impaired lymphatic drainage attributed of solid tumors and inflamed tissue of
tumor. These enhanced permeability and retention (EPR) effects permit NPs to
efficiently accumulate in tumor tissue. Active targeting using target ligands improves
the delivery of NP systems to a specific site. Typical targeting ligands include small
molecules, peptides, antibodies and their fragments, and nucleic acids. [1].
The ability of nanoparticles to adhere to and penetrate cell membranes is
governed by nanomaterials with very small dimensional face composition, and
surface charge and positive charge have been observed to pass through cell mem-
branes by forming membrane holes, generating noticeable cytotoxic effects in the
process. However, membrane disruptions can be reduced or even completely
avoided by modulating the surface charge density or surface. Therefore, it appears
feasible that synthetic materials with optimally engineered surface properties may
pass through membranes without disrupting the cell membrane. Colloidal semicon-
ductor core/shell quantum dots (QDs) hold great promise for applications in bio-
technology and biomedicine due to their small size (1–5 nm), brightness, and
photostability [2].
Drugs and other therapeutic agents are administered to treat specific diseases and
disorders with the goal of achieving desired pharmacological effects with minimal
side effects. The use of a controlled drug delivery system is a key strategy to enhance
the therapeutic efficacy and safety of therapeutic effect. The primary rationale for
using an appropriate drug delivery system is the ability to ensure a higher and longer
duration biocompatibility of drug as well as improve therapeutic efficacy. Various
27 Application of Nanoparticles in Medicine 613

materials with different structural forms are conjugated with drugs to produce nano-
drug delivery systems. Considering recent approaches, the most commonly used
drug delivery vehicles include nanoparticles (e.g., polymeric, ceramic, and metallic),
liposomes, micelles, and dendrimers, etc. A considerable number of preclinical and
clinical studies suggest that the materials are rapidly emerging for use in drug
delivery applications for the treatment of various diseases [3].

Neurological Disease Control Using Nanomaterials

The most common neurodegenerative diseases worldwide include Alzheimer’s

disease (AD) and Parkinson’s disease (PD). The common clinical feature of AD is
the extracellular deposition of amyloid beta (Aβ) peptide along with phosphorylated
tau protein, leading to irreversible neuronal loss and consequent to loss of memory
and decision-making ability.
Nano-drug delivery system for Alzheimer’s disease. Serious efforts have been
made by the scientific community to develop potent molecules and compounds that
could mitigate the progression of neurodegenerative diseases. The inability or
limited ability to cross the blood-brain barrier (BBB) is the main reason for the
limited therapeutic effect of currently available drug molecules. However, nano-
medicines are emerging as a new strategy to overcome the BBB and provide the
advantage of targeted and sustained release. Additionally, bioavailability over an
extended period of time limits the frequency of dosing and minimizes potential side
effects. In preclinical studies, RT-loaded poly(lactide-co-gycolide) (PLGA) and
polysorbate-80 (PBCA-80)-coated poly(n-butylcyanoacrylate) nanoparticles have
shown potential for targeting in the brain [4].
Cancer nanomedicine, the widely accepted paradigm of nanomedicine
enhanced permeability and retention (EPR), assumes that cytotoxic drugs can be
selectively delivered to tumors using nanomedicines (defined as drug-loaded nano-
particles of 1–1000 nm in diameter) to increase efficacy and minimize the risk of
systemic side effects. However, this approach has so far resulted in only modest
improvements in the cancer patient survival rate. In contrast, immune checkpoint
inhibition (ICI) has led to unprecedented improvements in the survival outcomes of a
subset of patients. However, an estimated 13% of cancer patients currently benefit
from ICI, and a substantial proportion of patients receiving these therapies develop
immune-related adverse events. Therefore, research interest in nanomedicine is
rapidly shifting to the adaptation of delivery platforms to increase the percentage
of patients who clinically benefit from ICI and other immunotherapies. Currently,
there are two paradigms for the use of nanomedicines to potentiate immunotherapy:
systemic delivery of nanomedicines that have a tumor-priming effect and local or
extratumoral administration of nanomedicines to induce local and/or systemic anti-
tumor immunity. The first paradigm is supported by data from a successful phase III
trial, in which women with metastatic triple-negative breast cancer (TNBC) received
the combination of nab-paclitaxel plus the antiprogrammed cell death 1 ligand
1 (PD-L1) antibody atezolizumab6. Various manifestations of the second paradigm,
614 M. M. Eid

such as vaccine delivery using lipid-based nanomedicines to promote antitumor

immunity, are the focus of preclinical and clinical investigations (e.g.,
NCT02410733). They hypothesize that the pathophysiology of the tumor microen-
vironment (TME) limits the uniform delivery of both systemically administered and
locally applied nanomedicines, thus compromising their efficacy even when they
accumulate in tumor. Therefore, they proposed that nanomedicines should contain
not only anticancer drugs but also agents that “normalize” the various components
and physiology of the TME, resulting in improved tumor perfusion and reduced
hypoxia. This normalization effect has the potential to facilitate not only drug
delivery but also oxygen delivery to slow tumor progression and convert an
immunosuppressed TME into an immunostimulatory TME [5].

Mechanisms of Nanoparticle Therapeutics

Nanomedicine-based drug formulations were originally developed to alter the phar-

macokinetics and toxicity profiles of chemotherapy agents and to promote their
accumulation in tumors. The ability to concentrate drugs within tumor cells and/or
the tumor microenvironment (TME) is also of relevance for enhancing immunother-
apy. However, nanomaterials also allow novel mechanisms of action for immuno-
therapy agents, including the ability to display ligands to immune cells, regulate
intracellular delivery of cell impermeable compounds, and control the timing of drug
release and/or activation.

Nanomaterials for Immunotherapy

Nanoparticle-based delivery systems have several advantages for cancer immuno-

therapy applications compared to conventional nanomedicine. Conventional cancer
nanomedicine usually aims to deliver cytotoxic agents directly to cancer cells;
however, immunotherapy often targets nontumor cells, such as resident immune
cells in secondary lymphoid tissue or immune and stromal cells in the tumor
microenvironment (BOX 2) cells and tissues that could be easily reached by
nanoparticles. In addition, the subsequent interaction between nanoparticles and
cells or organs can be regulated by functionalizing nanoparticles and modifying
their surface. The physicochemical properties of nanoparticles can also be tuned to
promote interaction with and stimulation of innate immune cells such as dendritic
cells and macrophages. Nanoparticle-based delivery can further enhance the phar-
macological properties of drugs, including their solubility, in vivo stability, and
pharmacokinetic profile, and protect biological drugs from premature release and
degradation [6, 7]

Promotion of Immunogenic Tumor Cell Death

Most antitumor drugs aim to kill cancer cells, but not all pathways of cell death are
immunogenically equivalent. Tumor cell death events that promote an antitumor
27 Application of Nanoparticles in Medicine 615

immune response are referred to as “immunogenic cell death” (ICD). ICD is

associated with the extracellular release of damage-associated molecular patterns
such as ATP and high mobility group protein B1 (HMGB1) and surface exposure of
calreticulin and heat shock protein 90 (HSP90). These factors promote tumor antigen
uptake by antigen-presenting cells and their subsequent activation. Traditional
ablative cancer therapies, such as chemotherapy or ionizing radiation, differ in
their ability to induce ICD, and their immunopotentiation can be abrogated by
toxic effects on responding immune cells. Nanomedicine formulations are an attrac-
tive modality for promoting ICD because they can concentrate cytotoxic agents in
tumor cells. In addition, nanomaterials can be designed to interact directly with
external energy sources, allowing for the enhancement of ICD induced by treatments
such as radiotherapy and magnetic hyperthermia.
Formulation of chemotherapeutic agents into nanoparticles that promote ICD can
improve antitumor immunity by enabling more effective delivery of drugs to tumor
cells. For example, Doxil, a clinically approved pegylated liposomal formulation of
the anthracycline chemotherapeutic doxorubicin, synergized with checkpoint block-
ade in the treatment of mouse models of colon adenocarcinoma and fibrosarcoma,
resulting in greater antitumor activity compared with treatment with free
doxorubicin.
A recent strategy to improve doxorubicin delivery and increase ICD was based on
synthetic high-density lipoprotein nanodiscs, in which the drug is covalently bound
to the nanoparticles via an acid-labile linkage. Delivery via nanodiscs resulted in the
upregulation of ICD markers in tumors and synergistic effects with anti-PD1 com-
pared to free drug in two mouse models of colon cancer.
Although radiation therapy is capable of inducing ICD, it is rarely effective as a
monotherapy in promoting sustained antitumor immunity. However, numerous
clinical trials are currently investigating radiation therapy as a component of com-
bination immunotherapies. Radiation kills tumor cells by inducing nonrepairable
DNA damage, but it can also trigger activation of the cyclic gMP-aMP synthase
stimulator-of-interferon genes pathway (cGAS-STING pathway) and subsequent
production of proinflammatory cytokines, promoting innate and adaptive antitumor
immunity. The radiotherapy dose must be carefully tailored, as high doses of
irradiation lead to attenuated STING activation through DNA exonuclease
TREX1-dependent cytosolic DNA degradation. An initial, successful pro-
inflammatory radiotherapy response may also be blunted by the recruitment of
immunosuppressive immune cells to the tumor. A long-standing concern is that even
localized radiotherapy may impair antitumor immunity. However, recent evidence from
preclinical studies suggests that radiotherapy can indeed activate tumor-resident T cells,
which are comparatively more radioresistant than circulating T cells [8]
Several approaches have used nanoparticles to enhance immunopriming triggered
by radiotherapy. For example, biodegradable polymer nanoparticles designed to bind
proteins from the surrounding solution have been shown to promote T-cell priming
following radiotherapy. Intratumoral injection of the nanoparticles after radiotherapy
resulted in the capture of protein antigens released from dying cancer cells by the
particles, which subsequently passed through lymphatic vessels and were
616 M. M. Eid

internalized by phagocytic professional antigen-presenting cells in the draining

lymph node. Nanomedicines can also be used as radioenhancers that interact directly
with ionizing radiation to upregulate ICD25. Materials containing elements with a
high atomic number (Z) can both absorb and scatter radiation, and therefore high Z
nanoparticles that accumulate in tumors can potentiate radiotherapy. In a recent
clinical trial, intratumoral injected hafnium oxide nanoparticles were shown to
double the frequency of pathological complete response to radiotherapy in patients
with sarcoma, leading to a first clinical approval in Europe [9].

Ligand Presentation to Immune Cells (Fig. 1)

Gene Delivery
RNA interference (RNAi) is a powerful biological tool that can be used in both cell
culture and living organisms. Since it enables targeted degradation of mRNA after
the introduction of sequence-specific double-stranded RNA into cells, it has histor-
ically been used to research gene functions. Effective siRNA delivery, on the other
hand, can necessitate overcoming a number of biological barriers: (1) High molec-
ular weight and negative charges make it difficult to reach the cell, (2) nuclease

Fig. 1 Pathways for the cellular internalization of different types of nanoparticles [10]
27 Application of Nanoparticles in Medicine 617

degradation inside the cell, (3) targeting to the appropriate cell compartment, and
(4) rapid clearance and instability in vivo.
As a result, effective and biocompatible delivery systems are needed to fully
realize the potential of RNAi. NPs can provide a solution to the problems associated
with siRNA delivery. Because of their ability to shape a condensed complex with
nucleic acids, cationic lipid or polymer NPs have been used to transport anionic
nucleic acids into cells [32]. This keeps them stable and prevents enzymatic degra-
dation. Cationic materials can also aid in the escape of NPs from endosomes and
lysosomes. Endosomal escape can be facilitated by increasing Cl influx in response
to groups such as the nitrogens in the cationic polymer polyethyleneimine (PEI),
which become protonated in the pH environment of endosomes/lysosomes. As a
result of the increased osmotic pressure and swelling, the organelle bursts and the
siRNA NPs are delivered.
The “proton sponge effect” is the name given to this phenomenon. However, a
recent study found that siRNA distribution in a cationic lipid NP system was
significantly reduced, with approximately 70% of internalized siRNA being recycled
to the extracellular media due to lipid NPs exiting late endosomes/lysosomes
[33]. Designing novel NP vehicles that can resist recycling pathways could thus
boost siRNA distribution. Fusogenic peptides and cell penetrating peptides have also
been used to investigate active targeting methods of nonendocytic absorption of NP
delivery of nucleic acids. SiRNA probes have been used to research intracellular
trafficking as well as the assembly and disassembly of siRNA NPs to better under-
stand siRNA NP interactions with biological systems. Since immune cells play
critical roles in homeostasis and disease, NPs have recently been used to deliver
siRNA to silence genes in these cells [11, 12].
In one study, NPs were used to silence Cyclin D1 (CyD1), a cell cycle-regulatory
enzyme, in leukocytes in vivo in order to establish the molecule’s exact function in
gut inflammation. CyD1 siRNA was loaded into NPs, which were then
functionalized with antibodies to the b7 integrin. The researchers discovered that
by suppressing leukocyte proliferation and T helper cell 1 cytokine expression, these
targeted NPs silenced CyD1 in leukocytes and reversed experimentally induced
colitis in mice. Another recent study identified the use of lipid NPs for in vivo
siRNA transmission to immune cells to silence disease genes. The study identified
the feasibility of targeting multiple gene targets in rodent myeloid cells and demon-
strated siRNA-mediated silencing in nonhuman primates’ myeloid cell types. Using
siRNA to target tumor necrosis factor-α, the therapeutic potential was verified
(TNF-α). Another research used NPs to investigate the immunological mechanisms
that cause nonalcoholic steatohepatitis (NASH) (Fig. 2) [13].
TNF-α developed by Kupffer cells can activate the development of NASH by
increasing the output of chemokines IP-10 and MCP-1, according to the researchers.
Furthermore, silencing TNF-α in myeloid cells decreased chemokine activity and
prevented the development of NASH, implying that TNF-α may be a new therapeutic
target in NASH. NPs have also been used to deliver siRNA to plant cells at the single
cell level to research cellular pathways. One group used amine-conjugated polymeric
NPs as vehicles to deliver siRNA to genes involved in cellulose biosynthesis. They
618 M. M. Eid

Fig. 2 The processes involved in generating I-tsNPs. Multilamellar vesicle (MLV)

discovered that NtCesA-1, a factor involved in whole-plant cell wall synthesis, is also
necessary for cell wall regeneration in isolated protoplasts [14].

Delivering Hydrophobic Compounds

Many biologically active compounds are hydrophobic molecules, meaning they
have a low water solubility. Because of their low solubility in aqueous conditions,
using such compounds in biological research can be difficult. Currently, a solvent,
such as dimethyl sulfoxide (DMSO), or an excipient, such as Cremophor, is used.
However, not all molecules can be dissolved in these solvents, and the solvents
themselves are often poisonous to living organisms, making the biological experi-
ment more difficult. For in vitro applications, wortmannin, a PI3 kinase inhibitor and
a widely used reagent in biology research, needs DMSO. DMSO has been shown to
have its own effects on cells and is thus unsuitable for in vivo use.
The use of NPs has been strengthened as a technique to solve the difficulty of
delivering these hydrophobic agents. Hydrophobic cores in polymeric NPs make
them suitable for delivering hydrophobic agents. The use of NP delivery vehicles
overcomes the active agent’s solubility while also protecting it from the environ-
ment before it is released from the NP. They developed an NP formulation of
wortmannin to show the proof-of-principle of this method. The solubility and
stability of NP wortmannin were improved. Furthermore, NP wortmannin has
the same cell signaling effects as wortmannin. Furthermore, in a mouse model of
cancer, NP wortmannin was found to be an effective and potent therapeutic agent
in vivo [15].

Delivering Agents to Subcellular Organelles

Delivering different agents to particular organelles is one field of active research.
The availability and accessibility of a target at the subcellular level is critical for the
successful delivery of therapeutic and imaging agents. Delivering agents to subcel-
lular organelles can also reveal molecular processes in organelles that are currently
27 Application of Nanoparticles in Medicine 619

unknown. Because of the ease with which NPs can be modified and functionalized,
there has been renewed interest in using these vehicles to deliver agents to subcel-
lular organelles.
Endocytosis enables targeted NPs to bind to targets on the cell surface and enter
the cell. If the target is intracellular, however, NPs and their cargo can be unable to
meet the desired target due to NP intracellular sequestration or a lack of subcellular
targeting capabilities. To be successful, NPs carrying oligonucleotides must first
escape the endosome and then be targeted. For targeted distribution to the nucleus,
cytosol, mitochondria, endosomes, and lysosomes, tools for efficient subcellular
targeting are evolving. For the design of NPs for subcellular targeting, two
approaches are being investigated: (1) passive targeting of NPs to a specific organ-
elle by varying NP characteristics such as scale, shape, and composition and
(2) active targeting of NPs to the organelle of interest by functionalizing NP surfaces
with targeting ligands directed toward the organelle.
These techniques have been used to varying degrees of effectiveness. Biolog-
ical barriers unique to the target organelle are obstacles to effective subcellular
targeting. NPs destined for the nucleus, for example, must pass through the cell
membrane, avoid the endosomal 4q-lysosomal pathway, connect with the nuclear
pore complex, and be small enough to cross the nuclear membrane [51]. The
active transport mechanism has been used to improve nuclear delivery by using
targeting ligands like the nuclear localization signal (NLS). The localization of
NLS conjugated gold NPs at the nucleus of a cancer cell caused DNA damage in
one study. In a different sample, NLS conjugated gold NPs were unable to target
the nucleus of cells from outside the plasma membrane because they could not
penetrate the cells or were stuck in endosomes. NPs conjugated with NLS and
receptor-mediated endocytosis (RME) peptides, on the other hand, were able to
enter the nucleus [16].
Biological obstacles to NPs targeting mitochondria include intracellular trans-
port to mitochondria, outer and inner mitochondrial membranes, and toxicity.
Most studies have focused on developing metal oxide or liposomal NPs for
transmission to mitochondria so far. Electrostatic interactions between the NP
and the organelle have also been used to deliver the NP to the mitochondria. In
comparison to other cellular membranes, mitochondria have a negative mem-
brane potential, which can lead to the accumulation of lipophilic cations. The
fabrication of stearyl triphenyl phosphonium (STPP) targeted liposomes with
anticancer agents ceramide and scarleol to target the mitochondria was based
on this definition. Since it has both cationic and lipophilic properties, STPP was
selected.
A polymeric NP device was used by another community to deliver mitochondria-
acting therapeutics to their target. A lipophilic triphenyl phosphonium (TPP) cation
was used to make the NPs, which has been shown to cross into the mitochondrial
matrix. By screening a library of NPs with varying charge and scale in vitro, the team
discovered an optimized targeted NP that increased efficacy and decreased toxicity
for cancer, Alzheimer’s disease, and obesity as compared to nontargeted NPs or
small molecule therapeutics [17].
620 M. M. Eid

Nanoparticles of Mesoporus Silica (MSN)

MSNs (mesoporous silica nanoparticles) are a promising candidate for drug delivery
systems because they have the ability to perform all functions at the same time.
MSNs used as drug delivery systems typically include an ordered array of 2D
hexagonal micro- or mesopore structure, uniform particle sizes (80–500 nm), large
surface areas (>1000 m2 g
1), high pore volumes (0.5–2.5 cm3 g
1), tunable pore
diameters (1.3–30 nm), controllable particle morphology, and both exterior and
interior surfaces that can be independently modified with a variety of techniques.
Unlike traditional polymer-based drug delivery systems, which have issues like low
drug loading ability and poor drug release control, MSN-based drug delivery
systems successfully avoid these problems. Because of the large surface areas and
pore sizes, a large payload of drug molecules can be carried. To improve drug
loading and releasing ability, functional groups preferred by drug molecules can
be added to the pore environment and surface. During drug administration, the
highly stable pore channels protect encapsulated drug molecules from degradation
in harsh environments. MSN materials have excellent biocompatibility at concen-
trations suitable for pharmacological applications due to their tunable particle
morphology.
Vallet-Reg was the first to investigate the use of mesoporous silica materials for
drug adsorption/desorption at the turn of the century. She was able to show that in
3 days, 80% of the previously loaded ibuprofen was released. In order to achieve an
accurate control of drug-releasing rate, a “stimuli-triggered release” concept was
brought forward simultaneously by Tanaka and coworkers and Lin and coworkers
2 years later. In Tanaka’s approach, coumarin ligands were immobilized at the pore
entrance and on the external surfaces by a grafting method. The uptake and release of
guest molecules from pore voids were photo-regulated. The coumarin molecules
underwent a dimerization reaction to completely seal the pore entrances when this
sample was exposed to UV light (λ > 310 nm). The cleavage of coumarin dimers
with UV light (¼ 250 nm) irradiation caused the release of guest molecules. The Lin
research group created the first example of using biocompatible MSNs as carriers
and inorganic nanoparticles as caps to efficiently deliver drug molecules into animal
cells with zero premature release [18].
They used 12 2-(propyldisulfanyl) ethylamine groups to functionalize spherical
mesoporous silica nanoparticles with a uniform particle diameter of 200 nm and pore
size of 2.3 nm. This MSNs sample was soaked in a concentrated vancomycin or ATP
solution to allow cargo molecules to diffuse through the pores. After that, water-
soluble cadmium sulfide (CdS) nanocrystals with mercaptoacetic acid groups were
added to react with the MSNs’ terminal amino groups. As a result, the CdS
nanocrystals were covalently bound to the MSNs and effectively blocked pore
entrances. The physiosorbed molecules were washed out of the vancomycin- or
ATP-loaded, CdS-capped MSNs. The loading efficiency of vancomycin and ATP
was determined to be 25 and 47 mol g
1, respectively, based on a quantitative study
of the amounts of each compound controlled by HPLC. This drug delivery system’s
controlled release output was assessed. Over a 12-hour period, the substance
27 Application of Nanoparticles in Medicine 621

released less than 1% of the drug in buffer solution, indicating strong pore blockage
and limited premature release. A rapid release was caused by the addition of
disulfide-reducing reagents such as dithiothreitol (DTT) or mercaptoethanol
(ME) to cleave the CdS-MSN linkage, with 85% of entrapped molecules released
within 24 hours.
By taking advantage of the acidic environment at tumor or inflammatory sites
(pH 6.8), endosomal or lysosomal compartments of cells (pH 5–6), and the stomach
(pH 1.5–3.5), a series of pH-responsive linkers have been exploited for controlled
release applications. These pH-responsive linkers have an inert physiological pH
response and a robust release at low pH.
Casacus et al. reported a pH- and anion-mediated drug delivery system as an
example of a pH-responsive release system. The MSN materials were made by
combining mercaptopropyl triethoxysilane and TEOS in a cocondensation reaction.
To get a preferential anchoring of amino groups on the external surfaces, a second
grafting reaction was carried out with N-(3-triethoxysilylpropyl-2-aminoethyl)-
ethylenediamine. The amines were deprotonated and tightly packed through
hydrogen-bonding interactions at high pH values, resulting in the delivery system
being in its “open gate” state. Due to the coulombic repulsion effect between
positively charged amine groups, when the amines were protonated at low pH
conditions, they repelled each other and covered the pore openings, and the delivery
system was monitored to its “near gate” state. In the presence of anions, which could
intercalate into the open-chain polyamines and close the pore openings, a strong
synergic effect was also observed. The size of the anion and the intensity of the
polyamine-anion are clearly linked in this effect [19] (Fig. 3).
Kawi and colleagues developed another pH-responsive drug delivery system for
protein drugs. MSN materials with pore diameters above 10.5 nm and pore volumes

Fig. 3 Schematic graph of opening and closing of the core-shell-structured nanoparticle triggered
by pH. With permission from Dr. Homg
622 M. M. Eid

around 1 cm3 g
1 were synthesized in this study to encapsulate bulky proteins
without denaturation. Cocondensation was used to add amine groups to these
MSN products, which were then filled with a model protein, bovine serum albumin
(BSA). After that, the positively charged BSA-loaded MSNs were combined with a
pH 5.35 polyacrylic acid (PAA) solution. PAA’s electrostatic assembly blocked pore
entrances and trapped BSA proteins; the final BSA loading number was estimated to
be 16.3%. In a pH 1.2 acidic medium, no BSA was released from the
PAA-encapsulated sample after 5 h, and only 10% was released after 36 h. In a
phosphate buffer solution at pH 7.4, however, the carboxyl groups on the PAA
chains dissociated and repelled each other, allowing PAA to swell and dissolve into
the buffer solution.
As a result, 40% of the entrapped BSA was released from the study, indicating
that their material is pH sensitive. PAA has also been discovered to shield proteins
from enzymatic degradation. They concluded that the BSA conformation has not
been significantly altered by the adsorption process by comparing the UV-CD
spectra of native and released BSA, implying that the protein activity has been
preserved. They proposed that this material could be used to deliver protein drugs
orally to target sites with higher pH, such as the small intestine or colon.
The Hong research group used a reversible addition-fragmentation chain transfer
(RAFT) polymerization of acrylic acid to study covalently immobilized PAA on
MSN materials as a pH-sensitive drug delivery device. In this case, the MSNs were
grafted with 5,6-Epoxyhexyltriethoxysilane before the template was removed. Via
an esterification reaction with the hydroxyl groups, an RAFT agent, S-1-dodecyl-S-
(,0 -dimethyl-00 -acetic acid) trithiocarbonate, was bound to the MSNs’ exterior sur-
face. Finally, under vacuum, acrylic acid polymerized to form a covalently bonded
PAA nanoshell coating on the MSNs.
The pH value of the medium had a major impact on the structure of the PAA
nanoshell. The PAA nanoshell is deprotonated and soluble in aqueous solutions at
pH 8.0, resulting in an open state with pore entrances that can be accessed. As the pH
falls below 4.0, however, the PAA nanoshell becomes insoluble and collapses onto
the MSN surface, forming a compact sheet. The pH-regulated drug release efficiency
of the PAA-coated MSNs was evaluated using fluorescein. At pH 8.0, they saw
fluorescein uptake and release from PAA-coated MSNs, but neither was seen at pH
4.0. Their findings confirmed that by modifying pH values, PAA-coated MSNs can
reversibly control the loading and releasing of guest molecules.
Release triggered by multiple stimuli from multiresponsive controlled release
systems has been designed to achieve complex release behaviors in either an
individual or synergistic manner, in addition to the comprehensive research
conducted on single stimulus-induced drug delivery. Angelos et al. [67] developed
a dual pH and light-controlled release mechanism based on the combination of
pH-sensitive pseudorotaxane and photo-sensitive nanoimpeller azobenzene.
To generate pore surface-functionalized MSNs, a silylated azobenzene derivative
was cocondensed with TEOS, and CB [6]/bisalkylammonium containing pseudo-
rotaxane was anchored on the exterior surface of MSNs. They demonstrated that this
material could function as AND logic gates, allowing cargo to be delivered only
27 Application of Nanoparticles in Medicine 623

when both stimuli were enabled. They imagined that using this device, they would
be able to manually monitor the delivery dose. Aznar et al. demonstrated yet another
pH and photo-switch release process. A boronate ester linker was formed between
saccharide-functionalized MSNs and boronic acid-anchored gold nanoparticle caps
in this study. To sever the boronate ester connection, two opening protocols have
been suggested. The first is to reduce the pH to 3; the second is to irradiate the
material with a laser beam at 1064 nm, which causes plasmon resonance excitation
in Au nanoparticles, resulting in a photothermal impact. By repeatedly administering
stimuli, both triggers were shown to be capable of generating a pulsatile release of
guest molecules [20–22].
Three independent stimuli were verified to be capable of sufficiently unblocking
the pore voids in another pseudorotaxane-based MSN recorded by Kim and
coworkers. An o-nitrobenzene ester with stalk and a -CD ring made up the pseudo-
rotaxane unit. UV light irradiation will rupture the stalk, which can then be
decomposed by lipase, and the -CD ring digested by -amylase. As a consequence,
the release of guest molecules can be activated in a number of ways, including by
enzymes, light, or both to achieve a synergistic acceleration effect.
Feng and coworkers developed a tri-stimuli-sensitive delivery system that
involved the development of pyridyldithio-containing polymer functionalized
MSNs that were a disulfide bond linked to thiol-modified -CD [70]. To prevent the
release of entrapped molecules, the -CD moieties were further cross-linked with diazo-
linkers. UV light irradiation, as well as the addition of DTT or -CD, is supposed to
affect their assembly. The transconfigured diazo-linkers will turn into a cis-azobenzene
under 365 nm UV light, losing their high-affinity for -CD molecules. The disulfide
relation between -CD and MSNs would be cleaved if DTT was added. Excess -CD
would result in the creation of a more stable -CD-diazo cross-linkage and would
displace -CD. The pore-blocking polymeric network was opened in all three cases,
resulting in tri-stimuli-triggered release. The Vallet-Reg group [71] used the ability of
magnetic nanocrystals to produce heat energy under a high-frequency alternating
magnetic field in the design of temperature-responsive delivery systems. MSNs
were decorated with a thermosensitive copolymer of poly(ethyleneimine)-b-poly
(N-isopropyl-acrylamide) (PEI/NIPAM), and magnetic iron oxide nanocrystals were
embedded within the silica matrix. They showed that this system could deliver pro-
teins with preserved activity as temperatures rose, as well as an alternating magnetic
field that heated the local environment through encapsulated iron oxide nanocrystals.
For site-specific drug delivery, light irradiation is a convenient remote-control
process. When exposed to certain wavelengths of light, the uptake and release of
guest molecules can be triggered quickly. Photochemically sensitive linkers such as
azobenzene, o-nitrobenzyl ester, and thymine bases are integrated onto the surface of
MSNs to make them photochemically susceptible for light-mediated release after
Tanaka and coworkers first demonstrated a coumarin-functionalized MSN material
to manipulate drug release. The pseudorotaxane method was also used to monitor
drug release with light by varying the stalk and ring components.
A photosensitive pseudorotaxane of azobenzene derivative (AB) and -cyclodextrin
(-CD) was created by Zink, Stoddart, and coworkers [185]. The pseudorotaxane stalks
624 M. M. Eid

were grafted onto unfunctionalized MSNs with 4-(3-triethoxylsilypropylureido)

azobenzene (TSUA) groups or more water-soluble (E)-4-((4 (benzylcarbamoyl)-
phenyl)diazenyl)benzoic acid groups. Both azobenzene derivatives isomerized
from the more stable trans form to the less stable cis form when exposed to
351 nm light. Then pyrene-cyclodextrin (Py-CD) or fluorescently labeled pyrene-
cyclodextrin (Py-CD) was added. The -CD rings were locked at the orifice due to the
high binding affinity between trans-AB and -CD. The isomerization of trans- to
cis-AB stalks, on the other hand, resulted in the dissociation of pseudorotaxanes,
allowing cargo molecules to be released due to the poor binding between cis-AB and
-CD. The AB stalks and Py-CD assembly were found to be stable in the absence of
351 nm UV radiation, but when the sample was subjected to a 351 nm excitation
beam for 400 min, full Py-CD dissociation was observed.
Similarly, findings from RhB-loaded samples showed that over a 7-h span, more
than 90% of RhB was released from the laser light-exposed sample, while less than
30% was released from the unexposed one. They came to the conclusion that their
material could be used in light-activated intracellular drug delivery systems. The
Kim group also used cyclodextrin to cover the porous reservoirs. MSN materials
were functionalized with aminopropyl groups, which were then treated with succinic
anhydride in the presence of triethylamine to produce a carboxylic acid-terminated
MSNs sample, according to their research. Via a coupling reaction with 2-nitro-5-
(2-propyn-1-yloxy)- benzenemethanol, the sample was further functionalized by
alkyne end groups, yielding a photosensitive o-nitrobenzyl ester moiety that decom-
poses when exposed to UV light at 350 nm (Fig. 2). The pores were capped with
mono-6-azido-CD using the Huigsen 1,3-dipolar cycloaddition reaction after calcein
dye filling. The fluorescence strength of the CD-capped calcein-loaded MSNs
sample suspension was tracked over time to see if their method was feasible. In
the dark, only a faint signal was observed, suggesting that the calcein molecules had
been preserved within the pores. The photolysis of the o-nitrobenzyl ester linkage
and the diffusion of CD and calcein molecules caused a significant increase in
fluorescence intensity when the sample was exposed to UV light.
Furthermore, they observed a periodic release activity of their sample in response
to successive UV irradiation over short periods of time. In a study conducted by Lin
and coworkers (Fig. 4) [72], gold nanoparticles were used as pore-blocking caps due
to their demonstrated excellent biocompatibility. Thioundecyl tetraethyleneglycol
esternitrobenzylethyl dimethyl ammonium bromide, a photoresponsive linker, was
immobilized onto the surface of Au nanoparticles (PR-AuNPs). Via electrostatic
interaction, these positively charged species attached to the negatively charged MSN
materials, resulting in a PR-AuNP-capped MSN system.
The fact that no cargo release was discovered even after 80 h in the dark
confirmed a high capping quality. The o-nitrobenzyl ester-containing linker was
cleaved by photoirradiation at 365 nm, resulting in negatively charged thioundecyl
tetraethyl eneglycolcarboxylate-functionalized Au nanoparticles. As a result, the
charge repulsion between Au nanoparticles and MSNs uncovered the pores, allo-
wing guest molecules to diffuse through. In addition, intracellular experiments were
carried out in human liver and fibroblast cells using an anticancer drug as cargo for
27 Application of Nanoparticles in Medicine 625

Fig. 4 Schematic illustration of photo-induced controlled drug release of PR-AuNP-capped

MSNs. With permission from Dr Juan Vivero-Escoto

controlled release. Both cell lines were exposed to light or held in the dark when
incubating with either drug-loaded or drug-free samples. Only cells exposed to UV
light with internalized drug-loaded MSNs died in large numbers, indicating that this
mechanism could transport and release drug molecules within living human cells
under photoirradiation regulation [23].

The Differences in Treatment Response and Toxicity

Cancer immunotherapy-related adverse events (irAEs) vary significantly from cyto-

toxic agent-related adverse events in terms of initiation, length, severity, and form.
The incidence of irAEs has been linked to a number of immunological, environ-
mental, and lifestyle factors. The use of nanomaterials in cancer immunotherapies
adds yet another layer of uncertainty to the toxicity equation, as nanomaterials can be
toxic to the immune system. Simultaneously, cancer immunotherapy can alter the
immune system’s interaction with nanomaterials, resulting in possible toxicity pro-
files that vary from those seen with either treatment alone. As a result, traditional
toxicity tests of nanomaterials are unlikely to be adequate to completely identify
possible cancer immunotherapy side effects and must be extended. Many preclinical
cancer nanomedicine experiments, for example, have used liver and kidney markers,
as well as blood cell counts and physiological parameters including animal weight
loss, as measures of treatment toxicity. These approaches, however, do not account
for variations in organ distribution, cytotoxic therapy kinetics, or immunotherapy
adverse events. Finally, nothing is understood on how the addition of nanomaterials
to cancer immunotherapy affects the immunotherapy’s toxicity profile. Targeted
delivery of therapeutic agents to desired tissues or tumors is the subject of conven-
tional cytotoxic cancer nanomedicine. As a result, its toxicity profile is mostly
localized and exists in places where nanomaterials have accumulated in higher
concentrations, such as the liver and spleen. However, as a result of the release of
626 M. M. Eid

proinflammatory cytokines or the nonspecific recognition of self-antigens by acti-

vated T cells targeting peripheral tissues, cancer immune nanomedicine may cause
systemic toxicity. As a result, cancer-immune nanomedicine may have a toxicity
profile that blends the worst of both worlds: the nanomaterials themselves cause
toxicity in the liver and spleen, while their immunostimulatory effects cause adverse
reactions in distant organs such as the colonic epithelium or skin. To accurately
assess the possible side effects of nanomedicine cancer immunotherapy, a thorough
examination of multiple tissues, organs, and organ systems is needed.
Aside from the variations in systemic organ involvement, irAE has a different
onset and length than cytotoxic therapy. GGI, hepatic, dermatologic, and pulmonary
toxicities often arise first, accompanied by endocrine and renal pathologies,
according to clinical findings. Although the majority of irAEs manifest instantly,
delayed dermatologic and endocrine toxicities are likely. As a result, in cancer
nanomedicine research, extended monitoring may be essential to account for late-
onset toxic effects [7].

Nanoparticles as Sensors

The Biobarcode
This route has been improved by the Mirkin community. This approach is devoted to
the use of gold NPs’ marvelous surface chemistry for signal transduction amplifica-
tion and, as a result, for protein and DNA [76] target detection. Metallic or magnetic
NPs are the most widely used biosensors. This method has been used to detect
cytokines at 30 aM (attomolar) concentrations, as well as a soluble pathogenic
biomarker for Alzheimer’s disease at a concentration of about 100 aM. The PSA
target protein is combined with a magnetic microparticle (MMP) that has been
functionalized with monoclonal antibodies to PSA. PSA gold NP probes are added
to PSA that has been bound to MMP. The PSA-specific DNA barcodes are released
into solution after further separation by magnetic field application and wash steps,
and analyzed using a scanometric assay that takes advantage of gold NP-catalyzed
silver enhancement. The sensitivity of this assay was 330 fg mL
1 of PSA (Fig. 5).
The DNA biobarcode approach combines the conjugation of several DNA strands
onto gold NP surfaces with the ability to detect these DNA strands using PCR
amplification or scanometric assays [24].

The Mechanism of the “Chemical Nose”

This method was developed by the Rotello group. They discovered that noncovalent
chemical interactions allow anionic fluorescent polymers to reversibly attach and
detach from functionalized cationic gold NPs. The fluorescence of the fluorescent
polymer is turned off when it is attached to the NP. The fluorescence is turned on
when it is detached from the NP. The target protein is detected in this system based
on the different fluorescence interactions it has as it binds to different forms of
surface-modified gold NPs. A fluorescence response pattern is developed and then
statistical methods are used to observe it. This process can distinguish between
 27
Application of Nanoparticles in Medicine

Fig. 5 The biobarcode method. (a) Development of the NP probe. (b) Method of detection using prostate-specific antigen-conjugated gold NP probes. With
permission from Dr Charudharshini Srinivasan [25]
627
628 M. M. Eid

various molecular targets by observing, quantifying, and recognizing them. This

method was first used to detect and sense proteins, and then improved for bacteria,
physicochemical distinction between stable, cancerous, and metastatic human breast
cells, and isogenic healthy and transformed cells [80, 81]. Since the identity of the
target analyte does not need to be identified in order to detect the analyte, “chemical
nose” sensing has the advantage of not needing antibodies for detection [26].

Raman Scattering with a Surface Enhancement (SERS)

The SERS method has been used to detect individual analytes based on their unique
vibrational spectra. SERS spectra have a small width, allowing for multiple analyte
detection in complex mixtures, including detection down to single molecules. SERS
methods have thus been used to identify biomolecules such as glucose, hemoglobin,
bacteria [82], and viruses [83] with extreme sensitivity. In vitro and in vivo, one
group investigated the ability of gold NPs encoded with Raman reporters and
conjugated with single-chain variant fragment (ScFv) antibodies to target cancer
biomarkers including epidermal growth factor receptors (EGFR) [27].
Recently, researchers demonstrated a SERS method for multiphase trace analyte
detection based on a thin-film NP array self-assembled at the liquid-liquid inter-
phase. This team was able to identify single-phase and multiple-phase analytes
dissolved in water and organic phases [28].

Supermagnetic Iron Oxide Nanoparticles (SPIONs)

SPIONs have been used as magnetic tags for a variety of sensors, including giant
magnetoresistive (GMR) biosensors [87, 88], which are based on magnetic particle
binding to a sensor surface. The magnetic fields of the particles will influence the
magnetic fields of the sensor, resulting in changes in the sensor’s electrical resis-
tance. Wang and colleagues at Stanford University recently demonstrated the effec-
tiveness of this technique for protein detection. An array of GMR sensors is used in
this assay to detect the engagement of proteins to arrays of surface-bound antibodies
using SPIONs as magnetic tags [89]. The target antigen is sandwiched between two
antibodies, one bound to the sensor and the other tagged with an SPION in this assay.
The underlying sensor detects the presence or absence of magnetized NP. The
researchers demonstrated that the assay is matrix insensitive to a variety of biological
fluids while still being capable of detecting proteins at molar concentrations and over
a broad concentration spectrum.
Using a similar strategy, they have shown that MACS particles (commercialized
SPIONs for cell separation) can detect cancer-associated proteins in 50% serum at
subpicomolar concentrations [90]. They used streptavidin-functionalized antiferro-
magnetic NPs to detect DNA with high sensitivity (10 pM) recently. Magnetic
relaxation switching is also based on the superparamagnetic property of IONPs.
Magnetic relaxation switches made of 3–5 nm SPIONs coated with 10 nm thick
dextran and stabilized by crosslinking were studied by the Weissleder group [92].
Functionalizing SPIONs with amino groups allows them to bind to a number of
sulfhydryl-bearing molecules, resulting in targeted SPIONs. In the presence of a
molecule recognized by the ligands immobilized on the NP, the nanoswitches will
27 Application of Nanoparticles in Medicine 629

undergo reversible assembly (clustering and declustering), resulting in a shift in the

transverse magnetic relativity (1/T2) of surrounding water protons. At the low
femtomole level (0.5–10 fmol), changes in relaxation rates caused by NP assembly
can be used to detect a number of biological targets, including DNA and proteins [29].

Diagnostic Magnetic Resonance (DMR)

The diagnostic magnetic resonance chip-based (DMR) device was developed by the
Weissleder group for rapid and quantitative detection of biological targets. IONPs
are also used as sensors in the DMR to amplify molecular interactions caused by
SPION assemblies. They proved their theory by detecting, with high sensitivity,
bacteria and the existence of proteins in parallel. The mass detection limit of the
DMR device was two orders of magnitude higher than that of the benchtop NMR
relaxometer (detection limit of 15 fmol) [30].

Magnetic NP Relaxation Sensors

The dominant mechanism for these NP biosensors is Brownian relaxation [97]. The
theory behind this approach is that when target analytes are recognized, MNP
accumulates, triggering slower Brownian relaxation responses than individual NPs
due to increased hydrodynamic size. Using this theory, a group recently used an AC
susceptometer to detect a bacterial antibody with a sensitivity of 0.3 nM [31].

Surface Plasmon Resonance (SPR)

Because of their small scale, the confinement effect favors solitary optical properties of
gold nanoparticles. The surface plasmon resonance (SPR) absorption of Au NPs
causes their colloidal solution to have a distinct characteristic of a strong vivid color.
Mie demonstrated this phenomenon theoretically by solving Maxwell’s equation for
the absorption and scattering of electromagnetic radiation by spherical particles.
Colloidal Au NPs’ sample is ruby red in color. This effect is known as SPR, and it
does not exist in individual atoms or in bulk form. According to the theory, as particle
size increases, a red change to longer wavelength occurs. The SPR frequency of Au
NPs has been shown to be affected by particle size, shape, dielectric properties,
aggregate morphology, surface alteration, and the surrounding medium’s refractive
index. The SPR peak of 13 nm spherical gold colloids, for example, is around 520 nm,
while the peak of 5–6 nm silver NPs is around 400 nm. By adjusting the scale of the
Au NPs, the SPR peak of the Au NPs can be systematically tuned [33].
Many studies have used functionalized Au NPs in an immunoassay to show
biosensing amplification. The technique of Au NP-enhanced SPR has also been used
to establish cholera cell detection assays. Other researchers developed an
Au-amplified SPR sandwich immunoassay that detected human immunoglobulin
at picomolar levels. These findings indicate that by fine-tuning the configuration
parameters, the detection limit of an Au NP-amplified SPR biosensor device can be
increased even further.
SPR sensors are now commercially available and are used as a powerful method
in biomolecular interaction detection, drug discovery, and life science research.
Surface plasmons or electromagnetic waves propagating over a metal/dielectric
630 M. M. Eid

interface are involved in the SPR sensor process. The wave vector of plasmons is
determined by the media’s dielectric constants and is highly sensitive to the proper-
ties of the dielectric medium in contact with the metal. In the Kretchmann config-
uration, surface plasmons are excited by directing p-polarized light to a glass prism
and reflecting from a gold film. Pumping light energy is passed to surface plasmons
when the incident optical wave vector’s tangential x-component matches the wave
vector of plasmons.
At a particular combination of angle of incidence and wavelength, the plasmon
coupling condition is usually followed by a dip in reflectivity. The sensing effect is
due to the fact that the refractive index of a thin 200–300 nm layer in contact with the
SPR-supporting gold is dependent on this resonance state. As a result, by carefully
observing the SPR coupling characteristics, knowledge about biological interaction
events on the gold film can be obtained. The knowledge of biomolecular interactions
is obtained in most SPR systems by measuring the angular or spectral characteristics
of light reflected under SPR. The detection limit in this case is usually 105 in terms of
refractive index shift, which corresponds to 1 pg mm2 of biomaterial accumulating
on the biosensor surface [34].
A photoelastic modulator was used to produce a weak delay amendment to
evaluate the SPR step. In the response of the second and third harmonic signals to
the polarization and phase change induced by SPR, the variable retarder plays a
critical role. The second harmonic signal has a narrower dynamic range than the third
harmonic signal without compensating for the phase introduced by SPR. They track
the second and third harmonic signals at the same time, with complete pre-
compensation of the SPR-induced initial step. These two signals are influenced by
two different properties of the optical beam, the first of which is the polarization
amplitude, and the second of which is the phase. As a result, over a large dynamic
range, the established system can detect a very small change in refractive index.
Functionalized Au NRs have been used as amplification labels in ultrasensitive SPR
biosensing. Longitudinal plasmonic resonance of gold nanorods was used to opti-
mize the sensitivity enhancement induced by the electromagnetic interaction
between the Au NRs and the sensing film. The nanorod-conjugated antibody’s
detection sensitivity is predicted to be 40 pg/ml, which is 25–100 times more
sensitive than currently recorded values in the literature.
Matsui et al. recently created an SPR sensor that can detect analytes with low
molecular weight. Essentially, the system was developed by molecularly preparing
SPR sensor detection using an imprinted polymer gel embedded with Au NPs on
a gold substrate of a chip. The analyte binding inside the Plasmonics polymer gel
caused the swelling effect of the polymer gel, which was used to detect the analyte.
The swelling effect increases the distance between the Au NPs and the substrate,
causing a change in an SPR curve’s dip to a higher SPR angle. In response to
increased dopamine concentration, the updated sensor chip displayed an increasing
SPR angle. More significantly, when compared to a sensor chip that was not
immobilized with Au NPs, the Au NPs were found to be successful at increasing
signal strength. Our findings corroborate their findings, suggesting that Au NPs are
needed to improve the sensitivity of the SPR sensor.
27 Application of Nanoparticles in Medicine 631

Thanh et al. also defined the creation of an Au NP-based antibody immunoassay

system. The assay relies on the aggregation of Au NPs that have been updated with
protein antigens in the presence of antibodies specific to those antigens. The
absorption changes caused by the aggregation of Au NPs were controlled using an
absorption plate reader. Monodispersed protein A-coated gold particles were used to
evaluate the amount of antiprotein A in serum samples to demonstrate the new
technique’s analytical capabilities. Antiprotein A had a dynamic range of two orders
of magnitude and a maximum detection of 1 g/mL.
There is space for progress in terms of increasing the biosensor’s sensitivity when
combined with Au NP technology. Many more research groups will concentrate on a
systematic study of using different sizes and shapes of Au NPs for SPR biosensing
applications in the coming years. For example, Nath et al. demonstrated that Au NPs’
specific optical properties can be used to create a label-free biosensor in a chip format.
The author demonstrated that Au NPs have a substantial impact on the bio-
sensor’s sensitivity. Chemisorption of Au NPs on amine-functionalized glass was
used to make sensor chips. The sensors made from 39 nm Au NPs were the most
sensitive to changes in the bulk-refractive index. A sensor fabricated from 39 nm Au
NPs had a 20-fold higher detection limit for streptavidin-biotin binding than a sensor
fabricated from 13 nm Au NPs [35–39].

Microfluidic Device
Using magnetic NPs coated with antibodies against surface antigens, this is one of
the most widely used pathogen detection techniques. The optical and magnetic
properties of NP are used in these devices. This immunomagnetic method was
used in a novel way by one group to attract molecules bound to magnetic NPs
from one laminar flow path to another using a local magnetic field gradient. E. coli
bound to streptavidin-coated SPIONs and labeled with a biotinylated anti-E. coli
antibody is effectively isolated from solutions containing densities of red blood cells
identical to blood.
Antibody-coated NPs were also used by the Weissleder community in a micro-
fluidic system to detect bacteria. They also discovered that core-shell NPs with Fe
metal cores have higher sensitivity for detecting bacterial cells than IONPs. The team
recently created a single-gene mutation detection assay based on a magnetic
barcoding technique that did not include antibodies. PCR-amplified mycobacterial
genes are sequence-specifically captured on polymeric beads that have been modi-
fied with complementary DNA, labeled with SPIONs, and identified using NMR in
this process. Within 2.5 h, the platform could detect tuberculosis and drug-resistant
strains from sputum samples.
A similar method that uses rRNA as a target marker for NP labeling was also
developed by the researchers. A universal and unique nucleic acid probe that detects
16S rRNA, which is abundant in and common to many bacterial organisms, was
used in the analysis. The system was sensitive enough to detect 1–2 E. coli bacteria
in 10 mL of blood and estimate bacterial load accurately. Small molecule
functionalized NPs have also been used to mark bacteria by a number of classes.
By using the bacterial interaction with carbohydrates on mammalian cell surfaces,
632 M. M. Eid

Fig. 6 Depiction of bacteria detection by magnetic glyco-NPs (MGNPs)

one group created a magnetic glyco-NP based device that could detect E. coli strains
in 5 min and allow up to 88% removal from the sample (Fig. 6).
In another study, vancomycin-modified SPIONs were used in a magnetic capture
assay for Gram-positive and Gram-negative bacteria [135]. They also showed that as
NP size and ligand coverage on the surface increase, the time needed for efficient NP
labeling of bacteria decreases.
Similarly, both metallic NPs and QDs have been used in optical biosensing of
bacteria. The biobarcode assay method allows for amplification and the
simultaneous detection of multiple targets in a single sample. Bacillus subtilis
double-stranded genomic DNA was observed at a concentration of 2.5 fM using
this method [136]. Salmonella enteritidis was also found at 0.2 fM. Pathogen sensors
have also been developed using QDs. In vivo biotinylation of engineered host-
specific bacteriophage and attachment of the phage to streptavidin-coated QDs
were described by Edgar et al. The method can detect as few as ten bacteria per
mL of the experimental samples and can detect E. coli among many different
bacterial strains [40–43].

Cell Search Device

These devices are used to isolate individual cells from complex mixtures, which is
necessary for biological research and a variety of biological applications. NPs have
been studied as sensitive instruments for detecting particular cell types and
low-frequency cells. The identification and capture of circulating tumor cells has
been one application of concern (CTCs). CTCs have been identified as a strong
prognostic biomarker for overall survival in patients with metastatic breast, colorec-
tal, and prostate cancer [139, 140]. They may help in the understanding of the
biology of cancer metastasis. Some of the most widely used methods for identifying
and capturing CTCs are NP immunomagnetic techniques. Using a ligand-receptor-
dependent method, these techniques use magnetic NPs to target and isolate CTCs.
Currently, the only FDA-approved test for CTC evaluation employs an
immunomagnetic technique. For the capture of CTCs in vitro, iron NPs coated
with a polymer layer carrying biotin analogues and conjugated with anti-EpCAM
27 Application of Nanoparticles in Medicine 633

are coated with a polymer layer carrying biotin analogues and conjugated with anti-
EpCAM. Using an anti-CD45-APC antibody as the NP-targeting ligand, this mech-
anism can also be used to mark and identify leukocytes.
A group of researchers recently demonstrated that anti-HER2 or anti-HER2/neu
functionalized IONPs could be used to isolate 73.6% of HER2/neu over-expressing
cancer cells spiked in 1 mL of blood. The cancer cells were preferentially captured as a
result of the receptor-ligand interactions. In a separate preclinical analysis, PEGylated
magnetic NPs were used to detect CTCs in vivo. The researchers used magnetic NPs
conjugated with plasminogen activator (uPA) and folate targeted nanotubes to target
CTCs in vivo for subsequent detection using photoacoustic flow cytometry. The
incorporation of polymers in other organic and inorganic NPplatforms, which can
allow targeted detection and surface capture, could lead to novel NP sensors for CTC
detection. A group of researchers recently used SERS and targeted polymer-coated
gold NPs to specifically test CTCs in the presence of white blood cells. EGF peptides
were conjugated to polymer-coated gold NPs that had QSY reporters embedded in
them. With a sensitivity range of 1–720 CTCs per mL of whole blood, the NPs
successfully detected CTCs in the peripheral blood of 19 patients with squamous
cell carcinoma of the head and neck. Biomimetic nanotechnology, which takes
advantage of naturally occurring processes, is another technique for cell identification
and separation. Biomimetic methods have been explored by the Hong group in order
to improve microfluidic devices for cell identification and separation. These devices
take advantage of the natural process of cell rolling, which occurs when selectin
molecules expressed on endothelial venules interact with glycoprotein receptors on
cancer cells. For improved surface sensitivity and specificity, the cell rolling method
using E-selectin was recently extended to CTC detection. G7 poly(amidoamine)
(PAMAM) dendrimers were also used to engineer cell capture surfaces that allowed
multiple ligands to bind to multiple receptors at the same time (multivalent binding).
CTC surface capture was substantially improved using a biomimetic combination of
dendrimer-mediated multivalent effect and cell rolling.

Nanoparticles in Imaging

In molecular imaging, NPs have been investigated as new labels and contrast agents.
Because of their special properties, NPs can be used to track molecular targets as
well as cell responses in diseases such as cancer and cardiovascular disease. To
image and detect tumor cells, molecular imaging methods are frequently used.
Fluorescence microscopy is the preferred method for investigating tissue and cells
with high spatial resolution. However, this method has a low sensitivity and requires
many time-consuming steps to prepare the samples for imaging. As a result, signif-
icant efforts have been made to develop effective biosensors aimed at enhancing
detection signals for more accurate disease diagnosis. Because of their utility for
sensing cells in small quantities, functionalized Au NP-based sensor systems have
gotten a lot of attention in biomedical diagnostics. A primary objective in the
creation of high detection limits for sensing cancer cells is to design and construct
a reliable biosensor with a high detection limit [45, 46].
634 M. M. Eid

Chitosan-Encapsulated Au NPs

This method, which involves neutralizing a designer nanocomposite solution, was

developed by Ding et al. The gel was created to immobilize cells and conduct
electrochemical studies on them, as well as to detect cell adhesion, proliferation,
and apoptosis on electrodes. As a model, K562 leukemia cells were used to create an
impedance cell sensor. The nanocomposite gel showed improved cell immobiliza-
tion ability and good biocompatibility, allowing immobilized living cells to maintain
their operation. The voltammetric response of living cells immobilized on glassy
carbon electrode was irreversible, and the electron transfer resistance increased. This
research demonstrated that nanocomposites gels based on biopolymer and NPs have
biosensing potential and will open up new avenues for electrochemical studies of
cell adhesion, proliferation, and apoptosis [47].

ICG-Functionalized Au NPs

SERS experiments on indocyanine green were recorded by Kneipp et al., who

demonstrated that the probe can be used to detect living cells. By tracking the
SERS local optical fields of the Au NPs, the ICG Au NPs provide spatially localized
chemical information from the cell environment. The functionalized Au NPs have
the potential to improve the spectral specificity and selectivity of current vibrational-
based chemical analysis approaches for living cells.
Souza et al. defined a method for fabricating biologically active molecular
networks by directly assembling bacteriophage with Au NPs. They discovered that
when phages are engineered with peptides, the cell surface receptor binding and
internalization are preserved. The networks can be used to detect living cells using
enhanced fluorescence, dark-field microscopy, and surface-enhanced Raman scat-
tering. The Au NP networks’ physical and biological properties provide multi-
modality for nanobiomedical imaging applications. Similar to oligonucleotide
chains, proteins have complementary countersections. Protein targets and biomole-
cules can be anchored to the surface of Au NPs for detection using other sensing
agents and techniques. Typically, the Au NP-based detection scheme can be used to
identify multiple protein targets in a single screening test.
For targeted imaging, NPs have a lot of potential. First, because of their wide
surface area, NPs can deliver a large number of imaging agents at once, improving
sensitivity. Second, NPs may be aimed to accumulate at sites where the molecular
target is expressed, raising the local concentration of contrast agents, or they may be
passively target tissues in vivo through the EPR effect. Because of their high
potential for NP adjustment, they can be used as in vivo imaging amplifiers. Finally,
they may conduct multimodality imaging by delivering a variety of imaging agents.
For cellular imaging, inorganic NPs like QDs are among the most promising
fluorescent labels. QDs can emit light at particular wavelengths and can also be
calibrated to emit in the near-infrared (NIR) region of the spectrum, which reduces
tissue autofluorescence while increasing excitation light penetration.
27 Application of Nanoparticles in Medicine 635

Individual proteins in cells and receptors involved in cell movement during devel-
opment and metastasis have been tracked using monofunctionalized QDs. QDs have
been used to image particular tumor biomarkers, such as the targeting of integrin avb3
with arginine-glycine-aspartic acid (RGD) peptide-conjugated NIR QDs. Targeted QDs
have also been investigated for their ability to perform multiplex imaging, which entails
imaging multiple molecular targets at the same time using different QDs with different
emission wavelengths. QDs have recently been used for multiplex molecular imaging
of lymph nodes, embryonic stem cells, tumor cells, and blood vessels.
Tiny organic molecules were used as near-infrared (NIR) SERS reporters to study
gold NPs as a noninvasive modality for in vivo cancer imaging. For the detection of
HER2-positive tumors in xenograft models, antibody-conjugated gold NPs were
recently used in conjunction with a responsive and stable cyanine reporter that was
generated and screened from a combinatorial library of SERS reporters. Other recent
in vivo imaging studies in mouse models have focused on the use of several targeted
SERS gold NPs for multiplexed imaging. One of the more well-studied NP systems for
targeted molecular imaging is magnetic NPs. Magnetic NP imaging systems have
shown potential for real-time visualization of biological events, such as cell migration/
trafficking, enzyme activities, and other biological interactions at the molecular and
cellular level.
Magnetic NPs have also shown promising use as contrast agents in magnetic
resonance imaging (MRI), a biomedical technique based on nuclear magnetic reso-
nance of various interacting nuclei. SPIONs, formed from iron oxide crystals coated
with dextran or carboxydextran, are widely used MRI contrast agents for cancer
imaging. SPIONs have been shown to stay in patients’ tumors for 24 h after injection,
compared to 1 h for gadolinium-based MR agents. This distinction is due to the tumor’s
easier absorption of the NP and the NP’s lower diffusivity out of the tumor. The use of
SPIONs for the selective identification of tumors and their metastases has been studied
extensively. SPIONs have also been used to kill cancer cells without the use of ligands.
A recombinant human heavy-chain ferritin protein shell containing IONPs was shown
to target tumor cells over expressing transferrin receptor 1 in one study.
In the presence of hydrogen peroxide, the iron oxide center catalyzed the oxida-
tion of peroxidase substrates, resulting in a color reaction that can be used to image
tumor tissues. SPIONs and targeting peptides were mounted on a modified viral
scaffold in another study to increase the amount of SPIONs reaching tumor cells.
M13, a bacteria-infecting virus, had glutamic acid residues added to its protein coat.
Negatively charged residues assisted in the electrostatic assembly of NPs along the
filamentous structure of the M13 coat. A peptide that targets the SPARC glycopro-
tein, which is overexpressed in various cancers, was also made into the viral coat.
When compared to conventional approaches in which NPs are directly
functionalized with targeting ligands, this method can increase MR imaging contrast.
For visualizing biological activities, novel NPs with advanced magnetic properties
have also been pursued. Metal-doped ferrite NPs with a composition of MFe2O4,
where M is a +2 cation of Mn, Fe, Co, or Ni, are one such class that can be used to
tune unique magnetic properties [180]. In vitro, MnFe2O4 NPs were found to be
nontoxic and to have the highest magnetic sensitivity, implying that they could make
636 M. M. Eid

better MRI probes. When these NPs were conjugated with antibodies, they improved
MRI sensitivity for cancer marker detection. Dendrimers (magnetodendrimers) and
liposomes (magnetoliposomes) are two other NP platforms that have been paired
with SPIONs. These SPIONs have been used for applications such as cell migration
control and in vivo visualization of bone marrow [48–54].

Application of Nanoparticles in Therapy

Photodynamic Therapy

Preclinical studies have documented the radiosensitization effect of gold nano-

particles (GNPs) in combination with various photon beams. While Monte Carlo
simulations of GNPs showed a physical dose enhancement of about 60% for
low-energy photons from 192 Ir brachytherapy sources and even X-rays in the
kilovoltage range [188], Jain et al. found a similar sensitization effect at kilovoltage
and megavoltage X-ray energies. Physical dose enhancement due to improved X-ray
absorption was proposed as a potential mechanism of sensitization. However, it
should be noted that the GNP measurements used in these studies were different. In
other words, GNPs with a diameter of 100 nm were used in the MC analysis, while
GNPs with a diameter of 1.9 nm were used in the biological study.
GNP with a diameter of 1.9 nm was injected intravenously into mammary tumor-
bearing mice in conjunction with 250 kVp X-ray in a groundbreaking study by
Heinfeld et al.
The new procedure had an 86% 1-year survival rate compared to 20% for X-rays
alone. Chang et al. used 13 nm GNP in combination with a single dose of 25 Gy of
6 MeV electron beam on melanoma tumor-bearing mice in another study. When
compared to a control group, it resulted in a substantial reduction in tumor volume.
Furthermore, the number of apoptotic cells was two times higher in GNP plus irradiation
animals than in irradiation alone. Interactions between X-rays and GNP are thought to
cause the release of photoelectrons from high-Z gold atoms as well as the generation of
auger electrons. These electrons have a very small range compared to photons, so they
deposit a lot of energy in cells containing GNP or in close proximity to gold atoms.
The discrepancies in GNP radiosensitization results may be due to variations in the
investigations conducted in terms of key parameters such as GNP shape, size, cell line
concentration and type, and radiation energy and type. Burn et al. evaluated the
influencing parameters in GNP X-ray radiosensitization in depth to resolve the prob-
lem. Large-sized GNP, high molar concentration, and 50 KeV photons were found to be
the most effective factors, with a potential dose enhancement factor of 6.4 [ 56–60].

Interaction of X-Ray and Gamma Radiations

Zhang et al. studied the irradiation stability and cytotoxicity of GNPs for radio-
therapy purposes. Following gamma radiation of 2000–10,000 Rontgen, they
found no apparent instability or size difference in spherical GNPs with a diameter
27 Application of Nanoparticles in Medicine 637

of 15 nm. The cytotoxicity results revealed that a very high concentration of GNP
could trigger a sharp drop in K562 cell viability, whereas a low concentration had
no effect.
Different types of interactions between photons and GNPs arise depending
on the energies of ionizing photons. For photons with energies ranging from
10 to 500 keV, the photoelectric effect is the most common method. The
emission of electrons, such as the characteristic X-ray of gold atoms or auger
electrons, is the result of this operation. A vacancy in a K, L, M shell following
photoelectric absorption results in de-excitation of the atomic system, either by
characteristic X-ray or Auger-electron emission, in photoelectric interaction
between photons and GNPs. The fluorescence yield determines the relative
likelihood of these de-excitation processes. Fluorescence yield is highly
influenced by the atomic number (Z), which is low for light atoms and high
for heavy atoms like gold.
Compton scattering and excitation are observed for photons with energies greater
than 500 keV. The photoelectric effect is caused by Compton scattering, which
causes atom re-excitation and the release of Compton electrons. After atom excita-
tion and phonon emission, there are certain selection laws that prevent photon
emission entirely. The excitation energy is transferred to the host lattice as
low-grade heat in phonon emission. This is known as the quenching method.
Since photon-phonon transfer processing is the dominant transition in GNPs, high
energy excitation in gold induces many phonons and few photons [193]. Pair output
dominates at photon energies greater than 1.02 MeV, resulting in positron and
electron pairs. Except for Compton scattering, the cross section of photon interac-
tions is highly dependent on Z for both of these interactions, when the photoelectric
and pair output effect probabilities are proportional to Z3 and Z2 of atoms. As a
result, it is assumed that the interaction of X-rays with gold atoms will release a
significant amount of energy, which will be converted into energetic, free electrons
and thermal energy
Suzy V. Tort et al. investigated the potential of multiwall carbon nanotubes
(MWCNTs) and near-IR (NIR) for photothermal cancer treatment. In addition to
direct thermal ablation of cancer cells, the thermal effects produced by MWCNTs
may have benefits, according to the researchers. When paired with chemotherapy or
radiotherapy, hyperthermia can increase the permeability of tumor vasculature,
which can improve drug delivery into tumors and enhance tumor cytotoxicity
synergistically. When this advantage is combined with other previously identified
MWCNT capabilities, such as the ability to transport chemotherapeutic compounds
and MRI contrast agents, MWCNTs have the potential to become multifunctional
platforms for cancer care [57].

Nanomedicine in Market

The FDA has approved for clinical use a significant number of drug products in the
nanometer size range (Table 1) [58].
 638

Table 1 FDA-approved drugs in nanometer size

Route of Approved
Drug name Generic name Company Indication administration date
Liposomal Doxil Doxorubicin HCl Ortho Biotech Products, Antineoplastic i.v. 17-Nov-
platforms Liposome Injection LP 95
Albelcet Amphotericin B lipid Enzon Pharmaccuticals Antifungal i.v. 20-Nov-
Complex Injection 95
DaunoXome Daunorubicin citrate Diatos Antineoplastic i.v. 8-Apr-96
liposome injection
Amphotec Amphotericin B Three Rivers Antifungal i.v. 22-Nov-
Cholesteryl Sulfate Pharmaceuticals 96
Injection
AmBisome Amphotericin B Astellas Pharma US. Inc. Antifungal i.v. 11-Aug-
Liposome Injection 97
Depocyt Cytarabine Liposome Enzon Pharmaceuticals Lymphomatous meningitis i.t. 1-Apr-99
Injection
Visudyne Verteporfin for Injection Novartis Photodynamic therapy for aged- i.v. 12-Apr-00
related macular degeneration
Nanocrystal Rapamune Sirolimus Wyeth Immunosuppressant Oral 22-Aug-
plalforms 02
Emend Aprepitant Merck & Co., Inc. Antiemetic Oral 26-Mar-
03
TriCor Fenofibrate Abbott Laboratories Hypercholesterolemia and Oral 5-Nov-04
hypertriglyceridemia
Triglide Fenofibrate Sciele Pharma, Inc. Hypercholesterolemia and Oral 7-May-05
hypertriglyceridemia
Megace ES Megestrol acetate Strativa Pharmaceuticals, Anorexia, cachexia, or an Oral 5-Jul-05
subsidiary of Par unexplained significant weight
Pharmaceutical, Inc. loss in AIDS patients
M. M. Eid
 27

Other Oncaspar pegaspargase: pegylated Enzon Pharmaceuticals acute lymphoblastic leukemia IM or IV 1-Feb-94
platforms L-asparaginase
Estrasorb estradiol topical emulsion Graceway Vasomotor symptoms associated Transdermal 9-Oct-03
Pharmaceuticals, LLC with the menopause
Abraxane paclitaxel albumin-bound Abraxis Oncology Metastatic breast cancer i.v. 7-Jan-05
particles for injectable
suspension
Feridex ferumoxides injectable Bayer HealthCare MRI Contrast Agent i.v.
solution Pharmaceuticals
(superparamagnetic iron
oxide)
Application of Nanoparticles in Medicine
639
640 M. M. Eid

Potential Hazards of Nanoparticles

Nanoparticles have the same possible hazards as bulk matter due to their extreme
microscopic size. These particles have the ability to cause a variety of diseases in the
respiratory, cardiovascular, and digestive systems. Carbon nanotubes have the ability
to cause a variety of lung pathologies, including epitheloid granuloma, interstitial
inflammation, peribronchial inflammation, and lung necrosis, as shown by
intratracheal instillation of carbon nanotube particles in mice. The toxicity of carbon
nanotubes was discovered to be higher than that of carbon black and quartz. C60
fullerene can induce oxidative stress and GSH depletion in the brain of fishes by
entering through the olfactory bulb. Nanoparticles can penetrate the central nervous
system either directly through axons of the olfactory pathway or through systemic
circulation. Inhalational exposure may cause the olfactory bulb to become involved
in humans. The olfactory pathway has been shown to accumulate carbon and
manganese nanoparticles in the olfactory bulb in monkeys and rats. This demon-
strates that nanoparticle-mediated delivery can one day provide an alternative route
for bypassing the blood-brain barrier. However, this can trigger inflammatory reac-
tions in the brain, which should be assessed.
In vitro research, Radomski et al. discovered that nanotubes facilitate platelet
aggregation and accelerate vascular thrombosis in rats. It was also discovered that
fullerenes had no ability to cause platelet aggregation. As a result, fullerenes may be
a safer option than nanotubes for developing nanoparticle-based drug delivery
systems. Nanoparticle toxicity may be extrapolated to the gastrointestinal tract,
causing inflammatory bowel disease. Nanoparticle toxicity may be linked to their
ability to trigger the release of proinflammatory mediators, resulting in an inflam-
matory response and organ damage. If ingested, nanoparticles may enter the blood-
stream and travel to various organs and systems, potentially causing toxicity. These
have been tested in vitro and in animal models, but extrapolating the effects to the
human system is difficult. Further testing and caution are needed before they can be
used in humans [59].

Conclusion

Nanoparticle in medicine is not an emerging field anymore, rather it is a very well-

established application. Although so much work has been done, we still need to
know more about the side effects and the limitations of introducing nanoparticles
into the body of patients.

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Characterization of Nanoparticles by FTIR
and FTIR-Microscopy 28
May M. Eid

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
Principal of FTIR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
FTIR for Monitoring Molecular Changes in Microorganisms Exposed to Nanoparticles . . . 650
FTIR Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
Toxicity of Effects of Silver Nanoparticles on Terrestrial Isopods . . . . . . . . . . . . . . . . . . . . . . . . . 653
Toxicity Tungsten Oxide (WOx) Nanofibers on Digestive Gland Tissue of Porcellio
scaber (Isopoda, Crustacea) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
Final Thoughts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
Subtoxic Exposure to ZnO Nanoparticles on Crustacean Digestive Glands Upon . . . . . . . . 655
Toxicity of Iron Oxide Nanoparticles on Liver and Kidneys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
Nano-FTIR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 658
AFM-IR Spectroscopic Imaging Benefits and Drawbacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Close-Loop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
Deliberation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
Nano-FTIR Chemical Mapping of Minerals in Biological Materials . . . . . . . . . . . . . . . . . . . . . . 661
Deliberation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
Carbonate-Forming Organism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
Subsurface Chemical Nano-Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Probe Single Bacterium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
Synchrotron FTIR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
Synchrotron Macro ATR-FTIR Microspectroscopic Analysis of Silica
Nanoparticle-Embedded Polyester Coated Steel Surfaces Subjected to Prolonged UV
and Humidity Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
Synchrotron FTIR Light Reveals Signal Changes of Biofunctionalized Magnetic
Nanoparticle Attachment on Salmonella sp. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671

M. M. Eid (*)
Spectroscopy Department, National Research Center (NRC), ElDokki, Cairo, Egypt

© Springer Nature Singapore Pte Ltd. 2022 645

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_89
646 M. M. Eid

Abstract
One of the most important analytical techniques available to today’s scientists is
infrared spectroscopy. Infrared spectroscopy has the advantage of being able to
study virtually every sample in virtually any state. With the right sampling
method, liquids, solutions, pastes, powders, films, fibers, gases, and surfaces
can all be tested. As a result of the improved instrumentation, a number of new
sensitive techniques for examining previously intractable samples have been
developed.
The Fourier transform infrared (FTIR) method is a type of spectroscopy that
can detect changes in the total composition of biomolecules by determining
changes in functional groups. The vibration and rotation of molecules influenced
by infrared radiation at a particular wavelength is measured using FTIR. This
method identifies structural differences in molecular binding between entities,
which can reveal details about the existence of their interactions. Transmittance
FTIR, attenuated total reflectance (ATR–FTIR), and micro-spectroscopy FTIR
are the most popular FTIR-based methods for characterization.

Keywords
FTIR · FTIR-microscopy · FTIR-AFM · Nanoparticles characterization · Nano-
toxicity

Introduction

In the 1950s, infrared (IR) spectroscopy was used to develop broad-spectrum

molecular analytical instruments [2]. Researchers invented Fourier transform IR
(FTIR) spectroscopy based on a modern computational analysis in the 1970s after
making many improvements to IR instruments, which led to Naumann and Helm [8]
introducing the FTIR technique for in situ analysis of bacteria. Due to the absorption
of energy in the infrared region, FTIR can classify molecular signatures in compos-
ites. Stretching [29], bending, scissoring, and twisting [1] are all examples of
biochemical bonds that can be detected based on their molecular rotational degree
and form of movement [18].
Optical spectroscopy techniques have gained greatly from recent developments in
instrumentation design, including detectors, sources, and the coupling of spectrom-
eters with microscopes that provide spatially resolved spectra (spatial resolution is
determined by incident light wavelength). Furthermore, data processing is being
intensively developed in order to provide rapid spectral resolution methods aimed at
evidencing the existence of multiple species and – ideally – at determining the sum
of each species present (more and more commercial packages are available for data
analysis). Mid-infrared (mid-IR) spectroscopy has recently been demonstrated to be
a basic, accurate, relatively fast, and cost-effective technique for analyzing complex
media and generating specific molecular fingerprints. From quality management to
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 647

forensic examination, it is used in a number of scientific and industrial

environments [19].
In this chapter, we will discuss various FTIR techniques used in the nanotech-
nology area, such as AFM-FTIR for characterization of nanoparticles or FTIR
imaging integrated with microfluidic cells for detection of nanoparticle biotoxicity
in vitro and in vivo. The synchrotron FTIR is shown at the end of the chapter to
demonstrate the effect of SR on the improvement of the IR beam and its impact on
measurements.

Principal of FTIR Spectroscopy

Molecules have distinct levels of rotational and vibrational energy. If (i) their energy
exactly matches the difference between two vibrational energy levels and (ii) the
dipole moment of the molecule changes during the vibration, the transition between
vibrational levels may occur following the absorption of photons with wavelengths
varying between usually 780 nm and 50 m (12800–200 cm
1) (IR selection rule
(Fig. 1)).
A linear combination of the so-called natural modes of vibration may be used to
express any typical molecular vibration. If a molecule with N atoms has nonlinear or
linear geometries, it has 3 N -6 or 3 N -5 normal modes, respectively (Fig. 2).
A simple harmonic oscillator model may define these modes. The infrared
behavior of normal modes can be measured solely by understanding the symmetry
of the molecule in question. The use of group theory to classify a molecule according
to its symmetry elements demonstrates the relationship between the molecular
structure and its vibrational spectrum. The bands seen on the spectra can be used
to distinguish the various types of bonds present in a sample.
These bands can be defined by their vibrational wavenumber (typical of the
transition energy involved, while shifts in wavenumber can reveal changes in
bonding and environment), their strength (related to the extent of the change in the

Fig. 1 Selection rule. http://butane.chem.uiuc.edu/pshapley/GenChem1/L15/2.html

648 M. M. Eid

Fig. 2 Vibrational energy levels. https://www.chem.uci.edu/~unicorn/old/H2A/handouts/PDFs/

LectureB4.pdf

bond dipole moment as well as the sample amount and bond polar character), and
their band profile (depending on the interactions of the bonding and environment).
The main challenge in a spectroscopy experiment is to obtain a good signal
intensity (high signal-to-noise ratio – SNR) when taking into account (i) the prop-
erties of the light source and its handling, (ii) the detector, and (iii) the sampling
conditions and spectral acquisition modes.
The incoming beam in infrared spectroscopy is usually given by black body
sources, which are temperature dependent and have a low to average brightness (e.g.,
a globar). Despite some limitations, these are simple, reliable, and inexpensive light
sources that emit a broad spectrum of light.
An interferometer made up of a beam splitter, a fixed mirror, and a moving mirror
moves the emitted radiation from an infrared source. The interferometer uses
interference patterns to calculate the wavelength of emitted light, which helps to
improve accuracy. Applying IR radiation to a sample and measuring the strength of
the passing radiation at a given wavenumber yields IR spectra. The number of scans
can be changed depending on the sample analysis quality requirement; currently, the
most common number of scans is two. Certain molecular groups’ IR radiation can be
detected at particular wavenumbers. The wavenumber is represented by the x-axis,
while the absorbance or transmittance is represented by the y axis. Transmittance
FTIR, attenuated total reflectance (ATR–FTIR), and micro-spectroscopy FTIR is the
most popular FTIR-based methods of characterization.
IN FTIR analysis of transmittance, strong samples should be ground with potas-
sium bromide (approximately 5% of the sample weight) and pressed onto a rough
pellet. The sample is then sandwiched between two transparent infrared plates. To
test various types of samples, various types of transparent material are used. Pick
compatible IR transparent windows, such as zinc selenide or diamond glasses, are
more suitable for liquid samples. The IR beam passes through the sample in both
cases. Since the pressed sample has a low number of spontaneous fluctuations of the
baseline, the transmittance process is beneficial because the pressed sample has a
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 649

low noise-to-signal ratio, resulting in higher sensitivity. The absorption sensitivity

varies within a sample containing various thicknesses, and the necessary time for
sample preparation are both limitations of this process. In general, the absorption
bands along the ATR–FTIR spectrum have a lower intensity than the transmitted
FTIR spectrum. The depth of penetration is the main difference between transmit-
tance FTIR and ATR–FTIR. The ability to transmit information ATR–FTIR can only
probe through samples up to 300 nm in thickness, whereas FTIR tests a range that is
an average of the bulk properties of the sample. The sample preparation criteria for
these two approaches are also different. The sample is directly mounted on the
crystal surface in ATR–FTIR, but the sample must be placed between two clear
glasses in transmittance FTIR [10, 24, 25] (Fig. 3).

Fig. 3 Methods of vibrational energy characterization

650 M. M. Eid

FTIR for Monitoring Molecular Changes in Microorganisms Exposed

to Nanoparticles

FTIR can classify molecular signatures in bacteria composition. Stretching, bending,

scissoring, and twisting are all examples of biochemical bonds that can be detected
based on their molecular rotational degree and form of movement.
Via the use of spectral libraries for each type of bacteria, FTIR techniques were
used to identify and classify bacterial strains. These libraries can be purchased as a
kit from some scientific firms. FTIR has also been shown in many studies to be
capable of distinguishing between intact and damaged cells in stress conditions.
Several possible antimicrobial mechanisms have been detected using FTIR:
(1) nanoparticles may change the fluidity of cell wall lipids by binding with –CH
groups of the membrane measured at 3100–2800 cm
1; (2) the binding of nano-
particles, or ions released from nanoparticles, with amino acids in proteins and
enzymes, which changes the protein structures detectable at 1500–1800 cm
1 nano-
particles bound to phosphate groups of nucleic acids in DNA or RNA altering their
structures, which are detected in the 600–1200 cm
1 wavenumber range; and
(3) nanoparticle catalyzed oxidation mechanisms and generation of reactive oxygen
species (ROS), which can cause alterations in polysaccharide structures measured in
the 900–1200 cm
1 wavenumber range.
Osmotic stress, temperature shock, pH tolerance, chemical shock, UV light, and
ultra-strong static magnetic fields have all been used to track bacterial properties and
composition in growth and non-growth environments. Similarly, the FTIR transmit-
tance technique was used to investigate the toxicity of selenium on Escherichia coli
(E. coli), as well as the exposure of E. coli and Staphylococcus aureus membranes to
a series of photocatalytic degradation accompanied by Ag/TiO2 nanoparticle
suspension.
For ATR–FTIR, a sample volume of 20 to 200 uL can be directly transferred or
dried and put onto a crystal surface, which can be produced from a variety of
materials with different refractive indices than the sample. The refractive index of
the sample, which should be lower than the crystal sample holder, is the most
important factor in ATR analysis. Various crystal surfaces exist depending on the
type of sample. The IR beam’s penetration capacity through the sample is approx-
imately 300 nm beyond the sample’s surface. To avoid interference from bulk water,
a probe may be used to direct the IR beam directly onto the sample in some cases.
Due to higher background noise, the resolution of this technique will decrease at
higher wavelengths as compared to transmission mode. This restriction does not
extend to bacteria analysis since bacteria signatures are observed in the mid-IR.
Bacteria are isolated from the liquid sample by membrane filtration before being
analyzed by ATR–FTIR. Metrical TM, polyethylene, Anodic, and aluminum oxide
are used for bacterial membranes filtration.
The toxicity of different nanoparticles, such as ZnO, quantum dots, and carbon
nanomaterial, has also been studied using ATR–FTIR. Wang et al., for example, used
ATR–FTIR to characterize nanowire photocatalysis in E. coli. The membrane
composition of treated cells changed structurally as a result of ATR–FTIR,
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 651

suggesting increased cell permeability. Fang et al. also looked into the toxicity of
different quantum dot nanoparticle sizes on E. coli. The toxicity effect of quantum
dots is size-dependent, as shown by changes in membrane structure in treated E. coli.
Smaller nanoparticles have a high inhibitory effect. Riding et al. investigated the
impact of long and short multiwall carbon nanotubes on gram-negative bacteria.
According to the scientists, the bactericidal effect of carbon nanotubes is dependent
on their size, with shorter tubes causing more toxicity than longer tubes based on the
signatures of lipids, amide II, and DNA components found in treated cells.

Benefits, Drawbacks, and Disadvantages

For the study of bacteria exposed to stress conditions, such as nanoparticle exposure,
both FTIR techniques have advantages and disadvantages. Since sample preparation
is simple, the time taken to achieve a spectral analysis is short, and samples can be
analyzed in various states (liquid or solid), FTIR is a time-saving technique. Fur-
thermore, only a small amount of the sample is required for analysis – typically in the
order of g (solids) or L (liquid) and the method is usually non-destructive. In
comparison to other widely used methods for bacterial detection, FTIR is also less
costly. FTIR also has three notable benefits: (1) a higher signal-to-noise ratio, (2) a
high energy throughput, and (3) high accuracy and stability. The “Fellgett
advantage“allows for a higher signal-to-noise ratio since the wavelengths are calcu-
lated simultaneously. The “Jacquinot advantage“refers to the high energy throughput
achieved by preventing light dispersion in FTIR. The use of a He–Ne (helium–neon)
laser, which serves as an internal reference for each scan and provides accurate and
stable wavenumber scales of an interferometer, is referred to as the “Connes benefit”
in terms of accuracy and stability. For nanotoxicology assays, these three properties
of FTIR are useful. In nanotoxicological research, all three of these FTIR properties
are useful in the solid phase rather than the liquid phase.
However, there are several drawbacks. To avoid artifacts and variations in the
spectra caused by the surrounding environmental conditions in sample heteroge-
neity, multiple background scans, and sample scans are needed. For example,
measuring the sample in culture media at various temperatures may affect the
sample’s FTIR spectra. Pretreatment of the samples may be necessary to purify the
sample and prevent peaks on the spectra from overlapping. Due to the large
absorption of water molecules in the 1637 cm
1 wavenumber, water from bacteria
samples in liquids will overlap the band of amide compounds and cause a loss of
information. This can be avoided in some cases by preparing a dried solid sample.
A library for characterization and identification is needed to identify bacteria
strains; however, this can be purchased from a variety of scientific companies.
Finally, the raw data may necessitate a considerable amount of post-processing
analysis. Additional methods to observe changes in intracellular composition in
addition to FTIR research.
The drawbacks of FTIR analysis can be overcome by integrating it with other
techniques. Raman spectroscopy, mass spectrometry, nuclear magnetic resonance
spectroscopy (NMR), and X-ray photoelectron spectroscopy are the most widely
used methods to determine the composition of bacteria [5, 6, 15, 26].
652 M. M. Eid

FTIR Imaging

Comparisons of healthy and dysfunctional tissue, which can be done using several
physical, biological, and biochemical techniques, can be used to detect biological
effects. Methods are chosen based on the predicted change, but when a greater
understanding of molecular and functional changes is needed, methods that can track
a wide variety of structural or functional changes are required. Among these, the
difference in molecular composition between normal and abnormal tissue using
Fourier Transform Infrared is very promising. This method is focused on the
absorption of infrared light, which causes molecular vibrations. The intensities of
these vibrations provide quantitative information, while the frequencies provide
qualitative information, such as oxidation, changes in cell membrane fluidity, and
protein and DNA alterations. Awareness of the existence of these bonds, their
structure, and their environment at the molecular level.
FTIR microspectroscopy is a non-destructive, label-free, and objective method
for distinguishing between normal and abnormal tissues. The backbone vibrations of
proteins, lipids, and nucleic acids are the key spectral features of complex structures
like cells. All of these contributions are reflected in the infrared spectrum of cells,
which provides information on the activation of pathways that protect against
oxidative stress, toxic response, and cell death.
The most recent FTIR technique, FTIR microspectroscopy, combines an FTIR
spectrometer and a microscope to obtain information through spatial and chemical
spectral information at the same time. The “replica stamping method” involves either
drying a diluted sample directly on an IR transparent plate or pressing the IR
transparent plates to a bacterial colony. Two to three bacterial layers can be imprinted
on the plate using this method. The advantage of both methods is that they allow for
the concentration of IR radiation on the sample and the collection of an accurate
spectrum. It also operates in the transmission and attenuated total reflection modes.
Although micro-spectroscopy FTIR has restricted spatial resolution, this does not
prevent bacteria from being identified using this accessory since they have different
degrees of morphologic heterogeneity.
FTIR micro-spectroscopy has previously been used to examine the heterogeneity
of Legionella bozemanii, Bacillus megaterium, and Candida albicans colonies, as
well as E. coli activities in biofilms, endospore bacteria changes after autoclaving,
discrepancies between intact and dead E. coli, and live and heat-treated Salmonella
typhimurium. The effect of a fullerene-based nanomaterial on Bacillus subtilis and
Pseudomonas putida membranes was also studied using FTIR micro-spectroscopy.
The researchers discovered that membrane fluidity and lipid composition are
influenced by nanomaterial concentration and cell wall composition.
In general, FTIR spectroscopic approaches enable high-throughput analysis.
Because the vibrational features of the sample are diagnostic biomarkers in FTIR
spectroscopy and microscopy, the technique is extremely promising in this regard,
and it was successfully exploited for highlighting the biomolecular mechanisms of
multiwalled carbon nanotube toxicity on both prokaryotic and eukaryotic cells, as
well as demonstrating the technique’s sensitivity to cellular changes indurated by the
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 653

nanotubes. Some authors studying effects of different substances and stress agents in
noninvasively, nondestructively conventional bioassays to study deviations in
molecular composition between normal relevant concentrations of contaminants.
Microscope infrared detectors have a high sensitivity and use broadband or
narrow-band mercury cadmium telluride (MCT). Others, such as focal plane array
(FPA) detectors, are made up of an array of infrared detector elements that allow for
simultaneous acquisition of spectra at multiple locations in the pixel array. These
instruments have been successfully coupled to interferometers, resulting in a sub-
stantial increase in the rate at which IR images can be obtained.
When FTIR is used in conjunction with microfluidic systems, the ultimate goal is
to recover spectra from reactive flows flowing within microfluidic channels. Single
point analysis, visualization, and imaging are the three most popular acquisition
modes. Single point analysis involves documenting a single FTIR spectrum at a
specific position on the dataset, obviating the need for a broad description or the
study of dynamic systems. However, high spectral resolution can be achieved, which
can be useful in applications such as trace detection.
The acquisition of several individual point spectra and subsequent recombination
to obtain a spatial image of the interrogated sample is referred to as mapping. This
method is time-consuming, but it offers a very high SNR for high-quality spectra.
FTIR imaging is not the same; in reality, the use of FPA or other array detectors
allows for the simultaneous acquisition of thousands of spectra. Despite the lower
SNR, a wide area can be mapped in a short period of time and with reasonable spatial
resolution due to the use of IR microscopes. When it comes to flow applications, this
choice is usually more convenient.

Toxicity of Effects of Silver Nanoparticles on Terrestrial Isopods

According to a review of the current literature on AgNP toxicity, it is still uncertain

which of the AgNPs’ properties plays the most important role in assessing their
negative effects. The release of Ag ions from AgNPs is widely acknowledged as a
key factor in assessing the observed toxic effects. Several authors have noted,
however, that the toxic effects are not exclusively due to dissolved ions, and that
NP size and shape also influence their biological effects.
In a FTIRI study, the intrinsic properties of silver nanoparticles, such as size,
shape, concentration, and ion release from dissolved nanoparticles, all play a role in
the molecular changes in the digestive gland tissue of isopods (Porcellio scaber,
Isopoda, Crustaceae) after oral exposure to subtoxic levels and that Ag accumulation
in tissues is just one of several factors.
The aim was to see how the intrinsic properties of AgNPs (size, shape, concen-
tration, and dissolution potential) interacted with their effects on a model organism
(Porcellio scaber, isopoda, Crustaceae) after subtoxic concentrations were con-
sumed. To accomplish this, the research species were fed AgNPs of various sizes
and shapes at various subtoxic concentrations: Ag cubical NPs (NCs) with an
average particle size of 60 nm, spherical NPs with an average particle size of
654 M. M. Eid

5–6 nm (NSs 5–6 nm), and spherical particles with an average particle size of
11–12 nm (NSs 11–12 nm).
The unfolding or misfolding of alpha-helix proteins, as well as a rise in both
nucleic acids and carbohydrates, detected by analyzing the specific spectral features
that characterize the spectral groups 2, while the sub-toxic effects of the spectral
group 3 interpreted as an accumulation of phospholipids and a downregulation of
protein synthesis, identified by analyzing the specific spectral features that charac-
terize the spectral groups 3. Many other authors have used the FTIR method to
demonstrate how different chemicals influence major biochemical constituents, but
there are few FTIR tissue analyses from in vivo nanoparticle studies. Other nano-
materials elicited a particular pattern of molecular response in the same experimental
set-up (a) in our previously published studies.
The effects of WOx nanowires (nano-WOx) were studied by Novak et al.,
and the effects of ZnO NPs and ZnCl2 salt were studied by Romih. In general,
after ZnCl2 ingestion, more pronounced spectra alterations were observed,
indicating that Zn ions are the primary cause of the observed effects. Novak
et al. found no effects on proteins or fullers in cells in their findings. These
researchers found a rise in carbohydrates after inducing oxidative stress in cells
with fullerols under visible light illumination. Proteins, mainly random domains,
and altered alpha-helix folding patterns, according to Romih et al. However,
when compared to the molecular pattern of spectroscopic group 3 as shown in
the research, they did not find alterations in the strength of both Amide I and
Amide II. All three studies registered alterations in the signal at 1740 cm1,
annotating more phospholipids. Changes in the number of phospholipids indi-
cate changes in membrane fluidity, which can be caused by a variety of
stressors, as calculated by FTIR in other studies. Vileno et al. used FTIR to
investigate the effects of fullerols on cells and found that they had a similar
effect on lipids. These researchers found a rise in the bands associated with lipid
peroxidation and protein phosphorylation in fullerol-induced oxidative stress in
cells exposed to visible light.
The survey revealed that finding generic sub-toxicity markers that could be
applied to any sample and any NP is likely difficult, and that admitting that the
response in both animal and NP-specific is more accurate. FTIR imaging, which
can also provide spatially-resolved information that can be compared with other
microscopy techniques, can clearly illustrate and partially disentangle this
specificity.
The takeaway from this study added to the growing body of evidence that
AgNPs effects at sub-toxic concentrations are caused by a complex interaction
between the scale, shape, and dissolution of ions from NPs, as well as their
combined interactions with tissue. Moreover, instead of searching for a single
NP characteristic that causes biological effects, we should look for methods and
approaches that can expose the biological implications of the combinatorial effects
of various NP characteristics, allowing us to distinguish low-hazard NPs from
highly biologically toxic NPs. In this regard, FTIR imaging appears to be a
successful candidate.
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 655

Toxicity Tungsten Oxide (WOx) Nanofibers on Digestive Gland Tissue

of Porcellio scaber (Isopoda, Crustacea)

Many studies have looked at how nano and microparticles affect lipid and protein
concentrations, as well as the organization and structure of the most basic macro-
molecules. Interactions between cells and nanoparticles cause changes in cell metab-
olism. However, determining the toxicity of nanomaterials is not always easy.
Nanostructures’ distinct chemo-physical properties, as compared to their bulk coun-
terparts, often tune the system response to traditional bio-assays in unexpected ways,
raising many questions about the results’ reliability.
In this study, authors used digestive gland tissue, from WOx nanofibers (nano-
WOx) fed animals to supplement the capabilities of FTIR imaging. The aim of this
study was to figure out how nano-WOx affects the digestive gland cells of a model
organism, the terrestrial invertebrate Porcellio scaber (Isopoda, Crustacea). Because
the exposure dose of each test organism can be estimated, the advantage of using this
organism is the ability to create a direct correlation between the real exposure dose to
nanofibers and the observed effects at various levels of biological organization. The
feeding parameters are an integrated organism-level response, as well as sufficient
evidence of the effects of various chemicals on the organism. Cellular and biochem-
ical analyses reveal evidence at the cell level following exposure to chemicals or
nanoparticles, as well as their mode of action to some extent. The digestive gland
cells (hepotopancreas) of terrestrial isopods, which combine the functions of the
pancreas and liver invertebrates, are a preferred tissue for studying the effects of
unknown or untargeted substances in the digestive system.

Final Thoughts

They were able to demonstrate that ingesting WOx nanofibers activates some
cellular mechanisms that may serve as a defense against adverse conditions. Before
oxidative stress and toxic responses, changes in protein to lipid ratio, lipid peroxi-
dation, and nucleic acid structural alterations were interpreted as responses indica-
tive of a non-homeostatic state. Both partial structural reorganization of nucleic acids
and mild lipid peroxidation is thought to be adaptation strategies of cells exposed to
irritating nanofibers, according to the researchers. More research is needed to
determine whether this is a nanofiber-specific response or a response to a variety
of unfavorable conditions.

Subtoxic Exposure to ZnO Nanoparticles on Crustacean Digestive

Glands Upon

Fourier-Transform Infrared Microscopy (FTIRM) is one such technique, which

provides spatially resolved information about a sample’s biochemical composition,
allowing for the investigation of the functional groups that distinguish a specimen.
656 M. M. Eid

Movasaghi et al., 2008 revealed that the concentrations, associations, structures, and
(bio)chemical environments of the cellular constituents are reflected in the infrared
spectra of cells. Although FTIR-based analytical methods have been widely used to
investigate the molecular changes associated with abnormal tissues, they have not
been widely used in ecotoxicological studies until recently ([18], Aja et al. 2014;
Palaniappan and Pramod 2010).
This study aimed to see if subtoxic concentrations of ZnO NPs and ZnCl2 (the
source of Zn2+) induced different biomolecular profiles in crustacean digestive
glands using the FTIRM. We propose that the effects of ZnO NPs are controlled
not only by Zn2+ but also by ZnO particulate matter. Data on Zn bioavailability as
measured by Zn assimilation into the digestive glands are included with the biomo-
lecular profile data. In conclusion, their findings indicate that ZnO particulate matter
alters the biomolecular profile of P. Scaber’s digestive glands and that the results of
ZnO NPs are not exclusively attributable to Zn2+. The animals exposed to ZnO NPs
had a significantly altered biomolecular profile, which was followed by a very low
assimilated fraction of Zn. Subtoxic ZnO NPs exposure alters the biomolecular
profile of the digestive gland, which is partly particulate-matter specific (distinct
protein conformation) and partly a nonspecific response to the external stimulus
(both ZnO NPs and ZnCl2 exposures) (increased protein and RNA content).

Toxicity of Iron Oxide Nanoparticles on Liver and Kidneys

FTIR microspectroscopy, a form of vibrational spectroscopy, is a physico-chemical

analytical technique for identifying biomolecules’ characteristic functional groups
based on their IR absorption. The process consists of a combination of optical
microscopy for identifying microscopic features of the sample under investigation
and infrared spectroscopy for determining chemical composition. FTIR micro-
spectroscopy’s high spatial resolution – down to single cells – helps researchers to
learn about the cellular content and distribution of major biological molecules
including lipids, proteins, and nucleic acids in microscopic areas of the sample.
Furthermore, FTIR microspectroscopy is sensitive to biomolecule conformation,
which is a unique property among spectroscopic methods. FTIR imaging is a
valuable method for biochemical analysis of biological samples because of these
features. Nanomaterials (NMs) have been extensively studied as possible biomedical
instruments for medical diagnostics, treatment, and tissue engineering. Objects with
one or more external dimensions in the range of 1–100 nm are the most common
definition. NMs can be categorized based on their core material’s chemical compo-
sition (organic, inorganic), structural features (consolidated materials, nano-
dispersions), form (spheres, cubes, rods), or aggregation state (gaseous, liquid,
solid). Engineered NMs for biomedicine is typically studied and focused on carbon,
silica, and metals of various sizes and shapes, such as nanocrystals, fullerens,
quantum dots, or nanoparticles. Nanoparticles (NPs), described as structures with
two or three dimensions between 1 and 100 nm, are the most extensively studied of
the various NMs used in biomedical research. The growing use of nanomaterials in
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 657

various fields of science and technology has raised concerns about their protection,
biocompatibility (defined as a substance’s ability to present an acceptable host
response in a specific application), and toxicity. The evaluation of these character-
istics is critical since the negative effects of nanomaterial exposure on living
organisms cannot outweigh their expected positive effects. Furthermore, understand-
ing the NM’s biocompatibility, identified as the ability to present an effective host
response in a specific application, is critical for determining their true potential in
biomedicine.
FTIR microspectroscopy was used to assess changes in cellular content and/or
structure of major biological macromolecules in the liver and kidneys of rats that had
been intravenously injected with a low dose of D-mannitol-coated iron (III) oxide
nanoparticles (M-IONPs). Iron oxide nanoparticles (IONPs) have been the focus of
extensive research in recent years due to their high potential in biomedical applica-
tions. The interest in these specific nanoparticles stems primarily from their relatively
simple and low-cost fabrication, superparamagnetic properties, and predicted biocom-
patibility and biodegradability. Furthermore, the ability to alter the nanoparticle
surface, such as by coating with organic shells or adding ligands, allows for improved
stability in solution, which improves biocompatibility and extends the range of IONP
applications. Nonetheless, the nanoparticles cannot be used as diagnostic or therapeu-
tic instruments until their effects on living organisms have been confirmed.
The physical, chemical, and structural characteristics of the tested nanoparticles
are highly dependent on their correct biodistribution, pharmacokinetics, and thus
potential side effects. As a result, before the particles are approved for clinical use,
the relationship between their properties and biological response must be
established. Only animal model-based studies may provide valuable information
on the systemic action of nanoparticles administered in vivo from a toxicological
standpoint. Wistar rats were used in this study to determine biochemical changes that
occurred in selected organs, such as the liver and kidney, after exposure to M-IONPs.
The liver and kidneys were chosen for analysis because of their critical role in
purifying the organism of toxins and foreign bodies, like nanoobjects. When nano-
particles are injected intravenously, they may go through metabolic processes such
as detoxification, solubilization, decomposition, and elimination. The liver and
kidneys are the organs that are most active in the aforementioned processes while
also being the most vulnerable to nanoparticle-induced adverse effects.
The M-IONPs under investigation had a hydrodynamic scale of 100 nm and a
core diameter of 10 nm. They were coated with water-soluble D-mannitol, a
polyhydroxy sugar alcohol compound. Due to its biological indifference,
D-mannitol appears to be a promising candidate as a coating material, despite its
limited use in particle manufacturing. Furthermore, since the vast majority of
existing studies have used doses that are equal to or much higher than those used
in medical practice, the current experiment used a relatively low dose of the NP. This
method may help to expand our understanding of the side effects of IONPs used in
low doses, similar to those used in medical diagnostics.
The findings demonstrated the utility of FTIR microspectroscopy in the study of
long-term biochemical abnormalities caused by intravenously administered
658 M. M. Eid

M-IONPs in the liver and kidneys. 7 days after being exposed to M-IONPs,
researchers discovered improvements in the content and structure of major bio-
molecules. Abnormalities in biochemical composition were even more pronounced
in the kidneys than in the liver. Although experimental animals were given a low
dose of M-IONPs, changes in the content and/or structure of lipids, phosphate
groups, cholesterol, and cholesterol esters in the renal tissue can indicate the
existence of oxidative stress within the organ. Such a disruption in redox homeosta-
sis most likely caused the development of LDs, a defense mechanism designed to
counteract oxidative stress [4, 16, 20–23, 27].

Nano-FTIR Spectroscopy

Binnig et al. pioneered scanning tunnelling microscope (STM) and atomic force
microscope (AFM), in which a sharp tip scans across a surface; the detection of
surface morphology relies on tunnelling current in STM and van der Waals forces
between atoms on the sample and atoms on the tip in AFM. Orthodox scanning
probe microscopy has a material blindness restriction. Recent research adds light to
scanning probe techniques to improve their ability to distinguish materials.
AFM-IR detects a photo-thermal effect by combining an AFM with tunable IR
radiation. AFM-IR is a technique that combines an AFM with tunable IR radiation to
detect photothermal effects and access chemical information at nanoscale resolution.
The limit and access chemical knowledge down to a nanoscale resolution using
AFM-IR. The limit resolution of subdiraction is obtained using AFM-IR. This is
accomplished by monitoring the diversion of an AFM probe with a sub-diffraction
resolution. This is achieved by tracking the diversion of an AFM probe that is in
contact with the sample surface and is deflected by rapid transient thermal expansion
of the sample as a result of the absorbance of an infrared pulse. This has previously
been observed to connect the sample to the absorbance of an infrared pulse. This has
already been shown to fit well with conventional macroscopic FT-IR measurements
of infrared absorbance.
Near-field spectroscopic methods usually combine vibrational spectroscopy con-
trast with AFM mapping. Near-field methods are vulnerable to objects, whose
understanding is crucial for optimizing analytical measurements but is still lacking.
IR scattering scanning near-field optical microscopy (IR s-SNOM) and tip-enhanced
Raman spectroscopy (TERS), for example, rely on specially designed probes to
enhance the near-field signal and complex, tip-specific models to interpret the
reported chemical data. Although tip models provide a much-needed but approxi-
mate understanding of the measured contrast, the difficult-to-predict tip-sample
interactions complicate quantification of results. Similarly, although improving the
near field signal is needed for accurate measurements, it may introduce confounding
factors that are difficult to monitor or mitigate experimentally. Small changes in
experimental parameters can result in significant changes in reported signals,
increased noise, and inconsistent (less repeatable) measurements, putting sample
preparation under constraints. This inconsistency stems from a lack of understanding
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 659

of the dominant inputs to the reported signal, which makes optimization difficult.
Innovative new techniques like photo-induced force microscopy (PiFM), for exam-
ple, have a lot of promise, but the documented signal is said to be a combination of
optical forces, tip-enhanced and direct thermal expansion, and photoacoustic effects.
A detailed fundamental understanding, assessment of relative contributions of nano-
scale systems, and systematic optimization of data recording are all used to establish
a near-field spectroscopic.

AFM-IR Spectroscopic Imaging Benefits and Drawbacks

It has a clear mechanism for detecting molecular absorption-induced thermal expan-

sion of the sample, needs no theoretical model for data interpretation, provides
chemical contrast without labels, and produces a signal that is correlated to
far-field absorption spectra.
Monolayer sensitivity in detection has been demonstrated using current state-of-
the-art resonance-enhanced methods; however, these studies depend on the signal
enhancement of gold or polymer-coated substrates. Furthermore, although the
observed signal is proportional to far-field IR absorption (to a first approximation),
recent studies show that the measured AFM-IR contrast is usually made up of
contributions from the chemical composition as well as mechanical features arising
from cantilever responsivity variations. The use of a subsample piezo expansion to
correct for cantilever responsivity has been shown to increase chemical accuracy of
recorded contrast, but it provides little improvement in sensitivity when compared to
the previous state-of-the-art. As a result, considering its relative simplicity and
ability, AFM-IR suffers from many of the same trade-offs as other near-field
methods. The analytical ability and fidelity of current AFM-IR methods to research
molecular properties of nanoscale materials on substrates of interest to the nano-
technology community, such as Silicon or gl, are all restricted by enhancement, the
need for narrowly defined sample preparation, convolution with confounding fac-
tors, and low chemical sensitivity (especially when compared to state-of-the-art IR
microscopy).

Close-Loop

The theory behind a robust closed-loop (CL) responsivity-corrected AFM-IR mea-

surement capability, as well as its implementation. The design is geared toward
minimizing measurement noise in AFM-IR, allowing for precise, high sensitivity
compositional mapping at the nanoscale without the use of excessively restrictive
sample preparation methods or specialized substrates. The theory of the strategy is to
modulate and record a harmonic voltage applied to a subsample mechanical actuator
(piezo) to maintain a near-zero amplitude harmonic cantilever deflection voltage by
real-time feedback control, in contrast to the current practice of recording signal
arising from cantilever deflection. This “closed-loop” method of operation
660 M. M. Eid

significantly reduces the reported chemical signal’s sensitivity to both spatial and
time-varying changes in cantilever resonance, increasing chemical precision while
minimizing noise. Furthermore, maintaining a null deflection eliminates detector
saturation, allowing high laser power and cantilever resonance amplification to be
used simultaneously. The CL strategy aims to make AFM-IR a more responsive,
precise, and user-friendly technique. To illustrate, we first provide a theoretical
description of the AFM-IR signals, followed by a complete design, study, and
characterization of the controls for reliable, high-quality measurements.
Nanomaterials’ molecular information is being mapped. AFM-IR imaging of
nano thin materials such as 2D materials, Self-assembled monolayers (SAM), and
isolated proteins has been demonstrated in a variety of studies; however, reliable
AFM-IR absorption measurements on arbitrary substrates are often constrained by
non-local signals, non-chemical effects (responsivity), and noise. The CL method
was developed to deal with these issues. In terms of measurement capacity, this work
expands AFM-IR sensitivity to include common organic monolayers such as
supported lipid bilayers and self-assembled alkanethiols with thicknesses of
1–5 nm. While this research has looked at some of the more obvious sources of
noise and presented a method for reducing them, the high quality data now allows for
further analysis into other sources of noise, which may lead to even greater changes
in the quality of recorded data.
This work showed how the established instrumentation outperforms previous
state-of-the-art methods by mapping the IR absorption of nanoscale-thick PMMA
films on glass and Silicon, which eliminates the need for time-consuming sample
preparation on gold or polymer-coated substrates.

Deliberation

Near-field spectroscopy methods often require tip- or sample-induced signal

enhancement, which allows for sensitive measurements but makes signal and
noise prediction and optimization difficult. As a result, AFM-IR has been limited
to tiny, isolated samples on unique substrates, but it has the potential for high
sensitivity and fidelity nanoscale chemical imaging. We first show that the output
of AFM-IR is limited by the effects of time-varying cantilever resonance, which
causes a significant increase in noise at large cantilever deflections, especially for
samples that produce a large DC bias signal. We then used this knowledge to develop
a CL AFM-IR process. Unlike traditional AFM measurements, which emphasize
larger cantilever deflections, the CL method uses feedback control to preserve near-
zero cantilever deflection when calculating an applied signal to a subsample piezo.
This CL control technique produces a regime with minimal noise and saturation
effects, allowing for high sensitivity IR absorption measurements on any substrate.
We include a thorough review of the proposed controls to ensure reliable and optimal
efficiency. We then put the principle to the test on a commercial AFM-IR instrument
to see how far we’d come. References improve data collection and processing to
allow nanoscale composition mapping on popular substrates such as Silicon and
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 661

glass, thanks to the CL method’s improved sensitivity and reliable phase signal. This
advancement enhances AFM-metrology IR’s capabilities in a variety of fields that
require accurate nanoscale composition imaging, including high-frequency nano-
electronics, NEMS and MEMS8, and photonics.

Nano-FTIR Chemical Mapping of Minerals in Biological Materials

In chemical analysis, Fourier-transform infrared spectroscopy (FTIR) is a standard

instrument. It uses the “fingerprint” of the molecular vibrational absorption spectrum
in the 3–30 m wavelength range to distinguish virtually any substance. Nano-FTIR
spectroscopic near-field microscopy is an exciting new development. It allows
scattering near-field optical microscopes (s-SNOM) to work at ultrahigh spatial
resolution through a broad mid-infrared spectrum emitted from either a coherent
supercontinuum source or an incoherent thermal source. The s-SNOM probes the
sample with a nano focused light field using a metalized AFM tip as a light-
concentrating antenna. The nanofocus is a light spot the same size as the tip radius
that distinguishes s-optical SNOM’s and topographic resolutions. Backscattered
light detection exposes local optical detail. The probed volume usually extends
20 nm laterally and into the sample (sometimes as little as 10 nm). The wavelength
has no impact on the high resolution. This allows for the use of long wavelengths,
which lead to infrared fingerprint vibrations. s-SNOM has been successfully used
with visible, infrared, and terahertz illumination on organic and inorganic materials
in fields as diverse as nanoelectronics, phase transition physics, and material recog-
nition. The near-field interaction that underpins it has been theoretically modeled and
experimentally confirmed. The measurable contrasts and spectra can be calculated
using the sample material’s complex dielectric function, which includes both the
absolute efficiency and the step of scattering. Only flat test samples of metals,
semiconductors, and polar crystals have been used to show Nano-FTIR.

Deliberation

FTIR has long been used to research biominerals in several environments, and nano-
FTIR expands this capability to include spectroscopic mapping at the nanometer
scale. Phosphates and carbonates in well-studied examples of M. edulis and human
dentin show exquisite detail, which fits what electron microscopy and nano-
indentation reveal. The discovery of biomineral chemical and structural mapping
opens up new avenues for research into mineral arrangements and heterogeneity in
biological systems. A noncontact and nondestructive imaging technique can now
map intricate carbonate-based natural skeletons inside and through interfaces, which
may include transient and stabilized amorphous phases. The approach is specifically
applicable to the investigation of stable and diseased types of vertebrate bones and
teeth when it comes to apatite studies. Mineral precipitation, aggregation, and ageing
can now be studied and quantified in submicrometer detail, allowing researchers to
662 M. M. Eid

gain a deeper understanding of the biological processes underlying bone formation,

abnormal growth, and healing in response to drug treatment.
The nano-FTIR method is extremely robust and useful for the study of biological
materials due to many technological advantages of surface scanning. The samples
don’t have to be thin; they just have to be relatively flat to avoid damaging thin-
section preparations. Cutting and polishing procedures create unavoidable topo-
graphic barriers, which are of little consequence: The off-resonant infrared ampli-
tude, as well as the resonant response in amplitude and phase, are unaffected by
height variations of 100 nm, as shown by the repeatability of the carbonate resonance
spectra within the sample area containing biocalcite. The s-SNOM amplitude is
known to be reduced over a distance equal to the spatial resolution at steep
topographic edges, resulting in “edge darkening.” This effect is thought to be
responsible for the dark regions seen between calcite crystals in, but it needs to be
studied further. The edges of the biocalcite crystals show a mechanical (AFM)
resolution well below 30 nm, demonstrating nano-remarkable FTIR’s spatial reso-
lution. The infrared resolution is greater than 20 nm, as shown by the abrupt edges of
the nano-FTIR line segment showing the phosphate resonance.

Carbonate-Forming Organism

The “phosphate” particles in Mytilus edulis (M. edulis) are easily identified by their
spectral signature. But their topographic presence alone would have been difficult to
detect. Notice that one of the carbonate resonances is also visible in the nano-FTIR
spectra of the “phosphate” particles, indicating that it originates from the crystals
underneath. To grasp this effect, remember that the simple near-field interaction probes
the sample to a depth on the order of the tip radius (or slightly deeper if the tapping
amplitude or average tip-to-sample distance is greater than the tip radius). Backscatter-
ing can be affected by buried artifacts if the covering layer is not thicker than a few times
the tip radius. This influence has also led to the suggestion that s-SNOM has tomo-
graphic mapping capability. The results are the first to demonstrate that different phonon
resonances occur in both the covering layer and the buried material. The thickness of the
“phosphate” particles is estimated to be on the order of 10–30 nm based on the observed
amplitudes, which is consistent with their topographic appearance.
In this proof-of-concept analysis, the origin of the “phosphate” particles is
unknown. Their irregular distribution may indicate an unidentified preparation
artifact. The substance may be a modification of materials in the organic matrix,
but the infrared images don’t show this. Nonetheless, the particles may not be dried
polishing material (Struers OP-A), which has a poor FTIR absorption at 1073 cm
1
but no discernible nano-FTIR resonance in the frequency range of interest. The
observed high spectral phase effect of about 80 , which exceeds that of bioaragonite
(50 ) and biocalcite (70 ), is a clear argument for the particles being labeled as
crystalline phosphate. For strong polymer vibrations, the spectral phase effect is
usually on the order of 30 , but on the order of 400 for strong crystal phonons. The
use of phosphate in shell architecture has not been confirmed in mollusks, but
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 663

calcium phosphate is known to be present in the radula (tooth structure) of chitons.

Phosphorylated proteins have been proposed as essential organic matrix components
in bones. Despite their ambiguous origins, our discovery of “phosphate” particles
shows that nano-FTIR can easily locate and chemically identify nanometer-sized
material even at high rarefaction. Finally, the observed particles are crystalline for
two more reasons: (i) their near-field scattering amplitude is around 103, similar to
calcite, and not much smaller than 3,103, as known for two strongly polar crystals,
SiC and SiO2; and (ii) their near-field resonance line shape is asymmetric, with the
steep high-frequency edge (Fig. 4) typical of strong polar crystals. As has been
shown routinely the disorder in a crystal reduces the amplitude significantly. Amor-
phous materials have a reduced, broadened resonance, while conventional organic
materials have an even weaker response, as demonstrated in this analysis by the
PMMA resonance peaking at 1.5 near 1150 cm
1.
The biomineral composition and density are revealed by the large phosphate
bands calculated by nano-FTIR in dentin. To begin, they estimate the local volume
fraction f of mineral particles (assuming f ¼ 1 for enamel) to be 0.54, 0.30, and 0.26
for spectra 1, 2, and 3, respectively, based on their peak and baseline amplitudes. In
the frequency range of 1020 to 1120 cm1, there are noticeable, position-dependent
variations. These differences indicate that (i) tooth materials are made up of many

Fig. 4 Principle of AFM-IR technique. With permission from Dr. Phuong

664 M. M. Eid

mineral types with different vibrational resonances, also on a 20-nanometer scale,

and (ii) the mineral composition varies with location. When spectral components are
too far below the surface, they can be detected. In contrast to SEM, where the
interaction of electrons with bony materials is known to cause damage, s-SNOM is
nondestructive. The edges of the tubule lumen are marked by the extracted BE
profiles and the extracted infrared profiles. The amplitude (red) and phase (blue)
outside the peritubular rim qualitatively correlate with the BE-defined mineral
material (black). The different probing depths of the s-SNOM and BE imaging
methods account for an exception in the 7.1–7.5 m segment. As a result, both
amplitude and phase tend to be capable of calculating minor density shifts. When
it comes to spectral variations within the phosphate band, the ratio r is approximately
0.8 and 0.7 for the peritubular and intertubular regions of the large tubule (x,y),
respectively, but only 0.7 and 0.6 for the small tubule (x,y). r ¼ 0.80 for enamel.
Since most apatite species of interest have not yet been measured as pure sub-
stances by s-SNOM, an assignment of the observed nano-FTIR spectral components
of a tooth at around 1020, 1055, and 1100 cm1 is unfortunately not straightforward.
From theory and studies, it is well understood that 1020, 1055, and 1100 cm are
present in enamel and peritubular dentin but not in intertubular dentin, and may be
related to the lack of collagen protein, while 1100 cm1 is present in all dentin but not
in enamel. We measured and plotted the distribution of three characteristic quantities
extracted from nano-FTIR spectral scans, namely, the peak s-SNOM amplitude
(red), the ratio r of amplitudes at 1053 cm1 and 1022 cm1 (green; not significant in
the tubule lumen), and the phase at 1080 cm1 (blue), in direct comparison with the
BEI profiles, to address potential assignments.
In general, the shape of the particles as a result of depolarization effects should be
taken into account when interpreting infrared absorption in bone. Based on whether
the particles are spherical, needle-like, or platelike, density functional theory has
recently been applied to the apatite v3 vibrational infrared absorption, predicting
strong spectral distortion and splitting (up to 50 cm1) due to macroscopic electrostatic
effects (not to be confused with microscopic distortion of lattice cells). Fluorapatite
absorption peaks were found at 1038, 1067, 1097 cm1, and hydroxyapatite absorption
peaks were found at 1034, 1053, 1105 cm1, with the last two peaks strongly separated
by the nonspherical shape of the particles. Similar findings were seen in other studies.
Since the mineral in dentin and bone is made up of isolated, locally arranged apatite
platelets, strong depolarization effects are likely to distort the infrared spectra in the v3
phosphate resonance area. A systematic investigation of near-field and far-field infra-
red apatite bands for various shapes of chemically and structurally well-defined
nanocrystals is needed. The weaker v1 phosphate band, which is less affected by
electrostatic effects than all Raman lines, should be included in such a study.

Subsurface Chemical Nano-Identification

Scattering-type scanning near-field optical microscopy (s- SNOM) is a scanning probe

microscopy technique that allows for nanoscale-resolved optical imaging of a variety
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 665

of samples, such as polymer, biological materials, semi-conductors, conductors, and

insulators. Monochromatic visible, infrared, or terahertz electromagnetic radiation is
focused onto the tip of a standard, metalized atomic force microscope (AFM) probe in
s-SNOM. At the very tip apex, the tip acts as an optical antenna, concentrating the
radiation into highly confined and enhanced near fields. The close fields communicate
with the sample surface, changing the amplitude and phase of the backscattered field
depending on the local optical sample properties. Nanoscale-resolved images of the
sample’s optical properties are obtained by recording back-scattered light as a function
of tip position1. The AFM is run in tapping mode, with the tip oscillating naturally to
the sample at a frequency to eliminate unwanted background signals. This operation
mode produces higher harmonic modulation of the tip-scattered field, but not of the
background scattering since the near-field interaction is strongly nonlinearly depen-
dent on the tip-sample distance. The pure near-field signal is obtained by recording the
detector signal at higher harmonic frequencies n (typically n>2). The extension of the
near fields, which is in the order of the tip apex radius, which is usually about
R ¼ 25 nm determines the spatial resolution.
Similar to infrared microscopy18, s-SNOM allows for extremely sensitive com-
positional mapping at infrared frequencies by probing vibrational excitations such as
those of molecules or phonons. Nanoscale-resolved infrared spectra can be recorded
using a broadband infrared source and Fourier transform spectroscopy of the light
scattered by the s-SNOM tip19. Nano-FTIR spectroscopy produces near-field phase
spectra that closely match the absorptive properties of organic samples, allowing for
nanoscale chemical detection using standard FTIR.
Even though s-SNOM and nano-FTIR are surface scanning techniques, the finite
penetration depth of near fields into the sample enables subsurface probing of
nanoscale structures and defects up to 100 nm. It has also been demonstrated for
s-SNOM that depth-resolved information – with the possibility of three-dimensional
sample reconstruction can be obtained by analyzing multiple higher harmonic
signals, each with a different probing depth. However, the potential capability of
nano-FTIR experiments for chemical identification of subsurface material is largely
unexplored territory.
An experimental and theoretical nano-FTIR spectroscopy analysis of thin sub-
surface organic layers is presented here. Authors show that (1) subsurface layer
nano-FTIR peaks are lower in frequency than bulk materials or thin surface layers,
and (2) surface and subsurface layers can be distinguished by examining the ratio of
peak heights obtained at different demodulation orders n, without using theoretical
modeling or simulations. They studied the well-defined C¼O vibrational mode of a
thin polymethyl-methacrylate (PMMA) layer on silicon covered by a polystyrene
(PS) layer of varying thickness, which we compared to variously thick exposed
PMMA layers on silicon. We also show how a semi-analytical model can be used to
deduce and predict nano-FTIR spectra in multilayered samples. Finally, to summa-
rize and analyze the results of a comprehensive theoretical and experimental analysis
of the nano FTIR peak characteristics of various thick subsurface layers exhibiting
various molecular vibrational modes, demonstrating the relevance and applicability
of our findings for a wide range of materials.
666 M. M. Eid

In conclusion, they discovered that the peaks in nano-FTIR phase spectra of

subsurface organic layers are spectrally red-shifted as compared to nano-FTIR
spectra of the corresponding bulk content and that the redshift is greater than that
observed for surface layers as their thickness is reduced. A semi-analytical model for
calculating nano-FTIR spectra of multilayered samples, which well describes the
observed patterns, backs up our findings. Our model also shows that peak shifts in
multilayer nano-FTIR spectra can be traced back to the sample’s momentum-
dependent Fresnel reflection coefficient, assuming chemically induced peak shifts
are removed. They point out that peak shifts caused by sample and momentum are
not exclusive to near-field spectroscopy; they also occur in far-field spectroscopy,
where the probing momentum is determined by the angle of incidence. Finally, we
showed that surface and subsurface layers can be separated without the use of
theoretical modeling or simulations by examining the ratio of peak heights obtained
at different demodulation orders n. Their findings will be critical for potential
applications of nano-FTIR spectroscopy, such as distinguishing peak shifts induced
by sample geometry from peak shifts caused by chemical effects including chemical
interaction at material boundaries.

Probe Single Bacterium

Infrared spectroscopy (IR) is a promising candidate for phenotypic bacterial probing

because it offers a molecular characterization of the sample. Due to the wavelength
diffraction spatial resolution limit, there have been a large number of examples of its
use since its early applications. Innovative techniques incorporating atomic force
microscopy (AFM) and vibrational spectroscopy have opened up a new frontier in
materials analysis in recent decades, developing chemical maps with resolutions well
beyond the Rayleigh diffraction limit, in the 10–100 nm range. Because of its
simplicity and flexibility, this rapidly developing area includes tip-enhanced Raman
spectroscopy (TERS), scattering scanning nearfield optical microscopy (s-SNOM),
and photothermal infrared techniques. The diffraction-limit associated with traditional
microspectroscopy optics is bypassed during AFM-IR by monitoring the thermal
expansion of materials caused by infrared radiation absorption, with an AFM probe
in contact with the sample surface serving as the detector. Unlike s-SNOM, this
method provides a direct measure of infrared absorption, making analysis easier.
Furthermore, unlike TERS, AFM-IR does not require precisely specified probe tip
geometries and is less susceptible to contamination. As a result, the AFM-IR method
has been applied to an ever-growing variety of specimens spanning material science
disciplines since its inception. Local degradation processes in organic coatings, fibers,
oil paint and solid-state insulators, minerals in bitumen, geological specimens, bone
and human dentin, the analysis of corrosion inhibitor films, nanoscale domains found
in polymer blends, thermosets and nanocomposites, the chemist. The implementation
and commercialization of a top-down illumination setup, which allows a wide range of
samples assisted by any underlying substrate to be analyzed, has been a significant
factor in the recent widespread application of AFM-IR. The original bottom-up
illumination experiment, on the other hand, involved the preparation of thin specimens
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 667

near a ZnSe prism. As a result of the top-down configuration, specimen geometries

have become less limited, allowing AFM-IR to become a routine analysis technique.
However, understanding and eliminating possible infrared imaging objects is a vital
consequence of this. Variation of 2,490 in the tip-sample contact area on rough
samples, locally enhanced infrared amplitude signals over regions of increased sample
thickness (i.e., increased volume of material underneath the probe), and the reliance of
the induced resonance on local mechanical properties are all previously recorded
sources of artifact in the infrared signal for AFM-IR (hardness). These effects are
currently regularly taken into account by experienced microscopists when analyzing
AFM-IR data. Since all of the above phenomena are wavelength-independent, nor-
malized local spectra and ratio maps can also be used to rule them out or exclude them
(where infrared maps taken at two different wavenumbers are divided, in a process
akin to spectral normalization). We present a previously unknown source of artifact
and knowledge in this chapter. AFM-IR infrared spectra and maps may display
features that are dependent on the reflection of incident infrared from an underlying
substrate. More specifically, since this effect is wavelength-dependent, normalization
methods will not be able to compensate for it.
Since the majority of bacteria are smaller than that (e.g., Staphylococcus aureus
has a diameter of less than 400 nm), traditional IR cannot be used to probe single
cells or intracellular structures.
Combining IR spectroscopy with Atomic Force Microscopy has recently solved the
spatial resolution constraint (AFM-IR). The IR absorption is observed indirectly in this
case, due to the material’s thermal expansion. In summary, IR absorption causes the
growth of antimicrobial resistance (AMR), which is currently one of the most pressing
global health issues and is expected to become the leading cause of death by 2050. The
development of resistance, as well as the spread of AMR strains, occurs either directly
or indirectly through the measurement of oscillation of the AFM cantilever probe,
resulting from force impulse, at an alarming rate that far exceeds the rate of 10 produced
by IR absorption technique, which allows for spatial resolution approaching 20 nm
(AFM-IR). It is possible to collect single spectra from selected spots as well as map the
strength of selected wavenumber values within a defined region. New antibiotics are
being discovered. New resistant phenotypes emerge regularly around the world,
although research into AMR-related changes is often sluggish and constrained by
available approaches. Furthermore, common methods like polymerase chain reaction
(PCR) and whole gene sequencing (WGS) concentrate solely on genotypic shifts.
These methods are insufficient to expose the mechanisms of resistance, necessitating
the urgent development of a research tool that can analyze the chemical composition of
bacteria. Phenotypic-based recognition of bacteria at the genus, species, and strain,
levels has been demonstrated in the literature. The spatial resolution of traditional IR, on
the other hand, is limited to a few microns. Given the spatial resolution of AFM-IR, it is
clear that the technique allows for chemical/phenotypic probing of individual bacte-
rium cells as well as their intracellular composition. Several examples of AFM-IR
applications for single bacteria have been published previously.
In summary, in local infrared spectra obtained with AFM-IR, reflection from the
underlying substrate produces distinct wavelength-dependent features. This means
that, in addition to chemical analysis of an overlying film, details about the local
668 M. M. Eid

composition of a buried substrate can be obtained in a nondestructive manner using

AFM-IR. This opens up the fascinating possibility of broadening the photothermal
infrared method to include the identification of metallic substrate discontinuities
indirectly. Nonetheless, these findings clearly show that the specular reflectance of
an underlying substrate, its thermal reaction, and mild interference effects have an
impact on local spectra and infrared maps for AFM-IR analysis of thin films. When
analyzing AFM-IR data, the nature of the underlying substrate and local variations in
specimen thickness should be taken into account [3, 11, 12, 14, 17].

Synchrotron FTIR

In most laboratory-based FTIR instruments, the extremely collimated synchrotron

infrared (IR) beam provides 100–1000 times greater brightness than traditional
thermal Global FTIR sources. The acquisition of high-quality FTIR spectra at
diffraction-limited spatial resolutions is possible with this extremely intense beam.
As a result, synchrotron FTIR is an excellent analytical tool for obtaining spatially
resolved chemical mapping of materials with a lateral resolution of 3–10um
(depending on the wavelength used).

Synchrotron Macro ATR-FTIR Microspectroscopic Analysis of Silica

Nanoparticle-Embedded Polyester Coated Steel Surfaces Subjected
to Prolonged UV and Humidity Exposure

A technique based on macroscopic (macro) attenuated total reflection (ATR)-FTIR

microspectroscopy was recently developed at the Australian Synchrotron IR
beamline to allow the coupling of the synchrotron IR beam to germanium
(Ge) ATR element. Because of Ge’s high refractive index (nGe ¼ 4), and
ATR-FTIR mapping measurement can be used to probe surface-specific molecular
information about materials with four times greater precision than comparable
transmission and reflectance modes. The macro ATR-FTIR method, unlike the
conventional microscopic (micro) ATR-FTIR approach, only involves a single
contact between the sample and the ATR crystal for the entire mapping measure-
ment, which not only increases scanning speed but also decreases the risk of sample
damage and cross-contamination between measurement positions.
After 3 years of exposure to the subtropical environment in Queensland
(Australia), we observed a decrease in the carbonyl (C¼O) band strength in the
pure polyester coating with no SiO2NPs present using the synchrotron ATR-FTIR
microspectroscopic technique, performed at low resolution in the early stages of
development. The chemical evolution of SiO2NPs-embedded polyester composite
coatings on steel substrata as a result of environmental factors was observed over
time and analyzed at the molecular level using the previously mentioned synchrotron
macro ATR-FTIR technique. For the surfaces of polyester composite coatings
containing various amounts of SiO2NPs, high-resolution chemical maps were
acquired. For 3 years, these samples were exposed to tropical and subtropical
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 669

conditions. In order to determine precise changes in the molecular structure of the

surface, a chemometric approach, specifically principal component analysis (PCA),
was applied to the synchrotron macro ATR-FTIR spectral data. The findings were
then compared to samples that had not been exposed to the atmosphere.
The changes in molecular structure, combined with surface topographical data
obtained from optical profilometry and atomic force microscopy (AFM), provided
insight into changes in the surface properties of coating materials as a result of
environmental exposure. This knowledge is crucial for developing methods for
increasing the durability of polymer composite coatings. It should be noted that
this work represents the first time that direct molecular evidence, performed using
high-resolution synchrotron FTIR mapping technology, has been reported to high-
light the chemical evolution of polyester composite coatings on steel surfaces as a
result of environmental exposure.
Final Thoughts, in this chapter, spatially resolved synchrotron macro ATR-FTIR
microspectroscopy was shown to be an effective technique in the molecular charac-
terization of surface coating materials when combined with a multivariate data
analysis approach. Via high-resolution chemical mapping technology, the technique
not only provided a clearer understanding of changes in the molecular distribution
over time, but it also provided useful insights into the molecular changes taking
place through PCA.
The findings obtained using this combined technique showed that changes in the
molecular structure of the polymer occurred as a result of environmental exposure.
Pure polyester coatings exposed to a tropical climate underwent different changes in
molecular structure than those exposed to a subtropical climate. Although changes in
the triazine ring and ether group in the melamine resin were two prominent changes
in the samples exposed to a tropical environment, changes in the carbonyl group of
the polyester resin, as well as changes in the hydroxyl groups, the triazine ring, and
hydrocarbon groups, were observed in the samples exposed to a subtropical climate.
After 3 years of exposure to both tropical and subtropical conditions, applying
SiO2NPs to the polyester coating resulted in similar improvements in the surface
chemistry of the surface coatings. The most influential factor that triggered the
separation between the control and exposed samples was found to be the v(C ¼ N)
stretching mode of triazine ring vibration in the melamine resins, which is possibly due
to the triazine ring being hydrolyzed in humid environments. A large number of
chemical bonds associated with the melamine/polyester networking structure were
shown to be affected at the higher SiO2NPs loading of 9%, resulting in significant
surface degradation after long-term exposure to a high UV/high humidity environment.

Synchrotron FTIR Light Reveals Signal Changes of Biofunctionalized

Magnetic Nanoparticle Attachment on Salmonella sp.

Via the use of a spectral library for each type of bacteria, FTIR techniques could be
used to recognize and classify bacterial strains. FTIR spectroscopy is also being used
to distinguish fecal Escherichia coli strains from pigs, poultry, and humans as a
bacterial source monitoring tool. The use of distinct peaks that are peculiar to various
670 M. M. Eid

bacteria strains or organisms is promising and warrants further study. For fecal
E. coli discrimination, FTIR spectra in the range of 2861 to 3026 cm
1 were
suggested as suitable specific peaks. Peaks in C-H stretching of CH2 in fatty acids
were found at wavenumbers 2852, 2924, and 2946 for C-H stretching of CH2, and
2960 for C-H stretching of CH3 in fatty acids. F. Faghihzadeh et al. announced the
discovery of structural changes in molecular binding between microorganisms and
metal atoms in nanoparticles. Due to the interaction of cells with AgNPs, FTIR
spectra changes in fatty acids, specifically –CH deformation, were recorded to alter
bacterial membrane permeability.
Compounds’ infrared spectrum and interactions have a special fingerprint for
microbial identification. For the screening of microbial bioprocesses, FTIR spec-
troscopy could be used as a single tool for the study of several cellular metabolites.
Pharmacological drug monitoring has also been recorded. The results show that
FTIR tracking can be used to track complex and sequential reactions including
pathogen attachment to target cells or supporting materials.
Synchrotron radiation-based FTIR (SR-FTIR) spectroscopy has a benefit for
these experiments because of its higher signal-to-noise ratio (by 100 to 1000
times), higher collimation, and luminance, which can exceed the diffraction limit
with 10 m or better compare to traditional FTIR with 75 m spatial resolution.
Final thoughts, the SR-FTIR signal changes of amino-functionalized FMN with
GA crosslink, antibodies, and Salmonella cells were monitored individually and
after reaction steps in this research. Controls, FMNs, glutaraldehyde, the Salmonella
antibody, and Salmonella cells alone had their spectra established.
At wave number 1672 of NH bending, FMNs had a one-of-a-kind peak (scissor-
ing). The aldehyde peak at wave number 1722 in the glutaraldehyde range showed
C¼O stretching. The following are the signal changes for each connection stage. The
aldehyde group (1460 cm
1) of glutaraldehyde reacted with the FMN spectrum at
wave number 1673 (N-H). The disappearance of FMN-GA peaks at 1763 and 1460
proved this relation. The availability of the aldehyde group on the FMN-GA
complex is indicated by the peak at 1778 cm
1 at this point. In the next step,
you’ll be able to connect this aldehyde group to Ab. Peaks at wave number 1244
(C-N stretching) were found in the FMNs-GA-Ab spectrum, suggesting that the
aldehyde group (GA) was attached to an amino group (Ab). The absence of a peak at
1788 cm
1 also means that Ab still has an aldehyde group connection. The FMN-
GA-Ab complex was then attached to Salmonella cells in the final stage. Peaks at
1655 cm
1 C¼O amine I react with the NH2 group of Ab, resulting in a CH2
scissoring peak at 1454 cm
1 as a result of the attachment. This phase produced
no 1655 cm peaks. At 1649 cm, amide I have a stretching vibration. The changes in
magnetic nanoparticle attachments on the Salmonella cell surface gave unique peaks
at 1542 and 1414 cm
1 of the amide II band of protein and C¼O symmetric
stretching of the COO- group in amino acids and fatty acids, respectively, according
to SR-FTIR results. Ab-FMNs without and with target cell attachment had distinct
bands at 1244 cm
1 and 1454 cm
1. The target Salmonella had specific SR-FTIR
peaks after rapid capture/- concentration and isolation, which could be used in
various applications for rapid detection of target Salmonella and the design of a
generic machine for rapid, noncontact, non-destructive, and culture-independent
28 Characterization of Nanoparticles by FTIR and FTIR-Microscopy 671

detection method/plat- type of pathogens in food products. In the future, the

approach may be applied to environmental and medical diagnosis [7, 9, 13, 28, 30].

Conclusion

In this sense, FTIR techniques provide diagnostic methods for various types of
samples. Complementary techniques such as NMR, Raman, XPS, and mass spec-
troscopy can help determine the intracellular composition and structures of treated
and untreated cells by increasing the information density.

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Websites

https://www.beilstein-journals.org/bjnano/articles/2/53
https://www.elettra.trieste.it/elettra-beamlines/nanospectroscopy.html
https://link.springer.com/article/10.1007/s00216-015-9033-3
Biomedical Applications of Nanozymes:
Disease Diagnosis and Therapy 29
Venkata Krishna Bayineni, Venkateswara R. Naira, and
Ravi-Kumar Kadeppagari

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
Applications of Nanozymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
Application of Nanozymes in Diagnosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
Immunoassays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
Tumor Theranostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679
Myocardial Infarction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
Glucose and Antioxidant Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
Detection of Superoxide Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
H2O2 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
Therapeutic Applications of Nanozymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
Antioxidation and Anti-inflammation Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
Stem Cell Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 682
Gold Nanoparticles for Therapeutic Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 682
Bioorthogonal Chemistry and Living Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
Neuroprotection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
Antibacterial Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
Tumor Theranostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
Cardiovascular Medicine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
Factors Affecting the Properties of Nanozymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
Status and Challenges of Practical Applications of Nanozymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Main Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685

V. Krishna Bayineni · V. R. Naira

Department of Biology, Prayoga Institute of Education Research, Bengaluru, Karnataka, India
e-mail: [email protected]
R.-K. Kadeppagari (*)
Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Department of Food
Technology, Jyothy Institute of Technology, Bengaluru, Karnataka, India

© Springer Nature Singapore Pte Ltd. 2022 675

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_91
676 V. Krishna Bayineni et al.

Abstract
Nanozymes are new-generation nanoproducts having enzyme-like catalytic prop-
erties and highly efficient than the native enzymes. As the catalytic mechanism of
nanozymes is gradually revealed, the application fields of nanozymes have also
been extensively explored. Recently, developments on nanozymes have made a
remarkable progress and attracted a lot of researchers to explore their biomedical
applications. Compared to the native enzymes, the nanozymes are highly bene-
ficial due to their better stability, easy production, surface functionalization,
reusability, and lower manufacturing costs. Moreover, the functionality of nano-
zymes can be remotely controlled by various physical factors including magnetic
fields, ultrasound, light, and heat. In general, these factors can be regulated to
advance the diagnosis and treatment of different diseases in the biomedical
environment. Considering the huge potential of nanozymes in diagnosis and
treatment (such as biological detection or biosensing, antibacterial, antioxidant,
bioorthogonal chemistry, anti-inflammatory treatment, and cancer therapy), wide
biological applications of different nanozymes are summarized in this chapter.
Also, the factors that affect the properties of nanozymes (such as pH temperature,
surface modification, and doping of other elements) are discussed. This chapter
will enable the researchers to understand better the recent status of nanozymes
and may help for new breakthroughs. At the end of this chapter, the prospects and
challenges of using nanozymes in practical applications are discussed.

Keywords
Nanozyme · Diagnosis · Treatment · Antibacterial · Antioxidation · Biosensing ·
Anti-inflammatory · Tumor theranostics

Introduction

Nanozymes are a large collection of laboratory-made nanotechnology products that

possess intrinsic enzyme-like activities similar to natural enzymes. The limitations in
storage, stability, manufacturing, functionalization, sensitivity, and reusability of nat-
ural enzymes have triggered scientists across the globe to explore/design a range of
nanoproducts for identification of nanozymes. The nanozymes are manufactured with
specific functional molecules and are capable of self-assembly to generate a robust
specificity to the native enzyme substrates. Moreover, like natural enzymes, the
nanozymes also follow the Michaelis-Menten reaction kinetics. The nanozymes
could overcome most of the above challenges involved with the use of natural
enzymes. These advantages have revolutionized the manufacturing of nanozymes to
facilitate an avalanche of applications in the field of biomedical engineering. Since the
advent of the first report on Fe3O4 magnetic nanomaterials exhibiting an intrinsic
peroxidase-like activity [8], the nanomaterial technology has been taken a radical shift
toward the development of artificial enzymes. Presently, numerous nanomaterials were
reported to be capable of mimicking a variety of catalytic activities (Table 1).
29 Biomedical Applications of Nanozymes: Disease Diagnosis and Therapy 677

Table 1 Novel nanomaterials with a wide variety of enzyme-like activities [24]

Type of bioactivity Nanoparticles
Peroxidase Fe3O4, Co3O4, CuO, V2O5, MnFeO3, FeS, graphene quantum dots, CeO2,
BiFeO3, CoFe2O4, FeTe, magnetoferritin, and gold@carbon dots
Oxidase Au, Pt, CoFe2O4, MnO2, CuO, and NiCo2O4
Catalase CeO2, Pt-ferritin, Ir, MoS2 nanosheets, Prussian blue
Superoxide CeO2, fullerene, FePO4microflowers, Gly-cu (OH)2, N-doped porous
oxidase C-nanospheres
Superoxide CeO2, Mn3O4, Prussian blue (PB), PCN222-Mn, Pt
dismutase
Haloperoxidase V2O5 nanowire, CeO2x nanorods
Sulfite oxidase MoO3
Phosphatase CeO2, Fe2O3
Phosphotriesterase Co3O4/GO nanocomposites, CeO2
Chymotrypsin Cr-MIL-101 (MIL-101 is a metal organic framework)
CO oxidase Cu2O@CeO2core@shellnanocubes
Protease Cu-MOF (metal organic framework)
Restriction CdTe
endonuclease
Carbonic Co-(2,6-bis(2-benzimidazolyl))@terbium-MOF
anhydrase

Applications of Nanozymes

The research advancement of nanozymes has paved the way to explore a wide range
of biomedical applications from in vitro diagnosis to in vivo therapy of critical
diseases. Based on the mode of application, Jiang and coworkers divided the
nanozymes into self-acting, synergistic, and remotely controlled. Many recent
developments in the field of nanotechnology have broadened the methods for
studying new enzymes. The potential catalytic mechanism of nanozymes has yet
to be explained when combined with computer theoretical calculations and simula-
tions. Nanozymes’ catalytic activity has been increased as a result of these studies.
Nanozymes have shown advantage in biomedical technology for diagnosing and
treating diseases.

Application of Nanozymes in Diagnosis

Imaging

Apart from the enzyme-like activity, nanozymes have exclusive physicochemical

properties like paramagnetism, chemiluminescence, and X-ray absorption. For this
reason, nanozymes have been developed as excellent disease imaging probes for
pathological staining, live cell/organelle imaging, and in vivo imaging [24]. For
678 V. Krishna Bayineni et al.

example, peroxidase nanozymes such as magnetoferritin, antibody-functionalized

Co3O4, and silica-gold nanoclusters could stain specifically overexpressed biomol-
ecules in tumor-specific tissues, thereby facilitating the contrast of the tumor cells
during disease diagnosis via imaging techniques. Therefore, peroxidase-like activ-
ity-exhibiting nanozymes were developed for diagnosing cancers related to breast,
colorectal, stomach, pancreas, esophageal, and bladder [24]. During the diagnosis of
cancer, the analysis of cytological features of cells through nanozyme-based detec-
tion has recently been emerged as a cost-effective and less time-consuming tech-
nique over the traditional methods like flow cytometry, smearing, and nucleic acid
tests. For screening the cancer cells, nanozymes are used to detect circulating tumor
cells that can be found in the blood, cerebrospinal fluids, chest water, and mucous
liquids. For example, a report on antibody-conjugated Fe3O4 nanoparticles has
suggested that nanozymes could isolate, visualize, and quantify the circulating
tumor cells concurrently via oxidation of colorimetric 3,30 ,5,50 -tetramethylbenzidine
(TMB) and spectroscopic estimation. Similarly, other nanozymes such as silica-gold
nanocluster, graphene oxide-gold nanocluster, folic acid-conjugated Pd@Au nano-
particles, magnetic nanoparticles, and Au/Ag core/double-shell nanoparticles have
been used to detect several cancers such as breast cancer, cervical cancer, myelog-
enous leukemia, melanoma tumor cell, and squamous cancer, respectively. Nano-
zymes have superior advantages (fast, easy, and low-cost) over known methods like
polymerase chain reaction (PCR), enzyme-linked immunosorbent assay (ELISA),
and flow cytometry. Even for cell organelle imaging, heterogeneous palladium
nanozyme was reported as specific mitochondrial probe due to its effective media-
tion via photo-driven biorthogonal reaction.
Eventually, the nanozyme-based disease imaging was also explored in identifying
other specific diseases like jaundice, acquired immunodeficiency syndrome (AIDS),
diabetes, and some infectious and neurodegenerative disease. Moreover, the special
physicochemical properties of nanozymes such as fluorescence, electricity, and
paramagnetism have encouraged the nanotechnologists to explore the nanozyme-
assisted MRI (magnetic resonance imaging) for effective in vivo disease monitoring
and imaging. For example, human-magnetoferritin nanoparticles conjugated with
125
I radionuclide were used as a robust biosensor for nuclear imaging of tumor
tissues that enhanced the imaging sensitivity up to 106-fold, compared to the normal
MRI [29]. Similarly, graphene quantum dots (peroxidase-like activity) and iridium
oxide (catalase-like activity) nanoparticles were also reported as excellent contrast
agents for the tumor imaging and treatment [24].

Immunoassays

The ELISA is a widely used immunoassay technique during the diagnosis of human
diseases. Traditionally, natural enzymes serve as biosensors in the biochemical
reactions that involve in the colorimetric detection of specific analytes related to
the disease. With the advent of nanozymes, the catalytic efficiency and sensitivities
in ELISA could be improved severalfold compared to natural enzymes. The Fe3O4
29 Biomedical Applications of Nanozymes: Disease Diagnosis and Therapy 679

magnetic nanoparticles were first nanozymes that are reported to use in

immunochromatographic strip for detection of glycoprotein of Ebola virus, which
was so rapid and easier than the conventional ELISA method [5]. In another
interesting study [18], a dual-mode detecting immunoassay (colorimetric and radio-
metric fluorescent) was developed using the nanoceria and graphitic carbon nitride
quantum dots to determine the concentration of cardiac troponin I, a key protein
involved in the diagnosis of acute myocardial infarction. In a very recent study on
detection of novel SARS-CoV-2 coronavirus, Co-Fe@hemin nanoparticles were
developed as nanozymes having high peroxidase-like activity along with the inte-
gration of chemiluminescence immunoassay activity [15]. This immunoassay is a
strip-based paper test that requires 16 min of reaction time with a detection limit up
to 0.1 ng/ml. Compared to the nucleic acid and serological antibody tests, this
immunoassay-based paper test was proved to be more effective in terms of time
and false-negatives.

Tumor Theranostics

Nanotheranostics has recently been recognized as personalized cancer treatment

by concomitant diagnosis and therapy using novel nanozymes. Among the many
nanozymes, magnetic Fe3O4 nanoparticles and their nanocomposites have gained
center of attention to explore the theranostic applications due to their intrinsic
magnetic and multifunctional properties to use in MRI, magnetic hyperthermia
treatment, phototherapy, drug delivery, chemotherapy, and gene therapy. The
unique ability of functional and surface modulation of Fe3O4 nanoparticle-
based nanozymes has also provided a great benefit to obtain high-contrast
imaging and enhanced therapeutic efficiencies. The Fe3O4-based nanozymes
have other benefits like extended blood circulation times, fast clearance, and
minimum side effects [30]. Moreover, the peroxidase-like activity of Fe3O4-
based nanozymes made an excellent mimic to the well-known Fenton reactions,
where endogenous H2O2 is catalyzed into hydroxyl radicals (•OH) leading to the
death of tumor cells. Therefore, food and drug administration (FDA-US) has
approved a few types of Fe3O4-based nanoparticles that are being used for
clinical applications, e.g., ferumoxide and ferucarbotran SHU-555A for liver/
spleen imaging, ferumoxytol and feruglose for angiography, ferumoxtran and
ferucarbotran SHU-555C for lymph node/bone marrow imaging, and ferumoxsil
for GI oral imaging [30]. Wang and his team developed a novel biodegradable
chemodynamic theranostics using nanomicelles, PAsc/Fe@Cy7QB, that facili-
tates tumor-specific multimodal imaging and improved generation of •OH radi-
cals for enhancing the therapeutic efficacy [25]. Other than iron oxide-based
nanozymes, Zhang and his coworkers have reported that carbon-gold hybrid
nanoprobes (OMCAPs@ rBSA-FA@IR780) have shown theranostic properties
on MGC-803 tumor-bearing mice by demonstrating simultaneous imaging via
near-infrared (NIR) fluorescence and photothermal/photodynamic therapy of
tumor cells with effective therapeutic efficacy [28].
680 V. Krishna Bayineni et al.

Myocardial Infarction

Myocardial infarction (heart attack) is mainly linked with the deposition of excess
amount of free cholesterol in the blood. For this reason, the detection of cholesterol
has a great significance in the food quality control and early diagnosis of various
heart-related diseases. As H2O2 is a by-product during the catalytic reaction of
cholesterol oxidase, the amount of cholesterol has been quantified indirectly using
a number of nanozymes that exhibit peroxidase-like activity. For example, one of the
early studies reported a chemiluminescent biosensor having CuO nanoparticles that
estimated the amount of cholesterol in the samples of milk powder and human serum
by transducing the oxidation of luminol by H2O2, produced during the oxidation of
cholesterol by cholesterol-oxidase [10]. Similarly, other nanozymes like graphene
quantum dots, Mo, S co-doped carbon quantum dots, Fe3O4-coated C/Ni nano-
composites, nanosized molybdenum disulfide, and carbon nanotube-assisted Prus-
sian blue were also reported as cholesterol biosensors with high catalytic activity and
sensitivities [17]. As a next step of advancement in nanozymes, cerium oxide
nanoparticles were reported as self-color-changing nanozyme for the estimation of
blood cholesterol without any requirement of chromogenic substrates like
3-ethylbenzothiazoline-6-sulfonic acid (ABTS) or 3,30 ,5,50 -tetramethylbenzidine
(TMB) [21]. In the future developments of cholesterol determination, novel nano-
particles with intrinsic cholesterol-oxidase activity have to be explored for making
robust and a complete nanozyme-based biosensor.

Glucose and Antioxidant Detection

Zn-doped CuO nanoparticles were confirmed to exhibit both glucose (as low as
0.27 ppm) and antioxidant (tannic acid, tartaric acid, and ascorbic acid) detection
[19]. Liu and his coworkers developed Pt/CeO2 nanocomposites as mimics of
peroxidase to detect ascorbic acid linearly in the range of 0.5–30 μM [14].

Detection of Superoxide Anions

The reactive oxygen species (ROS) have significant role in various signaling path-
ways of cell metabolism. Among ROS, the O2•- (superoxide anion) is an intermedi-
ate ROS that leads to the production of H2O2 and •OH (hydroxyl radicals) inside the
living cells. Uncontrolled release of ROS in living cells, on the other hand, can result
in cancer and aging. As a result, detecting superoxide anions in living cells plays an
important role in disease early diagnosis and pathological research. Though there are
several methods like spectrophotometry, chromatography, chemiluminescence, elec-
tron spin resonance, and bio-enzymatic for determination of O2•-, nanozyme-based
detection is more reliable, rapid, reproducible, and cost-effective. As a presumable
measure, superoxide dismutase-like activity-exhibiting nanozymes have been tested
for detection of O2•-. In several reports, nanozymes such as carbon-based manganese
(II) phosphate nanoparticles, SiO2-Mn3(PO4)2 nanoparticles, bacterial cellulose-
29 Biomedical Applications of Nanozymes: Disease Diagnosis and Therapy 681

based Mn3(PO4)2 nanoparticles, nano-Mn3(PO4)2-chitosan, MnO-embedded carbon

nanofibers, carbon-based Mn2P2O7-formylstyrylpyridine film, Pt nanoparticles, and
Co-based nanocomposites were used to detect O2•- in cancer cell lines, e.g., HeLa,
human melanoma, 4 T1, etc. [3, 6, 22].

H2O2 Detection

The H2O2 molecule is a by-product of partial oxidation in a number of biological

pathways that involve extensive redox reactions. As a result, early detection of H2O2 is
critical for human disease diagnosis and prognosis. The natural enzyme horseradish
peroxidase (HRP) has been used for colorimetric detection of H2O2 in the presence of
complex substrates, e.g., 2,20 -azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)
(ABTS) and 3,30 ,5,50 -tetramethylbenzidine (TMB), thanks to recent developments in
biosensors. Having an efficient catalytic activity and selectivity, the HRP-based bio-
sensors have some critical drawbacks such as degradation due to long-term storage,
harsh temperature, and pH conditions. Therefore, Fe3O4 magnetic nanoparticles which
exhibit intrinsic natural peroxidase activity along with high stability at critical pH and
temperature conditions can be used [8]. Eventually, other nanozymes like gold
nanoparticles [31], graphene quantum dots, and AuPd alloy-modified polydopamine
were also found to have peroxidase-mimicking properties that made researchers to
explore their applications in the diagnosis of human diseases. For example, Ma and his
coworkers reported that Fe3O4 nanoparticles could able to detect reduced glutathione
(an important tripeptide which is related to a number of diseases like liver damage,
cancer, AIDS, etc.) as low as up to 3.0–30.0 μM in A549 cell lines. The detection of
reduced glutathione was possible through the indirect estimation of H2O2 [16]. In
another study, graphene quantum dot nanozymes were used to detect H2O2 in vivo
from the nasopharyngeal carcinoma cells and therefore served as an excellent contrast
agent in deep-tissue tumor-targeted catalytic photoacoustic imaging [4]. In another
recent study, the detection of apolipoprotein E4 (APOE4) for the early diagnosis of
Alzheimer’s disease (AD) was made possible by using AuPd alloy-modified poly-
dopamine nanotubes (having intrinsic peroxidase-mimicking activity) in combination
with the gold nanobipyramid-coated Pt nanostructures.

Therapeutic Applications of Nanozymes

As mentioned above, nanozymes have been widely used in detection and diagnostic
methods. In addition to these applications, many researchers have also studied their
therapeutic applications.

Antioxidation and Anti-inflammation Therapy

Reactive oxygen species (ROS) are widely distributed in cells as a by-product of cell
metabolism. Excessive production of ROS will be very harmful to cells and cause
682 V. Krishna Bayineni et al.

many diseases, such as cancer, atherosclerosis, and arthritis. Nanozyme platform

shows good performance in the removal of reactive oxygen species and can protect
cell components from oxidative stress in vitro and in vivo. Generally, superoxide
dismutase is often used for therapeutic applications because of its protective effect as
a scavenger of reactive oxygen intermediates. Seal and coworkers have reported the
activity of CeO2 nanoparticles as superoxide dismutase mimic. Various studies have
been tried to develop superoxide dismutase that mimics nanozymes [13]. It is also
proved that nano-cerium oxide can be used for anti-inflammatory activity for
eliminating free radical oxygen in J774A.1 mouse macrophage [9]. The synergistic
effect of the combined nanozyme activity has been shown to protect cells from ROS
harm due to their antioxidant properties [23]. The observations of Singh and
colleagues (2019) showed that Mn3O4 nanoparticles have great potential in the
treatment of inflammation and other ROS-related diseases.

Stem Cell Growth

Superparamagnetic iron oxide (SPIO) nanoparticles have been used to promote the
growth of stem cells. It is reported that the commercial SPIO ferucarbotran can
promote the cell growth of human mesenchymal stem cells (hMSCs) by reducing
H2O2 in the cells and accelerate the cell cycle process. In this report, the intrinsic
peroxidase-like activity of SPIO significantly reduces intracellular H2O2 after inter-
nalization into hMSCs and free iron ions released by the lysosomal degradation of
SPIO, thereby affecting cell cycle control molecules [11].

Gold Nanoparticles for Therapeutic Applications

Colloidal gold nanoparticles (AuNPs) have recently demonstrated excellent

enzyme-mimicking activities that mimic catalase, peroxidase, superoxide
dismutase, oxidase, and reductase. The catalytic properties of AuNPs are
influenced by their surface chemistry, morphology, and external factors including
temperature or pH. Various application paths have already been investigated,
including the regulation of oxidative stress within cells using peroxidase-like
nanozymes through their superoxide dismutase and catalase activities. They have
also been shown to play a role in a number of biomedical treatments, including
photothermal therapy, which means they can absorb light and turn it to heat.
Different loading technologies, such as distribution, surface complexation,
attachment with capping agents, layer-by-layer assembly, and even encapsulation
of drugs in AuNPs, have been used as drug delivery tools. However, the most
promising biomedical application is the use of AuNPs as visible optical indica-
tors in pregnancy tests. In addition, they can also be used as protective agents
from reactive oxygen species (ROS) [7].
29 Biomedical Applications of Nanozymes: Disease Diagnosis and Therapy 683

Bioorthogonal Chemistry and Living Cells

The chemical reactions that can be carried out in living cells or tissues without
interacting with the organism’s biochemical reactions are known as orthogonal
biological reactions. Professor Sletten and coworkers first suggested this in 2009.
So far, biorthogonal reactions have assisted in various researches on cellular pro-
cesses and biomolecules by selectively modifying biological species in biological
systems. The findings show that nanoparticles made of platinum and gold have a lot
of potential for monitoring and regulating the state of living cells.

Neuroprotection

Fullerenes and their derivatives have long been established as free radical “sponges”
due to their excellent ability to scavenge various types of ROS. It has been proven to
protect the brain from neuronal damage caused by over-generated superoxide free
radicals. This fullerene nanozyme has been tested in the Alzheimer’s disease model
of Caenorhabditis elegans and has shown excellent neuroprotection against amy-
loid-β peptide aggregation. It is found that MoO3 nanozyme can be used as a sulfite
oxidase mimic for cell detoxification. The lack of natural or artificial sulfite oxidase
is related to nervous system damage and early childhood death. It has also been
proven that Mn3O4 nanoparticles show high potential for treating neurological
diseases caused by ROS [12].
It is reported that nano-cerium oxide, a mimic of superoxide dismutase, can
prevent retinal degeneration by inhibiting the production of reactive oxygen inter-
mediates. In their work, nano-cerium oxide in the presence of H2O2 prevented retinal
neuron apoptosis induced by reactive oxygen intermediates and the accumulation of
reactive oxygen intermediates in cells. They also demonstrated that injecting nano-
cerium oxide into rats’ eyes can protect retinal photoreceptor cells from light-
induced degeneration [1].

Antibacterial Effects

For a long time, many efforts have been made in the fight against infectious diseases
caused by bacteria. Various antimicrobial agents have been discovered. However,
disadvantages such as poor antibacterial efficiency and heat resistance of organic or
inorganic antibacterial agents still prompt us to develop new materials in the
antibacterial field. Recently, nanomaterials with catalytic behavior have shown
great potential in this field due to their stable and effective antibacterial properties.
Therefore, more and more new antibacterial nanomaterials with inherent peroxide-
like properties were synthesized. In particular, platinum-based nanocrystals have
been widely used in catalysis due to the good control of shape, size, morphology, and
684 V. Krishna Bayineni et al.

structure. For example, Wu and his colleagues [26] successfully fabricated Pt hollow
nanodendrites, which showed excellent peroxidase-like activity. In 2017, Ye and his
colleagues created an INAzyme based on a hydrogel system that generates •OH in
situ and has antibacterial effects. The cell wall structure of the bacterial membrane
can be destroyed by OH oxidation of the unsaturated bonds of phospholipids.

Tumor Theranostics

Effective methods for tumor diagnosis and cancer treatment have attracted many
research interests. Many recent studies have focused on the use of nanozymes in
tumor therapy, providing us with new tools in the battle against cancer and other
diseases. Due to their inherent catalytic behavior, Guo’s work in 2015 demonstrated
that nanozymes can be used for photodynamic therapy to treat hypoxic tumor cells
[2]. Zhang and colleagues reported in 2018 that metal-organic frameworks modified
with Pt nanoparticles can also enhance the effect of photodynamic therapy [2018].

Cardiovascular Medicine

By responding to challenges and advancing the imaging and identification of in vivo

and ex vivo biomarkers, as well as enhancing tissue regeneration and drug delivery,
cardiovascular nanomedicine aims to improve detection and address existing car-
diovascular problems and treatment issues. Nanocarriers are directly injected to
deliver the medication. Nanocarriers used to treat cardiovascular disorders, and
other diseases have chemical properties that vary from one another [20].

Factors Affecting the Properties of Nanozymes

The size and morphology of the nanozymes that determine the active site determine
the catalytic efficiency of nanozymes. Luo and colleagues evaluated the size-
dependent efficiency of glucose oxidase-like AuNP by preparing 13 nm, 20 nm,
30 nm, and 50 nm AuNPs. The experimental results show that the catalytic activity
increases with the decrease of the particle size. It is found from the literature that the
octahedral-shaped nanozyme performs better due to lower surface energy. The
catalytic activity of natural enzymes is known to be affected by pH and temperature.
Acidic conditions can promote peroxidase mimic activity, while neutral and alkaline
conditions are conducive to catalase-like properties. Moreover, there are some
nanozymes that are stable and perform well in a relatively wide pH and temperature
range. By changing the pH value from 2 to 12 and the temperature from 4  C to
60  C, it is found that the ceria porous nanorods have the greatest catalytic efficiency
at temperatures of 3–4.5  C and 35  C [27].
Similarly, altering the surface of nanozymes will affect the efficiency of the reaction
by reducing the active site’s exposure. Doping elements can increase the catalytic
activity of nanozymes. The results show that Fe@Fe3O4 core-shell nanoparticles have
29 Biomedical Applications of Nanozymes: Disease Diagnosis and Therapy 685

significantly higher catalytic activity than Fe3O4@heparin nanoparticles. This is

because the conversion is accelerated by the release of iron ions from the iron center.
As a result, the iron core is critical for improving nanozyme properties [27].
Despite the novel applications of the nanozymes, some critical questions are yet
to be solved.

Status and Challenges of Practical Applications of Nanozymes

There is a need to explore cost-effective manufacturing of nanozymes for decreasing

cost of disease diagnosis and therapies. A recent report on preparation of MoO3
nanorods for glucose detection has already been showing a great promise to use
algae for synthesis of nanozymes.
In the future, nanozyme technology that focuses on the technical improvements in
specificity, catalytic activity, reproducibility, and broad enzyme-mimicking activities
needs to be developed. The technical challenges of manipulating the microstructure
for improved sensitivity and selectivity still need to be addressed. During the clinical
testing level, issues like biofouling and false-positive results must be given more
attention. Most importantly, the establishment of an international governing body
that maintains standard protocols for synthesis and bioconjugation of biomedically
important nanozymes could efficiently tackle the reproducibility issue; therefore,
clinical acceptance can be made easy. In addition, there is great demand to develop
nanozyme-based biosensors as automated point-of-care testing platforms by inte-
grating pathological target isolation, separation, and detection on a single device.
In disease imaging techniques, detection sensitivity of nanozymes and quantifi-
cation of the staining results are the two major issues that require attention. As
sensitivity is directly correlated with the catalytic activity, the appearance of false
positives may arise while improving the sensitivity of nanozymes. Authors
suggested addition of functional amino acid residues or natural enzyme onto the
surface of nanozymes to improve the activity and substrate specificity.

Main Websites

https://pubs.rsc.org/en/content/articlelanding/2020/cc/d0cc05427e#!divAbstract
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6696937/
https://link.springer.com/article/10.1007/s40820-020-00532-z
https://www.tandfonline.com/doi/full/10.1080/21691401.2017.1313268
https://www.frontiersin.org/articles/10.3389/fchem.2019.00046/full

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Plant-Based Consumer Health Gold
Nanoproducts: Benign Nanoformulations 30
for Wound Healing and Treatment
of Infections

Shikha Gulati, Sanjay Kumar, Nandini Sharma, Prishita Sharma, and

Kanchan Batra

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690
Wound and Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
Types of Wounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
Stages of Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 692
Conventional Strategies for Wound Treatment and Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Need of Nanoformulations in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
What Are Nanoparticles? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
Nanoformulations in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
Role of Nanoformulations in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Metallic Nanoparticles in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Gold Nanoparticles: Prime Choice in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698
Significant Properties of AuNPs over Other Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 698
General Synthetic Approaches of Gold Nanoparticles (AuNPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 699
Conventional Methods of Synthesis of Gold Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 699
Plant-Mediated or Phytochemically Synthesized Gold Nanoparticles: Green Method
of Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 701
Advantages of Green Method of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 702
Factors Affecting the Quality of Plant Mediated Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
Steps Involved in the Plant-Mediated or Phytochemically Synthesized Gold
Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 704
Biomedical Applications of AuNPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705
Gold Nanoformulations in Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706

S. Gulati (*) · S. Kumar

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
N. Sharma · P. Sharma
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India
K. Batra
Department of Zoology, Kalindi College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 689

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_90
690 S. Gulati et al.

Applications of Gold Nanoparticles Synthesized by Green Method in Wound Healing . . . . . . 707

Concluding Remarks and Future Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 711

Abstract
In the past decade, there has been a tremendous amount of research and break-
throughs in the field of nanotechnology. From here, a new field of phyto-
nanotechnology or plant-based technology of nanoproducts has emerged, which
has widespread applications, especially in the field of health and medicine. Since
time immemorial we have known the benefits of plants and their parts (roots,
leaves, stem, flowers, and fruits). The advancements in nanotechnology have
made it possible to study the hidden treasures within plants from a new perspec-
tive. This has given rise to industries like nanoceuticals, cosmeceuticals, and
nutraceuticals that focus on consumer health via natural supplements conjugated
with nanoparticles. These plant-derived nanoproducts have a relatively high
internalization rate, proven stability in the gastrointestinal tract, and low immu-
nogenicity, making them far better than traditional formulations. Apart from this,
plant-based nanoproducts in therapeutics for diseases like various types of human
cancer, diabetes, and curing wound healing are being studied extensively. This
chapter focuses on the synthesis and application of plant based AuNPs in wound
healing and treatment of infections, highlighting the biomedical applications of
the same. In addition, future prospects of plant-derived gold nanoformulations in
biological activities are also discussed.

Keywords
Nanotechnology · Wound-healing · Gold-nanoparticles (AUNPs) ·
Phytochemicals · Green-synthesis · Nano formulations

Introduction

In recent years, the advancements in nanotechnology, particularly of metal nano-

particles, have significantly contributed to industries handling biomedical tasks.
Researchers are deliberately making use of metallic nanoscale formulations due to
their higher biocompatibility, lower toxicity, excellent surface functionalities, etc.
Uses of nanoproducts in therapeutics for diseases like various types of human
cancer, diabetes, and curing wound healing are being studied extensively. Nano-
particles, because of their small size, show high biocompatibility, low toxicity,
excellent antimicrobial and antibacterial properties, and effective target specificity,
due to which they can be considered as exemplary agents for wound healing
processes. Gold nanoparticles (AuNPs) are known to be the most potent in all
metal nanoparticles. Scientists have reportedly found high potential in plant-based
AuNPs in wound healing and treatment of infections. While treating a wound, the
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 691

level of complexity of the skin tissue structure also becomes a hurdle in choosing the
most appropriate method. Classic treatment methods for wound healing have various
drawbacks like low elasticity, durability, higher mechanical attachment to the surface
causing pain during replacement, ineffective wound closure, etc., because of which
researchers have considered the use of nanostructures, particularly phytochemically
assembled gold nanoformulations, as the chief approach in resolving the mentioned
problems. They can be easily synthesized and are also environmentally friendly.
Many plant products can be used in combination with gold nanostructures as
stabilizing agents to enhance the process of wound healing. In this chapter, the
synthesis and application of these plant-derived gold nanoformulations in wound
healing are discussed in detail. The biomedical applications of the same are also
highlighted in this chapter. In addition, future prospects of plant-derived gold
nanoformulations in biological activities are also presented.

Wound and Wound Healing

A wound is break in the continuity of a bodily tissue in which the cutaneous

membrane is damaged with or without the bones, nerves, or muscles getting affected.
Such damages can be caused by surgeries, infections or diseases, pressure injuries
and are highly problematic [1]. They adversely affect the quality of life for a large
number of people globally. The healing process starts as soon as any tissue is harmed
and is termed wound healing. Wound healing is a complicated process that takes
considerable time to be completed and is set off as a response to any stimuli causing
skin injury [2]. A number of internal and external factors contribute to the efficacy of
the healing process, the most important being the kind of dressing used and wound
management involved, including the clinical measures taken, interventions in wound
care, and methods used. Properties like the kind of wound present and its intensity
are usually taken into account while deciding the treatment [3].

Types of Wounds

Wounds can be classified into two basic types: 1. acute and 2. chronic. In simple
words, acute wounds have a shorter duration than chronic ones. But there are many
more factors that control the transformation of an acute wound into a chronic wound.

1. Acute wounds can range from small cuts and scabs to larger burns, abrasions,
and surgical incisions. These take an average of 2–3 weeks for healing and
usually have very low to no microbial presence in the initial stages. Additionally,
they follow normal stages of healing, unlike chronic wounds.
2. Chronic wounds can be defined as nonhealing wounds that do not follow the
normal course of healing and get stuck in one of the stages in the process. Many
scientists consider 6–8 weeks as the time limit for the healing of any normal
wound, beyond which it becomes a chronic wound [4]. Various factors that lead
692 S. Gulati et al.

to a wound getting arrested in a stage of healing are increased inflammation,

microbial growth or infections, irritation, presence of foreign particles that retard
the healing process, decreased macrophage functioning, low blood supply, dimin-
ished angiogenesis, and poor oxygenation. Chronic wound infections are easily
colonized by bacteria that form bacterial biofilms. These biofilms are nothing but
clusters of bacteria enclosing a surface, by producing an extracellular matrix that
can contain polysaccharides, proteins, etc. These biofilms protect the bacterial
groups against receiving any action by antibacterial medicines or the host
immune system. Comorbidities like diabetes also act as a risk factor in contrib-
uting to delayed wound healing. Chronic wounds represent a highly researched
field due to their large incident rates. Furthermore, many traditional and novel
approaches have failed to provide results in response to chronic infections that is
why there is a need for efficient utilization of nanoformulated products to
overcome the debilitating effects caused by these wounds [5].

Stages of Wound Healing

Typically, wound healing comprises of four overlapping stages, namely: 1. hemosta-

sis, 2. inflammation, 3. proliferation, and 4. remodeling (Fig. 1). These phases are
known to overlap due to a number of physiological and anatomical factors, inside the
body. Various cells involved in the whole process are platelets, progenitor cells,
fibroblasts, and keratinocytes.

1. Haemostasis: The initiation of wound closure takes place in this phase. When an
injury takes place, a series of clotting steps called the coagulation cascade begin.
Clotting factors of the damaged skin start the extrinsic clotting cascade and
attachment of platelets to the subendothelial surface initiates the intrinsic clotting
cascade. The thrombocytes accumulate to form a fibrin network, which is
supported by a vasoconstriction, caused due to release of histamine that stops
further bleeding. Numerous messenger molecules like platelet-derived growth
factor (PDGF) vascular endothelial growth factor (VEGF) and transforming
growth factor-β (TGF-β) are released and these help in the activation of
macrophages [6].
2. Inflammation: In this stage, debris and dead cells are cleared out with phagocy-
tosis. It overlaps with hemostasis and may last for 48 h after the injury. Various
leukocytes like neutrophils are released along with monocytes and lymphocytes,
which then differentiate into macrophages. These inflammatory cells then release

Haemostasis Inflammation Proliferation Remodelling

Stage 1 Stage 2 Stage 3 Stage 4

Fig. 1 Stages of wound healing

30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 693

proteinases and reactive oxygen species which help in the protection of the wound
against bacterial attack. Usually, this stage is prolonged in chronic wounds.
3. Proliferation: Here the formation of granulation tissue, deposition of collagen,
angiogenesis, epithelialization, and wound contraction take place. Elastin,
hyaluronic acid, collagen, and proteoglycans constitute the extracellular matrix
(ECM), which in turn builds the granulation tissue for substitution of the original
clot. Angiogenesis involves neovascularization, which is the formation of new
blood vessels and is promoted by the release of cytokines and VEGF. Epithelial
cells multiply during epithelialization and cover the wound. Finally, fibroblasts
differentiate into myofibroblasts which causes wound contraction [6].
4. Remodeling: This is the last phase of wound healing. It is also known as the
maturation stage. Remodeling is initiated two to three weeks after the injury. A
mature scar replaces the granulation tissue along with. Unwanted cells are
removed cell by apoptosis and blood vessels are generated in granulation tissue.
Remodeling may continue for several years. The reconstructed tissue never
regains the features of the original skin.

Conventional Strategies for Wound Treatment and Healing

The application of topical medicines on the wound and securing it with a dressing is
the standard method of treatment. Currently used dressings can be divided into three
main categories: 1. traditional (cotton and wool based), 2. artificial (foams,
hydrogels, sprays), and 3. biomaterial-based (tissue and xenografts). Further, based
on the method of application, they can be categorized as: 1. Primary dressings –
applied directly to the injured tissue and 2. Secondary dressings – applied over
primary dressings [7]. Conventionally, cotton gauze bandages have been used as a
popular choice of dressing materials. These dressings act as a protective barrier for
the wound and prevent contamination by foreign particles. But materials like cotton
only provide passive protection, not availing transfer of compounds to the injury, due
to which new products have been studied and prepared. Artificial wound dressings
like foams, gels, and sprays are interactive in nature and provide several advantages
like being impermeable to bacteria yet allowing water vapor and oxygen to pass
through, but in some cases, they may cause irritation and contact dermatitis [8].
Tissue and xenograft-based treatments are also highly effective but very costly.
Usually, the dressing used should create moist conditions to fasten the healing,
maintaining the cleanliness of the wound. Moreover, the dressing should be bio-
compatible, long-lasting, able to prevent bacterial infections, easy-to-apply, and
cost-effective. For treating infections in various wounds, topical treatment with
antibacterial and antimicrobials like tetracyclines, cephalosporin, etc., is also pro-
vided. They are very efficient, low in toxicity and are easy to apply but their
absorption is hampered by the stratum corneum. Numerous oral medicines are also
used for wound healing like chemotherapeutic drugs like different antibiotics,
nonsteroidal anti-inflammatory drugs, and steroidal glucocorticoids. Most of these
medicines are anti-inflammatory in nature also helping in overcoming nausea and
694 S. Gulati et al.

pain but suppress the immune system of the patient. Moreover, these agents are
usually very toxic, costly, and dangerous [9]. Additionally, chronic wounds cannot
be treated using oral medications as they have a lower target specificity for injured
tissues. Bacteria colonizing the chronic wounds may also acquire resistance to oral
or topical applications. Regular methods may not provide a desirable outcome, due
to which the use of various nanoproducts is currently being promoted to provide an
effective solution [10].

Need of Nanoformulations in Wound Healing

Currently, the topical route of drug/pharmaceutical administration is the backbone of

therapy in wound treatment worldwide. However, this topical delivery of medica-
tions is sometimes hampered by the presence of the stratum corneum, which is the
outermost layer of the epidermis containing dead cells that act as a barrier. To combat
this problem, nanoparticle-based drug formulations and delivery propose as a prom-
ising solution, especially in dermatological diseases. To understand the need of
nanoparticles in wound healing, it is vital to firstly understand what they are and
how they can be useful in effective treatment of wounds.

What Are Nanoparticles?

Discovered more than 50 years ago by Richard Feynman (“The Father of Nanotech-
nology”), nanoparticles are said to be ultrafine, submicroscopic units that are
measured in dimensions of nanometers (nm; 1 nm ¼ 109 m). The definition of a
nanoparticle was first given in 2008 by the International Organization for Standard-
ization (ISO) as a discrete nanoobject where all three Cartesian dimensions are less
than 100 nm. But in 2011 the Commission of the European Union approved a more-
technical but wider-ranging definition: a natural, incidental, or manufactured mate-
rial containing particles, in an unbound state or as an aggregate or as an agglom-
erate and where for 50% or more of the particles in the number size distribution, one
or more external dimensions are in the size range 1 nm–100 nm [11]. Under this
definition, a nanoobject requires only one of its characteristic dimensions to be in the
range 1–100 nm to be classed as a nanoparticle, even if its other dimensions are
outside the specified range.
Nanoparticles can be categorized into numerous types on a variety of basis like
shape, size, material properties, etc. Some classifications differentiate between
inorganic and organic nanoparticles, the first group comprises quantum dots, metal-
lic nanoparticles (gold, silver, silicon, etc.), metallic oxide nanoparticles, etc., and
the second group comprises of nanoparticles made of lipids, chitosan, dendrimers,
PLGA (polylactic-co-glycolic acid), etc. Nanoparticles can exhibit a variety of
effects in different compositions due to their three main properties:
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 695

1. High mobility in Free State

2. Having enormous specific areas
3. Known to exhibit quantum effects

The thermal, mechanical, and catalytic properties can be altered by increasing or

decreasing surface area/volume ratio and the new properties generated allow appli-
cations of nanomaterials in many biological fields like, drug delivery and novel drug
development, diagnostic tests, biosensors, and even in vivo imaging. The nano-
particles of chemically manufactured structures like polysaccharides, polymers,
metals, and plant-derived bioactive compounds incorporated with active drugs can
effectively fight against human pathogens like bacteria and even viruses and can be
efficiently used to treat various pathological conditions, like wound healing.

Nanoformulations in Wound Healing

Throughout the advancements of nanotechnology in medicine, a variety of innova-

tive nanoformulations have been created for treating many medical complications,
especially wound healing. The nanoproducts used are divided into two categories
based on their mode of function, namely:

1. The nanoparticles which exhibit intrinsic attributes that are advantageous for the
treatment of wounds.
2. The nanoparticles deployed as delivery agents/vehicles to transport the therapeu-
tic drugs/agents which are beneficial for wound healing.

Numerous nanoscale strategies have been tested and applied in the area of wound
healing, experimentation with a variety of nanoformulations (metallic and metallic
oxides, carbon-based, polymeric, etc.) has paved newer methods of treating as well
as preventing wounds of all kinds, be it superficial, internal, or even diabetic, and
nanotechnology in wound healing has been breaking barriers rapidly. For example,
many studies have been conducted to investigate the controlled release of NO (Nitric
oxide) from nanoscale delivery agents as NO is very important in cellular prolifer-
ation, matrix remodeling, angiogenesis, and inflammation, which are key aspects of
wound healing. Apart from this, antibiotics- and antioxidant-coated nanoparticles
have been formulated from a variety of sources to achieve faster and efficient wound
treatment. Even, growth hormone (FDA approved) incorporated nanoparticles have
been produced to increase the rate of cell regeneration in chronic wound tissues.
Scientists have also probed the avenues of the gene, RNA interference (RNAi), and
small interfering RNA (SiRNA)-based nanotherapies to combine gene-based ther-
apy with tissue regeneration as an effective wound healing treatment but since this is
a highly recent concept, in-depth research and experimentation are needed. There are
many mechanisms of action of nanoparticles inside the human body and such
aspects and their applications are discussed in the following sections [12].
696 S. Gulati et al.

Role of Nanoformulations in Wound Healing

Normal wound repair mechanism is a forced response to unfavorable stimuli at skin

tissues or any other organ. It is a cascade process involving various steps that finally
result in tissue restoration. It is normally divided into four phases: the hemostasis
phase, the inflammatory phase, the proliferation phase which is followed by the
remodeling phase. A variety of cells, enzymes, cytokines, proteins, and hormones
are involved in tissue repair processes [13]. The methods of treatment vary from
topical medications and dressings to Xenografts, but as observed, they have many
setbacks like wound dehydration, etc., thus requiring a better and more efficient
method of treatment. Consequently, nanomaterials-based treatments have achieved a
new horizon in the arena of wound care due to their ability to deliver a myriad of
therapeutics into the target site and to simplify the complexity of the normal wound-
healing process.
The nanoparticles selected when embedded with biomaterials can be used as a
potential nanogenerative material. Apart from this, nanotechnology offers new
avenues in regenerative medicine as well. In recent years, nanoresearch has furthered
to develop molecular engineering strategies for different self-assembling biocom-
patible nanoparticles. The inherent properties, mainly physicochemical, of the nano-
materials used are responsible for their application in wound healing, dressing, and
carriers for different therapeutic agents resulting in differential wound treatment
capacity of each nanomaterial. The various properties involved are biodegradability
and biocompatibility, size, colloidal stability, surface functionalization and charge,
etc. The additional effect of biocompatibility and biodegradability is seen over
particles that are nondigestible and nondegradable. But apart from physicochemical
properties, another property plays a very vital and indispensable that is the presence
of a payload (active ingredient) on the nanomaterial for the wound healing process.
The nanomaterials can portray proliferative, proangiogenesis, antibacterial, as well
as anti-inflammatory applications in wound healing due to its unique properties.
They can even modulate the level of expression of various proteins involved in the
cascade process of wound healing and are able to direct molecules to improve wound
healing in target sites. Their application is assessed keeping in mind the fact that the
smaller the nanomaterials are on the nanoscale the larger their surface area becomes
leading to enhanced properties.
The main types of nanomaterials used are: nanoparticles, nanocomposites, and
coatings and scaffolds. This chapter focuses on metal nanoparticles with special
emphasis on gold nanoparticles.

Metallic Nanoparticles in Wound Healing

Among all inorganic nanomaterials, the metallic nanoparticles like silver (Ag), gold
(Au), zinc oxide (ZnO), titanium dioxide (TiO2), selenium (Se), copper (Cu), etc.,
have acquired a special status due to impressive biomedical applications of their
metallic content. Metal nanoparticles like gold, silver, and zinc exhibit revolutionary
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 697

properties such as low in vivo toxicity along with bacteriostatic and bactericidal
activities. Metallic nanoparticles have a unique property of diminishing the toxicity
of metals due to their size and surface area to volume ratio. Therefore, the following
section of the chapter summarizes some metallic nanoparticles used till now for
wound healing.

1. Silver nanoparticles (AgNPs): Silver has long been used in wound healing in
both metallic and ionic forms due to its widely known antimicrobial activity. It
was prevalent even in the seventeenth and eighteenth century and was used for
disinfecting wounds in World War I. The Ag nanoparticles exhibit a plethora of
properties like anti-bacterial, antiviral, antifungal, antiangiogenesis, antiplatelet,
and anti-inflammatory. The nanoparticles with their extremely small size and high
surface to volume ratio are able to sustain the release of silver, thus minimizing its
toxicity and prolonging the impact. Ag nanoparticles are known to actively show
antibacterial activity against dermal pathogens like Pseudomonas aeruginosa,
Streptococcus pyrogens, as well as oxacillin and methicillin resistant S. aureus.
2. Gold nanoparticles (AuNPs): Gold has widely known therapeutic applications
in cancer diagnosis and treatment, but it is also used in wound healing, either
alone or in conjugation with other substances. The gold nanoparticles are attrib-
uted to their antioxidant ability and their capacity to penetrate the skin via
interaction with its outermost layer that is stratum corneum, which conventional
wound treatments mostly fail to do. When coupled with antioxidants, Au nano-
particles show migration and proliferation of dermal fibroblasts and
keratinocytes. Recently they were used to reduce the oxidative stress produced
during wound healing by eliminating the Reactive Oxygen Species (ROS)
created.
3. Copper nanoparticles (CuNPs): Copper exhibits power wound healing activity
due to its antibacterial, immune boosting, and angiogenesis amplifying proper-
ties. It also shows antioxidant activity by acting as a cofactor to enzymes like
cytochrome oxidase. In nanoforms, its catalytic activity and biocompatibility are
enhanced and stabilization along with a coating of various substances like folic
acid magnifies its effect manifold. This also minimizes its cytotoxic nature and
also increases its efficacy.
4. Silicon nanoparticles (SiNPs): Silicon is a trace element present in the human
body which is quite in abundance. It has mostly been used as wound dressings
due to its antimicrobial nature and also comes in use by penetrating the dermis
and epidermis to show its angiogenic and anti-inflammatory properties. Silicon
loaded nanoparticles are known to be quite efficient as they slowly release the
active molecule internally that enhances their potency. They are often coated with
bioactive molecules like siRNA that help in wound regression and increase the
healing process [14].
5. Zinc oxide nanoparticles (ZnONPs): Zinc has long durability inside living cells
and thus along with its antipathogenic property, it would to be a highly stable and
efficient method of wound healing. ZnO nanoparticles loaded with medicinal
drugs prove to be very effective on postoperative wounds. Cefazolin-loaded ZnO
698 S. Gulati et al.

Fig. 2 Metallic nanoparticles in wound healing

nanoparticles show amplified cell adhesion, collagen synthesis, and epithelial

migration that results in faster wound healing [15]. Also, it governs the auto-
phagocytosis of cells in the wound that is critical for wound repair (Fig. 2).

It is evident that metallic nanoparticles are promising and well advancing tool in
the field of wound healing, especially gold nanoparticles that will be discussed in the
following section.

Gold Nanoparticles: Prime Choice in Wound Healing

Extremely small particles of gold, with a diameter ranging from 1 to 100 nm, are
termed as gold nanoparticles (AuNPs). When dissolved in a fluid, like water, it is
defined as colloidal gold. Gold nanoparticles are being widely used in disciplines like
bio-nanotechnology, physics, and chemistry, due to their distinctive physical and
chemical properties [16]. Their properties make them excellent agents for various
functions and roles in numerous biomedical applications like in drug delivery, imaging
and sensing, cancer treatment, etc. Along with the controlled release of drugs, various
surface modifications developed have helped in enhancing their role as delivery
vectors [17]. Despite gold nanoparticles being thoroughly researched in the past few
years, there are some potent features that need to be further investigated. Scientists are
currently working towards increasing biocompatibility and lowering the toxicity of
these formulations to improve their functionality in biological systems [18, 19].

Significant Properties of AuNPs over Other Nanoparticles

Possession of various useful attributes has made gold nanoparticles the prime
choice in bionanotechnological applications. These particularly include higher
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 699

biocompatibility, lower toxicity, larger surface-to-volume ratio, easier synthesis,

shape tunability, desirable optoelectronic features, etc. Production of several shapes
such as tubes, rods, and spheres makes AuNPs extraordinary candidates for appli-
cations in genomics, biolabeling, and immunoassays. Nanogold formulations also
exhibit multiple colors when interacting with electromagnetic radiations, which
explains their role in bio sensing. Physical qualities present like fluorescence
quenching and Surface Plasmon Resonance (SPR-oscillation of free electrons in
the presence of a particular frequency of light) are also important. Based on their
SPR, spherical AuNPs lie in the visible and gold nanorods lie in the infrared region.
For the longest time, catalytic characteristics of AuNPs were thought to be absent or
not strong enough. It was in 1987 when Haruta et al. found out that oxidation of CO
can be catalyzed by AuNPs at or even below room temperature systematically.
Various studies after this revelation have explored the role of gold nanoparticles as
catalysts for a diverse range of activities. Due to these unique features, gold
nanoparticles not only have a wider field of application, but more extensive research
is also being carried out on them as compared to other metallic nanoparticles.

General Synthetic Approaches of Gold Nanoparticles (AuNPs)

Gold nanoparticle synthesis is described as being easier as compared to other

nanoparticles. Two basic approaches for the synthesis of gold nanoparticles are:

1. Top-down approach: In the top-down process, required nanostructure can be

achieved by removing the bulk material. It usually makes use of lithographic
patterning methods, with small wavelength sources. It has been used in assem-
bling integrated circuits and has successfully provided microscale production but
acquiring nanoscale products is quite challenging using this approach, which is
why bottom-up techniques have been considered better than that involved in
top-down.
2. Bottom-up approach: The bottom-up approach has been inspired by self-
assembly of atoms in various biological systems. Physical or chemical forces
are used to accumulate basic units into a large structure. The atoms are aggregated
till the desired size is obtained. Numerous techniques based on quantum dots and
micelles have been developed and utilized. Nanoparticles of several magnetic and
semiconductor materials have been synthesized using the same. DNA-assisted
assembly approaches are also being used increasingly due to significant advan-
tages like adhesiveness of complementary DNA strands.
Every method used is based on these two approaches [20] (Fig. 3).

Conventional Methods of Synthesis of Gold Nanoparticles

Synthesis can be classified as physical and chemical. Physical methods utilize

electron beam lithography, laser ablation, γ-irradiation, etc. In chemical preparation,
stabilizers, capping agents, etc., are used. Additionally, tween 20, a surfactant, has
700 S. Gulati et al.

Fig. 3 General synthetic approaches of gold nanoparticles

been widely used to prevent aggregation of AuNPs, when being functionalized using
thiolate ligands

• Physical methods: These frequently involve irradiation using ionizing or non-

ionizing radiation, which can lead to electron transfer and further, to the reduction
of metallic particles. Ionizing radiations, photochemical synthesis, and micro-
wave radiation are widely used processes.
• Turkevich method: This is the most popular method of AuNP synthesis. In
1951, Turkevich et al. had created AuNPs using hydrogen tetrachloroaurate and
citric acid. Citric acid was put in boiling water, where the citrate ions formed acted
as a stabilizer and a reducing agent simultaneously. Sometimes the citrate stabi-
lized AuNPs can undergo irreversible aggregation to avoid which stabilizers or
capping agents are used. To change the gold-to-citrate ratio, Frens had altered this
procedure in 1973. By this modification, particles of 10–20 nm diameter could be
developed more efficiently. Gold nanoparticles can also be functionalized using
organic ligands. Thioctic acid has also been used to carry out a two-step
functionalization process.
• Brust and Schiffrin method: In 1994, Brust and Schiffrin synthesized AuNPs
using organic liquids immiscible in water. Sodium borohydride (NaBH4) was
used as the reducing agent, along with a reaction between chloroauric acid
solution and tetraoctylammonium bromide (TOAB). TOAB acts as both the
stabilizing agent and the phase transfer catalyst yet it is not good at binding to
the gold nanoparticles, which is why other binding agents like thiols should be
used to prevent precipitation of AuNPs. The gold particles produced are 1.5–5 nm
in diameter and the size can be varied by varying the reaction conditions like
temperature, reduction rate, etc. The AuNPs procured by this method are
alkatheniol-protected, which provides them higher stability than others.
• Sonochemical synthesis: Additionally, Okitsu et al. used sonolysis in which
ultrasonic energy was used for experimental production of gold nanoparticles
under 10 nm. The nanoparticles created were under 10 nm in diameter [21].
• Navarro method: Navarro et al. synthesized gold nanoparticles using sodium
acetylacetonate and sodium citrate. This provided better control over the
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 701

nanoparticle size. It further helped in increasing local concentration and cell

internalization AuNPs [22].
• Seed-mediated method: This method is used to generate gold nanoparticles of
varying shapes. It involves reduction of gold salts using a reductant like sodium
borohydride creating seed particles. Perrault et al. had developed a seed-based
method of AuNP production, just like photography. Here a solution of hydroqui-
none and HAuCl4 is used, with hydroquinone as the reducing agent. This
modification, like Frens, provides better control of the size of the gold nano-
particles being assembled and is ideal for creating particles of 30–300 nm diam-
eter. Structural properties of the AuNPs synthesized can be monitored by
controlling the amount of reducing agents used [23].

Use of hazardous reagents and presence of toxic by-products in the mentioned

procedures make it essential for researchers to devise environmentally cleaner ways
for gold nanoparticle production. Moreover, toxicity of gold nanoparticles varies due
to several factors like particle size, surface modifications, etc. Kalimuthu et al. found
in their study that Bacillus licheniformis can also be used for synthesizing gold
nanocubes in the range of 10–100 nm. Bacterial-synthesized AuNPs are produced at
lower temperatures, unlike other chemical methods [24]. Furthermore, other micro-
organisms, biomolecules, plants can also be employed for creating AuNPs in
ecologically cleaner ways.

Plant-Mediated or Phytochemically Synthesized Gold

Nanoparticles: Green Method of Fabrication

In recent years, the pattern of engineering nano-sized particles mainly of metals has
grown, for various objectives (Fig. 4). There are two ways to characterize nano-
particles according to various need, namely, bottom-up and top-down. The bottom-
up technique involves increasing the material from the lowermost level: atom by
atom, molecule by molecule, or cluster by cluster, whereas the top-down approach
deals with slicing or successive fragmentation of a bulk material to get the desired
result. It has been observed that the bottom-up technique qualifies to be a superior
choice because of its involvement of catalytic substances like enzymes and reducing
agents that constitute a homogenous system. It does not have demerits like surface
structural defect that affect the physical properties of nanoparticles adversely which
can be observed in top-down approach [25]. These approaches can be applied to
various methods of nanoparticle production like physical, chemical, biological, etc.
The biological method, which comprises of utilizing plant/animal or microorganism
sources, has gained a lot of popularity due to its advantages over other methods as it
is simple and cost-effective, has low energy consumption, and is also eco-friendly
because it does not lead to environmental contamination by releasing hazardous by
products [26]. Due to this, a new term called “Green Synthesis” has been coined to
define the use of plant-based production of nanoparticles, involving a variety of plant
parts and metabolic substances. The plant parts being-stem, roots, shoots, leaves,
702 S. Gulati et al.

Fig. 4 Synthesis of AuNPs using phytochemicals

Fig. 5 Different phytochemicals used in nanoparticle formulations

flowers, bark, seeds, etc., and metabolic products like flavonoids, tannins, steroids,
alkaloids, saponins, etc. (Fig. 5).

Advantages of Green Method of Synthesis

It is evident from the conventional methods of synthesis that they possess a lot of
drawbacks with respect to energy consumption, cost, hazardous by products, toxicity
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 703

of AuNPs produced, etc. The novel method of phytosynthesis of AuNPs poses as an

apt solution to these problems because it simplifies the process, reduces the cost and
energy consumption, accelerates the process while making it less hazardous at the
same time. All the advantages are discussed below in detail:

1. Plant-mediated approach of synthesis of AuNPs is highly economical as well as

fast, making it easy for bulk production of stable AuNPs to be done.
2. With the help of downstream processing, optimization techniques, as well as
tissue culture of biocompatible plant source, industrial application of AuNPs is
easy and beneficial at the same time.
3. Contrary to conventional procedures, this synthetic approach utilizes aqueous
water for extraction of plant metabolite/chemical, which requires a normal/ambi-
ent range of temperature and pressure, thus saving a lot of energy.
4. Since the plant extracts act as both capping and stabilizing agents, the procedure
of green synthesis becomes simpler and can be completed in a single step as well,
making it an extremely viable alternative.
5. The phytoconstituents used are easily available and can be obtained from plant
parts almost effortlessly as compared to the traditional methods.
6. Because it is a green approach which cuts down on energy and uses simple
aqueous solvent for fabrication, it evidently produces zero or very fewer contam-
inating substances, making it eco-friendly and nonhazardous.

The advantages of Green synthesis of nanoparticles though numerous can be

summed up in the following points (Fig. 6).

Fig. 6 Advantages of
biosynthesized nanoparticles
Easy
availability

Industrial
Non-
scale
hazardous
application

MERITS

Use of
Cost-
Aqueous
effective
solvent

Simple
method
704 S. Gulati et al.

Factors Affecting the Quality of Plant Mediated Nanoparticles

There are various factors which play a significant role in determining the quality of
nanoparticles produced by using plants:

• Protocol used
• Concentration of plant extract
• Nature of reducing agents used
• pH of the Reaction mixture
• Time of incubation
• Temperature
• Light intensity, etc.

So far, green synthesis has mainly been used with respect to metallic nanoparticles,
especially gold and silver, because of their widely known properties and applications.
The fabrication of such nanoparticles is done by incorporating the desired plant
extracts with metal salt solutions like HAuCl4.3H2O [Gold (III) chloride trihydrate]
for gold biosynthesis and making them undergo a reduction reaction in optimized
conditions. The product obtained is then stabilized/capped to give biosynthesized
green nanoparticles. An additional step is done after stabilization which is character-
ization for determining the size distribution, surface area, wettability, porosity, zeta
potential, adsorption potential, orientation, crystallinity, etc. Several techniques of
characterization are used, namely, UV-visible spectroscopy (UV-vis), X-ray photo-
electron spectroscopy (XPS), transmission electron microscopy (TEM), etc. [27].

Reaction: HAuCl4.3H2O + plant extracts ! Au NPs + by products

Steps Involved in the Plant-Mediated or Phytochemically

Synthesized Gold Nanoparticles

The phytochemicals used in the process show dual nature and act as oxidizing and
reducing agents at the same time, making it primarily a single-step, energy efficient,
cost-effective, safe for clinical research, and environmentally benign process. Follow-
ing are the steps involved in plant-mediated/phytochemically synthesized AuNPs:

1. Isolation of plant extract/phytochemical is done. They are usually water-

soluble and comprise of metabolites like alkaloids, amino acids, flavonoids,
terpenoids, etc. The basic operations are prewashing, centrifugation, freeze dry-
ing, and then identification mostly by chromatographic techniques.
2. Reduction reaction. The plant extract which is isolated is then made to undergo a
reduction reaction with desired metal salt solutions, in this case- HAuCl4.3H2O
(Gold (III) chloride trihydrate). This reaction takes place in optimized conditions
of temperature, pH, radiation, light intensity, salt concentration, plant extract
concentration, etc., while constant stirring [28]. (Optimization).
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 705

Extraction of plant products/parts to obtain pure

extract by heat stirring or filtration.

Redox reaction of phytochemicals with HAuCl4 to

create biosynthesized AuNPs.

Optimization of temperature, incubation time, pH,

plant extract concentration etc

Centrifugation and subsequent sedimentation of gold

nanoparticles.

Characterization of AuNPs by UV-vis, XRD, TEM,

FTIR, AFM, EDX, DLS, Zeta potential etc.

Fig. 7 Steps involved in the plant-mediated synthesis of gold nanoparticles

3. Capping and stabilization. When the reaction is complete, a characteristic color

change is observed in the apparatus which is indicative of the product formation.
Followed by the bioreduction reaction, capping and stabilization of nanoparticles
obtained is achieved by the phytochemicals/plant extracts only to stabilize them
at their size and prevent their aggregation. That is why phytosynthesis of AuNPs
is economical and less hazardous.
4. Characterization. Various characterization techniques are utilized to understand
the potential of the formulated nanoparticle and its unique properties for better
application. Major techniques used are electron microscopy, atomic force micros-
copy (AFM), X-ray diffraction (XRD), UV-visible spectroscopy (UV-Vis), etc.
After all these steps are achieved, the desired nanoparticles with physical, chem-
ical, and biological properties are obtained [29, 30].
The entire steps of plant mediated synthesis of gold nanoparticles are summa-
rized in Fig. 7.

Biomedical Applications of AuNPs

Due to their unusual properties and numerous surface functionalities, AuNPs play
multiple roles in different procedures. Some of these include their use as:

• Biological sensors: Gold nanoparticles show a number of colors, because of

which they have been used for visualization purposes. SPR-based, enzymatic,
surface-enhanced Raman spectrum (SERS)-based, fluorescence-based, electro-
chemical, colorimetric gold nanobiosensors have been assembled and used for
706 S. Gulati et al.

detection of many biological compounds like proteins, enzymes and their activ-
ities, oligonucleotides, etc. [31, 32].
• Bio-imaging: For color-based imaging, organic fluorophores have been used
conventionally. But it has been reported that they have limited application due
to narrow excitation. AuNPs proved to be better bio-imaging agents due to their
flexible features related to size and surface modifications. They are increasingly
being used in techniques like photo acoustic imaging, MRI, such as X-ray
computed tomography, etc. [33].
• Synthetic skin: Scientists in Israel had created a touch and pressure sensitive ultra-
thin film, with the help of spherical gold nanoparticles, of 3–6 nm diameter along
with polyethyleneterepthalate (PET). The manufacturing process is cost effective,
but the challenge lies in connecting the artificial film with the brain. Mostly, the
film can be used in prosthetics.
• Cure for heart diseases: Cardiac cells cannot multiply, because of which self-
repair is nearly impossible. AuNPs contained patches have been found useful for
curing heart damage. Heart being myogenic in nature creates a hurdle in matching
the rhythm of the patches with its own pace.
• Cancer treatment: Photo thermal effect of AuNPs can destroy tumor cells
[34]. Gold nanorods are incorporated with cancer-specific compounds and
exposed to radiation. Only those nanostructures are selected that have SPR
frequency in the range of 650–900 nm, known as the near-infrared (NIR) region.
This region is where both water and tissue hardly absorb any radiation. After
exposure, the cancer tissue is locally heated which terminates the tumor
[35]. Higher circulation of AuNPs in the blood and better sensitivity of tumor
cells result in easier termination of cancerous tissues. Moreover, bio-imaging
using AuNPs is applied frequently for tumor detection. Gold nanoparticles can be
further conjugated with beneficial functional groups that improve the specificity
in recognition of the cancer cells [36, 37].
• Enhanced drug delivery: Due to the presence of attributes like larger biocompat-
ibility and surface-to-volume ratio, AuNPs are extensively used as drug delivery
agents. Drug particles can be loaded on to gold nanoparticles and controlled
release of these at target site is then possible.
• Gold nanorods are also being widely used to create vaccines against viruses
(Fig. 8).

Gold Nanoformulations in Wound Healing

Metal nanoparticles like gold, silver, zinc oxide, etc., have been considered extraor-
dinary instruments for wound healing. Gold nanoparticles are described as prime
candidates for utilization due to their easy and cost-effective synthesis, lower
toxicity, chemical stability, the capability of absorbing near-infrared radiation, and
antibacterial activity. Arafa et al. described antibacterial properties of AuNPs in both
in vitro and in vivo studies, wherein they acquire thermo-responsiveness by tuning
the SPR. AuNPs show bactericidal properties by hindering the uncoiling of DNA
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 707

Bio-sensing Bio-imaging Cancer Artificial skin

Blood clot
Heart diseases Drug delivery Vaccines
regulation

Sterlization
Brain implants
systems

Fig. 8 Biomedical applications of gold nanoparticles in numerous fields

during replication and transcription. They are also found to kill multidrug-resistant
bacteria like Staphylococcus aureus. Furthermore, they aid wound healing by acting
as antioxidants and interrupting the formation of reactive oxygen species. Addition-
ally, gold nanoparticles also show significant anti-inflammatory activity due to
increased release of angiopoietin-1 and vascular endothelial cell growth factor.
Another feature is enhanced skin penetration which enables higher efficiency in
wound healing. AuNPs also are known to exhibit a positive effect on the healing of
infections photo-bio modulation therapy. Repair of affected collagen fibers is also
promoted by antimicrobial effects of AuNPs.
Many of the methods involved in synthesis and applications of the mentioned
AuNPs are hazardous in nature due to the involvement of toxic chemicals like
several inorganic compounds, reducing agents, stabilizers, and the by-products
formed. High energy radiations used are also harmful. It is essential to develop
eco-friendly ways which are in addition economically feasible for producing as well
as using these nanoformulations to reduce their toxicity to a minimum. Principles of
green chemistry have been recommended to improve the procedures used in gold
nanoparticle formulation and to enhance sustainability. Green synthesized gold
nanoparticles should be used more often. Several studies reveal phytochemically
created gold nanoparticles to be excellent candidates for this purpose.

Applications of Gold Nanoparticles Synthesized by Green Method

in Wound Healing

Biosynthesis or green synthesis has created new avenues in nanotechnology and

medicine and the usage of gold nanoparticles with plant extracts and metabolic
products has proved to be more efficient and efficacious than normally produced
gold nanoparticles with respect to their production as well as function. Their roles in
all areas of medicine especially wound healing are highly advantageous and
708 S. Gulati et al.

beneficial. Substances like fenugreek seeds containing metabolites like flavonoids,

when used with gold nanoparticles, have proved to act as surfactants for the said
nanoparticles and have also stabilized the electrostatic stabilization of the tested gold
nanoparticles [38]. Apart from fenugreek seeds, the extracts of gold petals, Mirabilis
jalapa, and others have also been used for stabilized, and eco-friendly synthesis of
gold nanoparticles. Additionally, the extracts from medicinal plants like Nyctanthes
arbortristis are able to confer antipathogenic activity to gold nanoparticles that are
highly useful in wound healing [39].
Some wound healing applications of phytochemically synthesized gold nano-
particles are as follows:

1. Anti-inflammatory: Anti-inflammation is a highly essential step in the process of

wound healing. Scientists have for a long time searched for natural ways to reduce
inflammation while healing wounds and recent studies show that biosynthesized gold
nanoparticles are able to induce the healing process by giving a boost to inflamma-
tory mediators like T-lymphocytes, B-lymphocytes, and other enzymes which helped
achieve tissue regeneration via anti-inflammatory mechanism [40].
2. Anti-microbial: Green synthesized gold nanoparticles have paved the way for
wound healing to become highly efficient by showing properties like anti-
bacterial, antifungal, etc. They also offer a solution in management of drug
resistance problem in pathogens [41]. Recently, it was found that gold nano-
particles when coated with aqueous leaf extracts of Mussaenda glabrata
inhibited the growth of harmful microbes like Escherichia coli, Bacillus
pumilus, Staphylococcus aureus, Aspergillus niger, Pseudomonas aeruginosa,
Penicillium chrysogenum, etc. [42]. Also, it was found that green synthesis of
gold nanoparticles with plant extracts of Abelmoschus esculentes confer them
antifungal property against fungi like Puccinia graminis, A. niger, Candida
albicans, etc.
3. Antioxidant: The process of oxidation in places of wounds can lead to cell
damage and degeneration and diminish the rate of wound healing. The normal
synthetic antioxidants used cause unfavorable effects on health. That is why,
nanoparticles, especially gold, are a comparatively better solution for antioxidant
activity in wounds. It has been studied that ability of normal antioxidants when
conjugated with biosynthesized gold nanoparticles shows increased activity in
healing wounds [43]. Apart from this, gold nanoparticles also reported extraor-
dinarily enhanced antioxidant activity when created with help of fruit extracts of
cannonball fruit which is Couroupita guianensis [44].

Some of the remarkable applications of phytochemically synthesized/plant-

mediated gold nanoparticles are listed in Table 1.
It is highly evident that the gold nanoparticles when biosynthesized and mediated
with plant-products/extracts show increased and enhanced action as compared to
normally produced AuNPs. Not only do the green AuNPs show better activity but
their production process is relatively simpler, cost effective, energy efficient, non-
hazardous, and eco-friendly than other synthesis. Their stability is increased, toxicity
 30

Table 1 Some examples of plant-derived AuNPs and their wound healing applications
Part of plant Size of AuNPs Shape of Plant metabolites Applications in wound
Plant used nm) AuNPs involved healing References
Acalypha indica Leaves 20–30 Spherical Quercetin, plant Antibacterial [45]
pigment

Cassia fistula Stem 55–98 Spherical Hydroxyl group Antihypoglycaemic [46]

Mentha piperita Leaves 90–150 Spherical Menthol Antibacterial [47]

Mirabilis jalapa Flowers ~100 Spherical Polysaccharides Antimicrobial [48]

Trigonella-foenum Seed 15–25 Spherical Flavonoids Catalytic [49]

graecum
Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 709
710 S. Gulati et al.

is decreased, and harmful effects and limitations that are shown by conventional
AuNPs are not a characteristic of phytochemically produced/mediated gold nano-
particles, thus making them the science of our future [50, 51].

Concluding Remarks and Future Prospects

The usage of plant derivatives in biosynthesizing metallic nanoparticles especially

gold has peaked in the last two decades and the graph seems to be going upwards
as we move forward. The many advantages of green synthesis of nanoparticles
render a myriad of opportunities to scientists for testing novel theories based on
different combinations of plant extracts/products with numerous shapes/sizes of
compatible nanoparticles discovered till now. Due to this diversity, the potential of
phytonanotechnology is observed in a number of fields like pharmaceuticals,
therapeutics, medicine (cancer, diabetes, neurological disorders, wound healing,
etc.), renewable energy production, etc. In wound healing, plant-mediated gold
nanoproducts alone have shown huge potential which justifies the fact that nano-
technology is the future and we have to keep striving in the right direction to get
the desired solution. Since this is the new advent of nanotechnology, exploration in
this field is required to correctly and deeply understand the phytochemicals and
their mode of action in wound healing and how they are able to direct crucial
processes of tissue regeneration and antioxidation. It is also needed that the
number of all plant extracts/products be documented that can be useful in
wound healing while putting due emphasis on researching for newer phytochem-
icals as phytonanotechnology paves the way for a future which is energy efficient,
healthier, safer, and eco-friendly; thus, an opportunity of such high degree must
not be lost.

Important Websites

https://www.britannica.com/science/nanoparticle
https://nanotechnology.imedpub.com/synthesis-of-gold-nanoparticles-using-plant-
extract-an-overview.php?aid¼7649
https://www.mdpi.com/journal/biomolecules/special_issues/green_synthesis_
nanoparticles
https://www.understandingnano.com/nanotechnology-wound-healing.html
https://onlinelibrary.wiley.com/doi/abs/10.1002/lsm.22614
https://rjptonline.org/AbstractView.aspx?PID¼2021-14-2-102
https://www.x-mol.com/paper/1313952619503521792?recommendPaper¼547743
https://jnanobiotechnology.biomedcentral.com/articles/10.1186/s12951-018-0408-
4#:~:text¼Among%20the%20available%20green%20methods,2).
https://www.nanoscience.com/techniques/nanoparticle-synthesis/
https://www.grin.com/document/509334
30 Plant-Based Consumer Health Gold Nanoproducts: Benign Nanoformulations for. . . 711

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 Part X
Consumer Nanoproducts for Food
Consumer Nanoproducts for Food
31
Prasanth Rathinam, Sherly Antony, R. Reshmy, Raveendran Sindhu,
Parameswaran Binod, and Ashok Pandey

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718
Current Status on Food and Agriculture Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Current Status on Food Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
Current Status in Agriculture Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 723
Sensors for Environmental Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
Nanotechnology on Preservation and Shelf Life of Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
Nanotechnology and Food Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
Regulation of Nanotechnology on Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Food and Agriculture Associated Nanoparticles Available in Market . . . . . . . . . . . . . . . . . . . . . . . . . 725
Consumer Acceptability and Nanotechnology on Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Health Implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Consumer Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728

P. Rathinam
Department of Biochemistry, Pushpagiri Institute of Medical Sciences and In-charge of
Biochemistry Laboratory and Medical Biotechnology Laboratory, Pushpagiri Research Centre,
Thriuvalla, Kerala, India
S. Antony
Department of Microbiology, Pushpagiri Institute of Medical Sciences and In-charge of Microbial
Technology and Infectious Diseases Laboratory, Pushpagiri Research Centre, Thiruvalla, Kerala,
India
R. Reshmy
Post Graduate and Research Department of Chemistry, Bishop Moore College, Mavelikara, Kerala,
India
R. Sindhu (*) · P. Binod
Microbial Processes and Technology Division, CSIR-National Institute for Interdisciplinary,
Science and Technology (CSIR-NIIST), Thiruvananthapuram, Kerala, India
A. Pandey
Centre for Innovation and Translational Research, CSIR- Indian Institute for Toxicology Research
(CSIR-IITR), Lucknow, India

© Springer Nature Singapore Pte Ltd. 2022 717

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_50
718 P. Rathinam et al.

Regulatory Aspect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729

Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730

Abstract
The food and agriculture sector, both in developing and developed countries, had
witnessed a phenomenal revolution with the help of nanotechnology since 2003.
This smart technology has been facilitating transformations in the agriculture
sector, specifically through the means of (i) nano-modification of seeds, fertil-
izers, and pesticides (ii) interactive smart foods like nano-encapsulated flavours,
nano-emulsions and anti-caking agents (iii) novel food fortification and modifi-
cation strategies to elevate neutraceutical values with enhanced bioavailability of
nutrients. In addition, nanomaterials were also developed to evaluate cultivation
of food, quality and food safety, and checking of ecological circumstances.
Presently nanotechnology has a global impact on the food industry with predicted
profit over 3 trillion USD, and an abundance of nearly 6 million employment in
the surging industries worldwide. These food associated ventures are participated
in the growth and advertising of nanotechnology driven foods and related prod-
ucts with improved attributes like performance, aesthetic taste, and security.
Amazingly, there is an abundance of such goods that are developed and have
now been supplied by these food industries over the past decade. In this chapter,
the most recent nanotechnology driven prospects in cuisine and cultivation
sections are discussed as emphasizing nano-products that reached the consumer,
those under development, associated regulations and challenges from selected
recent studies.

Keywords
Nano-products · Nanotechnology · Nano-materials · Food processing ·
Agriculture

Introduction

Nanotechnology has begun swaying everyday life since the early guideline issued by
the United States Department of Agriculture on 9th September, 2003 [1]. Presently
with the increased research enthusiasm on nanotechnology, it practically comprise
the whole facets in the food and cultivation trade marching from farming, watering
and/or its quality improving, food refining and packaging, veterinary feed, and
aquaculture [2–5]. By 2020, nanotechnology is estimated with a recent global
economic impact of around $3 trillion and projected to provide 6 million associated
labourers [6]. As a matter of fact, many industries are associated in developing and
promotion of nanotechnology derived commodities intended for bettering manufac-
ture adeptness, food attributes and security. In fact, a large number of products have
reached the market and currently been adopted in the food industry. Indeed main
31 Consumer Nanoproducts for Food 719

stream of them are food containing materials but not for direct consumption by
people. Except for metal oxides like (TiO2 and Fe2O3), no other nanomaterial
containing products are put for direct human consumption, while these metal oxides
are used as food pigments and anti-microbial agents, already [2, 4].
Since nanotechnology derived products are used in various sectors, its public
acceptance is of utmost importance [7–9]. It ultimately determines the actual appli-
cation and/or acceptance by the customers [10]. Regardless of the public acceptance
and rejection, disposal of nanomaterial wastes will have a toll on the habitat and
bring out definite brunt on the plants, animals, and related ecological communities.
In the light of unavailable data about their impact on the environment, the proper
disposal methods have not been regularized yet by the scientific community, indus-
try, and the governing bodies [10, 11].
This chapter briefly covers the most recent nanotechnology driven opportunities
in food and agriculture sectors are discussed as emphasizing nano-products that
reached the consumer, those underdevelopment, associated regulations and chal-
lenges from selected recent studies. The chapter may also emphasize the immediate
need to bring insights towards estimating the danger and harmfulness for the purpose
of legislation and public acceptance.

Current Status on Food and Agriculture Nanotechnology

Nanotechnology, being a rapidly developing sector, is having its effect in trans-

forming various fields related to day to day life. Traditional sectors like food and
agriculture segments also have faced the nanotechnology guided revolutions. Nano-
technology deals with materials with no less than one aspect in the scope of 1 to
100 nm. As a matter of fact nanomatrials have significantly revolutionized each and
every aspect of food and agriculture sectors, from the fields to the plates [12].
Numerous nanomaterials have revealed inspiring capabilities in each feature of
the food and agriculture industry. The food industry in all its facets from the
ingredients to packaging to methods of food analysis is using nanotech tools
[12]. This results in numerous applications which are used for improving food
production, processing, packaging, and storage. In addition, nanotechnology is
used in targeted nutrient delivery as well. Biosensors for food quality monitoring,
smart food packaging systems and nanoencapsulation techniques are some of the
emerging applications of nanotechnology. Similarly, the agriculture sector has
numerous nanotechnology inspired tools like nano-modification of seeds, herbi-
cides, insecticides, intended genetic engineering, conservation, agrichemical distri-
bution, and sensors to track habitat circumstances [2, 12].

Current Status on Food Nanotechnology

There exists a discrepancy among the organic nanosystems and nanotechnology

influenced nanomaterials that synthesized for a particular specification. Analyzing
720 P. Rathinam et al.

the managerial necessity and interpretations, unlike the nanotechnology influenced

materials; organic nanosystems are not an outcome of nanotechnology [13].
Food comprises many nanostructured elements, including components which
reach out to nanoscale sizes (e.g., milk proteins, and micelles/lathers/colloids).
While nanotechnology inspired nanomaterials that synthesized for a particular
specification has motivated many aspects of food industry. Through, the potential
use of nanotechnology has been identified in each sections of the food business, the
major focus areas include: (1) food processing (entrapping and enhancing the
flavours or odours with the help of encapsulation techniques, quality and/or texture
improvement using gelation and viscosifying agents) (2) mineral and vitamin sup-
plements (highly stable nutraceuticals with enhanced bio-accessibility) (3) Packing
of foods (contamination and/or spoilage sensors; anti-counterfeiting gadgets,
safeguarding from harmful rays like UV, and sturdier, more resistant polymer
coatings) (4) agriculture (insecticide, manures, composts or vaccine transfer, animal
and plant pathogen identification and/or labelling, and directed genetic manipula-
tions). As a matter of fact, food nanotechnology-based innovations have revolution-
ized the food quality and safety to the end-users [13, 14].

Food Processing
Food processing comprises the course of converting raw elements to produce
commercial food harvests that prepared, and delivered with comfort, and ingested
safely by the end-user. The food processing sector includes the conversion of
prepared elements by physical/chemical methods and/or by other techniques.
Besides the primary processing techniques like chopping, slicing, freezing, or
desiccating, leading to secondary goods, representative activities in food processing
involve shredding and softening, condensation, emulsification, and cooking (using
various culinary techniques); diverse preservation and sterilization methods (pick-
ling, and pasteurization); and packaging techniques like canning, bottling and
tinning [15]. Such techniques are formulated and designed not only to keep the
flavour and quality of the food and its ingredients intact but to protect from various
means of food spoilage also. Food processing makes use of methods like irradiation,
ohmic heating, and high hydrostatic pressure to prevent microbial infestation and
guided food spoilage [15]. With the aid of food processing, the shelf life can be
increased and the producer can transfer food over distances without any spoilage.
Food processing benefits the customers, by providing the availability of different
kinds of foods such as seasonal ones (peas and corns) throughout the year. Producing
and consuming fresh food being a concern today, food processing also involves in
producing healthier food containing micronutrients as well [16].
Nanotechnology influenced nanomaterials hold a significant part in food handling
including the integration of vitamins and minerals, agents for gelling and visco-
sifying, efficient distribution of nutrients, fortification of nutraceuticals, and
enmeshing of flavours through nanoencapsulation [17]. Nanostructured food mate-
rials claim to offer improvement in taste, texture, and consistency. By increasing the
shelf-life of various food materials nanotechnology reduced the food wastage due to
spoilage. Nanosensors are used to identify the incidence of contamination, toxins,
31 Consumer Nanoproducts for Food 721

and other food pollutants [18]. The use of nanocarriers for the distribution structures
for food flavours and seasonings without altering the basic morphology of food. In
fact, nanotechnology driven formation of encasing systems, simple and complex
solution systems, and biocompatible matrices for packaging, offers effectual distri-
bution systems. In addition, nano polymers are used in food packaging substituting
conventional materials [15].
Nanoparticles exhibit superior encapsulation properties and release dynamics
than the conventional encapsulation systems. Nanoencapsulation can mask odours
and/or tastes, control the rate of discharge of active components, guarantee time
dependant availability at the target, protect from adverse conditions like moisture
and heat, and prevent biological and/or chemical degradation, storage, exploitation
and displaying compatibility with additional composites of system. Indeed, nano-
encapsulation can penetrate deep into the tissues using their lesser size and mediate
target-specific distribution of active principals. Man-made and organic polymer-
centred nanotechnology driven encapsulation delivery schemes with enhanced bio-
availability and preservation, are being developed. As a matter of fact the evaluation
of nanotechnology-based improvement in food processing is on the basis of;
improvements in food quality, presentation, taste, nutritional value, content, and
expiration [2, 12, 15, 16].
Nanotechnology influenced systems have brought about a range of improvements
in the quality of food, and its taste. Nanoencapsulation techniques revolutionized the
use of phytocompounds with important pharmacological activities in food pro-
cessing. The majority of these phytocompounds have properties like high reactivity,
instability, and have poor solubility which limited their use in the food industry.
Nanoscale capsulated form of plant pigment anthocyanin and dietary flavonoid:
routin encapsulated in ferritin nanocages are examples of the aforesaid advancement
which are currently used for controlling the flavour release and culinary balance in
foods [19–21]. In addition, such encapsulations enhance the stability of these
compounds towards thermal and UV radiation. Deliveries of lipid-soluble bioactive
compounds are now achieved with the use of nanoemulsions which not only
enhances the water dispersion property but the bioavailability as well [22]. Metallic
nanomaterials like titanium dioxide and silicon dioxide are used as food nano-
materials and utilized as colour and/or flow agents. Whereas SiO2 nanomaterials
were used as a flavour and/or fragrance carriers in the food industry [23, 24].
Nanoparticles due to their subcellular size are now used to improve the bioavail-
ability of nutraceuticals for enhanced drug bio-accessibility in comparison to the
conventional methods. Components like bio-macromolecules and vitamins are liable
to extreme pH conditions and enzymatic degradation at the gastrointestinal system
and non-capsulated form of these active components fails to achieve the required
bioavailability due to their low water solubility [25]. Bioactive compounds based
nanoparticles in the form of tiny capsules attain the aim of improved delivery and
bioavailability. In addition, this edible capsule machinery can be further extended for
the delivery of fragile micronutrients that required in the daily uptake to meet
significant health benefits [16]. Effective and targeted delivery of nutrients like
proteins and anti-oxidants shall be achieved using transforming them into miniature
722 P. Rathinam et al.

capsule forms using various techniques like nanocomposite formation, nano-

emulsification, and nano structuration. In addition, polymeric nanoparticles are
also used for encapsulation for the transport and delivery of various bioactive
compounds with potential health benefits to the targeted regions [26].

Food Packaging
Nano-based food packagings offer enhanced penetrability to have moisture and gas,
improved stability and environment friendly to that of conventional packaging
material. In addition they possess several advantages like barrier properties, anti-
microbial activity, pathogen detection ability (with the help of nanosensors) and
consumer alerting mechanisms about the safety status of food [27].
Nanoparticles with various properties can be used as active packaging and/or
coating material. Organic and inorganic compounds with antimicrobial property and
their use in polymeric matrices are considered for improving the food packaging.
Organic compounds being sensitive to the extreme conditions that prevail in food
processing steps do not fit for packaging and coating materials. On the contrary
inorganic nanoparticles exhibited strong antimicrobial property in reduced accumu-
lations and exhibited more resistance to unfavourable conditions. Hence inorganic
nanomatrials as antimicrobial packaging, when comes in contact with the food or the
inside space to exhibit bactericidal and/or bacteriostatic properties [28]. Many sub-
stances with potent antimicrobial activity like metals, metal-oxides, and chitosan
have been recently developed as packaging material [16].
Nanotechnology derived food packaging is categorized as following:

• Nanoparticles for improved packaging:

Here the nanoparticles are mixed with the polymer matrices for achieving the
improvement in the gas barrier properties, temperature, and humidity resistance.
Nanoparticles use as an improved packaging material is approved by various
national and international authorities [28].

• Nanoparticles as an active packaging:

The nanoparticles in the packaging will be directly interacting with the foodstuff
and the microenvironment within for enhanced safety. Majority of these nano-
particles will be utilizing the mechanism of antimicrobial property besides the
oxygen or UV scavenging machinery [15, 28].

• Nanoparticles as intelligent / smart packaging:

These packagings are designed to sense the physiochemical changes in the food,
sensing explicit food-related contaminants and/or detection of specific gases from
food spoilage. In addition, the development of ‘smart’ packaging can track food
safety and avoid counterfeit. Such devices are currently been used by Nestle, British
Airways, and MonoPrix Supermarket [15, 16, 28].
31 Consumer Nanoproducts for Food 723

Nanotechnology driven novel devices are now widely used in food wrapping
trades. These devices comprise nano-devices, automatic noses, range biosensors,
nanaocantilevers, solution-based nanoparticles, and test strips with nanoparticles.
Packing matrix containing Nanosensors could trace the external and/or internal niche
of food components, capsules, and filling tins aiding in tracing till reaching the
end-user. Nanosensors implanted in plastic packaging matrix can detect gases that
produced due to food spoilage and change the colour to alert the consumer. Simi-
larly, oxygen scavenging films made of silicate nanoparticles can keep the freshness
of the food for a longer period of time. In addition, these films can prevent the growth
of mould and other microbes in refrigerators and packaged foods, respectively.
Implementation of nanotechnology driven food packaging will result in cost reduc-
tion and attempts should be made from the government to accelerate the develop-
ment of cost-effective and efficient nano-packaging strategies [15, 28].

Current Status in Agriculture Nanotechnology

The farming sector make use of nanotechnology to upsurge food cultivation with
improved yet targeted nourishment content, value assurance, and care. Effectual use
of manures, insecticides, herbicides, developmental factors, controllers are essential
for improving crop production and ethical yet controlled use of aforesaid factors are
possible through nanocarriers. In comparison with the commercial atrazine, poly
(epsilon-caprolactone) based carrier for herbicide atrazine, exhibited significant
herbicidal activity in mustard plants [29]. In addition, these nanocapsules showed
less or no side effects to plants in comparison with the commercial atrazine. Other
widely used nanocarriers are silica and polymeric NPs with modified-release mech-
anisms used for the controlled delivery of pesticides [30, 31]. In addition, nanoscale
carriers are also used to achieve the controlled and slow release of these factors in
agriculture. Nanotechnology driven strategies are now been used to improve the crop
yields without damaging the environment (known as ‘precision farming) [32].
Nanoparticle facilitated nucleic acid transmission was utilized to advance pest-
resistance in plants. In fact, many nanomaterials can serve as insecticides with
improved pest sensitivity and less/no toxicity. Metal oxide nanoparticles with their
inborn toxicity are studied to protect plants from pathogens. Zinc oxide nano-
particles can effectively inhibit diverse pathogenic microbes like fungi and bacteria
[33, 34].
Unlike the conventional mineral fertilizers, the development and use of nano
fertilizers bring about the novel solution(s) for the advancement in the agriculture
sector. Nano fertilizers help in preventing nutrient loss and aid in nutrient incorpo-
ration. Nanoscale forms of micronutrients are been utilized as nano fertilizers
(Manganese, Copper, Iron, Zinc, Molybdenum, Nitrogen and Boron) [35, 36]. It is
eminent that the use of other nanomaterials like carbon nano-onions and chitosan
NPs, could help in increased production and value of yield. Applications and
acceptability of nano fertilizers have motivated and will transform the fertilizer
manufacture businesses by the subsequent decade [37–39].
724 P. Rathinam et al.

Sensors for Environmental Study

Nanotechnology driven Nanosensors (wireless in specific) have been developed

to monitor various aspects of agriculture sectors. These sensors can detect
chemicals in the environment (pesticides and herbicides), and trace amounts of
pathogens in the agriculture systems. Such real-time monitoring systems will
help to understand possible harvest damages and help in improving crop manu-
facture through the appropriate and rational practise of nano fertilizers, nano
pesticides, and nanoherbicides. Real time tracking of propineb fungicide in an
aquatic niche is possible with the help of copper dopped mont morillonite, which
have a lower limit of around 1μM [40]. In addition graphene-based nano-
materials are used to detect contaminants in wastewater and aid in improving
the water quality, with a potential application in aquaculture [41, 42]. An array of
nanomaterials like Cu, Au, Ag nanoparticles, and carbon nanotubes are in
pipeline as Nanosensors for the in situ monitoring of crop health and the
surrounding environment [43–45].

Nanotechnology on Preservation and Shelf Life of Foods

A major problem that associated with the functional food sector is the degradation of
the bioactive components and/or inactivation due to the unreceptive environment
until it reaches the target site or to the end-user. Prolonging the service life and/or
slowing the degradation process of the bioactive counterparts are achieved though
nanotechnology derived techniques like encapsulation and edible nano-coatings
[15, 46]. Nanotechnology derived, eatable coatings on the food materials will act
as a barricade to humidity and aid in efficient exchange of gas whereas in some cases
it delivers food additives, and agents for food quality improvement. Nano-coatings
are more advantageous as they boost the servable life of the factory-made foods,
though the package is unwrapped. It is well studies that the alterations to interfacial
surrounding layer properties will lose the pace of the degradation processes.
Curcumin, the least stable component in turmeric, exhibited reduced bioactivity
and found to be stable to pasteurization after nanotechnology derived encapsulation
[3, 46].

Nanotechnology and Food Safety

Nanotechnology and nanomaterial associated food safety is of significant health

concern, in fact, food borne diseases that associated with microbial pathogens
account for about 20 million cases/ annum, around the world. Food safety concerns
with the fact that, the food does not cause any harm to the end user either during the
process of food preparation and/or when eaten. With respect to the food safety aspect
all the foods should be protected from physio-chemical and organic adulteration by
the means of transformation, handling and delivery [28, 47].
31 Consumer Nanoproducts for Food 725

Regulation of Nanotechnology on Food

Regulations of nano-foods will help to revolutionize the role of nanomaterials in

food segment. The regulatory framework faces threats because of the fundamental
and technical complications in nanotechnology which are further enhanced by the
lack of a unidirectional yet extensive supervisory structure to safeguard end-user
safety [48, 49]. Impairments during the risk evaluation of nano-foods had been
associated with factors like limited data, lack of models reflecting real-world sce-
nario of nanotechnology derived materials, and reservations regarding the governing
bodies [49, 50]. The relaxed rate of risk analysis investigations is also a reason for
making the food-related regulations, a difficult task. Due to the potential migration of
nanoparticles the risk and/or safety assessment of food-related nanomaterials are
essential. Considering the growing interest in nanotechnology and related food
products, the synthesis and improvement of nanotechnology based products have
not considered the safety of end-users [49, 51]. In fact, the effective directive in food-
nanomaterials depends on the inclusiveness of descriptions, obligations of products,
and enlisting of nanoproducts that acceptable in the food sectors [49, 52].

Food and Agriculture Associated Nanoparticles Available in Market

Commercialized nanofood and agriculture products and their applications are shown
in Table 1.

Consumer Acceptability and Nanotechnology on Food

The commercial triumph of food merchandise is estimated based on consumer accept-

ability. In addition to the quality and nutritional values, in the case of foods that
irradiated and with intended nucleic acid modifications, the reception is affected by the
concerns over health and environment. The reluctance of end-users towards the
purchase of nanotechnology guided food products might be due to health concerns
[16]. Customer knowledge regarding food products significantly affects the accep-
tance. In addition necessary steps should be implemented to enhance the dissemination
of information about the role of nanotechnology in food industry, which will improve
the trust and perception among the end-users. To improve the end-user acceptance
regular and consistent efforts should be made on nano food and related products by
administrations, manufactures, and other establishments [49, 61].

Health Implications

The various properties of nanomaterials play a major role in their effect on the human
body. Cationic hydrophilic nanoparticles shown to have significantly increased circu-
lation time with respect to their counterparts [62, 63]. With the available study data, it
Table 1 Commercial nanoproducts and their applications
726

Product name Type of product Manufacturer Nanomaterial References

NutraLeaseanola active oil Food and beverage Shemen, Haifa, Israel Nanosized self-assembled [53]
liquid structures (NSSL)
Nanotea Beverage Shenzhen Become industry Nanoselenium [16]
Fortified fruit juice Health drink Co. Guangdong, China Micelles 5–100 nm in diameter [16]
High Vive. Com, USA
Nanoceuticals slim shake Health drink RBC Lifesciences, Irving, USA Conversion of vanilla or [54]
chocolate into nanoscale
NanoSlim beverage Food and beverage NanoSlim Liquid suspended nanoparticle [54]
Oat nutritional drink Food and beverage Toddler health, Los Angeles, USA – [54]
Tip top bread Food George Weston foods, Enfield, Nanosized self-assembled [16]
Australia liquid structures
Nano B-12 vitamin spray Food supplements Nanotech, LLC (USA) Nanodroplets [55]
Kimchi Korean fermented cabbage Korea NanometricLactobacillus [56]
dish plantarum
Neosino Health supplement Germany Silicon [55]
Aquanova Food supplements Germany Nanomicelles [57]
Oat chocolate and oat Vanilla Beverage Oat chocolate and oat Vanilla 300 nm of iron particles [25]
nutritional drink nutritional drink
Aquasol preservative Food additive Aquanova Nanoscale micelle [57]
Nano silver baby Milk bottle Health benefits for toddler Baby dream ® co. ltd. (south Nanosilver [16]
Food storage containers Food storage BlueMoonGoods, LLC, USA Silver [16]
Large kitchen appliances Food storage Daewoo ® refrigerator, Korea Nanosilver [16]
Nano-silver salad bowl Food storage Changmin chemicals, Korea Silver [58]
Nano storage box Food storage BlueMoonGoods™, USA Silver [16]
Novasol Sustain beverage Aquanova ®, Germany Nanomicelle [16]
Nanoceuticals™ Nanosized powders RBC life sciences ® Inc. (USA) Nanocolloidal silicate mineral [16]
and Hydracel ®
P. Rathinam et al.
 31

Lypo-Spheric vitamin C Supplements LivOn labs, USA Liposomal nanospheres [16]

Daily vitamin boost Fortified Jambu juice Hawaii, USA Silver nanoparticle [16]
SoluE Vitamin E Aquanova – [16]
SoluC Vitamin E Aquanova – [16]
Megace ® ES Nanocrystal dispersion with Par pharmaceutical, Inc., Bristol- Myers – [16]
micronized particles Squibb company, new
OilFresh™ Nanoceramic product US-based Oilfresh corporation – [59]
Bioral Nanocochleate BioDelivery sciences Interna- Calcium ions in GRAS phos- [60].
Consumer Nanoproducts for Food
727
728 P. Rathinam et al.

is confirmed that particles with increased circulation time affect the micro-circulation
in the host body. Particles in the micro-circulation may affect the lining of arteries and
veins, their function, and/or thrombus may occur [64]. In addition, these ultrafine
particles may get inhaled and can cause adverse cardiovascular effects. Brain, being
the well-vascularized organ aforesaid adverse effects were observed in studies using
immortalized brain microglial cells [65, 66]. As per the various literatures, some of
these nanoparticles are capable to cross the blood-brain barrier, interact with cellular
metabolism. Though the exact mechanism by which the toxicity due to nanomaterials
is not completely understood, it is supposed that the major mechanism is through the
oxidative stress mechanism [62].
In addition to the properties of nanoparticles, their concentration, and exposure
duration, the possibility of toxicity is also influenced by the biological state of an
organism and/or individuals susceptibility [67–69]. Chronic inflammation due to the
activation of oxidative stress is potent enough to cause fibrosis, mutations, cancers,
and secondary mutation. Carcinogenicity and genotoxicity are considered to be the
major adverse effects associated with the nanoparticle. Toxicity studies related to the
metallic nanoparticles suggested about particle size dependant ability for
genotoxicity in human epidermal cells. Persistent particles of substances like asbes-
tos may bring about developing granulomas and lung associated fibrosis. In addition,
inhalation of TiO2 (10 mg/m3) may result in lung tumours as well [67].

Consumer Safety

As the influence of nano science in the culinary and cultivation sector increased,
human exposure to these particles/materials also augmented, consequently
[70]. Knowingly or unknowingly anthropological disclosure to the nanomaterials
will upsurge in diverse methods, and it is unavoidable. Meagre knowledge is
available regarding the metabolism and bio-distribution levels of nanomaterials.
However, diverse studies have conducted aiming towards analyzing the possible
harmfulness of the nanomaterials that use in food and agriculture, by analyzing
diverse samples from crops, pesticides, food packaging, and additives. Nano-
materials, used in food and agriculture sectors will come in direct contact with the
human organs, and the exposure is directly comparative to the factors like (1) levels
of the nanomaterial present in the product (nanoscale edible coatings versus nano
matrices for packaging, and (2) the amount of the product that been consumed or
used (consumption of nanoscale edible coated food versus food from a nano matrix
packet) [71, 72]. Sometimes, unintentional exposure due to the leaching of nano-
package material is also possible. Nanoclay was found to be migrating from food
contact materials into the food stimulants [16]. Such migration may result in
accumulation of substances like aluminum (nano form and dissolved form), with
an estimated migration rate of 51.65 ng/cm2 for the Aisaika bags and 24.14 ng/cm2
for the Debbie Meyer bags [73]. Likewise, the analyzed migration rate of nano clay
from a thin-film is influenced directly by the contact time and temperature.
Workers at nano-material producing industries are also at high risk of particle
inhalation, skin penetration due to overexposure. Understanding the basic fact that
31 Consumer Nanoproducts for Food 729

the nanomaterial guided toxicity is dependent on the physiochemical characters and

dose, regulatory authorities should consider through characterization and assessment
of products at multiple levels (in silico, in vitro and in vivo) before and after it
reaches the end-user [4, 74, 75]. Factors like physio-chemical factors, osmotic
potentials, acid-base levels, chemical aspects, concentration of biomolecules, and
micro flora, their metabolism and eventual toxicity should be considered for
assessing the risk [71, 72, 74].

Regulatory Aspect

The use of nanotechnology in the culinary and cultivation sector is remarkable;

however, their interaction with human and animal health and environment raises a
concern. The nanoformulation products exert toxicity to the vegetation and wildlife,
but no customary regulations and/or policies in place regarding their use and
disposal. Consequently, operative regulations and guidelines are compulsory for
the harmless usage of nanoparticles in the food and agriculture sector.
In the USA, the regulations involved with nanofoods, food packaging other food-
related nanotechnology products are done by the United States Food and Drug
Administration (USFDA). Whereas in Australia and New Zealand, a regulatory
body under the Food Standards Code, known as Food Standards Australia and
New Zealand (FSANZ) regulate nanofood related aspects [16, 76]. Risk and safety
valuation of nanotechnology in the culinary and cultivation sector in the European
Union is achievedthrough the Scientific Committee on Emerging and Newly Identified
Health Risks (SCENIHR) [77]. According to the SCENIHR, all nanotechnology-
based food and agriculture products must undertake security and risk valuation afore
being issued to the end-user and all these food products are enclosed by the European
Union Novel Foods Regulation (EC 258–97). On the contrary, major nanomaterial
producing countries like Japan and China do not have regulations and policies for
nanotechnology specific food and/or agriculture products [78].
As mentioned earlier, the lack of regulations is mainly due to the scarcity of evidence
concerning exposure and harmfulness to humans, animals, and the environment.
However, several countries are coming up with regulatory systems to handle the
dangers related by the nanofood. Comprehensive government rules and legislations,
in addition to rigorous toxicological evaluation techniques, are vital for the lawful
nanotechnological uses. A generally acknowledged global governing scheme is imme-
diately essential for instructing the application of nanoparticles in the food sector
[79, 80].

Conclusion

Nanotechnology guided improvements in the food and agriculture sectors through

refining the food processing, wrapping, transport, quality, and safety to the
end-users. Smart nano-devices provide information regarding the state of the food
within the package and also aid in pathogen detection if any. Though nanoparticles
730 P. Rathinam et al.

and driven food substances are produced worldwide, very few countries have
regulations and policies for the ethical and efficient use. Incomplete and insufficient
scientific explorations on nano-food tools hampered the accuracy of any conclusions
regarding the associated safety and/or toxicity. Though it is understood that the
packaging matrix posses less harm than utilizing nanoparticles as a food ingredient.
With the threat of the access of nanoparticles in the body systems and the environ-
ment, appropriate regulations, labelling, policies for marketing are required to
guarantee the end-user safety to increase acceptability. Thus, if managed and regu-
lated correctly, nanotechnologies can revolutionize the food and agriculture industry
which will benefit human health and well being.

Acknowledgment Reshmy P and Raveendran Sindhu acknowledge Department of Science and

Technology for sanctioning projects under DST WOS-B Scheme.

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Zein-Based Nanoproducts in Nutrition and
Food Sectors 32
Soumitra Banerjee, Patel Chandra Prakash, and
Ravi-Kumar Kadeppagari

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
Corn/Maize . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
Zein: The Corn Protein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
Zein Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
Zein in Food and Non-food Sectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 739
Zein-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
Applications of Zein-Based Nanoproducts in Food and Nutritional Sectors . . . . . . . . . . . . . . . . . . 741
Food and Nutritional Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
Shelf Life Extension of Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
Micronutrient Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
Biodegradable Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
Sensor Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747

Abstract
The corn protein zein is commonly used in the preparation of edible films and
coating of candy, fruits, nuts, etc. Recently, zein nanoparticles were used to
reinforce the mechanical properties of edible films and in the manufacturing of
functional edible films. Antimicrobial zein coatings with essential oils were used
for the inhibition of pathogens on whole fruit surfaces. Colloids were developed
with zein-based nanoparticles for postharvest treatments of fruits. Nanomaterials
based on zein were used in the development of antimicrobial, bioactive, or biode-
gradable food packaging films/systems. Zein-based food packaging bioactive coat-
ings were also used here. Zein nanoparticles were also used for the development of
stable delivery or co-delivery systems for nutraceuticals by nano-encapsulation or
co-encapsulation process. They were further used in the development of controlled

S. Banerjee · P. C. Prakash · R.-K. Kadeppagari (*)

Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Department of Food
Technology, Jyothy Institute of Technology, Bengaluru, Karnataka, India

© Springer Nature Singapore Pte Ltd. 2022 735

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_51
736 S. Banerjee et al.

or targeted delivery systems for nutraceuticals. Nanomaterials based on zein were

used for the encapsulation of food components and nutrients, and their bioavail-
ability was also improved with zein nanoparticles. Food-grade pickering emulsions
were prepared with zein nanoparticles. Recently, gold-coated zein nanophotonic
structures were used for the development of platform for the detection of food
analytes. Also, zein networks were evaluated recently to check the possibility of
replacing animal meat with plant based meat and finding alternatives to cheese.
However, further work needs to be done in order to develop this kind of products.
This book chapter focuses on recent developments on zein-based nanoproducts
with respect to food and nutrition sectors.

Keywords
Zein · Edible films · Nanomaterials · Food packaging · Nutraceuticals ·
Encapsulation · Analytes · cheese

Introduction

Corn/Maize

Maize or corn (Zea mays) is one of the globally popular nutritious cereals besides
wheat and rice. It contains high amount of starch (72%), protein (10%), and fat (4%),
for which it is well utilized in different parts of the world as a food source. Besides
human food, in developed countries, maize is also used as major domesticated
animal feed source. In present days, maize is cultivated in a number of countries
as a popular cereal, which may have originated from Mexico about 7000 years ago.
The energy density of maize is 365 kcal/100 g, which is comparable to rice and
wheat. However, protein content of maize is lesser than rice and wheat. Maize is
cultivated in different countries of the world, out of which major cultivators are the
USA, China, and Brazil, which approximately contribute 31%, 24%, and 8%,
respectively, of total global maize production [31, 44]. Leading five countries for
maize production besides the USA are China, Brazil, Argentina, Ukraine, and India.
India ranks 6th position in global maize production and produced 25,000 thousand
MT of maize in the year 2019 [2].
Maize is one of the versatile cereal crops, which may be cultivated in varied
agro-climatic regions. The maize crop requires adequate moisture in soil and
temperature range of 18–23  C for the deposition and 28  C for the growth and
development of the plant. Similar in varied climatic condition, maize is found to
grow well in different types of soil, from loamy sand to clay loam. The soil should
contain high organic matters and sufficient soil bacteria and needs to have good
water holding capacity with proper drainage. All these conditions are considered
good for maize cultivation. Maize can grow in different soil except saline and
alkaline soil, which are believed not suitable for maize cultivation. Maize can be
grown as an intercrop cultivation system, i.e., maize with soybean, sesame, etc. In
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 737

India, maize is cultivated in all four agricultural seasons, namely, kharif (mon-
soon), post monsoon, rabi (winter), and spring. Similar to agricultural practice of
India, rabi and spring season cultivation needs additional irrigational support to
assure a higher yield of maize productivity. However due to availability of rain-
water during the months of kharif season, there is lesser need for irrigation
facilities. Sowing operation during monsoon season needs to be completed within
12–15 days before monsoon. Sowing time needs to be adjusted and needs to be
coinciding with coming monsoon [3, 38].
Changing climate, economical factors, technological development, and other
factors are quite responsible for changing global and Indian farming scenario, but
still maize cultivation has been identified as a successful crop which addressed
several local and global issues, i.e., food security, water scarcity, farming systems,
biodiesel, etc. According to the National Centre for Agricultural Economics and
Policy Research (NCAP), besides regular food source, maize has gained impor-
tance in non-food industrial sectors like textile, paper, glue, alcohol, pharma-
ceutical, etc., making maize to gain more popularity with time and human
population [38].
Maize after harvest can be utilized for manufacturing of various products of
versatile nature, i.e., corn starch, corn oil, corn syrup, alcohol, corn flakes, etc.
These products are described briefly below.

Corn Starch In maize, the major composition is starch, which accounts almost 3/4
part of the total maize grain composition. Hence, this starch received commendable
attention for various applications. Corn starch is a biopolymer made up of amylase
and amylopectin. Corn starch in natural and modified form can be used for a number
of food applications, i.e., thickener, texturizer, fat replacer, and stabilizer, for gel
preparation, and for moisture retention properties [9]. It is also used to make corn
syrup, dextrose (crystalline glucose), etc. [11].

Corn Oil Corn or maize is not known as oil seeds, because it contains low lipid
content (3–5%) in the kernel. During wet or dry milling operation, germ is
produced as by-product which will be used to extract oil by crushing and germ
contains 80% lipid. Germ represents 9–11% of total kernel weight. Corn oil is
suitable for food processing, which contains a significant amount of antioxidants,
namely, tocopherols and tocotrienol, besides the high amount of unsaturated fatty
acids, including linoleic and oleic acids. Refined corn oil finds its applications in
cooking, frying, as a salad oil, and also as raw material for the lipid modification
process [8].

Corn Protein Corn protein varies in different varieties from 6 to 12% (d. b.), the
majority of which is found in the endosperm tissue (75%) and remaining 25% in
the germ and bran. There are four types of proteins in corn, namely, albumin (water
soluble), globulin (salt soluble), glutelin (alkali soluble), and zein (alcohol
soluble). Out of the four proteins, zein determines the hardness of the corn
endosperm [49].
738 S. Banerjee et al.

Zein: The Corn Protein

Zein is a protein found in maize, which comes under the category of prolamine that is
found exclusively in cereals. It is similar to hordein protein found in barley and
gliadin protein found in wheat. Zein is known for its commercial importance which
consists of 45–55% of whole corn protein. Zein is basically an amorphous polymer
with plasticizing viscoelastic behavior and thermal stability. In the year 1821, John
Gorham identified zein presence in the endosperm, as alcohol-soluble protein. From
that time, zein has received interest from the scientific community for its possible
industrial applications as polymer. Zein has its characteristic soft and ductile nature
after precipitation from solvent. Researchers worked to utilize the characteristics to
develop plastic kind of materials, with or without added additives. After many
efforts, commercial production of zein began in the year 1939 from corn gluten
meal [4, 21, 23, 39, 49].

Zein Processing

Zein is water insoluble but is soluble in alcohol or high pH alkali solution (pH 11).
The presence of higher amount of nonpolar amino acid residues and less amount of
basic and acidic nature amino acids causes the abovementioned solubility charac-
teristics of zein. Zein bodies are located in the cytoplasm of endosperm cells in
between the starch granules. SDS-PAGE analysis revealed that zein is composed of
two distinct bands of molecular weight 23 and 221 kDA and minor bands of 13 and
9.6 kDA. Zein consists of two different peptides of different molecular size, solu-
bility, and charge, namely, α-zein and -zein.
α-Zein is the prolamine of corn soluble protein which is soluble at 95% ethanol.
This represents nearly 80% of total prolamine present in the corn, and α-zein is the
most abundant protein in commercial zein.
β-Zein is not soluble in 95% ethanol, but gets soluble in 60% ethanol solution.
This second category of zein is not stable and tends to coagulate, henceforth not used
for commercialized production.
Besides this, some other researchers categorized zein protein fractions based on
other techniques. Hydrophobic characteristics of zein were reported because of
larger peptides. Argos et al. [5] suggested high helical content possessing a
rod-like structure, wheel model for zein, with nine homologous repeating sequences,
all arranged in anti-parallel form, altogether stabilized by hydrogen bonding of slight
asymmetric nature. Matsushima et al. [32] presented revised Argos et al.’s [5] model
based on small-angle X-ray scattering (SAXS) of α-zein and concluded that α-zein
particles existed as asymmetric particles of 13 nm length and the model was
proposed as an elongated prism-like shape with axial ratio close to 6:1 [24, 28, 49].
For zein production from corn, it has to be extracted with a suitable solvent.
Nonpolar amino acids are abundant; hence, solvent used for the extraction needs to
have mixed properties, having ionic and nonionic polar groups and nonpolar groups
and may be pure solvents or mixed solvents. Different types of solvents may be used
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 739

for the extraction process, i.e., nonaqueous solvents like alcohol solution, ketones,
amide solvents, esters, glycols, etc., under different conditions. The dissolving
solvents must contain –OH, –NH2, –CONH2, or –COOH groups. Other researchers
have reported several organic solvents for zein extraction [45, 49]. Zein solubility in
water may be increased by acidic or alkaline deamidation or enzymatic modification.
Besides solvents, enzymatic hydrolysis can also be used to make zein soluble in
aqueous medium [49]. Different approaches are used for extraction of zein, and
major differences in the operation can be classified under the following heads:

• Nature of raw materials used

• Types of solvents used
• Purification protocol
• Method of recovery

For example, raw, dry milled corn may be used as raw material, where zein exists in
native form. However, the content of zein is much less, resulting in a reduction of
yield and concentration of zein in the extractant. During dry grind ethanol pro-
cessing, the protein received at the end is called as distillers’ dried grains (DDG) or
DDG containing “soluble” (DDGS), which contains 27–30% total protein content,
and it is not considered as desirable raw material for good quality zein production.
For solvents, most published literatures have indicated usage of two solvents, i.e., a
polar solvent like aqueous ethanol or isopropanol for extraction and another nonpo-
lar solvent like hexane or benzene for defatting and decolorization [49].

Zein in Food and Non-food Sectors

Zein finds its wide application in different sectors including food and non-food
domain. Zein has the capability to form tough, glossy, hydrophobic, greaseproof,
antimicrobial, flexible, compressible, grease, and solvent resistance coatings. Zein
protective coating on carton stock was found to be quite advantageous for transport
or maintaining stocks of doughnuts, crackers, pies, cookies, etc. Zein was also used
for coating fiber boards and papers for its grease resistance and other properties. In
pharmaceutical industries, zein finds its application for its film-forming ability and
antimicrobial properties for coating tablets. In food industries, zein found various
applications as coating materials for fortified rice, edible nuts, gums, confectioneries,
and candies. For the last two decades, a number of applications of zein were found in
the various fields. However, with the introduction of synthetic and petroleum-based
ingredients, zein became comparatively expensive. Recent interest on the develop-
ment of polymeric biodegradable materials made zein again topic of interest for its
various applications in the domain of biodegradable films, coating, and plastic
applications. Novel plastic materials made from zein were found to be less flamma-
ble and less expensive, which made its applications for fabric stiffeners, artificial
leathers, lacquer, filament, and films. As reviewed by Ibrahim et al. [21], the USA
740 S. Banerjee et al.

produces highest quantity of corn globally, of which 50% is used for feed purpose,
25% for ethanol production, and remaining 25% used for export and manufacturing
of food, fiber, and industrial purposes. Some specific applications of zein are in
adhesives, binders, biodegradable plastics, chewing gums, edible moisture-resistant
coating for food products, cosmetic powder, acid-sensitive drug delivery system,
textile fiber, microspheres, microencapsulated pesticides, paper surface coating,
reverse osmosis membranes, starch-based polymers, etc. [4, 21, 39, 41, 49, 55].

Zein-Based Nanoparticles

Nanoparticles have wide industrial and day-to-day life applications, but one major
problem associated with some nanomaterials is their toxicity [19, 20, 50]. Nanotech-
nology finds its various applications in food, bioprocessing, and agriculture sectors
[19, 20, 43]. Nutrition and quality wise, nanomaterials may have higher values
compared to conventional materials. Zein protein as food, it is considered safe.
Various applications of zein have been discussed, and adding nanoparticles with
zein would find more applications. Zein comes under the category of “Generally
Recognized as Safe” (GRAS) biomaterials [17], and no report or published literature
was found on toxic behavior of zein nanomaterials.
Osborne [36] reported about solubility of maize kernel proteins in 60–99%
alcohol but not soluble in water. Kasaai [24] reviewed about preparation of zein
nanoparticles by liquid-liquid dispersion method. In this method, zein extracted from
corn was taken and dispersed in aqueous ethanol solution and subjected to shear for
getting smaller droplets [58]. Due to inter-diffusion of ethanol and water, there was a
reduction in solubility of zein; hence zein precipitates as zein nanoparticles. Zein
nanoparticles can also be formed by spray-drying process, where zein was initially
dissolved in a solvent and is followed by spray drying. Zein nanoparticles made by
this method had 200 nm dimensions approximately. Muller et al. [34] reported their
work on development of microsphere-based zein by dissolving zein in aqueous
ethanol solution under continuous stirring. The solution was vigorously stirred for
15 minutes, and water was added slowly, which changed the ethanol to water ratio
from 1:4 to 2:3 (v/v), causing decrease in zein solubility and creation of zein
microsphere droplets. Obtained insoluble microspheres were separated from the
solution by vacuum filtration and then freeze-dried for 24 hours. Similarly, zein-
chitosan microspheres were also prepared. Similar principle of zein’s solubility in
mixed solvent was used for preparing microspheres and nanospheres for various
applications like pharmaceutical drug encapsulation, essential oil encapsulation, etc.
This method is simple and convenient to be adopted over other methods. The
described method is called anti-solvent precipitation method where the precipitation
of particles happens due to change in solvent concentration, in which the precipitate
remains in soluble condition. This method is simple to understand and adopt for
preparation of zein microspheres. In the overall process, concentration of zein and
ethanol in the dissolving solution is important, which affects the colloidal particle
forming process. Rise in ethanol concentration results in smaller-sized particles,
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 741

whereas high zein concentration leads to increase in particle dimension. Though

ethanol is primary solvent, methanol and isopropyl alcohol may also be used for
similar colloidal particle formation [40, 58]. Guo et al. [16] reported their study on
nanostructure of zein in aqueous ethanol solution, where it exists in small globular
form of dimension between 150 and 550 nm. The film formation mechanism was
also explained.

Applications of Zein-Based Nanoproducts in Food and Nutritional

Sectors

Food and Nutritional Applications

Zein is found in the endosperm of corn which has negative nitrogen balance and lacks
basic and acidic amino acids, i.e., tryptophan and lysine. Zein has poor water solubility
and doesn’t contain all essential amino acids, which makes zein not ideal protein
source for human consumption. As a food, zein was considered waste protein and
didn’t attract much attention, until its novel applications were found in different fields.
As a food source, zein may be not suitable, but as odorless and tasteless base material,
zein nanoparticles may be used as excellent edible carriers for bioactive substances
[58]. Zein-based nanomaterials are hydrophobic in nature, get digested slowly, and
have better biocompatibility, for which zein-based nano-delivery systems are consid-
ered good option compared to other protein sources for oral intake. Its water insolu-
bility property provides a moisture barrier for the coated materials, which in hand
increases the storage life and delayed degradation rate inside the gastrointestinal tract.
By varying the particle size, residence time inside the gastrointestinal tract can be
varied. Reduction in particle size would increase the residence time of the encapsu-
lated materials inside the gastrointestinal tract, which can be extended where slow
digestion rate is required for controlled release of encapsulated active materials
[24, 26, 47]. Zein nanomaterials can be utilized for nano-encapsulation of dietary
supplements [52].
Zein and chondroitin sulfate composite nanoparticles were prepared by anti-
solvent precipitation method for curcumin delivery. Degeneration resistance of
zein-chondroitin sulfate nanoparticles was improved by addition of chondroitin
sulfate, which was also responsible for increase in encapsulation efficiency of
curcumin. Developed nanoparticles showed good stability between pH 3 and
8 and thermostability till 80  C. Hydrophobic nutrients like curcumin in functional
foods can be delivered using zein nanomaterial base, which was also found to be
biocompatible [27]. Yuan et al. [56] reported about lutein as a beneficial bioactive
compound but with limited applicability since lutein is poorly soluble in water, is
unstable, and has low bioavailability. For overcoming these challenges, Yuan
et al. [56] worked on encapsulation of lutein with zein nanoparticles coated with
sophorolipid. Encapsulated lutein showed stable behavior with increased water
solubility and much better biocompatibility and bio-accessibility. Similarly, zein
nanoparticles can be used for encapsulation and stabilization of active biomolecules
742 S. Banerjee et al.

like quercetin, fucoxanthin, resveratrol, etc. [56]. In another study reported by Hu

et al. [17], zein-lutein nanoparticles were produced using solution-enhanced dispersion
by supercritical fluid method (SEDS). Spasojević et al. [51] reported their work on
development of composite zein/rosin nanoparticles by anti-solvent co-precipitation
method at different zein/resin mass ratio. The developed nanoparticles were found
suitable for carvacrol encapsulation. Encapsulation of nutraceuticals is important to
protect them from unfavorable storage and gastrointestinal conditions while develop-
ing new therapeutic functional foods.
Pickering emulsions can be defined as those emulsions which can be stabilized by
solid particles located at the interface between two phases. They are considered
much more stable compared to other emulsions stabilized by surfactants or bio-
polymers. Pickering emulsions have amphiphilic behavior, but still they are able to
stabilize the emulsion. They may be used for encapsulation of water-insoluble
bioactive compounds, although very few food ingredients possess capability to be
used as edible pickering emulsions, out of which zein is one. Babazadeh et al. [6]
worked on replacement of ethanol with non-flammable polyethylene glycol (PEG
400) for the manufacturing of zein nanoparticles for making zein-carboxymethyl
cellulose complexes. These complexes stabilized water in oil (W/O) emulsions and
were used for successful nano-encapsulation of rutin, a hydrophobic nutraceutical.
Carboxymethyl cellulose ensured better particle size, encapsulation, and stability
and more release time. There is growing demand for plant-based proteins with
unique textures. Mattice and Marangoni [33] studied on the rheological properties
of self-assembled zein network, in comparison with gluten network, chicken muscle
tissues, and cheddar cheese. Zein network showed stronger and elastic structure after
24 hours in comparison with meat analogues. However, more investigations need to
be carried out for the improvement of zein network strength and overcoming the
brittleness. Melting characteristics of zein and cheddar cheese were found to be
similar. These studies raise the hope for plant-based meat.
Hence it can be concluded that zein finds its wide application in food and
nutrition, especially encapsulation of unstable dietary supplements and bioactive
compounds like lutein, curcumin, and rutin. In their pickering emulsion form, zein
nanoparticles were successfully adopted for encapsulation of nutraceuticals. Also,
studies have shown the ability of zein network for the development of animal meat
alternate.

Shelf Life Extension of Food

Shelf life and safety are two major requirements of foods, and encapsulation by zein
nanomaterial along with active compound will be helpful to extend the shelf life of
food without compromising food safety. Efficient food-grade antimicrobial agents
having no toxic effects are in demand due to raising awareness about food safety
among the consumers and producers. Essential oils like thymol and carvacrol
contain phenolic hydroxyl groups, which are known for antimicrobial effects
which make these compounds natural antimicrobial agents. However those essential
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 743

oils are insoluble in water limiting their application in foods. Hence, those essential
oils were nano-encapsulated using zein nanoparticles by liquid-liquid dispersion
method which makes them well dispersed in water. Nano-encapsulated essential oils
were found suitable for food preservation [53].
Sanchez-Garcia et al. [46] reported their work on the development of nano-
biocomposites prepared from carrageenan blended with zein. Here, mica clay was
used as additive and glycerol as plasticizer. Developed biocomposite was concluded
to have high potency for its application as packaging films or coating for enhance-
ment of food shelf life. Epigallocatechin gallate is a major tea polyphenol, which has
higher antioxidant activity, but is not stable under high temperature, oxygen con-
centration, and pH and easily gets oxidized. Liang et al. [26] worked on the
preparation of zein-coated chitosan nanoparticles for the encapsulation and delivery
of epigallocatechin gallate, where it was claimed that zein coating increased the
controlled release of epigallocatechin gallate. These encapsulated nanoparticles
would be helpful to prevent lipid oxidation and increase the shelf life of fat-rich
food products [7]. Considering the poor water resistance properties of zein electro-
spun nanofibers, Niu et al. [35] fabricated zein/ethyl cellulose nanofibers for the
encapsulation of cinnamon essential oil, and they were used for the preservation of
Agaricus bisporus. Essential oils encapsulated in nanofibers were found suitable,
nontoxic, and biodegradable and to extend the shelf life of Agaricus bisporus.
Zein in its nano-form can be utilized for the encapsulation of natural essential oils
and is found to be a safe food preservative. Also zein nanomaterials have been
credited for stabilization of unstable essential oils and ensuring controlled release.
Zein can be used for making biodegradable packaging films, and incorporation of
antioxidants and antimicrobial agents ensures the extension of shelf life of food.

Micronutrient Encapsulation

Carboxymethyl chitosan (CMCS)-coated zein nanoparticles were developed using

low energy liquid-liquid dispersion method. Here, vitamin D3 was initially encap-
sulated into zein and then coated with CMCS. This complex was successfully used
for delivering vitamin D3. Encapsulated hydrophobic nutrients in zein/CMCS com-
plex nanoparticles would have better stability and controlled release property
[29, 49]. de Boer et al. [12] reported about lutein, which is a type of water-insoluble
carotenoid. Lutein is a permitted food color but is sensitive towards ultraviolet and
visible light and hence suffers from instability as a food colorant. de Boer [12]
prepared lutein-zein colloidal particles using anti-solvent precipitation method, and
ascorbic acid was added as antioxidant. It was found from the study that zein
nanoparticles were capable to protect lutein from degradation and antioxidant
ascorbic acid helped to further improve the photostability of lutein. Zein nano-
particles are suitable edible carriers of flavor compounds [29].
Bioactive materials, micronutrients, and other food components which are not
stable or having poor water solubility can be stabilized by using zein nano-form
along with other additives for longer storage life.
744 S. Banerjee et al.

Biodegradable Films

Synthetic polymers are widely used for different applications including food pack-
aging, but due to their nondegradable nature, environmental impact, and societal
awareness, they are not advisable. Hence, biodegradable films have received grow-
ing interest particularly in food packaging sector [15]. Zein films can be formed
along with plasticizers to improve their elasticity. However, the film’s mechanical
and physical properties were not near to synthetic films. Luecha et al. (2010)
reported the fabrication of zein montmorillonite (MMT) nanocomposite films
using solvent casting and blown extrusion technique. It was concluded from the
study that blown extrusion method resulted in the development of nanocomposite
film with better thermal resistance and solvent casting resulted in the formation of
films with better tensile strength. Several protein sources have been used for
biodegradable film development, out of which zein is considered most advantageous
film-forming material after physical/chemical processing, due to its tough, glossy,
hydrophobic, greaseproof, and antimicrobial properties. Ultraviolet/ozone treatment
on zein films controls the surface hydrophilicity, resulted from the conversion of
surface methyl groups to carbonyl groups. As a barrier material, zein is excellent,
and with controlled surface characteristics, it has several roles in the packaging
applications of food and non-food products [48].
Zein nanoparticles may find their utilization in improving the strength of bioac-
tive food packaging [29]. Xin et al. [54] developed zein and potato starch-based
biodegradable films containing chitosan nanoparticles incorporated with curcumin.
These films delayed physical/chemical changes in Schizothorax prenati fish fillets
and extended the shelf life till 15 days. It was further reported that films had good
mechanical properties, barrier properties, and oxidation resistance along with anti-
microbial and antioxidant properties. This packaging film was concluded to be a
better biodegradable alternative for improving storage quality and extending shelf life
of fish fillets. Composite films of hydroxypropyl methylcellulose were fabricated with
zein nanoparticles, and they showed decreased vapor permeability. While making
cellulose film, addition of zein nanoparticles showed the enhancement of film elastic-
ity at lower concentration [15]. Cheng et al. [10] reported about development of edible
packaging film using zein and chitosan as base materials along with phenolic com-
pounds and dicarboxylic acids, which were able to be recovered from the composite
film, and the developed film showed antioxidant and antimicrobial activities. In
another study, nano-TiO2-modified zein/chitosan films were prepared, where it was
found that addition of TiO2 nanoparticles could improve the mechanical characteris-
tics, hydrophobic properties, and thermal stabilities of the composite film. The devel-
oped film could be used for medical and food packaging applications [42]. In another
study, Oymaci and Altinkaya [37] reported their work on bio-nanocomposite film
development by solution casting method, where whey protein isolate was used along
with zein nanoparticles coated with sodium caseinate.
Addition of zein nanoparticles resulted in better water vapor barrier and mechan-
ical properties to films which could be used as biodegradable food packaging
materials. Zhang and Wang [57] successfully developed inexpensive, simple, and
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 745

highly ordered biopolymer nanocomposites for the improvement of tensile and gas
barrier properties by using magnetic nanofillers, where zein acted as biopolymer
matrix. Kashiri et al. [25] developed active zein films incorporated with essential oil
(10%) of Zataria multiflora Boiss for antimicrobial activities, and sodium bentonite
clay (2%) was used for the enhancement of the packaging material properties, i.e.,
water vapor permeability, UV light barrier, tensile strength, Young’s modulus, etc.
Antimicrobial activities of the active films resulted in the reduction of microbial load
[25]. Zein particles were used as fillers for the production of gelatin-based biode-
gradable films. Tannic acid was used for the modification of gelatin/zein film by
solution casting method. This film showed the enhancement of mechanical proper-
ties and hydrophobicity [18].
Zein finds its wide application for film development for food packaging applica-
tions. Water barrier properties, high mechanical strength, and good thermal stability
are some of those properties which make zein-based film as a good biodegradable
packaging film. Addition of essential oils or polyphenolic compounds enables zein
films with antimicrobial or antioxidant properties which ensure the extension of shelf
life of packaged food.

Sensor Developments

Zein, due to its unique properties, makes it ideal material for surface-enhanced
Raman spectroscopy (SERS) platform for manufacturing biosensors. Unique surface
properties of zein film allow its adhesion with gold and surface nanostructure
modification by soft lithography. Besides this, zein is environment-friendly, low
cost, and available easily as byproduct of ethanol production. Jia et al. [23] reported
their work on development of novel biodegradable SERS biosensor made up of
inverted pyramid gold-coated nanostructure formed on zein film. The imprinted film
was bettered with deposition and fixing of gold nanoparticles created on the gold
film surface. This newly fabricated platform was used for the detection of pyocyanin
(a toxin released by Pseudomonas aeruginosa) in the rapid sensitive test. This nano-
sensor was able to detect pyocyanin accurately in the water and can be used as point-
of-care detection method. Aghaei et al. [1] developed halochromic sensor, by
integrating alizarin dye in zein electrospun nanofibers for real-time monitoring of
the quality of rainbow trout fillets (i.e., freshness). Developed sensor was found to be
rapid (with only 0.75 min response time) and highly sensitive. Sensor shows real-
time color change which can be used in the intelligent food packaging system.
Gezer et al. [13] developed biodegradable sensor platform for the detection of
peanut allergen (Ara h1 protein) by using gold-coated zein nanophotonic film with
surface-enhanced Raman spectroscopy (SERS). Developed biodegradable platform
was capable of detecting and quantifying the peanut allergen by using principle
component analysis (PCA). However, more studies are needed to be conducted to
increase the sensitivity and to develop real food applications. In another study, Gezer
et al. [14] reported about the development of biodegradable zein/gold surface-enhanced
Raman spectroscopy-based sensing platform for the detection of acrylamide.
746 S. Banerjee et al.

Acrylamide is known for its carcinogenic properties and possibly harmful for humans.
Presence of acrylamide resulted in a unique peak at 1447 cm 1, which was used for the
detection and quantification of acrylamide within 10 mg to 10μg/10 mL solution
concentration. This novel concept will be helpful for the future application in the
detection of acrylamide presence in the food sample. Jhuang et al. [22] reported on
the immobilization of laccase (the enzymatic time-temperature indicator) on electro-
spun zein fiber for increasing the stability. The developed system had good stability and
was found suitable for food quality monitoring and as intelligent packaging for food
application. Ma et al. [30] worked on the fabrication of nanostructured zein-based
SERS platform coated with gold, silver, or silver-shelled gold nanoparticles, and they
were studied separately for further enhancement of sensitivity for making it as sensitive
as nonbiodegradable-based SERS platform. For checking the sensitivity of developed
biodegradable sensor, Rhodamine 6G was chosen as a Raman active molecule. It was
found that silver-shelled gold nanoparticles gave highest enhancement factor than silver
or gold nanoparticles-deposited surfaces.
Zein nanomaterials were found to be capable of acting as a potential alternative to
nonbiodegradable materials while developing sensors with high sensitivity, low
detection time, and easy detection. In addition, zein films were found to have
applications in the development of active packaging materials for easy detection of
food spoilages and changes in the properties of stored foods and rapid monitoring of
food safety and quality.

Conclusions

Zein finds its wonderful applications in different areas, because of its biodegradable
nature and other unique functional properties. In nano-form, zein was found to have
average dimension varying from 50 to 200 nm and has a number of functions in food
and nutrition domain, like carrier of nutrients in the core of encapsulated system,
encapsulation of water-insoluble nutrient components (i.e., lipids, essential oil,
water-insoluble vitamins, antioxidants, etc.), stabilizing unstable bioactive com-
pounds (i.e., food flavors, colors, etc.), increasing bioavailability of food and
nutrients (i.e., vitamin D3, curcumin, etc.), and more. As nano-delivery vehicle,
encapsulated zein nanomaterials are also having wide applications for efficient and
target delivery. Healthcare and pharmaceutical applications of zein nano-form are
other domains which need to be explored more. Zein nanomaterials are found to be
biocompatible with humans, although more studies are necessary on the immuno-
genicity of zein nanoparticles under in vivo condition. Zein nanoparticles find their
application as the nano-biosensor of their unique surface characteristics,
environment-friendly nature, low cost, and easy availability. Nanoparticles are
claimed to be efficient delivery vehicles for many bioactive compounds, which
have the penetration capabilities in capillaries and cells due to their smaller size,
larger surface area, robustness, intracellular uptake, and controlled release at target
site. Odorless and tasteless characteristics of zein offer advantage as carrier material
for various bioactive materials. Several studies have already been done on zein-
32 Zein-Based Nanoproducts in Nutrition and Food Sectors 747

based nanostructures although more studies on cytotoxicity, degradation, and chem-

ical properties of these structures need to done. Future work needs to address the role
of chemical process modification on the biodegradability of zein and zein-based
derivatives. In-depth studies need to be done on the influence of zein dimensional
geometry on the biodegradability since area of exposure is proportional to zein
degradation rate under enzymatic environment.

Acknowledgments Authors thank Sri Sharada Peetham, Sringeri, and Jyothy Charitable Trust,
Bengaluru, for their support and facilities.

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Nanotechnology: A Revolutionary
Approach Toward Food Packaging 33
Mansi Rastogi, C. V. Bhavana, and Ravi-Kumar Kadeppagari

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752
Nanotechnology and Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
Efficient Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
Active Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
Smart/Intelligent Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
Detection of Spoilage and Pathogenic Microbes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
Freshness Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
Time–Temperature Indicators (TTIs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
Consumer Acceptability of Nanotechnology Products in Food Packaging . . . . . . . . . . . . . . . . . . . . 757
Challenges with Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
Role Played by Stakeholders and Regulatory Agencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
Case Scenario: India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762

Abstract
Nanotechnology is upcoming field, essentially for the nano-packaging of foods
with greater consumer acceptability. This technology has many potential benefits
in various areas like food safety, quality, processing, packaging, and delivery of
bioactive ingredients. Although consumer is aware of the hazards and safety
issues associated with nanofood packaging due to the migration of nanoparticles
into food materials, if adequately harnessed this technology could revolutionize
food industry globally. Nanotechnology, when applied to food packaging, could
be categorized into three parts. The first one is efficient packaging, where
nanomaterials and polymer matrix are mixed for improving the tolerance for

M. Rastogi
Department of Environment Sciences, Maharshi Dayanand University, Rohtak, Haryana, India
C. V. Bhavana · R.-K. Kadeppagari (*)
Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Department of Food
Technology, Jyothy Institute of Technology, Bengaluru, Karnataka, India

© Springer Nature Singapore Pte Ltd. 2022 751

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_92
752 M. Rastogi et al.

humidity and temperature and gas barrier for the packaging raw material. The
second one is active packaging, where a direct interaction is put forward between
nanomaterials and the food for increasing the resistance against microbes. The
third one is smart packaging, where food is tracked for adulteration and safety
through the changes that occur due to the interaction between the nano-packaging
and food. Nanofood packaging could be bio-based, promoting biodegradability
and making the packaging environmentally friendly. In addition, this packaging
generates lesser waste material with enhanced food product quality. Envisaging
the several challenges that nanofood packaging has to face due to the knowledge
gaps, this chapter will discuss how application of nanotechnology to the area of
food packaging could enhance the efficacy of whole packaging process and
balance the environmental aspects. The role played by stakeholders and regula-
tory agencies for improving consumer health will also be discussed briefly.

Keywords
Nanotechnology · Food packaging · Active packaging · Adulteration · Smart
packaging · Biodegradability

Introduction

Nanotechnology is promising intervention with a higher application potency in

multidisciplinary areas, i.e., biological sciences, engineering, chemistry, and phys-
ics. Sir Richard Feynman conceptualized nanotechnology (in 1959), a study that
involves manipulation of matter at atomic or molecular levels. It is an emerging area,
where control on matter at atomic or molecular scale is possible when minimum one
featured dimension is being measured in nanometer. Nanotechnology includes
fabrication, accountancy, and maneuvering of nano-range (<100 nm) molecules
[18]. They are commonly classified and arrayed based on their features, size, and
structural composition [3]. Polymers are redesigned, manufactured, and processed
by filling them with nanoparticles for increasing their efficiency [17].
Food industry is facing a lot of pressure to satisfy consumers with respect to food
safety and healthy food products. Food contamination being biological, physical, or
chemical could significantly alter food quality and property, making it unfit for
human consumption [19]. Its contamination could happen at any stage in a food
chain, from production phase to final consumption phase. Consumers should be
motivated for demanding properly labeled food items which are safe, nutritious,
minimally processed, and ready to eat. Furthermore, the authenticity and safety of
these food items are required to be monitored timely within the supply chain of food.
Food regulatory authorities, manufacturers, traders, and buyers are in consistent
need of efficient and modern cost-effective tools that will monitor the quality of
packaged food.
Recently, food industry showed a remarkable growth by adapting innovative
packaging instead of traditional passive packaging process. In order to reach global
33 Nanotechnology: A Revolutionary Approach Toward Food Packaging 753

trends such as technological developments and consumer preferences, nanotechnol-

ogy was adopted as a stronger tool. This emerging field of research can cater several
sectors like medicine, food, electronics, agriculture, textiles, defense, cosmetics,
paper manufacture, agrochemicals, and H2O treatment [18]. In this connection,
food packaging can be thoroughly studied to develop methodologies that are
smart, intelligent, and efficient and balance the environmental issues [16]. In food
sector, nanotechnology could be utilized to monitor food processing, safety, bio-
availability, packaging, encapsulation, detecting pathogens, etc. This technology
encourages application of active packaging and offers multiple advantages over
standard food packaging like enhancing temperature resistance, recycling, resistance
to flame, better durability, and optical and barrier characteristics. It aims to detect
pathogens in nano-packaged foods and reduce/retard microbial growth once the
packet is unsealed by the consumer and then rewrapped for further usage [36]. Addi-
tionally, it favors the environment while improving the processability (lowers
viscosity) and ensuring competent delivery of these active constituents into biolog-
ical systems with minimized costs. Such headways mark it as an ideal candidate for
packaging of food in wide arrays like processing and packaging of meat, cereals,
confectionery, cheese, and boil-in-the-bag foods. It could also be applied while
extruding fruit juices, dairy products, beer, and carbonated drinks [34]. Nano-
packaged foods use nanomaterials as nano-fibers/nanoplates and nanocomposites
which will be integrated into polymers to configure a whole unit.
Nanotechnology being a more versatile approach could open a lot of avenues in
human life, improving health, quality of life, and wealth. However, one should seek
pros and cons too, taking necessary precautions while using nanotechnology and
considering its impacts on human health and environment [18]. In this chapter, we
will be discussing the several challenges encountered by nanofood packaging due to
knowledge gaps and how nanotechnology could enhance the efficiency of the whole
packaging process and balance the environmental aspects.

Nanotechnology and Food Packaging

Food packaging will continue to grow along with insurrections in material science,
fulfilling modern consumer demand to sustain the food quality with an extended
shelf life. Food commodities are required to be packaged properly and hygienically
and transported in such a way to avoid any alteration in its quality before reaching
consumer. To aid this, innovative packaging system should preserve the items, help
in effective delivery, and facilitate communication through the supply chain. Nano-
technology creates materials of nanometer scale while controlling the release of
preservatives/antimicrobials, ultimately increasing the packed product shelf life.
Nanomaterials possess better packaging barriers that maintain quality of food
throughout shipping and storing and protect poultry or meat from pathogenic
microbes. Thanks to their unique multifunctionality, food industry is experimenting
with a variety of engineered nanomaterials, such as nanometer salt grains that reduce
salt consumption while increasing the area of surface, thus resulting in minimizing of
754 M. Rastogi et al.

usage since little amount of nanosalt tends to provide the same original savory taste
of that food. Nanocapsules synthesized by encapsulation process act as carriers of
vitamins/minerals in foods and drinks without modifying their taste and appearance
and transmit them within human stomach. However, a possibility of unintentional
food contamination through migration exists. Several engineered nanomaterials
have been introduced as functional additives, i.e., nanoparticles of silver (AgNP),
nanoclay, nano-TiO2, nano-ZnO, and nano-TiN [32]. Each of them possesses dif-
ferent chemical structure and distinct properties toward host material which result in
diverse functions when applied to packaging [26].
Nanoclays (silicates) are finely grained, sheet-structured minerals which occur
naturally and help to create homogeneous matrix of polymer to enhance barrier
properties. The AgNPs are atomic clusters of metallic silver, engineered for antimi-
crobial purposes as they possess higher surface area/unit mass. They have greater
potential to release silver ions than the bulk silver. Nano-ZnO (less toxic) and nano-
TiO2 promote photocatalytic reaction by generating reactive oxygen species (ROS)
which oxidize bacterial cytoplasmic membrane and lead to cell death. Another
approved nanomaterial, nano-TiN, is generated by high temperature heating of
TiO2 in a nitrogen gas, and it is commonly used for giving mechanical strength to
food packaging materials.
Nanotechnology, when applied to food packaging, may be categorized into three
parts. The first one is efficient packaging, which involves the formation of a complex
between NPs and polymers for improving the package tolerance to adverse conditions.
The second one is active packaging, where a direct interaction is put forward between
nanomaterials and the food for increasing the resistance against microbes. The third
one is smart packaging, where food is tracked for adulteration and safety through the
changes that occur due to interaction between the nano-packaging and food.

Efficient Packaging

Packaging being an important component to maintain the segmental flow in food

industry, nanotechnological interventions might play a massive part in the packaging
of food [9, 27]. The concept of efficient packaging involves mixing of nanomaterials
and matrix of polymer for improving the tolerance for humidity and temperature and
to develop a gas barrier for the packaging raw material. Nano-based indicator/sensor
(s) are directly integrated either in food products or material of food packaging. It
further includes their interaction with internal food components and external envi-
ronmental factors. These advanced polymers augmented with nanomaterials, by
virtue of being smaller in size, hold a higher surface-to-volume ratio and exhibit
enhanced surface activity and physicochemical properties. They get affixed to
anticipated polymers resulting in improved properties like mechanical strength,
thermal stability, and electrical conductivity.
Besides addressing environmental apprehensions, they improve food packaging
properties (mechanical and barrier) of existing polymers. Final packaging material
works toward combating any serious interface between food substances and
33 Nanotechnology: A Revolutionary Approach Toward Food Packaging 755

packaging. In connection with environmental issue, effective packaging checks the

concerns related to consumer’s health, quantity of generated waste material, barrier
shielding (gases and light), biodegradability of package, and emission of CO2.
However, challenges such as overcoming safety and regulatory barriers and cost–
performance competitive ratio need regular upgrading of polymer nanomaterials to
pack the food materials effectively [30].

Active Packaging

Active packaging involves direct interaction with food or the environment. It is

purposely designed packaging system which incorporates constituents either to
release (antimicrobial or antioxidants) into or absorb (oxygen or water vapor) from
the packaged food. Unlike conventional food packaging, carrier components can
interact directly with internal and/or external elements, thus fueling process of
improving the product shelf life, safety, and quality.
Active compounds (e.g., zinc oxide) amalgamated with O2, preservatives, anti-
microbial agents, ethylene removers or absorbers of water vapor, etc., will boost the
shelf life. Further certain factors like light, quality, and size of particles positively
influence the antibacterial activity. The ZnO will directly act upon the microbial cell
wall, destroys bacterial cell integrity, liberates antimicrobial ions (Zn2+), and gener-
ates ROS [29]. Another compound, PBS (polybutylene succinate), when amalgam-
ated with zinc oxide composite films, displayed significant antimicrobial resistance
and zero odor [20]. Similarly, silver nanoparticles and coatings displayed effective
antimicrobial properties.
Oxygen scavengers were used. Oxygen is known to reduce product shelf life
owing to rapid degradation including browning, aerobic microflora growth, color
changes, rancidity, vitamin depletion, odors, and off-flavors. Specifically, during
storage, food products (fruits and vegetable) produce certain metabolites that accel-
erate the ripening (postharvest), thus reducing product shelf life. These detrimental
effects can be circumvented by eradicating/lessening O2 entry within headspace of
package via vacuum sealing, inert gas atmosphere (N2, CO2) creation, or oxygen
absorbent usage [23]. For example, an O2 scavenger film, incorporated with TiO2
NPs, or a high-density polyethylene (HDPE) film integrated with iron–kaolinite
could act as an ideal substitute for packaging film. Here, deoxygenated closed
environment will be formed due to vapor removal (photocatalytic properties of
TiO2). The constant vapor removal approach could be utilized while doing long
transport to delay the fruit ripening.
Another method used for active packaging in food industry is enzyme immobi-
lization, where enzymes are directly utilized in food matrix. These can play multi-
faceted role due to their sensitivity to temperature, pH, and/or enzyme inhibitors
[25]. Along with boosting the process performance enzyme when immobilized at
nanoscale, tend to improve the surface area, enhance process atmospheric stability
and increase resistance to denaturing components [2]. Cholesterol reductase or
lactase and glucose oxidase are utilized in active packaging.
756 M. Rastogi et al.

Smart/Intelligent Packaging

This packaging senses the microbiological or biochemical changes in the food

components, which can be the reason for food spoilage. These changes include the
growth of specific pathogens or gases that develop in food which could be used for
tracking safety of food and to avoid counterfeiting in processed foods [18]. Herein,
nano-packaging has been found to be very effective for package designing, improv-
ing quality and shelf life of product by releasing antimicrobials, enzymes, antioxi-
dants, and flavor [11]. In addition, intelligent/smart packaging might just advance the
communication part of a package as well by maintaining register to recognize
package elements (existing quality or condition of the food). Several innovative
communication approaches, such as nanosensors, oxygen sensors, time, tempera-
ture, freshness indicators, etc., can be used [14].
Nanosensors are applied to label or coat to ensure package integrity and detect leaks
in response to environmental changes. They indicate time–temperature variations or
microbiological safety (foodstuff deterioration) [5]. Gas sensors detect the gaseous
analyte present in the package. Optical O2 sensors work (based on luminescence
quenching) by directly interacting with the analyte, whereas the opto-chemical sensors
use gas analytes (hydrogen sulfide, CO2, etc.) to check product quality.
The O2 sensors are utilized in detecting defects of food packaging, carried out under
vacuum or with nitrogen gas. In case of UV-based colorimetric O2 sensor (with TiO2
nanoparticles), UV irradiation causes bleaching that remains colorless unless exposed
to O2 again. Another modified atmosphere packaging (MAP) sensor deliberately
reduces the headspace O2 concentration either to an optimal level or eliminate it
entirely as per product requirements depicting enhanced oxygen sensitivity.
The CO2 sensor is mainly used to monitor the freshness of packaged foods during
storage. A CO2 indicator based on chitosan with an additive, 2-amino-2-methyl-1-
propanol (AMP), was developed as an easily usable sachet to enhance signal strength.
Another opto-chemical CO2 sensor, optimized to CO2 sensitivity and O2 cross-
sensitivity, was mixed with a phosphorescent reporter dye and naphtholphthalein
and incorporated into package matrix [1].

Detection of Spoilage and Pathogenic Microbes

Smart packaging explores immunological assays and antibody–antigen interac-

tions for indicating spoilage of food and activity of pathogens in the packaged
material. Antibodies are conjugated to nanomaterials with high fluorescence effi-
ciency, such as quantum dots (QD) for the food pathogen detection (E. coli and
Salmonella). They have high sensitivity, wider and continuous absorption, and
narrow emission spectra and stability for photobleaching, with extended decay
lifetime. An UCNP-based sensor being extremely sensitive can be utilized to detect
bacteria, enzyme, pH, NH3, nucleic acid, protein, CO2, etc. Further, it can be
applied for multiple toxin and pathogen detection in food matrix and applied
successfully to label products.
33 Nanotechnology: A Revolutionary Approach Toward Food Packaging 757

Freshness Indicators

Smart packaging ensures product freshness and provides information about food
quality during transiting and displaying. These indicators react with microbial
metabolites (such as volatile amines and sulfides) to give visual information on
microbial attributes of a product [5]. For example, a transition metal like copper or
silver is coated (1–10 nm thick) on packaging (plastic/paper) film, and turning of this
coating to a darker color (after reacting with volatile sulfide) detects meat spoilage.
Another sensor consisting of carbon nanotubes was developed for detecting spoilage
for fruits (volatile substances and ethylene will be detected).

Time–Temperature Indicators (TTIs)

The time–temperature (environment) exploitations of food while storing, transiting,

and distributing are mainly responsible for a reduced food shelf life. To counter this
situation, TTIs are utilized to screen thermal history of food product, allowing
retailers to make sure safe food storage throughout supply chain [25]. This further
helps consumers to determine the quality of food product while purchasing and helps
manufacturers in monitoring supplied foodstuff [15]. The three types of TTIs that
link the color development to change in quality of food due to temperature change
have been mentioned below:

(i) Abuse indicators: work when a particular temperature is attained

(ii) Partial temperature indicators: display the time–temperature history, when the
temperature exceeds a critical set limit
(iii) Full temperature indicators: constantly monitors the temperature changes with
time

Consumer Acceptability of Nanotechnology Products in Food

Packaging

The development of a new product is mapped on consumer acceptance which will be

influenced by environmental and health concerns of such products [24]. Nano-
packaged foods are generally low priced with wider benefits, which could be
consumer-friendly but with anticipated health risks. When used as food additives,
nanomaterials will be directly contacting human organs, resulting in higher human
exposure as per the concentration present in food and quantity of food consumed.
Acceptance of nano-packaged products of food can be improved through the infor-
mation channel, education, and building social trust among consumers. Besides
educating the consumers, research focusing on know-how to apply nanotechniques
in food industry (processing and packaging) and their effects after human exposure has
to be done. Additionally, research should explore bioavailability and biodistribution of
these nanomaterials and also monitor their toxicity.
758 M. Rastogi et al.

Nanofood packaging being the fastest growing research field aims to alter the
traditional packaging system and to ease storage, transportation, and handling of
such food products. This ensure food products are consumer friendly, prevent
leakage and safe against microbial contamination and provide requisite information
on the enclosed food products. Nanomaterials are mixed with polymer matrix
(packaging material), which enhances gas barrier properties and resistance to humid-
ity and temperature [28]. Some major nanoparticles that confirm to food packaging
standards are silver, titanium nitride, nano-titanium dioxide, nanoclay, and nano-zinc
oxide [32]. Furthermore, the development of nanobiodegradable materials to replace
the nondegradable plastic polymer materials could aid in monitoring the global
environmental problem [11]. Nanosensors can be utilized as integral part of food
packaging, to track food conditions across food supply chain. Nanoparticles in
solution, electronic noses, nano-cantilevers, array biosensors, and nano-test strips
can be utilized as sensors to control food deterioration and spoilage [6]. Additionally,
they detect gases evolving from food and alert the consumers about food spoilage
through color changes. For example, nanosensors have been successfully utilized for
detecting E. coli and antimicrobials causing contamination of the packaged food.
An increased utilization of nanomaterial additives in foods is under radar, whether
for flavor or color. Nano-edible coatings are utilized to preserve food quality and
prevent microbial food spoilage [4, 6]. They are being used as gelatin-based edible
coatings, chitosan/nano-silica coatings, chitosan film with nano-SiO2, and alginate/
lysozyme coatings to extend food freshness and quality. However, a check is
required on the fate and toxic effects of these nanomaterials added to foods and
food packaging [7]. Nanoparticle exposure (e.g., Ag and carbon nanomaterials)
could induce allergic reactions like pulmonary inflammation, lung inflammation,
increased ROS production, etc., thus requiring an advanced research on food
allergen management [10]. In addition, heavy metal ions that are released from
nanomaterials will lead to main pathway toward toxic outcomes. These metal-
based nanoparticles when integrated with polymers could lead to betterment of
barrier and mechanical properties, initiate plastic photodegradation, and act effec-
tively to shield microbes. However, the long-term ill-effects of accumulated metal
ions on human body could not be ignored.
A comprehensive information regarding the nanoparticles (NP) and human
interface (cells, tissues, and organs) is required to understand its possible hazards
to human health. They could enter the body via three major routes, i.e., ingestion,
cutaneous exposure, and inhalation [13]. They inevitably enter and accumulate in the
bodily fluids (interstitial fluid) and biomolecules like lipids, sugars, and proteins
[4]. They might migrate and unintentionally raise safety concerns for consumers
depending on food and polymer properties (chemical and physical). Besides the
route, nanoparticle concentration, size, toxicity, solubility, duration of exposure, pH
value, molecular weight, diffusivity, temperature, and polymer structure, mechanical
stress and viscosity along with contact time are major affecting factors. Higher
surface area in comparison to the total mass of small NPs could lead to adverse
responses, enhancing the interaction possibility, with the biological molecules.
When these nanoparticles enter the bloodstream, blood vessel linings might get
33 Nanotechnology: A Revolutionary Approach Toward Food Packaging 759

diluted, promoting clot formation in blood, cardiovascular effects, hinder metabo-

lism and migrate into fetus. Apart from toxicity, nanoparticles (ZnO, asbestos, TiO2)
in foods could cause genotoxicity (human epidermal cells), fibrosis, lung tumors,
and carcinogenic effects. Some of them (MgO) can enter olfactory bundle (fore
brain) and through systemic inhalation travel to the whole brain. In case of Ag NPs,
their nano-size makes them permeable to the cellular barrier, generating free radicals
in tissues. These free radicals eventually display an oxidative stress-related mecha-
nism, ultimately causing oxidative damage to human cells and tissues [22].

Challenges with Nanomaterials

The mechanical and barrier characteristics regarding food packaging can be

improved by polymer blending, following conventional methods. This might require
the usage of complex multilayered films or blended polymers with higher production
and material costs creating complexities for the recycling process. Consequently, a
single-layered film with a bio-friendly material like nanoclay will be an appropriate
choice, with regard to manufacturing process, cost, and recycling potential. This
began with the usage of montmorillonite nanoclays with polymers like nylon,
polyethylene (PE), polyvinyl chloride (PVC), and starch for enhancing the barrier
and mechanical characteristics of the plastic packaging. It was presumed that this
may alter or influence the environmental aspects (physical, chemical, and biologi-
cal), including effects on humans. Nevertheless, levels of nano-exposure that could
cause toxicity (bioaccumulation) across food chain and environmental deterioration
still need comprehensive understanding.
Understanding the production, usage, treatment, recycling, and disposal of nano-
generated products (nanoparticulates) is of prime concern for having knowledge on
the environmental damage. This will also include the formation of ROS (reactive
oxygen species), phagocytosis function disruption, protein denaturation, and mito-
chondrial disconcertion as affected by the composition, dimensionality, structure,
uniformity, and aggregation of NPs. Herein, information about size-dependent
properties of these nanoparticles, specifically their miniaturization, can present a
better idea of their toxicological effects when they get associated with human cells,
tissues, and organs. In lieu of the above, the development of reliable analytical tools
to assess and conduct a safety risk evaluation about these engineered NPs is an
immediate need. This will further require investigation on the restrictions that
regulatory agencies can impose on their utilization in food components.
One such contraption involves a designed apparatus, to assess substrate and detect
food embedded engineered NPs, identifying their size and distribution being nonin-
vasive and unrestrictive. The substrate is utilized as reference material to collect
regulatory information, utilizing various methods like positron emission tomography
(radio-tracing), imaging and analytical systems, dynamic light scattering, optical
emission spectrometry (trace-level elemental analysis), and mass spectroscopy.
Another method to monitor harmful substances in food includes a sensor system,
consisting NPs. In this, a solution proficient to respond to changes, essentially for
760 M. Rastogi et al.

metal roughness and electronic states of adsorbate through electromagnetic and

chemical signal enhancement (result from chemisorption at the surface of NPs of
that particular biosensor), is traced [21]. Besides the abovementioned techniques,
Raman Nano Chip™ [33] is another proven food safety sensory system for detecting
NP migration in packaged foods. This device utilizes nanorods for collecting test
samples, through molecular adsorption onto nano-surface or a suspension of NPs
(polymeric, metallic, or oxide).
Besides abovementioned concerns, the nonbiodegradable nature of certain nano-
composites could trigger intense environmental impacts as well. Ambiguous results
regarding toxicity of NPs lead to vague situation and incomplete information. Thus,
ecotoxicological studies on these nanoparticles are mandatory before being com-
mercially applied. The studies describe that nanoparticles have lesser probability for
migrating into food matrix, being completely encapsulated by polymer matrix.
However, an unintentional mechanical impact or aberration on the food contact
surface could hamper the smooth properties of nanoparticles, releasing them into
food matrix. Hence, nanoparticle quality reassurance, ensuring full incorporation in
to films/molded articles by manufacturers, stands mandatory [31]. A safer nanofood
packaging requires systematic description and evaluation in silico, in vitro, and
in vivo, along with regulating factors (physical, chemical, and biological). Their
toxicity, metabolism, absorption, distribution, and lastly their excretion is necessarily
evaluated for risk assessment toward consumers [6].

Role Played by Stakeholders and Regulatory Agencies

As nanotechnology involves intensive knowledge, the government or regulatory

authorities and expert stakeholders must be capable enough to conduct risk assess-
ments and ensure their safe manufacturing, storage, and transportation. This essen-
tially requires the establishment of government frameworks that are effectual,
trustworthy, and legitimate. Besides this, the development of nanomaterials arguably
necessitates collaboration of interinstitutional and organizational, among a broad
range of social factors. However, an effectual collaboration will result only when
appropriate knowledge of problem definition, characterization, and their specific
concepts is gained. The attitude of experts toward risk assessment is generally
influenced by perceived benefits, specific application and regulatory tools, organi-
zational goals, and affiliation. In addition, factors such as self-rated knowledge,
ethical considerations, education level, and gender will influence risk assessment and
benefit derived. This information is ultimately utilized to develop risk assessment
policies, keeping in mind the opinions formulated by various stakeholder groups.
The experts with specialized knowledge in nanotechnology perceived lower risks
and higher benefits keeping in mind the ethical implications of the respective field.
They are majorly influenced with the value predisposition and heuristics, instead of
public outlook toward nanotechnology bylaws [8].
To be precise, research scientists will rather emphasize on benefits associated with
nanotechnology over their risks, whereas downstream scientists emphasize risks
33 Nanotechnology: A Revolutionary Approach Toward Food Packaging 761

over benefits. Thus, disciplinary nature of these experts (NGOs, academia, industry,
or government) impacts risk assessment involved in nanofood packaging (Johansson
and [12]). Conventionally, industries or trade organizations will endorse innovation
and commercialization, while environmental safety and public health are regulated
by environmental NGOs and governmental organizations [35]. Other than these,
ethical concerns and nanotechnology significance in the food packaging are deter-
mined by the respondent’s organization. Herein, organizational experts are more
concerned for ethical concerns and less positive toward guideline regulations.

Case Scenario: India

In India, for meeting the prerequisites of the growing population, nanotechnology

has been exploited in food industry for minimizing food waste and better product
safety. The groundbreaking nano-intervention in food industry has made it possible
to generate low-cost and highly potent results with respect to products. Strict
guidelines have been formulated for evaluating safety and toxicity associated with
NPs used for food industry. This further needs a multidisciplinary approach, for
modifying the existing policies and development of newer strategies and standard
guidelines with scientific understanding. Synergizing of data from different disci-
plines (chemistry, biology, materials science, engineering, physics, and medicine)
will make nanotechnology an important field for facilitating scientific and technical
prospects. Nanotechnology and nanoproducts in food sector are dealt under different
ministries and departments, requiring the interdepartmental and ministerial conjunc-
tion. They ensure that appropriate guidelines have been prescribed for ensuring the
quality, safety, and efficiency of the commercialization process of nanotechnology-
based innovations. Some provisions, placed globally for nanomaterials, are REACH,
OECD, EPA, AVMPA, and FAO/WHO with specified guidelines to verify and
validate quality, efficacy, and safety of the nanoproducts. Moreover, case-by-case
basis assessment approach accentuating higher benefit-to-lower risk ratio, compared
to the bulk counterparts, is advocated for NAPs.

Conclusion

Nanotechnology application in food industry with an improved outlook focused on

research could alter the whole food packaging scenario while providing increased
productivity of food and long-term economic benefits. Assessing safety of these
nanofoods in food preservation and packaging sector, they possess a huge positive
impact on environment, sustainability, and human health. Despite the advantages
with cost-effective returns of nanofood packaging, the associated potential health
risks have to be registered as well. Hence, dire need of filling the knowledge gaps by
balancing innovation and regulatory guidelines with robust and reliable risk assess-
ment tools exists. Apart from these, the consumer acceptability addressing benefits
and risks associated with nanotech foods with greater transparency should be
762 M. Rastogi et al.

improved. Lastly, better collaboration between stakeholders and regulatory agencies

favoring environmental and social interests will allow humans to enjoy these high
technology products safely.

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Application of Nanotechnology
for Encapsulation of Micronutrients 34
Chandan Kumar Sahu, Shelke Dhanashri Sanjay, and
Ravi-Kumar Kadeppagari

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
Core and Wall Materials Utilized During Nanoencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
Nanoencapsulation Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
Emulsification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
Emulsification/Solvent Evaporation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
Supercritical Fluid Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
Inclusion Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
Coacervation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
Nanoprecipitation or Solvent Displacement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
Drying Methods Used After Nanoencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
Improvement of Vitamin and Mineral Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Nanotechnology for Fortification of Vitamins and Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Nanoapproaches for Improving the Bioavailability of Nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Safety Issues with Nanoencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
Main Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771

Abstract
Nanoencapsulation of micronutrients is an important process in food and pharma-
ceutical industries. Advantages associated with nanoencapsulated micronutrients are
higher bioavailability, improved stability, and controlled release of active compounds
at the target site. This method is useful for encapsulating lipophilic and hydrophobic
micronutrients like vitamins, without compromising on safety of food and con-
sumer’s health. Nanoencapsulation can be novel approach for efficient micro-
nutrients’ delivery and protecting these compounds from destructive environment

C. Kumar Sahu · S. Dhanashri Sanjay · R.-K. Kadeppagari (*)

Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Department of Food
Technology, Jyothy Institute of Technology, Bengaluru, Karnataka, India

© Springer Nature Singapore Pte Ltd. 2022 765

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_93
766 C. Kumar Sahu et al.

during the processing and transportation. Nanoencapsulated micronutrients would

find their applications in fortifying complementary and staple foods so that nutritional
deficiencies can be overcome and food enrichment will happen. There is growing
consumer’s demand and subsequent industrial interest in food formulations for joint
administration of vitamins and other micronutrients for providing multidimensional
health benefits, i.e., bone support, promoting cardiovascular health, and helping to
boost immunity. Nanoliposomes with chitosan-loaded micronutrients were found to
act as more favorable nano-covering material and also enhance the muco-
adhesiveness and stability of the produced liposomal structures. Nanoencapsulation
of micronutrients has led to new horizon in food and nutrition fields, which is techno-
economically feasible for further commercialization. But one needs to address the
safety aspects of these nanoencapsulated carriers used for beneficial micronutrients’
delivery.

Keywords
Nanoencapsulation · Micronutrients · Bioavailability · Vitamins · Immunity ·
Nanoliposomes

Introduction

Nanotechnology led to next revolution in most of industrial sectors including food

and agriculture. It could revolutionize food industry with respect to processing,
production, and storage and by developing innovative products. It could also lead
to the improvement of sensory attributes and shelf-life of food products. In addition,
it could improve the bioavailability, thermostability, and water solubility of bioactive
molecules [7, 11]. In recent times, nanotechnology is focusing on improving the
properties of food packaging materials, developing nanobiosensors for the identifi-
cation of deterioration of quality and contamination in food, and developing nano-
encapsulation technologies or nanocarriers for controlled and targeted release of
micronutrients and nutraceuticals [12, 14]. But there are only few reports on the
nanoencapsulation with respect to food-related ingredients.
In the encapsulation process, the particles forming core materials were packed
inside the wall material for making capsules. This method was utilized for
protecting bioactive molecules like micronutrients, nutraceuticals, and antioxi-
dants from harsh environment and for releasing the molecules in controlled
manner at the target sites. Diameter of microcapsules will be in the range of 3–
800 μm and that of nanocapsules will be in the 10–1000 nm range. Nanocapsules
were vesicular systems where bioactive compound will be limited to cavity which
is surrounded by specific polymer membrane. The size of the particle will directly
affect delivery of bioactive molecules to the various sites in the body. Hence,
nanoencapsulation has greater potential for enhancing controlled release, im-
proving bioavailability, and precisely targeting bioactive molecules compared to
microencapsulation.
34 Application of Nanotechnology for Encapsulation of Micronutrients 767

Core and Wall Materials Utilized During Nanoencapsulation

The micronutrients and nutraceuticals constituting core can be hydrophilic or lipo-

philic. Few of the hydrophilic nanoencapsulated compounds are polyphenols,
ascorbic acid, other water-soluble vitamins, etc. Lipophilic nanoencapsulated mol-
ecules are β-carotene, phytosterol, lycopene, lutein, docosahexaenoic acid (DHA),
water-insoluble vitamins, etc. Hydrophilic compounds exhibit faster release rates.
Release kinetics of hydrophilic compounds will be dictated by suitable combination
of diffusion and erosion mechanisms. But lipophilic compounds result in incomplete
release since they are poorly soluble and have lower dissolution rates via erosion
mechanism. However, lipophilic molecules will exhibit high permeability due to
facilitated diffusion and active transport. They are readily absorbed through intes-
tine. Hydrophilic compounds exhibit slow permeability across the intestine via only
active transport.
Lipids or biocompatible polymers were used as wall materials while encapsulat-
ing micronutrients or bioactive molecules. Archaeosomes, nanoliposomes, and
nanocochleates were three kinds of nanocarrier systems that are based on lipids,
and they have applications in cosmetic, pharmaceutical, and food sectors. Naturally
available polymers like gelatin, albumin, alginate, α-lactalbumin, chitosan, and
collagen were also utilized while formulating nano-delivery systems. Whey protein
was used as nanocarrier to deliver minerals and vitamins and to improve bioavail-
ability of nutraceuticals [3].

Nanoencapsulation Technologies

These methods can follow either top-down or bottom-up approach. Emulsification/

solvent evaporation and emulsification methods follow the top-down approach,
whereas the supercritical method, coacervation, inclusion complexation, and nano-
precipitation methods will follow the bottom-up approach. Emulsification, supercrit-
ical fluid method, and coacervation methods may be utilized for encapsulating
hydrophilic and lipophilic molecules. But inclusion complexation, nanoprecipitation,
and emulsification-solvent evaporation methods are mostly utilized for lipophilic
molecules. Some of these methodologies are discussed below.

Emulsification

This method was generally utilized for encapsulating bioactive molecules within aque-
ous solutions by producing nanoemulsions. These emulsions will be colloidal disper-
sions consisting two immiscible liquids, and one (droplet sizes will be 50–1000 nm) will
be dispersed within another. This method has more potential for encapsulating higher
levels of oil-soluble food supplements and other nutraceuticals within different foods.
Lipophilic molecules like plant sterols, β-carotene, carotenoids, and fats are encapsu-
lated by using oil-in-water (o/w) emulsion, whereas water-in-oil (w/o) emulsion is used
768 C. Kumar Sahu et al.

for encapsulating water-soluble food molecules [16]. Nanoemulsions may be utilized

directly as liquids, or they can be dried to obtain in powder form through drying
methods like spray drying or freeze-drying.

Emulsification/Solvent Evaporation Method

This is a modified method of solvent evaporation. Here, polymer solution will be

emulsified into aqueous phase, and polymer solvent will be evaporated which will
induce precipitation of polymer as nanospheres. The bioactive molecules or micro-
nutrients could be made distributed finely within polymer matrix. Commonly uti-
lized polymers are PLGA, PLA, cellulose acetate phthalate, polyhydroxybutyrate,
ethyl cellulose, and PCL. High-speed homogenization or ultrasonication process was
regularly employed to obtain particles of small size. Encapsulation of curcumin into
a polymer (Eudragit S 100) was carried out by adopting this method, and it was
followed by freeze-drying [4].

Supercritical Fluid Method

Supercritical fluid may be either liquid or gas which will be utilized at a pressure and
temperature higher than its thermodynamic critical point. Above critical point, these
fluids will show the properties (low viscosity, high solvating ability, high diffusivity,
low density, and higher transfer rate of mass) which are in between the gases and
liquids. More compounds could be made supercritical, for example, N2, CO2, H2O,
and propane. Similar to the spray drying method, this method was used for encap-
sulating the compounds which are sensitive to heat. During this method, micro-
nutrients or bioactive molecules were solubilized with polymer using supercritical
fluid. Then mixture will be expanded through the nozzle. Solute particles will be
precipitated by evaporating the supercritical fluid. Lutein was encapsulated within
HPMCP (hydroxypropyl methylcellulose phthalate) by using this method. Bioactiv-
ity of the molecule was maintained, and thermal degradation was avoided [6].

Inclusion Complexation

In this method, generally ligand will be encapsulated into the cavity of the substrate
(shell) via van der Waals force, hydrogen bonding, or hydrophobic interaction.
However, molecules having appropriate cavities are least available in food industry.
Nevertheless, linoleic acid was encapsulated into α- or β-cyclodextrin through this
method to enhance its thermal stability [5]. This method was chiefly used for encap-
sulating the volatile molecules (essential oils) and vitamins. This method was useful
for preserving aromas. This method will lead to enhanced encapsulation efficiency and
stable core. But few molecules like β-lactoglobulin and β-cyclodextrin are suitable for
encapsulation via this method.
34 Application of Nanotechnology for Encapsulation of Micronutrients 769

Coacervation

During this process, phase separation of electrolyte (single or mixture) from the
solution occurs, and subsequently the new coacervate phase formed will be depos-
ited around active molecule. Hydrocolloid shell will be cross-linked with an enzy-
matic (transglutaminase) or chemical (glutaraldehyde) cross-linker to improve
stability of coacervate. The process will be simple coacervation, if one polymer
used, and it will be complex coacervation, if two or more polymer types used.
Capsaicin nanocapsules of 100 nm size were obtained through simple gelatin-
based coacervation process by using glutaraldehyde as cross-linking agent. Later
capsules were dried with vacuum oven [13].

Nanoprecipitation or Solvent Displacement

This method comprises the polymer precipitation from the organic solution and
diffusion of organic solvent into the aqueous medium. Here, solvent displacement
will lead to nanosphere and nanocapsule formation. Commonly used polymers are
PACA, eudragit, PCL, PLA, and PLGA. Curcumin was encapsulated into PLGA by
using PEG-5000 as the stabilizer [1]. Here nanoprecipitation was followed by freeze-
drying. These nanocapsules exhibited higher cellular uptake and enhanced bioactivity.

Drying Methods Used After Nanoencapsulation

Nanocapsules will be instable, and encapsulated molecules will be leaked due to

hydrolysis of the polymers used. Hence, their stability could be enhanced by drying
nanocapsule suspensions [10]. Hence, nanoencapsulation methods are utilized in
combination with drying methods in order to convert encapsulated suspensions into
a stable and dried form. Nanosuspensions are commonly dried by using spray drying
or freeze-drying method. Spray drying comprises transformation process where feed
suspension will be converted into dry particles by spraying it into hot drying
medium. Spray drying process is widely utilized in food industry as it incessantly
produces low-moisture dry powders. Spray drying method is commonly utilized for
encapsulating different food ingredients like vitamins, flavors, minerals, fats, and
colors. This will protect the ingredients and extend their shelf-life.
Freeze-drying or lyophilization process is used for dehydrating heat-sensitive
items and aromas. This process involves four stages, i.e., freezing, sublimation
(primary drying), desorption (secondary drying), and storage. This method will
lead to high-quality products which could be easily reconstituted, and they will
have prolonged shelf-life. This process is energy intensive and takes a long time for
processing. This process will lead to the formation of pores on the particles due to
sublimation of H2O, and it is completely not encapsulation since food ingredients
will be exposed as pores form on surface of particles. The effective alternative will
be spray freeze-drying method since it reduces drying time and pore size [2].
770 C. Kumar Sahu et al.

Proliposomes containing vitamin E were produced via thin-film ultrasonic disper-

sion followed by freeze-drying [15]. Vitamin E within proliposomes showed higher
stability and retention compared to traditional liposomes.

Improvement of Vitamin and Mineral Delivery

As they have smaller size, the compounds obtained after nanoencapsulation will get
absorbed very easily in the body. Various nanobased compounds are utilized for the
improvement of delivery of minerals and vitamins. Nanoemulsions can be utilized
for delivering multiple compounds sequentially or simultaneously. Solid lipid nano-
particles are stabilized by coating with surfactants, and they are made by using
emulsion technologies. They can be utilized for the delivery of hydrophobic mole-
cules. Liposomes can be utilized for delivering hydrophilic compounds. Whey
proteins can form nanoparticles, and they can be utilized for delivering different
hydrophilic molecules to the mucosa of intestine. Chitosan can form nanocapsules
which could be utilized for delivering various molecules orally. Nanoporous silica
could be utilized for delivering different hydrophilic nutrients to silica.

Nanotechnology for Fortification of Vitamins and Minerals

Food fortification is defined by FAO/WHO as addition of 1 or more number of

essential nutrients to food item, though it is present naturally in that specific food, so
that it will prevent the exhibited deficiency of 1 or more number of nutrients in the
population. Most commonly fortified staple products are cereals, milk, oils, rice, salt,
wheat flour, fats, and sugar. Minerals and vitamins are required in appropriate levels
to our body to maintain the health and fitness.
Fortification through nanoencapsulation will provide effective, real, and economical
health benefits to people by increasing micronutrient supply and thereby alleviating
malnutrition. Fortification should make sure that food utilized as the carrier has to be
homogeneous and stable and its intake limits (lower and upper) have to be made clear.
This process should also make sure that added nutrient should be sufficient to prevent
targeted deficiency after consuming the regular amount of food by the risk people.

Nanoapproaches for Improving the Bioavailability of Nutrients

Compounds like vitamins, antioxidants, and minerals have been introduced into
beverages and foods to promote well-being and human health. But it is very difficult
to incorporate nutraceutical compounds into foods as they have poor solubility,
stability, and bioavailability. These problems can be addressed by utilizing nanobased
systems for carrying and delivery of these nutraceuticals. Nanohydrogels and nano-
fibers are the few examples for the modern and efficient nanocarriers for the vitamins
or nutraceuticals [9]. Bioavailability of these molecules will increase with the decrease
34 Application of Nanotechnology for Encapsulation of Micronutrients 771

in the size of the carrying particle since small particles will penetrate mucus layer
easily and get digested faster and cells can directly uptake them. Nanocarriers may be
formulated in such a manner that they can survive after passing across different areas
of gastrointestinal tract and at specific region they will release the nutraceutical,
thereby maximizing bioavailability of nutraceutical or vitamin or other nutrient and
its health benefits. Nutrient-loaded nanocarriers may be fabricated by using biopoly-
mers or lipid formulations or other natural carriers [8]. Livethesource is the commer-
cial maker of the nanoencapsulated liquid vitamins, herbal supplements, and minerals.

Safety Issues with Nanoencapsulation

There is very scanty knowledge available with respect to impacts of nanomaterials on

the environment and human health. This has raised the regulatory, safety, ethical, and
environmental issues with respect to nanoencapsulation, though this process has the
merits of protecting, enhancing the bioavailability, and controlling delivery of bioactive
molecules. The information about the biotransformation and excretion of nanoparticles
is not clear once consumed via oral route. The existing methods for evaluating toxicity
of nanoparticles are not sufficient. Moreover, nanofood material complexities in living
systems are uncertain, and risks linked with their exposure are unforeseen since toxicity
of nanomaterials will be influenced by their size, composition, mass, and their surface
properties. Hence, the existing methodologies should be modified to evaluate risks
linked to nanotechnologies. There exists an ambiguity over utilization of nanomaterials
as an approved food additives or ingredients and food contact substances. Regulatory
authorities should be clear about the usage of nanomaterials for food products and
consider them as novel products requiring evaluation and approval.

Main Websites

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https://www.elsevier.com/books/book-series/nanoencapsulation-in-the-food-
industry
https://www.azonano.com/article.aspx?ArticleID¼1875
https://www.tandfonline.com/doi/abs/10.1080/10408398.2018.1484687?
journalCode¼bfsn20
https://nanoscalereslett.springeropen.com/articles/10.1186/s11671-018-2829-2

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Nanosensors: Consumer Nanoproducts
for the Detection of Adulterants 35
and Toxicants in Food

Shikha Gulati, Sanjay Kumar, Anantpreet Kaur Sood, and

Vaidehi Sharma

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
Adulterants in Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
Health Risks Caused Due to Adulteration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
Conventional Methods for Detection of Adulterants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
Drawbacks of Conventional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
Technological Advancements in the Food Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782
Merits of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784
Development of Nanotechnology in the Food Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
Detection of Adulterants and Toxicants Using Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 788
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793

Abstract
Due to the sudden increased demand for food for the ever-increasing population,
there has been a surge in the presence of adulterants and toxicants in the food items
available for the consumers. Nanoscience and nanotechnology are new frontiers of
this century, and food nanotechnology is an arising innovation. The expansion in
the development and usage of nanotechnology connotes wide utilization of nano-
materials particularly in the food area with varieties of expected advantages in the
territories of food safety and quality, micronutrients and bioactive fixing convey-
ance, food handling, and processing. Nanotechnology may allow us to develop
nanosensors that can help us to detect adulterants and toxicants in food, especially
in their applications for food quality and security. They can be fused in the
compound and natural sensors empowering the plan of fast and touchy gadgets

S. Gulati (*) · S. Kumar

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
A. K. Sood · V. Sharma
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 773

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_94
774 S. Gulati et al.

to evaluate newness and distinguish allergens, poisons, or pathogenic pollutants.

The future part of these nanosensors will turn out to be significantly more signif-
icant as the food lab is confronted with the expanding strain to lessen cost, time, and
multifaceted nature. Along these lines, this part will zero in on one of the multip-
arous advances of nanotechnology in the field of an arrangement of non-defilement
food. In this chapter, we discuss the potential and applications of nanosensors for
the development and availability of adulterant and toxic-free food.

Keywords
Consumer products · Nanotechnology · Adulterants · Nanosensors · Detection of
toxicants · Food nanotechnology

Introduction

The term “nanotechnology” was coined a few decades ago to include a variety of
methods, materials, and applications found in a wide range of physical, material, and
environmental sciences and hardware and design with a basic production and appli-
cation scale in nanometre size scale. One nanometre is a billionth metre (1
109 m).
How modern intelligent devices can detect and expose various physicochemical
components of nanoscale materials has further contributed to advances in the field,
and nanotechnology has begun to provide a systematic approach to the investigation
and modification of materials to suit specific applications.
A major requirement for the definition of nanotechnology is that the nanostructure
has a variety of properties caused only by nanoscale extents. This definition depends on
the number of dimensions of an object, which is outside the nanoscale range (<100 nm).
Ideally, in zero-dimensional (0D) nanomaterials, all measurements are measured within
the nanoscale (no dimensions greater than 100 nm); on two-dimensional (2D) nano-
materials, two dimensions are outside the nanoscale; and three-dimensional
(3D) nanomaterials are objects that can be stored in a nanoscale at any rate. This
phase can contain as much powder, dispersion of nanoparticles, packets of nanowires,
and nanotubes as many nanolayers. The quantitative features of the material are
constantly changing with the nanoadjustment [14]. Compounds produced using parti-
cles of nanosize ceramics or metals less than 100 nanometres without foundation can be
much more fundamental than what was expected of existing-science species. The
properties of building materials can vary from nanoscale for two main reasons:

• First of all, nanomaterials have a much larger surface area compared to the mass
of material delivered by a larger structure. This can make building materials more
acceptable (sometimes the elements lying in their main structure respond when
they are built into their nanoscale structure) and affect their cohesion or electrical
properties [6].
• Second, quantum impacts can begin to control the nanoscale process – especially
in the lower extremities – affecting the optical performance of the material,
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 775

electrical, and attractive. Nanoscale materials can be delivered in one dimension

(e.g. nanowires, nanorod, and nanotubes), in two dimensions (plate-like forma-
tions such as nano-coatings, nanolayers, and graphene), or each of the three
dimensions (e.g. nanoparticles).

Nanotech materials available today are less advanced materials (using flexible
nanotechnology) in which a particular type of nano-energy material (e.g. carbon
nanotubes, nanocomposite, or nanoparticles of a particular substance) or process
nanotech (e.g. nanopatterning or quantum clinical thinking areas) is used for coor-
dination. Nanotechnology works to greatly improve, even transform, many new and
industrial areas: data innovation, national security, medicine, transportation, energy,
food management, and environmental science, among many others.
Over the years, nanotechnology has gradually become regarded as one of the most
exciting new technologies in the world. It is new to the nanometre scale and controls
iotas, atoms, or macromolecules measuring 1–100 nm to make and use materials with
novel properties. Current nanomaterials have at least one external measurement, or
internal structure, at a scale of 1 to 100 nm that allows for detection and control of
nanoscale emissions. These materials have special properties, completely independent
of macroscale partners due to their high volume in proportion to volume, and other
natural novel properties such as tone, solvency, strength, contrast, toxicity, magnetic
strength, optical, thermodynamic, etc. Nanotechnology has brought some trouble.
Modern, created, and non-industrial countries are committed to investing more in this
innovation. After all, nanotechnology offers many opportunities for the evolution of
events and the use of designs, building materials, or structures with new structures in
various fields such as agriculture, food and medicine, and so on. The chemical compo-
sition of materials that can be used to make ENPs is very different. Theoretically, any
material with particles can be produced by nanoform either by top-down (e.g. grinding
large objects in nanoscale) or bottom-up (e.g. a high association of atoms/molecules to
form nanoscale particles). The nanomaterial can therefore be inanimate, natural, or
composite. In addition to the nanoparticles produced, other nanomaterials can be
found in natural sources – for example, montmorillonite is clay found in volcanic or
rock volcanoes. Adulteration in food has become increasingly common nowadays, and a
variety of methods have been devised to detect specific adulterants in food. Such
conventional methods are accurate but they have several disadvantages including
sophisticated handling needs and time-consuming nature. Therefore, several technolog-
ical advancements have emerged among which nanotechnology has played a very
crucial role. Nanotechnological instruments such as nanosensors, nanofibres, and nano-
metals are now being applied in the food sector commercially for the detection of
adulterants and toxicants in food items. These methods are comparatively more efficient
and lesser in cost with easy handling. Nanotechnology is now being used collaboratively
with such conventional techniques to ensure the proper detection of food adulterants. In
this chapter, we have discussed various aspects of nanotechnology in the food sector
and highlighted the use of nanotechnological methods for the detection of adulterants.
We have also emphasized the types of adulterants present in common food items, and
the harmful effects that such toxic additives have on our health and well-being.
776 S. Gulati et al.

Adulterants in Food

Food adulteration or food fraud is the act of degradation of the food quality by the
incorporation or removal of substances from it. The substances that make the food
impure and decrease its nutritional value are known as adulterants. Adulteration of
food is illegal beyond certain prescribed standards, and it has hugely detrimental
effects on the health of the people. Food adulteration may be accidental or deliberate.
While incidental adulteration may be caused by a lack of proper knowledge and
awareness, it is usually done deliberately for financial profits. Adulterants such as
insects, pesticide residues, rodent droppings, larvae, etc. cause accidental adulteration
whereas intentional adulterants commonly include chalk powder, brick powder, bak-
ing soda, harmful colours, water, minerals, mud, etc. Certain metallic compounds such
as arsenic, lead, chemicals from industries may also contaminate the food and thereby
act as adulterants. Food may also be spoiled due to microbial contamination, and
hence microbes may also act as adulterants. Colour adulteration is the most common
intentional adulteration such as the addition of extraneous matter to ground spices,
water to liquid milk. Certain chemicals, radicals, or organic substances that are present
in the food naturally may also act as adulterants. Malignant varieties of pulses, green
vegetables, seafood, and mushrooms are some examples of natural adulterants (Fig. 1).
According to an estimate, approximately 22% of food is adulterated each year [8].

Fig. 1 Commonly adulterated foods and their adulterants

35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 777

With the increasing demand for food, the incidences of food adulteration have
also shown a proportional increase. The main reasons that lead to food adulteration
are escalated demand, a surge in competition, inflation of profit margins, poor cost
management, and supervision.

Health Risks Caused Due to Adulteration

Food adulteration can cause a variety of health risks and diseases that may be mild or
may even be life-threatening. It has the potential to cause skin diseases, liver
diseases, stomach-related problems, and vision problems depending on the type of
adulterant. One of the most common illnesses caused due to food contamination is
food poisoning or foodborne illness. It is mainly caused due to the presence of
bacteria, viruses, parasites, or other toxins in food mainly Salmonella, Escherichia
coli (E. coli), or norovirus, causing the food to become spoiled or toxic. Symptoms
include vomiting, diarrhoea, cramping, abdominal pain, and nausea.
The most widely caused diseases as a result of chemical adulterants such as
formalin include asthma, cancer, and skin diseases. Edible oil is adulterated with
mineral oil and hence becomes a potent source of cancer. Lead poisoning is caused
by the addition of lead to water or other food items; it may also be caused due to
contaminated seafood. Lead poisoning can lead to brain damage, constipation,
anaemia, abortion, and even paralysis. Spices are adulterated with lead chromate
(red lead), red brick powder, dung powder, Rhodamine B dye soluble salts, synthetic
salts, etc. and may cause constipation, mental retardation, insomnia, and paralysis.
Fishes contaminated with mercury and mercury fungicide-treated grains may also
result in brain damage and even death. The addition of cobalt, tin, or zinc added to
water may result in cardiac arrest, diarrhoea, and vomiting. Food colour beyond
permitted values may result in hypersensitivity, infertility, birth defects, allergies,
and cancer. When fruits and vegetables are sold and kept in open for longer periods,
they become contaminated with smoke and dust particles. Often the fruits are coated
with chemicals, wax, and harmful preservatives to increase their shelf life. Multiple
organ failure can also be caused if the dyes, urea, and preservatives are used in
excessive quantities. Other problems such as peptic ulcers, blood disorders, liver
failure, kidney failure, colon cancer, and electrolyte imbalance are also observed.
The contaminants largely affect the neurological systems and digestive system and
result in compromised overall functioning, indirectly causing a shorter lifespan [5].

Conventional Methods for Detection of Adulterants

Adulteration in food may be done either partially or totally. While detection of total
substitution by adulterants is easy to be detected, the detection of adulterants during
partial swapping requires more elaborate methods. To ensure the nutritional stan-
dards and authenticity of food available to the consumers, a variety of methods
derived from morphological, chemical, and anatomical characterization have been
778 S. Gulati et al.

developed. Numerous methods that are based on the organoleptic properties of the
food item including colour, texture, and odour have also been developed and used
from time immemorial. Adulteration in any food item may be present in several
ways, such as substitution/addition of foreign substances, deviation in the nutritional
values beyond/below the allowed standard values, etc.
The various methods available for the detection of adulterants and toxicants in
food can broadly be classified as destructive and non-destructive. Traditional
methods available for the detection of food adulterants are usually destructive,
i.e. they require the destruction of the food materials during the testing procedure.
The most widely used detection methods are the physical methods that involve
analysis of the physical properties of the food materials including its organoleptic
properties, bulk density, macroscopic details, etc. A detailed macroscopic, as well as
microscopic, analysis is done using microscopes. Electron microscopy particularly
scanning electron microscopy is very useful in the case of chemical and microbial
adulteration. Recently, several advanced optical techniques such as computer vision
are also being used. These techniques are non-destructible in working and are
usually associated with the physical parameters of the sample [13] (Fig. 2).
Other traditional methods are based on the biochemical properties of the sample
food material as well as that of the adulterants. These include chromatographic,
spectrophotometric, and immunological techniques. These techniques are intensive
but are also more accurate than the rudimentary visual methods. The common scheme
for the detection of adulterants involves extraction, separation, chromatographic
analysis, and detection of components. High-performance liquid chromatography is

Fig. 2 The most common traditional methods of detection of adulterants in the food
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 779

used often for the characterization of the various constituents. Other widely used
methods include the mass spectroscopic methods, Fourier transform infrared spectros-
copy (FTIR), near-infrared spectroscopy, nuclear magnetic resonance, atomic absorp-
tion spectroscopy, and gas chromatography [41].
Spectroscopic and chromatographic techniques are usually used in different
combinations and durations such as GC-MSA, solid-phase microextraction-gas
chromatography-mass spectroscopy (SPME-GC-MS), LC-MS-MS, etc. Milk,
meat, beverages, edible oil, fish, etc. are the most common food items analysed
via spectral imaging techniques. Raman spectroscopy techniques are one of the
newest innovative collections of spectroscopy techniques based on the Raman
scattering effect. These include Raman imaging, micro-Raman spectroscopy,
FT-Raman, shot distance standoff Raman, and SERS. Certain electrophoretic tech-
niques are also applied for the validation processes such as the capillary zone
electrophoresis, urea-PAGE, etc. Immunological techniques mainly enzyme-linked
immunosorbent assays (ELISA) are used for immunoassay analysis [8].
Modern methods of imaging and spectroscopy which are purely non-destructive
have gained popularity in recent years. Hyperspectral imaging, laser-induced break-
down spectroscopy, terahertz spectroscopy, terahertz imaging, fluorescence spec-
troscopy, and photoacoustic spectroscopy are some modern biochemical methods
utilizing diverse principles for the detection mechanism. Technological advance-
ments in the detection procedure have even led to the generation of electronic
systems like E-nose and E-tongue to imitate the physical detection methods but
more accurately and systematically [7].
DNA-based methods are also widely used as detection methods for the detection of
adulterants mainly involving sequencing, hybridization, or PCR techniques. In the case
of partial substitution with similar-appearing adulterants, molecular analysis of species-
specific genomic regions can be used as a useful method. For analysis using structural
components, omics approach is applied which involves the combination of genomic,
transcriptive, and proteomic studies. Adulterant-specific primers are designed by using
the already available information for amplification. PCR is a simpler way of adulterant
detection which is used to amplify and quantify DNA samples either by searching for
DNA barcodes that are sequence specific to species or by localizing the search to look
for single nucleotide polymorphism (SNP). The fragments of sequences before cleavage
that are amplified using PCR are called cleavable amplified polymorphic sequences
(CAPS). Examples of some PCR-based methods include arbitrarily primed PCR
(AP-PCR), DNA amplification fingerprinting (DAF), inter-simple sequence repeat
(ISSR), directed amplification of minisatellite-region DNA (DAMD), PCR restriction
fragment length polymorphism (PCR-RFLP), random amplified polymorphic DNA
(RAPD), etc. The use of PCR in adulterant detection has gained momentum due to its
fast, accurate, and sensitive nature, and a variety of food materials including coffee,
celery, sesame, meat products, and processed food items are checked for adulterants
using PCR [34]. Various forms of DNA arrangements and samples are used for
molecular studies including conventional duplex DNA analysis, single-strand confor-
mation polymorphism (SSCP) using single-stranded DNA-based identification of
genetic variations, identification of microsatellites, etc. [30].
780 S. Gulati et al.

The loop-mediated isothermal amplification (LAMP) technique is another molec-

ular technique, highly specific single test tube process that uses 4–6 primers along
with DNA polymerase for the synthesis and identification of target DNA. This
technique is widely used as a substitute for PCR because of its rapid and easy
performance. These DNA-based methods are also used for the identification of
genetically modified foods and microbial adulterants in food samples [40].

Drawbacks of Conventional Methods

Conventional techniques for the detection of adulterants are used extensively for the
determination of the presence and the type of adulterants in food. Though conventional
methods have high popularity among food industries and food fraud detection, they
are not exempt from having disadvantages. Predominantly, traditional methods such as
gas chromatography-mass spectrometer, high-performance liquid chromatography,
ion chromatography, capillary electrophoresis, etc. are destructive, i.e. the food sample
gets destroyed or becomes unsuitable for consumption after these procedures. These
methods have complex pretreatment and operational processes that are essential for
accurate results. Such methods are elaborate and time-consuming and cannot be
applied to an industry-scale detection process due to their lab-intensive studies.
These techniques also work in a target-specific manner and thereby are conducted
specifically for targeting only one adulterant at a time. Food fraudsters have started
avoiding the target-specific detection methods by using advanced ways, and therefore
such methods have proved to be non-conducive in a variety of ways. [13].
In opposition to destructive methods of adulterant detection, several
non-destructive methods have also emerged. Non-destructive methods are less
time-consuming and are technologically advanced. They don’t require a large
sample size, and the sample also remains undestroyed during the entire procedure.
Nanotechnological techniques, optical imaging techniques, nuclear magnetic tech-
niques, and electrical techniques are some examples of non-destructive methods.
These techniques are relatively easier to perform and need minimum pretreatment.
They also have a wider search range with the management of large databases and
libraries for various adulterants. For example, spectroscopic studies require exten-
sive laboratory work including the collection of samples and comparison with
chemometric models already available. The cost of such methods is also high,
while non-targeted methods are comparatively cheaper or have a one-time installa-
tion cost with reduced maintenance expenses. The new non-destructive methods
including nanotechnological techniques have therefore arisen as effective substitutes
which have a wider range of commercial uses. [22].

Technological Advancements in the Food Sector

The food industry is a complex chain of global production, management, and

marketing of food to the consumers. It mainly consists of various networks built-
in together to ensure proper production and supply of food majorly food grains,
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 781

beverages, fruits, vegetables, pulses, dairy products, meat, fisheries, etc. Various key
components of the food sector include agriculture or farm service, producer service,
food processing, and marketing. Food production and processing require a high
degree of labour and time-intensive work which comprises distribution, transporta-
tion, storage, processing, and packaging of various food products. The food industry
is the backbone for every nation in terms of both economic and its intrinsic growth.
According to Plunkett Research 2018 estimates, the global food industry accounts
for about 10% of the world’s GDP or about $8.7 trillion value estimates.1 Depending
on whether the country is developed or developing, the advancement technological
or economical is varying and consists of different GDP values. Food production or
agriculture is the practice of cultivation of crops or rearing animals for human use.
In recent years a large number of problems have emerged in the food sector
including food insecurity, poverty, inflation of food prices, adulterated food, hidden
hunger, increased competition, etc. The food sector is therefore in need of immediate
reforms and advancement. The major ways by which such a revolution can be
created are digitalization, proper management, new and innovative agricultural
reforms, advanced packaging methods, vigilant storage methods, and technological
advances. Several technological advancements have emerged in recent years that can
change the entire food sector, but proper management and cost-effectiveness are the
current requirements. The first technological revolution in the food industry was
caused in the nineteenth century by the introduction of steam engines and processing
machines during the period of industrialization. The second major reform was stirred
by the green revolution in the 1950s by the introduction of advanced biological and
technical alternatives. The twentieth century marked the beginning of the emergence
of sophisticated mechanical as well as electrical reformations that included robotics
and automatization [9]. In recent years, a variety of strategic, technical, technolog-
ical, and methods have been introduced including robots, smart sensors, intelligent
greenhouses, vertical farms, wireless sensor networks, and modern production
systems [42]. The current agricultural system focuses on modern machinery, tools,
minimized cost, sensible, sustainable measures, and smart methods [23].
Technological advancement is based on a variety of collaborations including human-
human, machine-machine, and human-machine. The human-machine collaboration
includes touchless gesture user interfaces (TGUIs), voice user interfaces (VUIs), tangi-
ble user interfaces (TUIs), brain-computer interfaces (BCIs), etc. Machine-machine
interface includes automatic systems, robots, and UAVs [24]. Devices and machines
that allow us to sense events, data, and changes form part of the sensing systems that
gather information from their surroundings and process and present the data in an
understandable form. These systems are mainly being employed in weather forecasting,
control systems, optimization methods, etc. Various types of sensing devices have
emerged in recent years including both wired and wireless sensing devices such as
virtual sensors, smart sensors, sensor networks, digital sensors based on sensor fusion,
and interconnected devices [31].
Smart technologies or smart products are intelligent devices that can stimulate
and process data on their own. These technologies are being implemented in several
different spheres of agriculture and the food industry [26]. An intelligent hydroponic
greenhouse is one such smart technology that is now being used for the cultivation of
782 S. Gulati et al.

crops such as tomatoes. These smart greenhouses can detect and manipulate their
conditions by sensing the outside conditions, and the information can be accessed
via a human-machine interface and manipulated by a machine-machine interface
system. It can evaluate conditions like wind speed, rainfall, humidity, solar intensity,
and temperature. Solar panels and sun trackers have also become increasingly
popular, and clean energy sources such as wind energy are now being harnessed.
Automated systems such as harvesting systems, automatic fertilizer systems, climate
controllers, irrigation systems, and agri-robots such as sheep shearing robots, driv-
erless tractors, fruit picking robots, etc. are also being explored [24].
Smart aerial vehicles such as drones or quadrotors are unmanned aerial vehicles
(UAVs) that can be used diversely in agricultural practices such as UAV sprayers,
UAV monitors, and UAV irrigation devices and collection of information about crop
growth, harvest, and image capturing [17]. Another such smart product is an
agricultural hexapod robot which is a walking robot created to capture and monitor
the data obtained on the field [4].
Technological advancements are also being made in food processing and mar-
keting strategies. Packaging materials derived from polymeric materials and films
are being used to ensure food protection and adulteration. Examples of polymeric
packaging substances include nylon, ethylene vinyl alcohol (EVOH), and polyeth-
ylene terephthalate (PET). Multilayered packaging strategies are also being used to
increase the shelf-life of various food products [37].
Therefore, the food sector is moving towards an era of technological establish-
ment and innovation wherein new measures are being implemented at all levels of
food production and supply.

Consumer Nanoproducts

The current use of nanotechnology takes up a wide range of areas, especially

cosmetics and personal care, medicine, paint and clothing, agricultural food,
wraps, and hardware (Fig. 3). Nanotechnology applications have also been widely
recognized for transforming the entire agricultural food industry, from creation,
preparation, integration, and transport to storage. Examples could be outstanding
dietary/therapeutic benefits, new or improved preferences, composition, and addi-
tionally low-fat foods, for example, sugar, salt, fat, additives, and flavours. Nano-
technology applications for food mixing have also enabled the development of
lightweight but sturdy wrapping materials that can keep basic foods safe during
travel, more plentiful, and protected from microorganisms. Sharp labels using ENPs
are created to provide notifications to the buyer when the combined diet begins to
deteriorate. Another emerging R&D and application area identifies the use of water
carriers in the advanced delivery of additives and other organic products,
nutraceuticals, cosmeceuticals, and health food products. Such descriptions are
often found in the nanoscale for preparing food to enclose micelles or liposomes
or to make bioactive enhancements in materials or engineered polymeric materials.
Any improvement in the acquisition and availability of bioavailability, or a focus on
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 783

Fig. 3 Consumer products

and applications of
nanotechnology in consumer
fields

physical delivery, of certain minerals that are not adequately supplemented with
other health-enhancing enhancements, can benefit consumers in all circles, for
example, the elderly, patients, and athletes – especially [28].
Nanotechnology has emerged as one of the key developments to join, providing
an opportunity for new developments in collaboration with other technology sectors.
There are examples of nanotechnology combined with biotechnology as well as new
data that have enabled the development of small detection and monitoring devices,
such as nano-biosensors. Such improvements can be relied upon to enable the
detection of microorganisms and food contamination during handling, transport,
and energy and to improve the welfare and safety of food items. If you look at the
well-known events of pregnancy, it is not surprising that the food business is among
those places that are looking for ways to understand the potential benefits of
nanotechnology [18].
Nanotechnology speaks of a fast-growing business sector, which brings a com-
bination of benefits, guarantees, risks, and risks. Nanotechnologies have developed
many equipment areas, some of which are close to our daily lives, for example,
horticulture, sanitation, medicine, drug store, rehabilitation, and self-care. Consid-
ering the number of application sites you can think of, the list of ENPs that can be
disrupted in nature and have concerns is long, but apparently, not all of them affect
the market in the same way. Classes of nanomaterials, which deliver a large market
volume, include rare metal nanomaterials, carbon NPs based on carbon, and natural,
chromolecular, or polymeric materials.
Determining whether a nanotechnology product is safe for the intended use or in
the event of possible well-being and/or environmental impacts (transport, future,
contact with biodiversity) should be assessed on various physical and functional
parameters. These include size and shape, distribution status, physical and drug
properties, more space, and more science. Size, texture, and more in all morphology
are the hallmarks, influencing NP levels of toxins by influencing where they drop,
784 S. Gulati et al.

time from the body, and the natural response such as inflammation. In any case, how
NPs interact with living organisms or the climate depends largely on the surface and
the science above, both of which determine equally the dispersing properties of
molecules and the release of particles and biomolecules. This means that even the
actual structure and redesign of the integration must be examined equally because
both are equally important [14].
The recognition, evaluation, and evaluation of NPs contained in consumer goods,
for example, food, food packaging, cosmetics, and personal care items are in high
demand. The type of lattice in which the NPs are dispersed (e.g. liquids, liquids or
thin, solid solids, emulsions, syrups, oils, polymers) refers to a critical test system to
measure the boundary structure of physicochemical required. Complete exposure to
NP will probably not work in all cases, but the combined use of various techniques,
for example, a scientific strategy (e.g. FFF, chromatography) combined with ID and
measurement method (e.g. ICP-MS), should provide the first phase of in-depth
tests [28].

Merits of Nanotechnology

Nanoscale addition to products or surface coverage to its composition can provide a

simple light direction close to the body cover, or it can help them resist wrinkles,
spots, and bacterial growth [39]. Nanoscale materials are beginning to empower
intelligent, readable, durable fabrics equipped with sensors and flexible nanoscale
gadgets capable of monitoring life and reaping energy through the movement of the
sun. Saving cars, trucks, planes, boats, and specialty space can create critical
investments. Nanoscale adds materials to polymer composites applied to polished
ash, tennis rockets, bicycles, bicycle helmets, car parts, luggage, and fittings, making
them lightweight, durable, durable, and flexible. Carbon nanotube sheets are cur-
rently being shipped to be used to reduce air traffic. The combination of low weight
and behaviour makes it ideal for applications, for example, electromagnetic protec-
tion and warm handling.
Protein nano-bioengineering is expected to enable the conversion of cellulose
from wood chips, corn cobs, hollow grass, etc., to fuel ethanol. Cellulosic nano-
materials have demonstrated potential applications in a wide range of modern
environments, including gadgets, development, wrapping, food, energy, medical
care, automotive, and protection. Cellulosic nanomaterials are expected to be more
affordable than many other nanomaterials and, among various properties, promote
greater cohesion in weight ratio.
Nano-based materials in the automotive range include high-capacity battery
components, thermoelectric materials for temperature control, tires with low moving
restrictions, highly sensitive sensors and gadgets, small film savvy boards on the sun,
and petroleum extracts and extended accessibility.
The cover made of the notes shows significantly more durability than the tradi-
tional safe wear of the machine parts. Nanotechnology-powered oils and automotive
oils further reduce mileage, which can completely extend the lifespan of moving
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 785

parts in everything from electrical devices to modern devices. Nanoparticles are

continuously used in catalysis to support material reactions. This reduces the number
of raw materials that are essential for creating the desired results, setting aside
money, and reducing toxins. Two major applications are in oil refining and auto-
extraction systems. Nanomaterials make basic household items, for example,
degreasers and stain removers; natural sensors, air purifiers, and channels; anti-
bacterial cleaning agents; and some paints and repair materials like self-cleaning
house paint especially against stains and stamps. Nanoscale building materials are
further being integrated as part of the considerations to improve performance.
Nanoscale titanium dioxide and zinc oxide have been used for quite some time on
sunscreen to provide sun protection while appearing invisible on the skin.
Nanotechnology has added dramatically to significant improvements in hardware
acquisition and performance, promoting faster, more efficient systems that can
monitor and maintain large data steps (Fig. 4). Flexible, folding, and stretchable
items go to a variety of locations and are included in integrated items, including
wearables, clinical applications, flight plans, and the Internet of Things. Flexible
gadgets are built using, for example, semiconductors and software applications for
mobile phones and tablets. Some nanomaterials such as graphene and cellulosic
nanomaterials are used for a variety of flexible gadgets.
Nanotechnology is currently expanding clinical devices, data, and treatments as
they are now available to clinicians. Nanomedicine, the use of nanotechnology in

Fig. 4 Merits of nanotechnology

786 S. Gulati et al.

medicine, draws on the size of the natural wonder to bring direct answers to disease
expectations, analysis, and treatment. Nanotechnology finds application in conven-
tional fuel sources and dramatically develops options for resilience to meet the
growing global energy demand. Many researchers are exploring ways to grow
more efficient, balanced, and sustainable energy sources, reduce energy consump-
tion, and reduce toxic problems in the climate [1].
The benefits of nanotechnology in the food industry are many and are expected to
grow over time. These fast-growing new technologies are impacting every aspect of
the food system from farming to food production to processing, packaging, trans-
portation, shelf-health, and access to nutrition. Commercial applications for nano-
materials will continue to impact the food industry because of their unique and
innovative designs. Human exposure to nanomaterials, as a result, is increasing and
will continue to increase over time. Therefore, the health impact of nanomaterials on
diet is of public interest and concern. Public acceptance of food and food-related
products containing nanomaterials will depend on their safety [1, 3, 14].

Development of Nanotechnology in the Food Sector

Over the past few years, nanotechnology has become an increasingly attractive
technology that will transform the food industry. The food sector has seen dramatic
growth in recent years in both developed and developing countries. The use of
nanotechnology includes food management, food integration, and food monitoring,
nanotechnology and sanitation, and a guide to nanotechnologies to ensure sanitation
(Fig. 5). Nanotechnology’s assistance in food preparation, food wrapping, food
testing, processed food sources, development of ready-to-diminish foods, flavours,
or their healthy food properties as indicated by human dietary requirements and the
production of more flavour, colour, and nutritional supplements cannot be measured.
Reducing drug rehabilitation costs and increasing the time frame for real food use can
be achieved by using nanotechnology. Smart packaging can be used to improve the
shelf life of materials using nanotechnologies, and such binding frames will have the
option to fix small openings/tears; react to environmental conditions, for example,
temperature and humidity changes; and warn the client if food is contaminated.
Another area that can be used in the application of nanotechnology is turning it into
sensible food strategy events that identify small steps of integrated pollution, infection,
or very small objects in the food framework. In any case, there is a need for
management structures that can deal with any risks associated with nanofoods and
the use of nanotechnologies in food preparation and material development to prevent
future fiasco in the potential use of nanotechnologies in food preparation [35].
Food preparation joins the preparation of raw food to deliver attractive hand-
prepared food items served by the consumer. Food management typically includes
activities, for example, digestion and digestion, liquid, emulsification, and cooking
(e.g. boiling, closing, roasting, or boiling a flame); picking, cleaning, and many other
types of protection; and canning or other wrappings. Important handling, for exam-
ple, dicing, cutting, cooling, or drying, when adding optional materials is added.
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 787

Fig. 5 The advancement of nanotechnology in the food sector

Food preparation techniques include nanomaterials including fusion for

nutraceuticals, gelation and viscosifying specialists, additional delivery, the site of
minerals and nutrients, and nanoencapsulation [32]. Nanotechnology creates a time
frame for the practical use of different types of food and also helps to reduce the rate
of food wastage due to germs. Nowadays, nanocarriers are used as a framework for
transporting extra food to food items. Nanotechnology is used in the preparation of
epitome, emulsions, grid biopolymer, basic preparations, and colloid compounds to
provide productive delivery structures with all the aforementioned features. Nano-
sensors can be used to indicate the presence of toxins, mycotoxins, and microorgan-
isms in food. Nanoparticles have better epitome structures and more efficient
delivery than conventional synthetic frames. Nanoencapsulations cover odours or
tastes, control dynamic interaction with food lattice, control the arrival of powerful
specialists, ensure timely availability and specific value, and protect them from
moisture, heat, compound, or environmental degradation during handling and stor-
age. Besides, these transport structures have the ability to penetrate deep into the
tissues because of their modest size and thus allow the productive delivery of
powerful compounds to identify areas in the body. Food “smart” nano-“dynamic”
food packages highlight a few points of interest in traditional integration techniques
ranging from providing better blending with improved mechanical strength,
blocking properties, antimicrobial films to nanosensing detecting microorganisms,
to alarming consumers in the food environment. A few types of nanosensors used in
788 S. Gulati et al.

food mixing include nanoparticle-based sensors, electronic noses, biosensors, nano-

cantilevers, a synthetic nanoparticle, and nano-test strips. The combination of
nanosensors is important to track the external or internal conditions of food items,
pellets, and holders throughout the food network. Nanosensors are packaged in
plastic that can detect gases in food if it damages more than that, the wrap itself
changes tone to shock the consumer. In addition, a film loaded with silicate nano-
particles can reduce the flow of oxygen in the pile, and spill moisture outside the pile
can keep food fresh. It can prevent form development within the refrigerator.
Nanotechnology can be used to produce a collection that desires to increase the
time frame of the actual usability of an object and to enable it to move further.
Intelligent packaging containing nanosensors and antimicrobials is developed to
identify food spoilage and the delivery of nano-antimicrobials to extend the shelf
life, enabling conventional stores to save nutrition long before its sale [35].
Normally the nanounits of cells, strands, gels, emulsions, froths, and fluids thus
give nourishments to the surface, flavour, period of usability adjustment through
antimicrobials, and other nourishing characteristics like cell reinforcements or
explicit bioactive compounds. They are colloids like emulsions, micelles, mono-
layers, and bilayers. They increment food material bioavailability; improve taste,
surface, and consistency of staples or cover the bothersome taste or smell; and
modify the molecule size, size circulation, expected agglomeration, and what’s
more, surface charge. Moreover, in the buyer care industry, nanotechnology helps
in purging consumable water, sustaining nutrients and minerals, and likewise as
antimicrobials. Nano-emulsions give wanted characteristics like surface, fragrance,
shading, flavour, satiety, mouthfeel, and rheological properties to the food items and
what’s more, accordingly, are normal among nutraceuticals, cosmeceutical, drugs,
cell reinforcements, flavours, and antimicrobial specialists. Nanomaterials are
promptly utilized in the food bundling industry where it gives low penetrability
and gives high-strength bundling arrangements. Eminently, the inorganic particles
like mud alongside surfactants when added to the biopolymeric network help
guarantee the feasible biodegradability of bundling material or could assist with
different functionalities [27].

Detection of Adulterants and Toxicants Using Nanoproducts

Conventional methods such as chromatography and spectroscopy for the detection

of food adulterants and toxicants are complicated and require intensive laboratory
procedures. A series of methods including purification, extraction, quantification,
etc. are required to be followed, and the information obtained may also be inaccurate
and not very specific in certain cases. With the current development in technological
areas and with the emergence of nanotechnology, the entire adulterant detection
process can be revolutionized. Nanotechnology has led to the development of
advanced methods involving the use of biosensors and nanoparticles which are
rapid and much more efficient. Metal nanoparticles are one of the most popularly
used nanoproducts. Nanomaterials are now being used as functionalized catalytic
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 789

Fig. 6 The above figure illustrates the concept of food adulteration and its types

agents in biosensing for adulterants and toxicants in the food industry. Nano-
materials such as nanowires, nanorods, nanostructured metal oxide nanoparticles,
and carbon nanomaterials are increasingly being employed in the form of biosensors.
They work by reacting or binding with biological targets or components and allow
the signals generated to be detected, thereby allowing the detection of adulterants
and toxicants. Biosensors based on nanomaterials are being produced for the detec-
tion of food toxins ([29] (Fig. 6)).
A nanosensor as the name suggests is a complicated yet sensitive device that is
capable of detecting a stimulus. It is highly accurate and reactive and is therefore
used as a biological and chemical tool. When used for its biological properties, it is
known as a nano-biosensor which includes metal and metal oxides, carbon nano-
tubes, graphene, carbon nanofibre, electrospun, and magnetic nanoparticles
[10]. Commonly used metal nanoparticles and metal oxides include gold nano-
particles and silver nanoparticles [11]. Gold nanoparticles or Au NPs have a very
high surface area, thereby illustrating a high rate of bioconjugation with ligands,
DNA, and antibodies. Gold nanoparticles are currently being used to detect mela-
mine in milk products. Au NP is originally red but turns blue on the addition of milk
adulterated with melamine due to the aggregation of molecules [38]. Au NPs are also
being used to detect detergents in water which result in the formation of synthetic
milk. They are also used to detect food fraud mainly by the addition of biogenic
amines in the case of meat products and also help in the detection of microbial
790 S. Gulati et al.

adulterants in milk. Au NPs are used in combination with other methods such as
PCR and recombinase polymerase amplification (RPA) [21]. Silver nanoparticles
show better properties and similar results with melamine with a colour change of
yellow to red. These are also used to detect food spoilage in the case of milk by
showing the colour change in the presence of lactic acid in spoiled milk. Silver
nanoparticles may be used to detect spoiled onions as they show a colour change in
the presence of sulphur compounds. They can also be used to detect spoiled fruits
post-harvest and microbial adulterants in food. Studies on hybrid nanometals and
nanopapers are currently being performed to detect meat spoilage working on the
same principle of colour change [20] [29].
Nanoproducts such as carbon nanomaterial-based nanosensors are based on the
usage of carbon for the development of nanosensors [15]. Carbon nanosensors are
stable and are being employed as nanotubes, nanofibres, and other nanoscale
structures. Carbon nanotubes are one of the oldest carbon-based nanosensors to be
developed. They are known for their high electrical, mechanical, as well as thermal
properties. They are composed of cylindrical carbon atoms and are very efficient in
terms of their analytical capabilities. Depending on the number of graphene cylin-
ders encircling the carbon nanotubes, they can either be single-walled or multi-
walled. The side walls increase the binding capacities of the nanotubes to bind with
specific molecular targets. Carbon nanotubes have carbon atoms bonded tightly with
van der Waals forces and hence show lesser reactivity with the surrounding mole-
cules. Their structural and functional properties can therefore be modulated to obtain
specific nanotubes. In the presence of contaminants, the intrinsic properties of these
nanotubes are hampered and therefore can be detected. Carbon nanotubes are often
used in collaboration with other detection methods such as high-performance liquid
chromatography and high-performance capillary electrophoresis. Chemiresistive
single-walled carbon nanotubes are being designed for the detection of biogenic
amines. Carbon nanotubes are also being used in combination with other nano-
materials such as silver for the detection of amines even in lower concentrations [25].
Different nanosensors and nanoproducts are sometimes used simultaneously to
detect adulterants in a precise and efficient manner. The adulterant may be extracted
via nanometal binding and detected even in lower concentrations by using nanotubes
and nanomatrices. Enzyme-based nanosensors are increasingly being employed for
the detection of urea.
Single-walled nanotubes are being used in various electrochemical techniques to
enhance their sensitivity. Biosensors are now widely made up of graphene which is
an allotrope of carbon for the detection of adulterants such as xylene, cholesterol,
urea, uric acid, etc. Graphene nanoplatelets and nanodiamonds in combination with
urease are being used for the detection of urea. This method is an example of an
enzyme-based nanosensor. It is also used in conjugation with amylopectin for the
detection of adulterants in meat products by the selective absorption of haemoglobin.
Nanomaterial-based electrochemical immunosensors are now being developed and
used for the detection of yeast adulteration in red wine. Graphene can also be used
for the development of E-nose when functionalized with fluorine for the detection of
toxicants in seafood [16].
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 791

Carbon nanofibres are used for the detection of porcine serum albumin (PSA) in
pork as well as for the detection of vanillin in flavouring agents in combination with
electrochemical methods. They mainly work by causing the immobilization of
targeted analytes by specific binding. Detection of lactate in beverages and eggs
can be done using carbon nanofibres by enzyme immobilization [19, 36].

Nanoparticle-based technology Adulterant detected

Metal nanoparticles – gold and silver Detection of melamine in milk products, presence
nanoparticle of lactic acid in spoiled milk, detect sulphur in
spoiled onions, detect spoiled fruits post-harvest
and microbial adulterants, etc.
Carbon nanomaterial-based nanosensors, Detection of biogenic amines, of adulterants such
graphene nanoplatelets, and nanodiamonds as xylene, cholesterol, urea, uric acid, etc.,
detection of toxicants in seafood
Enzyme-based nanosensors Detection of adulterants in meat products by the
selective absorption of haemoglobin
Nanomaterial-based electrochemical Detection of yeast adulteration in red wine
immunosensors
Carbon nanofibres Detection of porcine serum albumin (PSA) in
pork, detection of vanillin in flavouring agents,
detection of lactate in beverages and eggs
Magnetic nanoparticles Detection of adulterants in meat products
extraction of DNA via nanoparticles
Ultrathin nanofibres Detection of adulterants in milk and colorimetric
visualizations, etc.

Nanoparticles containing magnetic elements such as iron, nickel, etc. are known
as magnetic nanoparticles. These NPs are comparatively different from constituent
elements. Iron oxide nanoparticles are the most frequently used magnetic nano-
particles due to their non-toxic nature, compatibility, and functional diversity.
Magnetic nanoparticles are often coated with layers to ensure that they do not
form aggregates, prevent oxidation, and only allow specific reactivity. Magnetic
NP-based DNA extraction is another method of adulterant detection in meat prod-
ucts that are based on the extraction of DNA via nanoparticles. They can also be used
to increase the electron transfer rates during an electrochemical method and hence
act as electrode modifiers. Gold-coated magnetic nanoparticles show a very high
degree of biocompatibility with biomolecules such as proteins and nucleic acid and
are therefore being used to detect toxicants in a variety of food samples [2].
Ultrathin nanofibres are produced by electrospinning with novel nanoparticles
according to the requirements and specificity. Such ultrathin nanofibres are used for
the detection of adulterants in milk and colorimetric visualizations [33]. These
nanofibres can be embedded with the food material as a chemical barcode that is
sensitive to the presence of adulterants and toxicants. The development of tailor-
made nanosensors to detect the presence of adulterants in specific food items is the
next milestone in the nanotechnological advancements in the food sector [29]. Nano-
material-based detection has a large number of advantages over the traditionally used
792 S. Gulati et al.

methods for the detection of adulterants due to their accuracy and less time-
consuming nature. But they still require advancement in terms of cost and produc-
tion. Food adulterants can be detected and managed at the processing or packaging
levels via processes that ensure that the presence of the toxicant is known immedi-
ately. For such immediate and enhanced response nanoparticles including nanotubes,
nanosensors, and nanofibres are becoming increasingly popular in the food industry.

Conclusions and Future Outlook The utilization of characteristic mixtures for

ailments is extending and is accepting developing attention. Nano-based detecting
approaches incorporate the utilization of nanoparticles (NPs) and nanostructures to
upgrade affectability and selectivity, plan new identification plans, improve test
planning furthermore, and increment compactness. This chapter sums up late head-
ways in the plan and improvement of NP-based sensors for evaluating food han-
dling. The most well-known kinds of NPs utilized to manufacture sensors for the
location of food foreign substances are discussed. Despite the numerous advantages
of applying nanotechnology for the better conveyance of regular items, there are still
a few concerns that face the turn of events of nanoproducts with common items, one
of the main ones being the progress from seat to bedside. The trouble of repeating NP
combination on a scale required for commercialization, the absence of comprehen-
sion of how NPs interface with bio-surface, and inadequate information about the
destiny of NPs and potential NP harmfulness likewise should be further researched,
particularly if these frameworks are to be utilized to forestall and to treat illnesses.
Towards the end, nanotechnology examination, improvement, and commercializa-
tion of the nanoproducts should guarantee that these items go through to the market
with no danger (or insignificant danger). The equilibrium among advantage and
danger should be in every case fundamentally dissected, completely portrayed, and
what’s more, plainly ideal. The accomplishment of these headways will be subject to
buyer acknowledgment and the investigation of administrative issues. Food makers
and producers could make extraordinary steps in food handling by utilizing nano-
technology, and buyers would receive rewards too. Numerous organizations are
directing examination in nanotechnology and its application to food items, and as
a greater amount of its functionalities become clear, the degree of interest is sure to
increment. To keep up administration in the food and food-preparing industry, one
should work with nanotechnology and nano-bio-data later on. The future has a place
with new items and new cycles to tweak and customize the items. Improving the
security and nature of food will be the first step. Planning and delivering food by
forming particles and iotas are the fate of the food industry around the world. Future
work to adjust these sensors with the goal that they can be connected to food
bundling to show defilement would be profoundly significant for online control
and security of handled and stored food.

Important Websites https://www.foodqualityandsafety.com/article/food-adultera

tion-history-of-food-safety-laws-and-what-it-means-today/
https://www.nanowerk.com/spotlight/spotid¼35646_2.php
35 Nanosensors: Consumer Nanoproducts for the Detection of Adulterants and. . . 793

https://www.degruyter.com/document/doi/10.1515/ntrev-2018-0076/html
https://www.frontiersin.org/articles/10.3389/fmicb.2017.01501/full
https://www.nano.gov/

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Plant-Based Nanomaterials: Novel
and Highly Effectual Preservatives for Food 36
Shikha Gulati, Sanjay Kumar, Kartika Goyal, and Ambika Singh

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 798
Food and Its Deterioration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 799
Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
Need for Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
Tenure of Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
Conventional Food Preservation Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
Nanotechnology in Food Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
Role of Nanotechnology in Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
Nanoencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
Nanoliposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
Edible Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
Essential Oils and Nanoemulsion-Based Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
Indirect Methods for Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
Food Packaging and Its Conventional Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
Role of Packaging Material in Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
Bio-based Packaging and Their Action in Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
Food Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 812
Role of Food Processing in Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 812
Antimicrobial Properties of Plant-Based Nanoparticles Useful in Food Preservation . . . . . . . . . 814
Some Nanoparticles with Antimicrobial Activity Against Phytopathogens . . . . . . . . . . . . . . . . 815
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821

S. Gulati (*) · S. Kumar · K. Goyal

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
A. Singh
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 797

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_95
798 S. Gulati et al.

Abstract
Nanoparticles have emerged to have a wide application in various industries due
to their small size and higher surface to volume ratio, but the most controversial
uses of nanoparticles are their application to improve food quality and safety as
metal/metal oxide nanomaterial causes oxidative stress through formulation of
ROS (reactive oxygen species). Synthesis of nanoparticles using chemical and
physical techniques is expensive, and the chemicals used are toxic and pose a risk
to the environment. The plant-mediated synthesis of nanoparticles is considered
for production of nanomaterials for food-based use due to the easy availability of
plant material, short time span needed to obtain materials, provision of protection
from light and moisture, and prevention of oxidative stress. Some of the appli-
cations of nanotechnology in food sector are improved food production, pro-
cessing, packaging, and preservation. In this chapter, we have discussed the
application of nanoencapsulation of plant extracts in the domain of food science
in detail. Other applications include nanoemulsions, nanocomposites, etc., and
highlights on nanocellulose and nano-starch are discussed in brief. Numerous
plant-mediated synthesized metal nanoparticles exhibit antibacterial effects
against a wide range of microorganisms including some important foodborne
pathogens. The antifungal and antioxidative effects are also discussed in brief.
This chapter aims to provide an overall insight about the effectiveness of plant-
based nanomaterial as food preservatives. In addition, impact of nanotechnology
in food science has also been discussed from the perspective of food preservation.

Keywords
Nanomaterials · Food · Preservatives · Plants · Human health · Food packaging

Introduction

Among the global population of six billion, the food industry calls for safer and
sustainable ways to preserve food from pathogenic organisms. With increasing con-
sumer demands, scientists and food processing industries are evaluating diverse
approaches for augmenting the food quality, safety, freshness, and shelf life through
the use of natural, edible, and biodegradable polymers [1, 2]. New materials are being
introduced by researchers across the globe for advancement in the foodstuff industry.
Nanotechnology appears as an upcoming approach that sets the new horizons for food
technology in terms of biocompatibility, preservation, storage, and packaging. It has
diverse domains in food-related applications where certain nanomaterials are encapsu-
lated in food material to enhance its property [3]. However, oxidative stress by metal/
metal oxide nanomaterial through the formulation of reactive oxygen species sets
controversies for using nanostructured material in the food industry. Therefore, the
increased use of nanomaterials has urged for development of safe and nontoxic nano-
structures from plant-based ingredients using eco-friendly approaches. Nanotechnology,
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 799

when combined with green approaches can create miracles for human health, environ-
ment, and industries [4, 5]. Biological approaches use plant extracts and microorganisms
for the synthesis of metallic nanoparticles, and they have been identified as viable
alternatives to other types of chemical methods reported earlier. Recently, it was reported
that silver nanoparticles (AgNPs) were synthesized using various natural products/
extract such as green tea (Camellia sinensis), neem (Azadirachta indica) leaf broth,
natural rubber latex, aloe vera plant extract, and latex of Jatropha curcas [6, 7]. However,
there are other immensely important metals also, such as copper, zinc oxide, iron, and
gold nanoparticles (AuNPs), which also produce extremely useful green nanoparticles
by reduction method via biological materials such as plant extracts [6]. In other words,
the reducing capacity of biological products such as proteins, carbohydrates, and
secondary metabolites is harnessed to produce another type of economically and
environmentally useful metal nanoparticles. However, to reliably generate biologically
functional NPs, several parameters such as pH, chemical concentration, reaction time,
and reaction temperature are important [8, 9].
Furthermore, unlike the use of the microbial system, the generation of NPs from
plants does not have to maintain the microbial culture, thus reducing the costs of
isolation of microorganisms and the preparation of culture media. NPs with promising
antibacterial activity are synthesized by green technology using the whole plant or
other plant extracts such as leaves, fruits, roots, barks, seeds, rhizomes, peels, flowers,
and calluses. Essential oils (EOs), one of the compounds obtained from plants, have
antioxidant and antimicrobial properties [10]. They can therefore be enclosed in a
nano-coating to form a high-efficacy capsule, a process known as nanoencapsulation
[11]. Essential oils are one of the main classes of natural antimicrobial components that
have been considered sophisticated in the food industry preservation system. Solid
nanoparticles of lipids, liposomes, and emulsions are some of the encapsulation
systems. Overall, nanotechnology interventions in food preservation have shown
some positive results in terms of extended shelf life without compromising organo-
leptic properties and apparent food safety concerns [11, 12, 13].
In recent years, researchers have been searching for less reactive plant-based
nanomaterials for safer food technology. Plant-derived formulations have shown
advanced behavior in nanoencapsulated structures due to increased surface area,
protection from light and moisture, etc. Holistically, this chapter will highlight the
important role played by nanoparticles in food technology and their role in food
preservation and human health protection. Rapid advances in nanotechnology have
led to a significant transformation in the food industry in the fields of preservation,
packaging, and storage [14, 15].

Food and Its Deterioration

Food is an essential part to sustain human health. It helps in cellular detoxification,

regeneration, and the healing of many diseases. However, mechanical, physical,
chemical, and environmental factors and pathogenic organism lead to food spoilage
800 S. Gulati et al.

and deterioration. This perishable nature further results in the short postharvest life
of food products [16, 17]. Damage can start at any level:

• Harvesting level – Any negligence like harvest before optimal maturity date
leads to contamination till the food product reaches the market that can have
deadly effects on health if consumed.
• Processing level – At this level cross-contamination is often observed due to
germ-contaminated surfaces and kitchen tools.
• Distribution level – Often refrigerated food materials are left in warm weather
that causes temperature variation further causing bacterial growth. Also, contam-
ination in transporting vehicles can cause deterioration and decreased shelf life.

Figure 1 depicts the different sources of contamination by organisms majorly at

processing level where direct exposure to insects, mites, or rodents causes degrada-
tion in food quality. As shown, food substance in the first picture is attacked by fungi
due to unfavorable environmental conditions, whereas in second and third case, open
food became the site of attack by insects and rodents, respectively [18, 19]. Also,
some other examples for deterioration can be stated as follows:

• Cellular damage in fruits and vegetables during ripening

• Leafy vegetable water loss in low-humidity environment
• Open packaging food is attacked by rodents and ants

However, this deterioration can be prevented if necessary precautions are taken at

the desired level of food processing and packaging [20].

Microorganisms Insects and mites Rodents

a) Fungi a) Directly by a) Directly by
b) Bacteria eating. consuming food.
c) Phages b) Indirectly by b) Indirectly by
spreading diseases. spreadng diseases.
d) Protozoa

Fig. 1 Organisms that spoil food

36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 801

Food Preservation

It is a practice that is used to prevent the growth of microorganisms and slow the rate
of oxidation of fats and oils that are responsible for rancidity. An integrated approach
needs to be considered for studying preservation techniques [18]. Preservation
includes the following aspects to be considered:

• Identification of the property that needs to be preserved

• Techniques for maintenance of desired food quality against the related property

Need for Food Preservation

The tradition of “food preservation” goes back to ancient civilization, when the primitive
troupe first felt the need to conserve food after hunting a large animal that could not be
consumed at a time. Knowing food preservation techniques was the first and most
important step toward the establishment of civilization. Different cultures at different
times and locations used almost similar basic techniques to conserve food items. Further,
the outbreak of foodborne diseases has raised the awareness of public about the
necessity of prevention from microorganism contamination [21]. Quality is an ever-
changing phenomenon that may reach its undesirable state if stored for a longer duration
or kept under inappropriate conditions. The presence of any pathogen in food can result
in its poisoning, which can be deadly. The consequences of contamination can vary from
minimal of slight color loss to adverse food poisoning. Such effects pose risk to human
health and safety. Therefore, it is of utmost importance that the food must be protected at
all levels. Quality loss can be controlled at any level of the food chain.

Tenure of Food Preservation

After a certain period of storage, foodstuffs are exposed to reach an undesirable state.
The required best-before date depends on the purpose that the product will serve to the
consumer. For example, meals in dinner can have a shelf life of 1 day and hence does not
need any typical preservation; however, the opposite can be the case where foodstuff is
required for space travelers as it may even need a shelf life longer than a year [22].

Conventional Food Preservation Strategies

Food preservation strategies have three common actions of mechanism:

• Inhibition of microbial growth – This is generally performed by using a wide

variety of chemicals to maintain appropriate pH. For example, phenolic antiox-
idants obtained from natural sources are used for preservation. A range of herbs
and spices possessing antimicrobial properties have been used.
802 S. Gulati et al.

• Inactivation of bacteria, fungi, yeasts, or enzymes – Heat energy is utilized for

inactivation. Also, low electric field stimulation is known to control bacterial
growth in meat products.
• Avoiding recontamination – It is an indirect approach used for preservation via
active packaging strategies.

Preservation techniques greatly vary depending on the origin of the food product.
For example, fish products (animal origin) require chilling and electrical stimulation,
while plant origin products often need preservation against temperature and gas
compositions [23].
Some conventional methods are reported below:

• Drying – Water plays an important role to activate food spoilage mechanisms as it

supports the growth of microorganisms and enzymes above activity of 0.95. In
this process, water content is lowered by evaporation. Besides, its advantage that
it reduces the weight of food products possesses some major drawbacks:
(i) Loss of functional groups like lipids, vitamin C and proteins is observed
during drying process.
(ii) Loss of flavor and aroma is also observed in some cases.
• Chilling – In this process, temperature of food material is maintained between 1
and 8  C. This reduces the rate of biochemical and microbiological change.
Additionally, it also extends the shelf life of fresh and processed foods. Apart
from its certain advantages like retardation of growth of microorganisms, it also
has a plethora of disadvantages which limits its use. For example, it is capital
intensive as it requires special equipment.
• Irradiation – It is a physical process in which food substance is treated with a
particular dose of ionizing radiation (IR). Increased shelf life and disinfestation
were observed in food treated with IR. Like other conventional techniques, it also
has certain limitations as high doses of IR cause the loss of micronutrients.

Apart from these three, there are many other conventional strategies like freezing,
retorting, thermal sterilization, etc. Also, chemical reagents are long known for
preservation and food additives. But continuous usage of hazardous chemicals had
shown an adverse effect on human health. Also, all these conventional techniques
require high capital intensive and more human power, and moreover they are time-
consuming. It shifts the focus of food scientists to look for greener and eco-friendly
approaches like use of plant-mediated nanomaterials to preserve food [18].

Nanotechnology in Food Science

Nanotechnology has changed the domains of food science especially in fields of

preservation and safety of food due to their physiochemical nature and antimicrobial
property. In nanoform, properties are modified that possess enhanced and versatile
surface chemistry with wide range of applications. For example, a large variety of
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 803

nanomaterials from inorganic metal oxides and their nanocomposites to nano-

organic bioactive agents have been identified for their wide application in food
industry. It comes from physical, chemical, and mechanical understanding at the
atomic level. It considers interdisciplinary science for enhancing the property of food
material [24, 25]. The brief explanation about application of nanotechnology in food
science is shown in a schematic manner in Fig. 2 [26]. As represented, it serves
following purposes:

• Food packaging – For example, intelligent sensing nano-coated packaging,

bio-based packaging, etc.
• Food preservation – For example, encapsulation, humidity treatment, etc.
• Food processing – For example, nano-additives, nanocarriers, etc.
• Nanosensors – For example, nanosensors used for food analysis

Biomaterials are being widely used material in food science industry. They are
made by mixing nanostructured materials with other polymers. Combining nano-
structure materials with other polymers, biomolecules, and other nanostructure

Fig. 2 Nanomaterials in food

science

Food
packaging

Food
preservation

Nanomaterial
in Food science

Food
processing

Nano-sensors
804 S. Gulati et al.

materials or existing in aggregate form may result in a relatively larger particle size
(>100 nm) resulting in the formation of nanocomposites. These high surface-
volume ratio nanomaterials exhibit inimitable physiochemical characteristics such
as solubility, toxicity, strength, magnetism, color, and thermodynamics. Applications
of these nanomaterials are growing in a variety of sectors, including agriculture,
medicine, clothing, cosmetics, food, and public health, due to their unique ability to
be used in these fields.

Role of Nanotechnology in Food Preservation

The key objectives of food preservation are to overcome inadequate planning in

agriculture, to produce value-added products and to provide for dietary variation.
Following the limitations of conventional techniques, nanotechnology seems to be
an emerging branch for effective food preservation. Nanostructured food ingredients
are being developed on the grounds that they offer improved taste, texture, and
consistency [20]. Nanotechnology increases the shelf life of different kinds of food
materials and also helps to reduce the amount of food wastage due to microbial
infestation because of their unique surface properties [24].
Figure 3 states the different methods with examples that can be applied to modify
the properties of food products in terms of preservation and safety using nanotech-
nology. For example, edible nano-coatings provide resistance to moisture and gas
exchange with additional enhancement in terms of flavor, appearance, and aroma to
food products. Special attention is given to plant nanoparticles and their use in
preservation techniques [27, 28]. In addition, functional foods where the bioactive
component are often degraded and eventually inactivated due to the hostile environ-
ment; nanoencapsulation of bioactive components increases the shelf life of food
products by slowing down degradation processes or preventing degradation until the
product is delivered to the target site [11].
The above method depicted in Fig. 3 is discussed below in detail.

Nanoencapsulation

Nanoencapsulation is a technique in which the particles of the active substance (core

material) are polymerized with incredibly small capsules (wall material) [11]. Nano-
materials on a scale of 1 and 100 nm are commonly being used in different areas of
the food industry. The polymer or nanocapsule provides a protective film, separating
the inner center of the active agent and preventing the impact of insufficient
exposure. A major aspect in the development of a nanoencapsulated product is the
choice of the wall material; usually, a polymer is chosen based on the physicochem-
ical characteristics of the active agent and the intended application. A vast array of
natural and synthetic polymeric matrixes was used, such as carbohydrates (starch,
cellulose, and chitosan), polyethylene, protein (casein, albumin, and gelatin), lipids
(fatty acids, wax, and paraffin), and gum (alginate, carrageenan, and Arabic gum).
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 805

NANOLIPOSOMES EDIBLE COATINGS

• Vitamins, nutraceuticals, nutrients, • Thin materials made from food-grade

and antimicrobial compounds. components that are added to the outer
surface of the food.
• Fuses with the microbe deliver
owth and
payload and prevents the growth ndd • H
Helps improve the shelf life of fresh-
replication of the bacteria. cu
cut fruits.
NANO

TECHNOLOGY
NANOENCAPSULATION
N POLYMER
IN FOOD NANOCOMPOSITES
• Preserve their antimicrobial
activity. PRESERVATION • Nanoparticles integrated with
nano clay, carbon nanotubes, etc
• Nanomaterials encapsulate
essential oils which improve • Protects food by showing
their antifungal and antibacterial inhibitory activity against
properties. Pseudomonas, Staphylococcus.

•
NANOEMULSION-BASED
COATING

• Essential oils extracted from plants

have good antioxidant and
antimicrobial properties.E.g
oregano and thyme.

• Lemongrass nanoemulsion, present

in edible coating increases the shelf
life of apples, grape berrie.

Fig. 3 Different nanomaterials used in food preservation

Nanoencapsulation technologies for bioactive compounds with antimicrobial

activity can be used to protect EOs (essential oils) during the process of their
integration into the polymeric matrix. Essential oils (EOs) are aromatic substances
generated naturally as secondary metabolites by a particular plant species [11]. EOs
typically comprise terpenoids and phenolic and aromatic compounds, and their
composition may differ depending on the edaphoclimatic characteristics of the
plant, the part of the plant (flower, seed, fruits, leaves, stems, and others) used for
extraction, and the extraction method. Encapsulation greatly improved EO’s effi-
ciency against Aspergillus flavus. In vivo research showed important antifungal
properties of encapsulated oils at concentrations greater than 700 mg/L [11].
However, the effective integration of EOs into packaged food or food pack-
aging is minimal, since EOs are volatile compounds, have substantially lower
solubility, and are highly prone to oxidation. Encapsulation techniques can
also improve their oxidation stability, light-induced reactions, moisture, and
high temperatures and therefore preserve their antimicrobial activity, which is
crucial.
806 S. Gulati et al.

Nanoliposomes

Nanoliposomes are efficient in the targeted delivery of vitamins, nutraceuticals,

nutrients, and antimicrobial compounds, as liposomes are tiny in size and have a
greater surface area for surface interaction with biological tissues, making nano-
liposomes more bioavailable [29]. Earlier, the ability of targeted nanoliposomes to
transfer antibiotic compounds to food materials has been exploited, making nano-
liposomes an effective vehicle for administering antibacterial activity to food against
the growth of spoilage-causing and pathogenic microorganisms and consequently
increasing the shelf life of food.
Recently, several factors have been identified for liposome fusion with bacterial
cells, such as bacterial membrane characteristics, divalent cations, pH at the
surface of the bacteria, and temperature. The entry of negatively charged liposomes
is enabled by nonspecific receptors on the cells, followed by particle recognition
and adhesion, ultimately leading to endocytotic processes in the cells [29]. The
liposome fusion to the bacterium is largely based on the lipid composition of the
bacterial membrane. The high phosphatidylethanolamine content of gram-negative
bacteria appears to stimulate the merging of fluid liposomes. As a result, the extent
to which the properties of the liposome affect the fusion with the bacterial cell is
essential to develop an optimized system that effectively fuses with the microbe,
delivers a payload, and destroys or prevents the growth and replication of the
bacteria.

Polymer Nanocomposites

Nanocomposites can be generally defined as biopolymers integrated with nano-

reinforcements such as nanoclays, carbon nanotubes, metal nanoparticles, cellu-
lose microfibrils, etc. [29]. They have also shown that structural and biological
properties required for food packaging applications are improved. The incorpora-
tion of nanofillers in composites provides additional functions in food packaging
materials, such as the conferring of antimicrobial activity, oxygen or ethylene
scavenging, and implanted nanosensors to indicate the safety of the consumer.
Polymer bionanocomposites with antimicrobial activity are extremely suitable for
reducing the growth of post-processing pollutant microorganisms, thus increasing
the shelf life of food products as well as improving food safety [30]. Through the
growing sustainability trend of packaging materials, paper and polymer nano-
composites present a new class of packaging materials. In this study paper sheets
from rice straw (as waste agricultural materials) coated with 5 or 10% polystyrene
(PS) nanocomposites using titanium dioxide nanoparticles (TiO2NPs) which may
or may not comprise silver nanoparticles (AgNPs) were prepared, and the inhib-
itory effect of modified paper sheets was shown to be contrary to Pseudomonas,
Staphylococcus aureus, Candida, and Staphylococcus. Polymer nanocomposites
have also been shown to be able to protect food by inhibiting the growth of
foodborne microbes [30].
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 807

Edible Coatings

Edible coatings (ECs) are usually very thin materials made from food-grade components
that are added to the outer surface of the food, thereby being part of the food product and
stay in the product through use and consumption [29]. ECs contribute to food preser-
vation by decreasing moisture and controlling oxygen and carbon dioxide permeability,
thereby reducing the migration, respiration, and oxidation rates without sacrificing the
quality or quantity of the commodity. ECs have a high potential to serve as a carrier
vector for anti-browning agents, color pigments, flavoring compounds, micronutrients,
and antimicrobial agents that help to improve the postharvest life of food products by
suppressing the development of food spoiling pathogens on the food surface [31].
Edible coatings made from nanoemulsion-based solutions represent an important
approach to placing active ingredients on the surface of minimally processed foods.
Usually, edible coatings are used in fresh-cut fruit as a technique to reduce the
adverse effects of limited processing [49]. Also, edible coatings can help to improve
the shelf life of fresh-cut fruit by minimizing moisture and solute migration, gas
exchange, respiration, and oxidative reactions, as well as by minimizing or even
suppressing physiological disorders [49]. Experimental results indicate that
nanoemulsion-based edible coatings containing 0.1 percent (v/v) of LEO (lemon-
grass essential oil) presented higher suppression of E. coli as well as slower growth
of psychrophilic bacteria on fresh-cut apples during storage compared to edible
coatings with traditional emulsions at almost the same concentration. This research
opens up new perspectives for the use of nanoemulsions as edible coatings to ensure
the protection and quality of fresh-cut goods [17, 19].

Essential Oils and Nanoemulsion-Based Coating

Essential oils (EOs) are bioactive compounds extracted from plants with potent antiox-
idant and antimicrobial properties. The potential of essential oils (EOs) to keep food
products protected from gram-positive and gram-negative pathogenic bacteria was
defined in the study [50]. To perform active antibacterial action in food uses, the addition
of high loading of EOs is usually needed, which could affect the odors and flavors of the
food products. Among the best active EOs, thyme and oregano EOs have been identified
for maintaining good antimicrobial activity in meat packaging, which could be due to
the presence of phenolic compounds, primarily thymol and carvacrol [51].
Figure 4 shows the interaction of foods with nanoemulsions formed in edible
coatings with a polymeric matrix. Also, it can be seen that oil droplet and emulsifier
forms a nanoemulsion which forms edible coating on the surface of food that further
helps to prolong the shelf life of the food. Essential oils (EOs) derived from spices and
plants have antioxidant and antimicrobial effects [52]. They are also known to be
special additives in the food industry. Also, most of them are classified as widely
accepted as safe and nontoxic. However, their use as food preservatives is mostly
limited due to their strong taste. EOs are inserted into edible films to avoid this.
Considering the avoidance of the use of chemical additives in food products,
808 S. Gulati et al.

Fig. 4 Nanoemulsions in edible coating of fruits

researchers have given further attention to the use of natural food additives with
antioxidant and antimicrobial properties that have no harmful effects on human health.
Recently, the need for natural elements to build new food preservatives against
spoilage and pathogenic microbes has increased exponentially. Essential oils are one
of the main classes of natural antimicrobial components that have been considered an
effective food industry preservation system. Solid nanoparticles of lipids, liposomes,
and emulsions are among some of the encapsulation systems [10].
Lemongrass nanoemulsion, present in edible coating or sodium alginate, has been
used in research to increase the shelf life of apple slices under specific refrigeration
conditions as shown in Fig. 4. The inhibition of the E. coli population was observed
to an untraceable amount, shortly after coating, which remained unidentified
throughout the 14 days of storage in the refrigerator [52]. In another study, nano-
emulsion coating with tiny droplets of lemongrass oil demonstrated greater efficacy
in the protection of grape berries and in enhancing the safety of microbes against
Salmonella than coatings with large droplets [52].

Indirect Methods for Preservation

In addition to the direct approach, other measures, such as packaging and quality
management tools, need to be implemented in the process of preservation in order to
avoid contamination or recontamination. Although these measures are not preserva-
tion techniques, they play an important role in the production of high-quality safe
food through indirect methods [32]. With regard to procedures that restrict access to
food by microorganisms, the use of aseptic packaging techniques for thermally
processed food has increased considerably in recent years, both in terms of the
number of applications and the number of alternative techniques that are commonly
available. A great deal of progress has been made from skins, leaves, and barks in the
development of diversified packaging materials and equipment. Packaging has three
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 809

• Role of packaging material in food

preservation.
• Biobased packaging and their action
FOOD PACKAGING in food preservation.

• Antimicrobial Properties of plant

Nanoparticles useful in food
preservation.
FOOD PROCESSING • Some Nanoparticles with
antimicrobial activity against
Phytopathogens.

Fig. 5 Schematic representation depicting indirect methods used for food preservation

main functions. The first is to control local environmental conditions in order to

improve storage life. The second is the display, i.e., the preservation of the product in
an attractive manner to the potential purchaser. The third function is to protect the
product while it is in transit to the consumer. The new concept of active or lifesaving
packaging materials allows for a one-way transfer of gases away from the product or
absorption of gases that are harmful to the product, antimicrobials in packaging,
release of preservatives from controlled release surfaces, oxygen scavengers, carbon
dioxide generators, absorbers or scavengers of odors, and absorption of selected
wavelengths of light, and there are capabilities for controlled automatic switching.
Another concept of edible or biodegradable packaging has also been evolved for
environmental reasons. Processing and packaging can be integrated to improve
efficiency. Figure 5 depicts the indirect methods through packaging and better
processing of food products that ultimately helps in preservation.
These indirect approaches are discussed further in detail below.

Food Packaging and Its Conventional Strategies

Food packaging is essential to protect the material from physical, chemical, and
environmental factors that can result in its contamination. Additionally, packaging is
also a useful marketing strategy to attract consumers.
Essential packaging strategies involves material that exhibits:

• Flexibility
• Appropriate gas permeability
810 S. Gulati et al.

• Increased shelf life of products

• Wastage reduction

Conventionally, plastic packaging has gained much success because many of

them can be molded, cast, and blown in different shapes or membranes. Further-
more, they are known for increasing the shelf life of food products. For example,
unwrapped cucumber loses moisture and becomes dull within 3 days, but 1.5 g of
plastic wrapping can keep a cucumber fresh for 14 days. However, post-consumer
waste generated by plastic packaging has been a major concern. Also, most materials
used are nonbiodegradable, which remain in the environment for long periods and
cause threats to human health as well as to the environment. Thus, bugs reported
with plastic packaging demand for its preferential elimination. The future of
eco-friendly packaging relies upon the use of biopolymers, plant-based polysaccha-
rides, and plant-based nanomaterial or nanocomposites [33]. The utilization of
nanotechnology in packaging applications is an emergent area as they are known
to exhibit finer barrier and mechanical properties as well as biodegradability
[30]. Besides this, some packaging material holds the potential for improving the
active antibacterial, antifungal, and antioxidant properties of food material.

Role of Packaging Material in Food Preservation

Food is a perishable item, and hence packaging of food is the most crucial step for
food safety and preservation. Therefore, packaging with the potential to inhibit the
activity of pathogenic microbes in food has been extensively studied to overcome
these issues and deliver safer food products.
The incorporation of nanoparticles as an antimicrobial agent has emerged to aid
advances in food preservation. Nanotechnology-derived food packaging can be
classified into two different categories:

• Active packaging
• Smart packaging

Active packaging involves the direct interaction between the nanoparticles with
the food products or the environment to achieve a greater degree of preservation in
food products. It serves multiple functioning such as antioxidant, oxygen scavenger,
flavoring, moisture absorber, ultraviolet barrier, and antimicrobial properties. Some
nanocomposite materials have been used in active packaging to prevent oxygen,
carbon dioxide, and moisture from reaching the food [34]. Further to increase gas
barrier properties, these NPs are integrated with the polymer matrix. The contact of
these nanocomposites with food material is permissible. On the other hand, smart
packaging is created to sense any microbial or biochemical changes in food prod-
ucts. Some such smart packaging has been designed and developed to be used as a
tracking device for food security levels [1]. Nanotechnology has been employed to
create “smart” packaging, which elongates the shelf life of food and also permits it to
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 811

be transported to a longer distance. Some nanosensors are utilized in designing

microchips (invisible to the naked eye) that are further embedded into food products
that act as electronic barcodes [35]. Nanoceramic particles are used for clustering dirt
molecules to maintain the freshness of cooking oil [36]. Nanotechnology has created
a benchmark in food preservation by developing highly sensitive and low-cost
nanosensors, which respond actively to a subsequent change in environmental
conditions during storage, degradation products, or contamination by microbes.
Such nanosensors can be effectively utilized in packaging materials [37, 38].

Bio-based Packaging and Their Action in Food Preservation

Bionanocomposites are good alternatives to petroleum-based plastics in packaged

foods. The combination of bio-based nanocellulose develops a green bionanocomposite
with improved antimicrobial behavior. Besides, the nanocomposite can serve as a good
packaging material that not only helps protect food from microorganisms but also
addresses issues related to the aggregation of agricultural waste and environmental
pollution. Among all biopolymers, polylactic acid (PLA) is the most suitable candidate
in terms of its unique mechanical properties comparable to the common plastic
packaging material. The production of PLA by fermentation of agricultural resources
(or waste) can reduce carbon dioxide emissions, possibly leading to reduced pollu-
tion, as well as addressing the problem of the depletion of fossil fuels. Also, the
abundant availability of agricultural residues can be used to produce nanocellulose.
Nanocellulose may be incorporated into a biopolymer (e.g., PLA) to develop greener
bionanocomposites.
[30] documented new polymer bionanocomposites as packaging material using
chitosan, carboxymethyl cellulose, and ZnONPs, which were produced using casting
techniques that showed finer thermal and mechanical properties. Scientific research
is being conducted by mixing natural antibacterial agents, e.g., plant extracts are
mixed into the biopolymer films, to meet the consumer needs for safer food items.
Figure 6 below represents the structure of important biopolymers commonly used for
production of bionanocomposites.

O n

Polylactic acid
Cellulose

Fig. 6 Some biopolymers used to develop bionanocomposites

812 S. Gulati et al.

Food Processing

Food processing can be defined as the process of preserving food by means of methods
and techniques for converting food into a consumable state. These techniques are
designed to keep the taste and quality of food intact, but they are also protected from
infestation by microorganisms that lead to spoilage of food [39]. Radiation, ohm
heating and high hydrostatic pressure are few of the conventional methods of food
processing. Food processing methods involving nanomaterials include the incorpora-
tion of nutraceuticals, gels, and viscosifying agents; the delivery of nutrients, mineral,
and vitamin fortification; and nanoencapsulation of flavors. Food processing is mainly
carried out in order to keep the food intact and also to increase its shelf life. Processed
food helps the producer to transfer it over a very long distance without running the risk
of spoiling the food. The annual availability of different kinds of food, especially
seasonal food such as peas or corn, is also one of the benefits of processed food. Fresh
food is not the sole aim of the food processing industry. Producing healthier food is
also a concern, and therefore these days, processed food contains micronutrients which
are of great benefit to consumers. Hence these methods of food processing play an
important role in reducing food waste and improving food preservation, thus reducing
the overall environmental impact of agriculture and improving food security [40]. The
importance of nanotechnology in food processing can be evaluated by considering its
role in the improvement of food products in terms of (i) food texture, (ii) food
appearance, (iii) food taste, (iv) nutritional value of the food, and (v) food shelf life.
Nanoparticles have finer encapsulation and release efficiency properties than
traditional encapsulation systems [53]. Nanoparticles mask odors or tastes; monitor
the interactions of active ingredients with the food matrix; control the release of
active agents; ensure availability at a given time and rate; protect them from
moisture, heat, chemical, or biological degradation during processing, storage, and
utilization; and also exhibit compatibility with other compounds in the system.
Nanotechnology offers a variety of choices to increase the quality of food and
also helps to improve the taste of food. Nanoencapsulation techniques have been
commonly used to enhance flavor release and retention and to deliver the culinary
balance used by nanoencapsulation for highly reactive and unstable plant pigment
anthocyanins with various biological activities. By encapsulating cyanidin-3-O-
glucoside (C3G), molecules inside the inner cavity of apo recombinant soybean
seed H-2 subunit ferritin (rH-2) improved thermal stability and photostability.

Role of Food Processing in Food Preservation

Food preservation involves different food processing steps to maintain food quality
at the desired level so that maximum benefits and nutritional values can be achieved
[41, 18, 42]. This can be achieved by applying the following food processing
techniques:
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 813

• Blanching – It is a thermal pre-freezing treatment with the aim of inactivating

enzymes such as polyphenol oxidase (PPO) and peroxidase (POD) that are
responsible for browning reactions and lead to off flavor development. Blanching
also destroys microorganisms on the surface of the product and makes some
vegetables more compact. Microwave blanching could be an alternative to
conventional blanching, with precise process control, shorter processing time
and less energy consumption, and a reduction in the blanching time of the product
center. Many studies have concluded that the microwave technique leads to firmer
products, equal or better nutrient content, and similar colors compared to con-
ventional processing.
• Tempering – It is the method of bringing a food product to a temperature
where there is a considerable amount of water in the product in the form of ice,
but not all of the water has become ice. Tempering can be considered to be the
initial phase of the complete thawing process. Thawing is often seen as simply
reversing the freezing process. Most of the bacteria that cause spoilage or food
poisoning are found on the surfaces of many foods. During the freezing
operation, the surface temperatures are rapidly reduced and the bacterial
multiplication is severely limited, with the bacteria becoming completely
dormant below -10  C. These same surface areas are the first to rise in
temperature during the thawing operation, and bacterial multiplication can
start again. Surface spoilage may occur on large objects subjected to long
uncontrolled thaw cycles before the central regions have fully thawed. The
thawing of frozen food is an important unit of operation in the food industry.
Large quantities of food must be preserved by freezing at harvest time
for use throughout the year. In microwave thawing, electromagnetic waves
are absorbed directly by the product without the use of conductors or
electrodes.
• Baking – It is a complex process, described as a simultaneous transfer of heat and
mass. Baking involves a series of physical, chemical, and biochemical changes in
food, such as starch gelatinization, protein denaturation, carbon dioxide release
from leaven, volume increase, water evaporation, crust formation, and non-
enzymatic browning. Microwave baking allowed a reduction of up to 93 per
cent in baking time compared to convective baking. Microwave-baked cakes
showed improved textural properties such as moisture content and firmness.
Another advantage of microwave baking is that the final product has a higher
nutritional value.
• Pasteurization – It is a physical preservation technique in which food is
heated to a specific temperature to destroy spoilage-causing microorganisms
and enzymes. Almost all pathogenic bacteria, yeasts, and molds have been
destroyed by this process. As a result, the shelf life of food is increasing.
Sterilization is the inactivation of microorganisms and their spores,
which are generally more heat-resistant than the vegetative cells. Microwave
heating of food offers an excellent opportunity to pasteurize or sterilize the
products.
814 S. Gulati et al.

Antimicrobial Properties of Plant-Based Nanoparticles Useful

in Food Preservation

Nanoparticles (NPs) derived from plants that show promising antibacterial activities
have a high potential to be developed into future antibacterials mainly due to their
low toxic effects [43]. NPs are reported to inhibit gram-positive bacteria, like
Staphylococcus spp., Streptococcus spp., and Bacillus spp., and gram-negative
bacteria such as Escherichia spp., Pseudomonas spp., Salmonella spp., Shigella
spp., Proteus spp., and Vibrio spp. More promisingly, NPs also inhibit antibiotic-
resistant bacteria such as methicillin-resistant S. aureus (MRSA) and drug-resistant
E. coli. Gram-negative species that have been targeted the most are E. coli and
P. aeruginosa, whereas the gram-positive species that are mostly targeted are
S. aureus followed by B. subtilis and B. cereus. Also, the type and the total number
of gram-negative bacterial species being targeted in the study are more than gram-
positive species. This highlighted the potential of NPs as antibacterial agents because
they could effectively penetrate and destroy gram-negative bacterial species known
to penetrate multilayer membranes. Potent antibacterial killings of NPs have shown
their potential to develop into antibacterials capable of working against intestinal
bacteria (e.g., E. coli, P. aeruginosa, B. cereus, K. pneumonia, S. flexneri, and
S. typhi) and skin-related bacterial infections (S. aureus).
Many NPs have been approved by either the Food and Drug Administration
(FDA) in the United States or the European Medicines Agency (EMA) in the
European Union for numerous clinical applications including imaging (e.g., Reserv-
ist), iron-replacement therapy for anemia treatment (e.g., Vifor), delivery of antican-
cer drugs (e.g., Onivyde and Mepact), vaccines for viral diseases (e.g., Epaval
against hepatitis A and Inflexal V against influenza), fungal infection (e.g.,
AmBisome), and so on. However, not any of the currently approved NPs is used
for controlling the bacterial infection. The only liposomal NP formulation that has
undergone a clinical trial is CAL02, which has been designed for bacterial pneumo-
nia management. Understanding the bactericidal mechanism of NPs helps to control
and overcome the emerging issue of bacterial resistance to NPs. Antibacterial NPs
that are produced with the help of green technology have tremendous potential to be
developed into future antibacterials and can positively enhance the efficacy of
antibiotics.
Conventional chemical methods for AuNP synthesis usually involved the reduc-
tion of gold (III) through the use of chloroauric acid metallic salt (HAuCl4) in
aqueous citrate solutions. The reducing agent greatly affected the size of the syn-
thesized AuNPs. However, chemical synthesis methods have contributed to reduced
stability and a high accumulation of AuNPs, which can be solved by the use of a
two-phase liquid-liquid system. In this, a two-phase redox reaction was carried out
with the aid of two reducing agents, such as toluene and borohydride, in the presence
of dodecanethiol. However, during the synthesis and recovery procedures, the
leakage of the chemical reducing and stabilizing agents to the environment causes
negative effects on human health and the environment. It has therefore become very
important to consider alternate options and solutions for the reduction of gold and
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 815

the stabilization of AuNPs that can reduce or avoid the associated adversities. Plant-
derived natural compounds can be used as effective reducing and stabilizing agents
that can provide stable size and agglomeration of synthesized AuNPs.
Plant-based AuNPs have been well reported as an antimicrobial agent [6]. This
property of AuNPs might be attributed to their smaller size (250 times smaller than
bacterium), which helps them to bind with the cell wall of the microorganism and
hence leads to the death of the cell. AuNPs are known to be active against both the
gram-positive (Staphylococcus aureus) and gram-negative (Klebsiella pneumonia,
Escherichia coli) bacteria; however, it is slightly more effective against gram-
negative bacteria which maybe because of the thin peptidoglycan layer in the cell
wall of gram-negative bacteria, which allows AuNPs to break the cell wall, bind to
the cell membrane, and interact with proteins and DNA. In contrast, gram-positive
bacteria contain a thick peptidoglycan layer in their cell wall which is actually
made up of linear polysaccharide chains cross-linked by short peptides and hence
presents a more rigid structure and makes it very difficult for AuNPs to pass
through it.

Some Nanoparticles with Antimicrobial Activity Against

Phytopathogens

Plant extracts are used in these techniques, and they represent a promising opportu-
nity to obtain nanoparticles with antimicrobial activity, taking advantage of the fact
that plants are considered as bioactive molecule reservoirs with several biology
applications, in particular antibacterial, antifungal, and antiviral properties
[44]. Every plant organ (leaves, flowers, seeds, root, bark, etc.) is an important
source of phytochemicals that can ultimately be used to synthesize nanoparticles due
to their excellent reduction and stabilization properties. The use of plant extracts
contributes to the generation of biocompatible NPs, as nontoxic compounds are
produced during their synthesis, which reduces their hazardous environmental
impact. Nanoparticle green synthesis is a highly viable alternative when plant
extracts are combined with ions such as Ag, Au, Cu, Cd, Al, Se, Zn, Ce, Ti, and
Fe, as most of these ions are found to be toxic in their ionic form and are widely used
for their antimicrobial properties. These nanoparticles may then be used to develop
products with antimicrobial activity and with the potential to improve the shelf life of
food and food products (Table 1).

Silver Nanoparticles (AgNPs)

AgNPs were synthesized with the help of Justicia spicigera extracts and demon-
strated significant antimicrobial activity against several foodborne bacteria (Bacillus
cereus, Klebsiella pneumonia, and i) and phytopathogenic fungi (Colletotrichum sp.,
Alternaria alternata, and Macrophomina phaseolina). In this study, AgNPs with
particle sizes ranging from 86 to 100 nm and having spherical morphology are found
to show effective antibacterial and antifungal activity against the microorganisms
tested.
816 S. Gulati et al.

Table 1 Mechanisms of action of nanoparticles naturally synthesized showing antimicrobial

activity against phytopathogens
Types of A plant extract used Phytopathogen Mechanism of action
nanoparticles to obtain the NP type of NP References
AgNPs 1. Justicia spicigera Bacteria and 1. Release of ions [30]
extract fungi which proved to be
2. Fresh fruit extract toxic toward
of Solanum torvum pathogens
2. Enhance the
permeability of the
bacterial membrane
3. Disrupt the
bacterial membrane
Al2O3NPs 1. Cymbopogon Bacteria 1. Release ions that [44]
citratus leaf extract are toxic toward
pathogens
2. Augment ROS
production
AuNPs 1. Ocimum Bacteria 1. Disrupt the [43]
tenuiflorum flower bacterial membrane
and leaf extracts and alter metabolism
2. Extracts from 2. Cause damage to
Azadirachta indica cell organelles (cell
and Mentha spicata wall and
leaves mitochondria)
3. Green synthesis
with okra
CeO2NPs 1. Plant extracts such Gram-positive 1. Inhibit transport [44]
as Aloe barbadensis, bacteria and through pumps
Gloriosa superba, fungi 2. Induce oxidative
Camellia sinensis, degradation of lipids
and Acalypha indica and/or proteins of the
plasma membrane of
the pathogen
CdONPs 1. Extracts obtained Bacteria 1. Cause release of [44]
from Leucaena ions which are toxic
leucocephala leaves against pathogens
2. Induce oxidative
stress on the cells of
bacteria
CuNPs/ 1. Extracts from Bacteria and 1. Increase ROS [44]
CuONPs papaya leaves fungi production
2. Cause damage to
important molecules
such as DNA
SeNPs 1. Extract from Bacteria and 1. Cause depletion of [44]
propolis plant fungi intracellular ATP
2. Induces oxidative
stress through ROS
production
(continued)
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 817

Table 1 (continued)
Types of A plant extract used Phytopathogen Mechanism of action
nanoparticles to obtain the NP type of NP References
SiNPs/ 1. Synthesized using Bacteria and 1. Inducts physical [29]
SiO2NPs plant debris, such as fungi damage to the
bamboo, rice husks, bacterial membrane
and bagasse from 2. Increase ROS
sugar beets production
TiO2NPs 1. Extracts from Bacteria and 1. Cause an increase [44]
Trigonella foenum- fungi of ROS production
graecum and 2. Induces
Azadirachta indica photocatalytic
damage
Fe2O3NPs 1. Aqueous extracts Bacteria and 1. ROS production [45]
of neem leaf fungi causes oxidative
(Azadirachta indica) stress
2. Yuquilla leaf 2. Destroys cell
extract (Ruellia membranes and
tuberosa) thereby inducing
3. Extracts from changes in the
eucalyptus leaves morphology of cell
(Eucalyptus robusta) and cause the release
of cell components

In a recent study, AgNPs which were obtained from fresh fruit extract of Solanum
torvum have shown antibacterial activity against the phytopathogens [44]. The
effectiveness of AgNPs was tested against the plant pathogen Xanthomonas
axonopodis pv malvacearum. Campestris and the growth of these microorganisms
were inhibited which would prevent the plant from getting infected.
Taking these results into consideration, some studies have indicated that the
antibacterial effects of these types of nanoparticles can be improved by modifying
their surface charge to neutralize the bacterial cell membrane charge to ultimately
help in the induction of depolarization. AgNPs not only attach to the bacterial cell
wall but may also enter the cell and then interact with structural components and
biomolecules, like lipids and DNA, through the functional groups on their surfaces.
The bactericidal activity of AgNPs results from their interaction with thiol groups in
L-cysteine residues of the proteins and subsequent inhibition of enzymes. Recently,
it was indicated in a study that AgNPs induced ROS production, caused DNA
damage, and inhibited DNA replication in phytopathogenic bacteria.

Aluminum Oxide Nanoparticles (Al2O3NPs)

Aluminum (Al) is known to be one of the most versatile, economic, and attractive
elements among all metals. Typically, it is found in the form of alloys with other
elements and also shows electrical conductivity and thermal properties [45]. Based
on this, Al is a widely used material with numerous applications which range from
structural engineering to food and beverage technology.
818 S. Gulati et al.

Al2O3NPs obtained through green synthesis using citronella (Cymbopogon

citratus) leaf extract showed in vitro antibacterial activity against Pseudomonas
aeruginosa [44]. It has been previously shown that these bacteria affect plants and
humans. The antimicrobial effect of Al2O3NPs may be attributed to the ionic
interaction of Al3+ with the pathogen cell components. Al2O3NPs are positively
charged at neutral pH. The positive surface charge promotes an electrostatic inter-
action between negatively charged pathogenic cell membranes and Al2O3NPs to
induce adhesion to the microbial surface, thereby decreasing cell viability.

Gold Nanoparticles (AuNPs)

AuNPs have antifungal properties, and it is synthesized using Mentha piperita
essential oil against Aspergillus niger. These nanoparticles have shown a spherical
structure, having a 60 nm mean size. Additionally, it was reported on the synthesis of
AuNPs with a 20–30 nm mean size by using Ocimum tenuiflorum flower and leaf
extracts, Azadirachta indica, Mentha spicata leaves, and Citrus sinensis pee
[44]. These particles showed antibacterial properties against Pseudomonas
aeruginosa. In a study, it was shown that AuNPs were obtained by green synthesis
with okra (Abelmoschus esculentus) and had important antimicrobial effects against
phytopathogens such as Aspergillus flavus and Aspergillus niger [46].
AuNPs inhibit peptidoglycan synthesis, which causes porosities in the cell walls
and ultimately leads to the leakage of cellular content toward the exterior, inducing
cell death. It is also possible that AuNPs may bind to bacterial DNA to prevent its
uncoiling and transcription [46].

Cerium Oxide Nanoparticles (CeO2NPs)

Nanoparticle synthesis using plant extracts such as Aloe barbadensis, Gloriosa
superba, Camellia sinensis, and Acalypha indica is one of the most commonly
used methods for obtaining CeO2NPs, primarily due to their antimicrobial properties
against phytopathogens, like Aspergillus niger, Aspergillus flavus, Fusarium solani,
and Pseudomonas aeruginosa.
CeO2NPs have shown antimicrobial activity against gram-positive and gram-
negative bacteria, and the highest inhibitory effect was found against the latter
[44]. Gram-positive bacteria possess a thick peptidoglycan layer, which contains
linear polysaccharide chains with short peptides to form a rigid structure and prevent
CeO2NP passage. Conversely, gram-negative bacteria, with a thin peptidoglycan
and lipopolysaccharide layer, are more vulnerable to attacks from external agents.

Cadmium Oxide Nanoparticles (CdONPs)

The use of Agathosmabetulina leaves to obtain environmentally friendly CdONPs
with a high potential for use in medicine and agriculture was reported in a recent
study [44]. CdONPs were obtained by green synthesis using extracts obtained from
Leucaena leucocephala leaves and were effective against bacteria. Furthermore,
the antimicrobial activity of CdONPs has been tested against clinical strains of
Streptococcus pyogenes, Staphylococcus aureus, Escherichia coli, and Candida
albicans.
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 819

CdONPs cause increased oxidative stress in cells, which further leads to oxidation
of cellular components, disruption of the cell membrane, and interruption of trans-
membrane electron transport. The detrimental effects caused by ROS126 contribute
to altering cell replication and transcription processes, and they may even induce
mutations to induce cell death.

Copper/Copper Oxide Nanoparticles (CuNPs/CuONPs)

It is found that CuNPs show antimicrobial activity against a wide range of patho-
gens, either bacterial or fungal. In particular, CuNPs synthesized by green chemistry
have been of interest as an ecological option because of their effectiveness in
controlling phytopathogens [44]. CuNPs have also been found to be used as anti-
microbial agents due to their high surface/volume ratio and also their easy interaction
with other particles to which increases their antimicrobial effectiveness.
Furthermore, in a study, it was obtained that CuONPs were synthesized using
extracts from papaya leaves with bactericidal activity against Ralstonia solanacearum,
the causal agent of bacterial wilt. The results showed that CuONPs had strong
bactericidal effects and that CuNPs act as fungicides by generating highly reactive
hydroxyl radicals (• OH), which may induce damage in biological macromolecules
like DNA of fungal pathogens. This damage subsequently causes their death [47].

Selenium Nanoparticles (SeNPs)

The antioxidant and antimicrobial properties of SeNPs synthesized with propolis
extract have been demonstrated to be effective against fungal strains as well as gram-
positive and gram-negative bacteria. SeNPs, synthesized by green chemistry, have
been reported to possess antimicrobial activity against phytopathogens such as
bacteria and fungi [44].
SeNPs are electrostatically repelled by the liposaccharides of gram-negative
membranes. Conversely, gram-positive bacteria exhibit a considerably less negative
charge, which may allow for a higher SeNP deposition on the membrane surface,
thus inducing bacterial death.

Silicon/Silicon Dioxide Nanoparticles (SiNPs/SiO2NPs)

It has been reported that Si induces defense responses toward multiple pathogens,
thus having a positive effect on the control of bacterial and fungal diseases. For this
reason, Si is one of the most widely used elements, making it a powerful antimicro-
bial agent against phytopathogens, such as Fusarium oxysporum, Aspergillus niger,
Penicillium citrinum, Pythium, Blumeria graminis f. sp. tritici, and Magnaporthe
grisea [44]. NPs are synthesized through biological methods using plant debris, such
as bamboo, rice husks, and bagasse from sugar beets. Recent studies have shown that
large spherical SiO2NPs did not cause mechanical damage to the bacterial mem-
brane. Therefore, the possible antibacterial mechanisms of coatings with SiO2NPs
may be (i) induction of dose-dependent cytotoxicity and lipid peroxidation of the cell
membrane mediated by excessive ROS production, (ii) mechanical damage to the
cell membrane, and (iii) functionalization of the nanoparticle surface caused by
several elements.
820 S. Gulati et al.

Titanium Dioxide Nanoparticles (TiO2NPs)

TiO2NPs obtained by green synthesis using extracts from Trigonella foenum-
graecum and Azadirachta indica displayed important antimicrobial activity against
several bacterial strains and drug-resistant fungi (Bacillus subtilis, Salmonella typhi,
Proteus mirabilis, E. coli, Staphylococcus aureus, and Klebsiella pneumonia)
[44]. The antimicrobial activity of TiO2NP is particularly attributed to its crystal
structure, size, and form. However, a commonly proposed mechanism by which
TiO2NPs induce specific damage to DNA is oxidative stress caused by ROS.
TiO2NPs act by degrading the cell wall and plasma membrane through a
ROS-mediated (• OH and H2HO2) process. This cell wall degradation firstly leads
to the release of cell contents and then ultimately cell lysis. Generally, the catalytic
properties of TiO2 induce damage to microbial cells.

Iron Oxide Nanoparticles (Fe2O3NPs)

The synthesis of Fe2O3NPs through the use of plant extracts allows for the gener-
ation of a large number of antimicrobial agents with ecological materials, which
saves time and energy, in a sustainable way and with less toxic effects. An example
of Fe2O3NPs with antimicrobial activity was reported by using aqueous extracts of
neem leaf (Azadirachta indica), obtained Fe2O3NPs for the control of phytopatho-
gens from apple orchards (Alternaria mali, Botryosphaeria dothidea, and Diplodia
seriata) [44].
Fe2O3NPs, synthesized with yuquilla leaf extract (Ruellia tuberosa), inhibited the
growth of clinical and plant pathogens, such as Staphylococcus aureus bacteria. It
was studied that eucalyptus leaves (Eucalyptus robusta) were used to obtain
Fe2O3NPs capable of inhibiting the growth of pathogenic bacteria, such as Pseudo-
monas aeruginosa and Bacillus subtilis. Finally, Fe2O3NPs synthesized with aque-
ous extracts of Tridax procumbens showed maximum antimicrobial activity.
The antimicrobial activity of Fe2O3NPs could be due to their accumulation in the
cytoplasm because smaller NPs have a greater capacity to penetrate the cell mem-
brane. This would cause leakage of cellular material as well as NP accumulation
inside the cell, increasing the interaction between the Fe2O3NPs and the cellular
biomolecules, which causes conformational changes in the structure of the proteins
and the DNA and finally leads to the death of the bacteria [48].

Conclusion

The food industry has come so far meeting the needs of its consumer. However,
increasing the shelf lives of food without causing any reduction in an original food
product is still critical and under research. Conventional strategies like drying,
chilling and, freezing have been preferentially eliminated with growing demands
due to certain shortcomings. Multiple chemicals are reported to enhance the food
properties. However, their excessive use poses a limitation when human and envi-
ronmental factors are considered. These days nanotechnology has gained attention
due to its unique surface properties. Particularly plant nanoparticles, edible film
36 Plant-Based Nanomaterials: Novel and Highly Effectual Preservatives for Food 821

coatings, and nanoencapsulation are reported to be greener and eco-friendly

approaches in food preservation. Also, some modifications in synthesis of metal
nanoparticles were reported in literature which are greener in nature and avoid the
use of hazardous chemicals.

Important Websites

1. https://www.downtoearth.org.in/news/food/nanotechnology-can-make-plant-
based-food-preservatives-more-effective-64286
2. https://www.thehindubusinessline.com/news/science/nanotechnology-can-
make-plant-based-food-preservatives-more-effective/article27001583.ece
3. Highly effective natural plant-based food preservative discovered %2D%2D
ScienceDaily
4. Food Preservatives from Plants | IntechOpen
5. Scientists discover natural plant-based food preservative (phys.org)
6. Use of Natural Antimicrobial Agents: A Safe Preservation Approach |
IntechOpen
7. The long road to all-natural preservatives (acs.org)
8. A natural line of defense in food preservation: “Combating food degradation,
fighting food waste” (foodingredientsfirst.com)
9. Extending Shelf Life With Natural Preservatives (acs.org)
10. What Are Natural Preservatives? - Public Goods Blog
11. 13 Natural Ways to Make Food Last Longer Without Toxic Preservatives
(paleohacks.com)
12. Nano-coated ‘killer paper’ developed to extend food shelf life (foodnavigator.
com)
13. Chemical-reducing innovations for food preservation & processing | Food and
Farming Technology
14. Edible, plant-based coating developed for fruit packaging | Engineering360
(globalspec.com)
15. Advances in cellulose-based food packaging material move to testing phase of
industrial production (phys.org)
16. Nanotechnology and food - FoodBev Media
17. Role of sustainable packaging in brand preservation (bizcommunity.com)

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01501
 Part XI
Consumer Nanoproducts for Textile and
Packaging
The Design, Synthesis, and Characterization
of Iron Oxide-Based Coating-Based 37
Nanoproducts

Fatma Kubra Ata, Seda Yalçınkaya, and Serap Yalcin

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
The Chemical and Physical Properties of Iron Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
The Synthesis and Design of Iron Oxide-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
Physical-Based Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
Chemical-Based Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
Biological-Based Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
The Characterization of Iron Oxide-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
Functionalization of Iron Oxide-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
Applications of Iron Oxide-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842

Abstract
Iron oxide-based nanoparticles have great interest in biomedicine, due to their
wide range of applications. The synthesis of iron oxide-based nanoparticles is a
very important procedure so both physical and chemical properties of the nano-
particles must be controlled with different analyses. The properties of the syn-
thesized nanoparticles are determined by these analyzes, energy dispersive X-ray
(EDX) spectroscopy, Fourier transform infrared spectroscopy (FT-IR), infrared
(IR) absorption spectroscopy, atomic force microscopy (AFM), dynamic light
scattering (DLS), hydrophobic interaction chromatography, vibrating sample
magnetometry (VSM), scanning electron microscopy (SEM), and transmission

F. K. Ata
Department of Genetics and Bioengineering, Kirsehir Ahi Evran University, Kirsehir, Turkey
S. Yalçınkaya
Department of Food Engineering, Süleyman Demirel University, Isparta, Turkey
S. Yalcin (*)
Department of Molecular Biology and Genetics, Kirsehir Ahi Evran University, Kirsehir, Turkey
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 827

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_56
828 F. K. Ata et al.

electron microscopy (TEM), etc. Nanoparticles that are successfully synthesized

and optimized can be used safely and allowing widespread biomedical uses such
as targeted drug delivery, bioimaging, hyperthermia, biosensors. This chapter
focuses on synthesis and characterization methods of iron oxide-based nano-
particles and also includes in future perspectives in iron oxide-based cancer
therapy.

Keywords
Iron oxide-based nanoparticles · Synthesis · Characterization · Nanoparticles

Abbreviations and Symbols

AFM atomic force microscopy
ATR attenuated total reflection
CPT coprecipitation
DLS dynamic light scattering
DLS dynamic light scattering
EBL electron beam lithography
EDX energy dispersive x-ray
ESEM environmental SEM
FCS fluorescence correlation spectroscopy
FT-IR Fourier transform infrared spectroscopy
GISANS grazing-incidence small-angle neutron
scattering
GISAXS grazing-incidence small-angle x-ray
scattering
IONs iron oxide nanoparticles
IR infrared
İron oxide-based nanoparticles nanoparticles
MRI magnetic resonance imaging
MS mass spectroscopy
MTB magnetotactic bacteria
NMR nuclear magnetic resonance
NSOM near-field scanning optical microscopy
PVD physical vapor deposition
RS Raman scattering
SANS small-angle neutron scattering
SAXS small-angle x-ray scattering
SEM scanning electron microscopy
SERS surface-enhanced Raman scattering
SPIONs superparamagnetic iron oxide nanoparticles
STM scanning tunneling microscopy
TEM transmission electron microscopy
TERS tip-enhanced Raman spectroscopy
TGA thermal gravimetric analysis
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 829

VSM vibrating sample magnetometry

XPS x-ray photoelectron spectroscopy
XRD x-ray diffraction analysis
α alpha
γ gamma
emu electromagnetic unit
eV electronvolt
g gram
3D three dimensional
NH4OH ammonium hydroxide
O oxygen
Fe iron
nm nanometer
K kelvin
psi pound-force per square inch
Cl
chlorides
w/o water-in-oil
o/w oil-in-water

Introduction

The concept of nanotechnology was first introduced with Richard’s hypothesis

“Why can’t we write all 24 volumes of Encyclopedia Britannica on a pin?”
[18]. After Feynman discovered this new field of research, it has attracted the
attention of many scientists. Undoubtedly, nanotechnology has become a rapidly
growing field with the development of nanoparticles (iron oxide-based nano-
particles) that produced by different methods, especially physical and chemical
methods [18, 25, 26].
The iron oxide-based nanoparticles are commercially produced materials with
diameters ranging from 1 nm to 100 nm [11]. Their size-dependent features make
these materials excellent and essential in the diagnosis and treatment of various
diseases. İron oxide-based nanoparticles serve as a unique delivery system for the
transport of substances such as DNA, monoclonal antibodies, proteins, and drugs,
especially in the field of medicine [54]. On the other hand, iron oxide-based
nanoparticles also present significant potential for many technological field applica-
tions such as aeronautics and space exploration, nanoelectronics and computer
technology, biotechnology, and agriculture [24, 27, 60].
So far, iron oxide-based nanoparticles have been formed from polymeric
materials, bioceramics and metal or nonmetallic materials according to their
sizes and shapes [10]. While carbon and silica-based nanoparticles are included
in the group of nonmetallic, aluminum, copper, gold, iron, silver, titanium, and
zinc-based nanoparticles are included in the group of metallic [1, 6]. Interestingly,
it is stated that iron, the metal found in the earth’s crust, forms the basis of iron
oxide-based nanoparticles [23]. This metal chemically combines with oxygen
830 F. K. Ata et al.

and forms the iron (III) oxide [6]. Iron (III) oxide mineral is commonly found in
forms of hematite (α-Fe2O3), magnetite (Fe3O4), and maghemite (γ-Fe2O3)
[6]. These oxides are increasingly attracting interest as they show unique elec-
trical, optical, and magnetic features for nanotechnology applications [13,
28, 29]. Especially their low toxicity, superparamagnetic properties, and simple
separation methodology make them suitable in some biomedical applications
such as diagnostic magnetic resonance imaging (MRI), thermal therapy, 3D cell
culturing, cell separating, and drug delivery [2, 6, 49]. In vivo and in vitro studies
have shown that iron oxide-based nanoparticles remain in the organelles after
entering the cells and are released into the cytoplasm after decomposition. At the
same time, it is stated that it contributes to diagnosis and treatment of many
diseases, especially cancer [10, 45, 50, 76].
In the past two decades, many chemical-based, physical-based, and biological-
based methods of preparation have been developed to obtain iron oxide, α-Fe2O3,
Fe3O4, and γ-Fe2O3 on the nanoscale [6, 13]. Among these methodologies,
coprecipitation, sol-gel, microemulsion (one or two-phase method), and thermal
decomposition chemical-based methods are commonly preferred due to low cost
and high efficiency [6, 13, 37, 44]. In addition, iron oxide is also synthesized by
using new methods such as an automated droplet reactor and a single-step green
synthesis method [5, 30]. However, synthesis method, size, shape, and quality of
iron oxide-based nanoparticles significantly affect the reaction parameters and
determine the attitude of nanoscale iron oxide in different applications.
Because the size of iron oxide-based nanoparticles is even smaller than the
light wavelength, it is stated that it is very difficult to detect by human eyes
[16]. Therefore, special devices such as transmission electron microscopy
(TEM), scanning electron microscope (SEM), and atomic force microscope
(AFM) are used to view them [16, 46, 48]. Those devices can image of iron
oxide-based nanoparticles, measure their size directly, and reveal shape data, yet,
they are limited to running several particles at a timeone time. Another charac-
terization technique is devices belonging to the “reciprocal space” category such
as small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS),
grazing-incidence small-angle neutron scattering (GISANS), and grazing-
incidence small-angle X-ray scattering (GISAXS) [16, 40]. The advantage of
those devices is that they take a large number of samples at the same time and
usually do not need any specific sample preparation. However, the most signif-
icant restriction of techniques like SAXS is that their resolutions are compara-
tively lower compared to others [6, 16].
In the current era, interest is increasing in the synthesis, design, and charac-
terization of iron oxide-based nanoparticles for use in different areas in industrial
production and medical purposes. Based on this current interest, information
about the design, synthesis, and characterization of iron oxide-based nano-
particles is given in this chapter. Moreover, it is aimed to shed light on future
studies by indicating the advantages and disadvantages of characterization and
synthesis methods.
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 831

The Chemical and Physical Properties of Iron Oxide

Iron is known to be a ferromagnetic substance with a high magnetic moment density

of 220 emu/g, making up 5% of the Earth’s crust. This material is magnetically soft
and shows a superparamagnetic property below 30 nm. However, since iron gener-
ally contains some impurities such as oxides and carbides, iron oxide-based nano-
particles synthesis from pure iron is indicated as a very complex process [20].
Chemically, the most common forms of iron are iron (II) and iron (III) oxide
mineral. These forms have become the center of attention with their some applica-
tions, such as catalysts, electromagnetic devices, magnetic storage media, pigments,
optical devices, and sensors [38]. Also, they find in wide polymorphs and hydration
states. Therefore, their physical and chemical properties generally vary according to
particle size and hydration rate [20]. Iron oxide-based nanoparticles with diameters
above 30 nm are defined as hydrodynamic and those with hydrodynamic diameters
below 30 nm are defined as supermagnetic IONs (SPIONs). Especially SPIONs are
used to determine the differences between healthy and pathogenic tissues due to their
high magnetic sensitivity and saturation and low toxicity. The production ways, size
and shape of these particles greatly affect their biological distribution [20, 39, 47].
SPIONs usually consist of an iron oxide in the center and can be coated organic or
inorganic components. Among iron oxides, Fe3O4 is predominantly preferable. This
oxide is seen as one of the oxides with the most interesting crystal phases due to its
polymorphism (Fe2+ and Fe3+ ions) [3, 8]. Also, Fe3O4 presents an inverse spinel
structure, which formed by stacking plans as a polyhedral model, and it has a face-
centered cubic unit cell based on 32 O
2 ions [13]. Although it is rarely antiferro-
magnetic, this form generally shows the ferrimagnetic property at temperatures
below 858 K (Curie temperature or Néel temperature) [17]. The other two iron
oxides used in the center of SPION are rhombohedral hematite (α-Fe2O3) and cubic
maghemite (γ-Fe2O3) and the less common ε-Fe2O3 phases. Hematite is the most
common polymorph found as a mineral in rocks and soils. It has paramagnetic
property above 956 K and weak ferromagnetic or antiferromagnetic property at room
temperature. The structure consists of the ion O
2 reticle as a close-packed hexag-
onal system and Fe+3 ions. However, α-Fe2O3 have become attractive materials due
to its widespread applications such as gas sensors, pigments, and magnetic recording
materials in catalysis [20]. Maghemite, another ferrimagnetic mineral, is thermally
variable and transforms into hematite at a temperature above 673 K ([74]; Oliveira
et al. 2013). It has a spinel crystal structure similar to magnetite, but the gaps in the
cation sublattice are not. Two-thirds of the zones have loaded with regularly
arranged Fe (III) ions, and the two filled zones have followed by a gap zone
((Fe+3)8[Fe+340/3□8/3]O32) [13] (Fig. 1).
β-Fe2O3, E-Fe2O3, wustite (FeO), FeOOH, and Goethite (α-FeOOH) are other
rare structures of iron oxide. The thermodynamically unstable form transforms into
α-Fe2O3 or γ-Fe2O3 when exposed to heat [36]. E-Fe2O3 is defined as an ortho-
rhombic crystal structure formed by the close folding of the oxygen molecule.
Although its magnetic behavior is not fully understood, it has regarded as a
832 F. K. Ata et al.

Fig. 1 A schematic representation of the core, coating, and ligand of iron oxide core [17]

polymorphous intermediate (two magnetic transitions: one near 495 K and the
other at 110 K) [36]. Wustite, another iron oxide, is a paramagnetic crystal of Fe
and O with a cubic symmetry structure [57]. It also shows high concentration
imperfections, so it is quite hard to obtain a pure crystal. The other structure is
Goethite (α-FeOOH), which belongs to the oxide and hydroxide group. The form
has a Curie temperature of 393 K and shows the antiferromagnetic property in the
bulk state (Koch et al. 1986).

The Synthesis and Design of Iron Oxide-Based Nanoparticles

Many chemical-based, physical-based, and biological-based synthesis methods have

developed to obtain iron oxide magnetic iron oxide-based nanoparticles in nano-
metric scales used in today’s technology [6, 13, 75, 76]. Among these methods,
chemical-based synthesis methods are the most preferred because of low cost and
high yield. However, it is not known exactly which method of synthesis is better. It is
stated that the precise requirement must ensure that all steps are controlled in the
realization conditions of the preferred method for obtaining nanoparticles. The effect
of synthesis method on properties such as crystal structure, size, shape, and pore
structure is also important on the iron oxide-based nanoparticles structure (Table 1).

Physical-Based Synthesis Methods

Mechanical pressure, thermal or electrical energy, and high-energy radiation are

applied to ensure abrasion, melting, evaporation, and condensation of iron oxide
nanoparticles with physical-based methods. Some of the physical methods used in
iron oxide-based nanoparticles synthesis are electron beam lithography, physical
vapor deposition, inert gas condensation, high energy ball milling, laser ablation,
and laser pyrolysis [15, 32]. These methods do not contain contamination from the
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 833

Table 1 Advantages and disadvantages of iron oxide synthesis methods [6]

Techniques Methods Advantages Disadvantages References
Physical Electron beam Well-controlled Need expensive and [32]
lithography interparticle spaces complex machinery
Deposition of Easy to execute Particle size difficult to [15]
gas phase control
Oxidation Narrow size Ferrite colloids of small [71]
distribution and size
uniform size
Chemical Easy and effective Unsuitable for high [72]
coprecipitation purity synthesis and
stoichiometric phase
Chemical Flow injection Well homogeneity, Under a laminar flow [59]
accurate control and regime in a capillary
reproducibility reactor, the need to
constantly mix reagents
Aerosol/vapor Large-scale products Requires very high [33]
phase temperatures
Sonochemical Size distribution in Still, mechanism is not [67]
decomposition narrow particle well understood
Using Possibility to Complicated conditions [66]
nanoreactors specifically control
the size of iron
oxide-based
nanoparticles
Biological Microbial High yield and low Slow and laborious [52]
incubation cost

solvent component and produce monodisperse iron oxide-based nanoparticles;

therefore, they are advantageous. However, the most significant disadvantage of
these methods is that they require expensive and complicated machines.
Electron beam lithography (EBL) that emerged in the late 1960s is created by
electron irradiation of a surface coated with electrons-sensitive resistance by means
of a focused electron beam. Energy absorption in certain regions causes intramolec-
ular events that define the properties in the polymeric layer. This lithographic
process, which consists of three stages: expression of sensitive material, pattern
transfer, and development of resistance, can create submicronic structures. It is also
important to know that these are not considered independently and that the end of the
process depends on the cumulative effect of each step [32].
Physical vapor deposition (PVD) is an ecofriendly vacuum deposition technique,
which is widely used to accumulation thin layers of material, generally in the range
of few nanometers to several micrometers [63]. It consists of three main stages:

– Evaporation of material from a hard source

– Transportation of evaporated material
– Nucleation and development for iron oxide-based nanoparticles formation.
834 F. K. Ata et al.

Sputtering, pulsed laser deposition, and electron beam are the most widely used
PVD methods for nanoparticle synthesis (Dhinakar 2016).
The laser pyrolysis method was first developed in the early 1980s. This method,
which is a vapor phase synthesis process, is used in the synthesis of oxide (Al2O3,,
Fe2O3, SiO2, TiO2) and nonoxide (MoS2, Si, Si3N3) iron oxide-based nanoparticles.
The technique is summarized in two steps:

– Laser energy absorbed by gases causes molecules to dissociate (nuclei).

– Fast homogenous nucleation, then the growth of nanoparticles takes place

Using this technique, maghemite particles of different shapes from 5 nm to 60 nm

are formed by different iron precursors (Dhinakar 2016).

Chemical-Based Synthesis Methods

These methods are known as easy to apply, followable, and effective methods.
Chemical vapor synthesis, hydrothermal synthesis, microemulsion technique,
plasma-enhanced chemical vapor deposition technique, polyol synthesis, and
sol-gel method are some of the most widely used chemical methods for the iron
oxide-based nanoparticles synthesis. The shape, size, and composition of the iron
oxide-based nanoparticles synthesized using these methods depend on the ratio
of Fe2 + and Fe3 +, the type of salt used, ionic strengths, and some factors such
as pH [6].
The sol-gel method, which developed with the need for new synthesis
methods in the nuclear industry in the 1960s, refers to hydrolysis [58]. The first
step of this method is to convert the starting material to a more gel consistency
(sol). Metal alkoxides or chlorides (Cl
) are commonly used precursors in the
method. These precursors are hydrolyzed and concentrated to colloid form. In the
reaction that takes place at room temperature, heat treatment is applied to form
the final crystal structure [31]. In the equation shown below, the reaction steps of
magnetite particle formation from the Fe+3 solution by the sol-gel method are
summarized.

1. Disproportionation: Fe+3 + H2OFe(OH)x

2. Oxidation: Fe(OH)x
3. Magnetite dehydration: Fe3O4 (pH 9.0, 60  C)

This method, besides being economically feasible, is preferred in terms of being

suitable for production at low temperatures in order to provide better control
opportunity. However, it should be taken into consideration that magnetic iron
oxide-based nanoparticles show high chemical activity and surface energy, which
may cause dispersion and agglomeration of the iron oxide-based nanoparticles.
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 835

Fig. 2 Iron oxide-based nanoparticles (Yalcin et al., Unpublished data)

Coprecipitation (CPT) is another method used to generate Fe3O4 and γ-Fe2O3. In

this method, it is applied by mixing ferric and ferrous ions in an aqueous media
containing sodium hydroxide (NaOH) or ammonium hydroxide (NH4OH) [62]. İron
oxide-based nanoparticles created by this method are between 5 and 20 nm in
diameter. The important parameters for the method are temperature, type of salt to
be used such as chloride, sulfate, ferric and ferrous ratios, pH value, ionic forces in
the media (Wu et al. 2008). The technique results in a reduction of the Fe+2 and Fe+3
ion mixture shown in the following chemical reaction [53] (Fig. 2).

Feþ2 ðaqÞ þ Feþ3 ðaqÞ þ 8OH
ðaqÞ ! Fe3 O4 ðsÞ # þ4H2 O

Microemulsion method is defined as thermally stable, isotropic dispersions

consisting of polar phase (usually water), nonpolar phase (usually hydrocarbon
liquid or oil), and surfactant. In this technique, monodisperse spherical droplets of
water in oil (w/o) or oil in water (o/w) depending on the surfactant are used.
Especially, the w/o reverse micellar system provides a perfect reaction area in NP
synthesis [34]. This micellar is a water-in-oil emulsion, forming the polar head
groups of the surfactant and showing inward orientation, and the organic tails of
the surfactant molecules are located outward as shown in Fig. 3.
The negative effects of surfactants on the properties of the micelles and the
difficulties in scaling the procedure are major drawbacks of the method [65].
The hydrothermal method occurs in a sealed container at high vapor pressure
(>2000 psi) and in an aqueous solution where high temperature (>200  C) is
maintained. The method is divided into two categories as the Batch hydrothermal
or the Continuous hydrothermal process. While the continuous hydrothermal reac-
tion takes place at a higher rate in a short time, the batch hydrothermal takes place in
836 F. K. Ata et al.

Fig. 3 (a) typical reverse micelle system, (b) one microemulsion process

phases at the desired rate. With this technique, dislocation-free single crystal parti-
cles are grown so high crystalline iron oxide-based nanoparticles are obtained [60].
Sonochemical synthesis is the process of producing various nanostructured materials
using powerful ultrasound radiation [75]. Ultrasound chemically causes cavitation in an
aqueous environment where foaming and collapse occurs (Ashokkumar et al. 2007).
Flowchart of synthesis:

FeCl3 :6H2 O þ NaOH ! Mixing ! Sonication ! Drying ! Sintering ! Fe2 O3

Biological-Based Synthesis Methods

Biological-based synthesis method called green synthesis is preferred because it is

ecofriendly, low cost, and efficient. Biological organisms such as bacteria, fungi,
yeast, and plant extracts are used for the synthesis of nanoparticles with the green
synthesis method [21] (Fig. 4). In a study conducted in 2006, it was observed that the
pathogenic fungus Fusarium oxysporum and the endophytic fungus Verticillium
sp. produced magnetite nanoparticles [12].
In another study, it was found that magnetotactic bacteria (MTB) use the iron
source to convert magnetite or greigite (Fe3S4) into magnetic crystals [68]. However,
advances in the practical use of MTB-Iron oxide-based nanoparticles have been
slow, highly due to production limitations. These properties in living organisms are
important in nanotechnology and other application areas (Fig. 5).

The Characterization of Iron Oxide-Based Nanoparticles

After synthesis of the iron oxide-based nanoparticles is completed, iron oxide-based

nanoparticles properties must be determined. For this purpose, characterization
techniques are used to understand some properties such as the morphological
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 837

Fig. 4 Green synthesis of iron oxide-based nanoparticles

Fig. 5 Magnetosome formation in Magnetotactic bacteria (a) Magnetotactic bacteria

structure of the iron oxide-based nanoparticles surface, chemical structure, and

determination of functional groups. These techniques are divided into two categories
as microscopic techniques and spectroscopic techniques [13].
Microscopic characterization techniques generally include the use of scanning
electron microscopy (SEM) and transmission electron microscopy (TEM). SEM offers
the opportunity to examine the surface and subsurface regions of nanoparticles. It also
provides a high depth of field, high resolution, and a 3-dimensional image [51]. On the
other hand, TEM has a higher and spatial resolution that is effective in atomic analysis
of iron oxide-based nanoparticles. Also, TEM readily produces projected 2D images
of the nanoparticles between 1 nm and 100 nm.
838 F. K. Ata et al.

Spectroscopic characterization techniques are used to determine the crystal struc-

ture properties of iron oxide-based nanoparticles such as width, density and angle and
chemical structure. Energy dispersive X-ray (EDX) spectroscopy, Fourier transform
infrared spectroscopy (FT-IR), Infrared (IR) absorption spectroscopy, atomic force
microscopy (AFM), dynamic light scattering (DLS), hydrophobic interaction chroma-
tography, vibrating sample magnetometry (VSM) are some of the devices used in this
technique [13]. In addition, nanoparticle tracking analysis, thermal gravimetric anal-
ysis, and zeta-potential measurements are also performed in the characterization of
iron oxide-based nanoparticles [6, 76]. In characterization studies, it is stated that
besides spectrophotometric and optical techniques, textural and structural features are
also important. In this regard, the Brunauer-Emmett-Teller method is generally pre-
ferred to determine the specific surface area of a solid, using nitrogen gas as the
adsorbate and nitrogen (77 K) as the coolant [13]. Another method, Barret, Joyner, and
Halenda, is used to characterize the shape, size, and pore distribution of iron oxide-
based nanoparticles by calculating desorption-absorption isotherm [35].
Magnetic characterization techniques are used to determine the magnetic prop-
erties of iron oxide-based nanoparticles. VSM are the most important technique to
measure iron-oxide-based nanoparticles, such as saturation magnetization, remnant
magnetization, etc. [64] (Table 2).

Functionalization of Iron Oxide-Based Nanoparticles

For medical applications, organic/inorganic coatings of iron oxide-based nano-

aparticles improve dispersion, surface activity, physicochemical and mechanical
properties, and biocompatibility. Therefore, iron oxide-based nanoparticles are

Table 2 Analytical techniques for characterization of iron oxide-based nanoparticles [6]

Technique Properties of technique
Dynamic light scattering (DLS) Size distribution
Zeta-potential Surface charge
Near-field scanning optical Shapes and size in nanomaterials
microscopy (NSOM)
Infrared spectroscopy (IR) Surface properties
Scanning electron microscopy Size and shape distribution
(SEM)
Transmission electron microscopy Shape heterogeneity, size, dispersion and accumulation
(TEM)
Atomic force microscope (AFM) Shape heterogeneity, size, dispersion, accumulation
Nuclear magnetic resonance Indirect analysis of size, structure purity, concentration and
spectroscopy (NMR) conformational variations
X-ray diffraction (XRD) Crystalline properties, size
Small angle X-ray scattering Shape, structure, size, and size transportation
(SAXS)
Vibrating sample magnetometry Magnetic properties
(VSM)
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 839

used for specific drug targeting, hyperthermia, biosensor, antibacterial activity, and
magnetic separation of cells [22, 42].
Functionalization of iron oxide-based nanoparticles of iron oxide have been made
various methods include ligand exchange, ligand addition, silane coating,
aminosilane coating, polymer coating. Ligand addition is the addition of a ligand
molecule to the external surface of nanoparticles. The hydroxyl, carbohydrate, thyol,
and phosphonate, etc., groups can bind to the surface of nanoparticles [14].
Ligand exchange method play important role to control the surface properties of
nanoparticles [70]. Silica is the most used compound for surface coating of iron
oxide-based nanoparticles to reduce the toxicity. Silica coating is used to reduce the
toxicity of nanoparticles and to improve stability in water and it protects them in an
acidic environment [41, 73] (Fig. 6).
Polymer coating of iron oxide-based nanoparticles has been commonly investi-
gated for their unique physical and chemical properties. Polymer coating prevents
aggregation of nanoparticle, a steric/electrostatic repulsion can be produced by
coating the particles with polymers, and coating is important for MRI and drug
delivery applications [4, 43]) (Fig. 7).

Fig. 6 Functionalization of iron oxide-based nanoparticles

840 F. K. Ata et al.

Fig. 7 The organic and inorganic materials used for the functionalization of iron oxide-based
nanoparticles

Applications of Iron Oxide-Based Nanoparticles

Iron oxide-based nanoparticles commonly used for medical therapy such as mag-
netic separation, targeted drug delivery, magnetic resonance imaging (MRI), mag-
netic fluid hyperthermia and thermoablation, modulation of macrophage
polarization, and biosensing (Fig. 8) [22].
Iron oxide-based nanoparticles are linked with drugs, gene (siRNA, miRNA),
antibody, aptamer, protein, etc. and then magnetic nanoparticles have been widely
studied in biomedical areas(Fig. 9).
Table 3 summarizes some biomedical applications of iron oxide nanoparticles.

Conclusion

This chapter is focused the synthesis, surface functionalization, and characterization

of iron oxide nanoparticles, as well as their preclinical use in medicine as summary.
Iron oxide nanoparticles are important tools, especially biomedical applications
37 The Design, Synthesis, and Characterization of Iron Oxide-Based. . . 841

Fig. 8 Biomedical applications of iron oxide-based nanoparticles

Fig. 9 Schematic illustration of iron oxide-based nanoparticle

because of magnetic driving via the external field and their unique properties. Today,
iron oxide-based nanoparticles have been developing as multifunctional nano-
platform, which can be binding with antibodies, drugs, aptamer, etc. Up to now,
842 F. K. Ata et al.

Table 3 Application of iron oxide-based nanoparticles

Topics Application References
Iron oxide nanoparticle- MRI [61]
lipidic micelles
miRNA-loaded iron oxide- Cancer [76]
loaded nanoparticles
Fe3O4-aminosilane-coated Hyperthermia [56]
iron oxide nanoparticles
Titanium and iron titanium Biosensor [69]
oxide nanoparticles
Polymer-iron oxide EPR-independent drug delivery [55]
composite nanoparticles
Multifunctional graphene Magnetic targeted drug delivery dual magnetic [19]
oxide/iron oxide resonance/fluorescence imaging and cancer
nanoparticles sensing

many papers, reviews, book chapters have been written in the literature on iron
oxide-based nanoparticles. In the future as now and before, there seems to be a
luminous and extensive use of iron oxide nanoparticles and it will continue to be
discussed as in this section.

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Skin Substitute: An Eco-friendly
and Nano-Based Transdermal Wound 38
Dressing Material

Sneha Paul and Changam Sheela Sasikumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Common Types of Wounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Phases of Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Factors Affecting Wound Healing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Intrinsic Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
Extrinsic Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
Bottom- up Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
Top-down Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
Micro-Nano . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
Introduction and History of Silver Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
Properties and Application of Silver Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
Diameter, Surface Area and Volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Shape and Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Nanoparticle Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Particle Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Surface Chemistry and Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Measuring SNP Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
Types of Silver in the Term of Nano . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
Methods of Synthesizing Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
Characterization and Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
Transdermal Drug Delivery System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
Administration of Drug . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
Advantages and Limitation of Transdermal Drug Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 861
Characteristics of Several Drug Permeation through Transdermal . . . . . . . . . . . . . . . . . . . . . . . . . 861

S. Paul (*)
Medical division, Scope eknowledge, A Straive company, Chennai, India
C. S. Sasikumar
Clinical research, S.S healthcare; Clinical Research, Hycare Super specialty, Seed Fund Technical
sub committee; Golden Jubilee Women Biotech Park; Department of Biochemistry, Saveetha
Dental College, Chennai, India

© Springer Nature Singapore Pte Ltd. 2022 847

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_83
848 S. Paul and C. S. Sasikumar

Transdermal Film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 861

Technologies for Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 862
Polymer Membrane Permeation-Controlled TDDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 862
Polymer Matrix Diffusion-Controlled TDDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
Drug Reservoir Gradient-Controlled TDDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
Microreservoir Dissolution-Controlled TDDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
Types of Transdermal Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
Multiple-Layer Drug Adhesive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
Drug Reservoir in Adhesive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
Drug Matrix in Adhesive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
Drug Delivery Routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 865
Methods of Skin Penetration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
Basic Components Required for Transdermal Dressing Material . . . . . . . . . . . . . . . . . . . . . . . . . . 868
Characteristics of Polymer Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
Characteristics of Drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
Properties that Need to Be Considered . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 874
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 877

Abstract
It is an inevitable truth that nano-transdermal technology in act of temporary
wound healing skin substitute is a complicated and controversial theme indeed.
Therefore, a lot of attempts were carried out to formulate bio-nano-transdermal
dressing material, effective especially for wounds. The local route of administration
of a drug is taken into consideration within that the skin plays an important factor in
the targeted and systematic flow of drug delivery system. Wound healing is a
complicated and dynamic process. With that dealing with nanomaterials such as
transdermal films made of synthetic or natural polymers with antimicrobial prop-
erties, silver nanoparticle-embedded patches or dressing materials, bio-nano-scaf-
folds, etc. is a debatable topic due to their beneficial effect on accelerating wound
healing as well as the fear of their toxic nature. Hence, this chapter highlights the
nano-dressing materials, process of wound healing, and methods of synthesizing
silver nanoparticles which have always showed promising role in wound healing
process, about the transdermal drug delivery system, and formulation of the same.

Keywords
Transdermal technology · Nanotechnology · Silver nanoparticles · Wound
healing · Dressing material

Introduction

Nanotechnology is about designing the particles and materials in the nanoscale

production. Itinvolves numerous physical and chemical methods for synthesis,
in addition to control size and shape of the nanoparticles. These types of
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 849

nanoparticles create pressure and toxicity to environmental factors. Therefore,

the research on biodegradable nanoparticles is a fast-growing field which plays
a vital role in the field of nanomedicine and nanotechnology [1].
Furthermore, dressing of wounds during home accidents or in the war field has
been traditionally followed according to particular regional medications. In our
country (India) especially in olden times, the people used to cover the wounds
with turmeric paste, neem leaf, honey, Aloe vera pulp, and clay and may wrap it
with cotton fabric or cloth as an alternative form of protective barrier to the
wounded site. Then, slowly, advancement of the medicine leads to the develop-
ment of topical creams exclusively impregnated with silver nitrate as it has high
antimicrobial potential, tincture, alcohol rub, and fibrous synthetic material to
cover the wounds such as nylon, polyethylene, and polypropylene [2, 3]. Steadily,
there was improvement in the field of wound dressing. Incorporation of various
techniques like grafting and biotechnology has been taken into different era of
protective covering using skin from fish, pig, and even humans through cloning
procedures. Nowadays, large amount of money is spent in the research and
development of wound care, and currently, there are varieties of dressing such
as dry dressing, wet to dry dressing, chemical impregnated dressing, foam
dressing, alginate dressing, hydrofibre dressing, transparent film, hydrogel,
hydrocolloid dressing, or self-adaptive dressing [2, 3]. Hence, the limitation in
the conventional dressing material has opened new pathway in the research of
eco-friendly dressing material.

Wound Healing

Wound healing is a complex process. Apoptosis and necrosis are parts of

the normal development of healing. Apoptosis is a complex network of bio-
chemical and molecular pathway that regulates cell death. It is one of the main
mechanisms in the process of wound healing. This helps in the removal of
inflammatory cells and evolution of granulation tissue in the scarred
area [4–6]. In healthy individuals, the repair and wound mechanism are as
follows:

• Neutrophils are first cells that arise during wound, as they prevent invasion from
bacteria. Their activity is implicated in local and distinct tissue damage through
free oxygen radicals and protease.
• Neutrophils that enter the wound would have eliminated microorganism, under
apoptosis, and are later consumed by macrophages.
• Thus, further leading to the cycle of inflammation process.
• Migration of inflammatory cells to colonize the provisional matrix.
• Proliferation of fibroblast and vascular cell apoptosis.
• Synthesis of extracellular matrix to reconstruct the dermal architecture.
850 S. Paul and C. S. Sasikumar

Common Types of Wounds

The common types of wound are shown in Fig. 1.

Phases of Wound Healing

There are four phases of healing, namely, inflammatory phase, migratory phase,
proliferative phase, and remodelling phase. It is a continuous and steady process
merging with the next phase (Fig. 2) [6, 7].

Haemostasis and Inflammation Bleeding usually occurs during skin injury and
serves to flush out bacteria or antigen from injured site. Bleeding activates
haemostasis which initiates an exudate component such as clotting factor. Fibrino-
gen elicits the clotting mechanism resulting in coagulation and together the forma-
tion of fibrin network to stop bleeding. Clot further dries up and forms scab which
gives protection to the wounded site. This is simultaneously followed by inflamma-
tion, lasting for a few minutes to 24 hrs or 3 days. Necrotic tissue releases yellowish
colour mass, and platelet liberated from blood vessels becomes activated as they
contact with mature collagen and forms aggregates as part of clotting mechanism.

Migration It involves the movement of epithelial cells and fibroblast to the

wounded site. These cells regenerate from margin towards the centre site of the
wound, to form a scab accompanied by epithelial thickening.

Proliferation It is the next step after the migratory phase; observe skin tightening
and epithelial thickening taking place until collagen bridges the wound. The prolif-
eration of fibrin and collagen synthesis lasts for 2 weeks that results in a decrease in
blood vessels and oedema.

Maturation It is the final stage of the healing phase. During this phase, the tensile
strength of skin gets increased, and re-epithelization of skin takes place up to
12 months, according to the condition of the wound.

Factors Affecting Wound Healing

There are various factors that affect or delay the healing of wounds in an individual.
Therefore the lists of the factors are given out below in the flow chart (Fig. 3).

Intrinsic Factors

Health Status Blood flow and better circulation to wounded sites help in faster
healing of wounds, e.g. angiogenesis is an important parameter in wound healing;
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 851

Fig. 1 Common types of wound

852 S. Paul and C. S. Sasikumar

Fig. 2 Phases of wound healing

anaemic condition decreases the haemoglobin content that leads to slow blood
circulation in the wounded site [8, 9].

Immune Function If the immune system is weak, then the body loses its ability in
pervading the pathogens entering through the wounded site [8, 9].

Diabetes It is one of the cause of chronic wound, delaying capillary response to the
injury site. Hyperglycaemia is a prevailing condition in diabetes that results in the
delay of wound healing, as it lacks the synthesis of insulin and more prone to
infection [8, 9].

Age Factors As we age, the oil content of the body diminishes, thus resulting in
tearing of the skin, furthermore losing sensory cells. It is more prone to physical and
chemical damage [8, 9].

Body Build Obese individuals may have issue with wound healing because of the
inability of the body to deliver oxygen and nutrients to the wounded site. Even
underweight individuals also face the same problems with the healing process [8, 9].
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 853

Health status

Immune
function

Diabetes

Intrinsic

Age factors

Body build

Nutritional status

Factors

Mechanicalstress

Debris

Temperature

Extrinsic

Maceration

Infection

Chemical stree

Fig. 3 Flow chart of factors affecting wound healing

Nutritional Status Proteins, carbohydrates, fats, vitamins, and trace elements have
played a vital role in wound repair. Amino acid (arginine) as a supplement can
improve the rate of wound healing [8, 9].
854 S. Paul and C. S. Sasikumar

Extrinsic Factors

Mechanical Stress Immobile and sudden pressure results in tissue damage.

Debris The debris released on wound such as scab, eschar, and wound dressing
debris will disturb the healing process [8, 9].

Temperature Temperature plays an essential role in wound healing, e.g. moist

conditions cause difficulty in wound healing, hence leading to various infections.
Increased temperatures may lead to changes at the wound site with risk of cellular
breakdown, thereby limiting healing process.

Desiccation Exposed wound may significantly cause more pain and itchiness and
have scab material during healing [8, 9].

Maceration It will cause destruction of tissue and slows down healing.

Infection Bacterial colonization of wound site may cause difficulty in the healing
process.

Other factors can be alcohol, smoking, and synthetic medicines.

Nanotechnology

Nanotechnology can be characterized as designing of particles with a remarkable

property at a nanoscale. In 1959, Richard Feynman proposed a thought regarding
nanotechnology in the discussion “A lot of room at the base,” and Norio Taniguchi
(1974) instituted the term nanotechnology. A nanometre is one billionth size of a
metre. Atomic force microscope and scanning tunnelling microscope are the two
filtering tests that lead the way into the field of nanotech [10]. Emergences of
nanoparticles have prompted its applications in different parts, for example, elec-
tronics, biomedical, cosmetics, catalyst, and other materials. Nanotechnology is not
a new technology. In Ayurveda or sages era, some medicines are in the form of
churunam (fine powder), and size of particles suspended in the powder was in
nanosize. Still today it is available in the worldwide market.

Bottom- up Approach

The materials and devices are fabricated from atomic segments. Bottom-up, or self-
get together, ways to deal with nanofabrication use substance or physical powers
working at the nanoscale to mass essential units into bigger structures [11]. As
segment size abatements in nanofabrication, bottom-up methodologies give an
undeniably vital supplement to best down systems. Motivation for bottom-up
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 855

methodologies originates from organic frameworks, where nature has saddled sub-
stance strengths to make basically every one of the structures required by life.
Specialists want to reproduce nature’s capacity to deliver little groups of particular
molecules, which can then self-assembly into more expanded structures [11].

Top-down Approach

Nanoparticles are built without nuclear level. The most widely recognized top-down
way to deal with creation includes lithographic designing strategies utilizing short-
wavelength optical sources [12]. A key favourable position of the top-down method-
ology – as created in the manufacture of incorporating circuits – is that the parts are
both designed and constructed set up, so that now get together step is required [12].

Micro-Nano

Day by day the progress of nanotechnology has been noticed in biomedical field
such as drug delivery system, medical imaging, and lots more of military purposes
[13–17]. There are different kinds of metallic nanoparticles such as gold, silver,
platinum, iron, copper, etc., which have shown their unique application in the
biomedical sector, e.g. gold and ceramic oxide nanoparticles are used in tumour
and anti-inflammatory, silver nanoparticles are proven as an antimicrobial agent,
anti-inflammatory, disinfectant, and less toxic to the human system. Thus, silver
nanoparticles are given a lot of significance in the wound healing industries.

Introduction and History of Silver Nanoparticles

Novel strategies are being developed to probe and manipulate single atoms and
molecules. Among all nanoparticles, the metallic nanoparticle, such as silver has
application in different ranges, e.g. gadgets, cosmetics, and biotechnology. The
benefits of nanoparticles are to penetrate through the skin and target the specific
site. Earlier nanoparticles were synthesized by using different physical and chemical
methods. Biosynthesis/biological method was later reported. The present chapter
emphasizes on synthesis of silver nanoparticles by using biological sources. Silver
nanoparticles have differing properties like catalysis, attractive and optical polarizability,
electrical conductivity, antimicrobial action, and surface plasmon reverberation [11].
The overall history of nanoscience and nanotechnologies is summarized in the
flow chart (Fig. 4) [18]. Nanosilver is a type of nanomaterial which has been
subjected into a lot of investigations. Discussions were carried out with base of
silver nanoparticles as new and available in this modern era. But the history of
nanosilver goes back more than 120 years, and the impact of it with the medical field
and lots of other applications is very strong [19–28]. Metallic silver is the third metal
known to ancient Egypt and to Chaldean as early as 4000 BCE. Over a millennium,
856 S. Paul and C. S. Sasikumar

Nanoera (BC)
Natural fabric-flux, cotton, wool, silk:network pore 20nm
Eypt-dyeing of hair by lime, leadoxide & water, process of dyeing leads
ingalentine nanoparticles (lead sulpide)
British museum-Lieurgs bowel:silver and gold used are in the size of 50-
100nm

Back groud
1959-Richard feyman:Plenty of room at bottom
1974-Norio tariguchi co:Coins the term Nanotechnology
1986:Eric Dexler:engines of creation, the coming era of
nanotechnology

Founding events
2001-National technology initiative
2002-National technology infrastructure network

Science-Society concern
2003-Michael crichton's prey ispublished
2005-NSF funds two"center for nanotechnology in society
2007-Nanoethics journal launched

Science-Science concerns
2008-EU adopte "code of conduct for responsible nanoscience and nanotechnology research
2010-NSF new ethics education requirement

New discoveries
2010-2015-
Nanotech meets contact lens & virtual reality
Axel scherer-detector of heart attack
Dragon fly-ispired black silicon fights of bacteria
Jenifer Alewis-Tiny 3 printed batteries
Zurich-microrobots for eye surgery
Creating biodegradable electrodes

Fig. 4 Flow chart showing the history of nanotechnology

silver has been used in various medical conditions. Hippocrates used it in various
treatments such as ulcer and wound healing. Mostly silver nitrate was used medically
and in published pharmacopeia in Rome 69 BCE. Silver nitrate was used as a
medical agent by Gabor 702–705. In 980 AD, Avicenna used silver fillings for
blood purifier. By 1800, a wide range of silver used in the transportation of water,
wine, milk, etc. have shown longer period of storage [28]. The 120 years of
nanosilver has been given in Table 1.

Properties and Application of Silver Nanoparticles

Silver nanoparticles have diverse properties such as catalyst, magnetic and optical
polarizability, electrical conductivity, microbial activity, and Raman scattering. The
properties of it vary according to different parameters [29, 30].
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 857

Table 1 120 years of nanosilver

Year Inventor and invention Size Reference
1889 Lea M. C. – Citrate-stabilized colloidal silver 7–9 nm [19, 21]
1902 Further by protein stabilization – [22]
1897 Collargol 10 nm23 [23]
1907 Termed as nano range 10 nm23 [24]
1953 Moudry – Gelatin-stabilizing silver nanoparticles 2–20 nm [25]
1970s Silver impregnated water filters >100 nm [26, 27]
Last 20 decades Collargol >100 nm [28]
in market Argyrol
Protargol was used in various diseases such as
syphilis and bacterial infections

Diameter, Surface Area and Volume

• It has unique properties depending upon the size.

• Solubility and stability also vary according to the nature of nanoparticles.
• High surface area, compared to volume ratio, is important for catalyst properties.

Shape and Crystallinity

• It can be produced with various shapes and size.

• Anisotropic shape formed with stabilizing polymer binds with one crystal face
and moves in one direction – faster complex SNPs from highly faceted.

Nanoparticle Surface

• Tannic acid, citrate, and PVP gave very good capping agent for SNPs.
• Especially PVP binds strongly to SNP surface and provides greater stability than
citrate and tannic acid.

Particle Stability

• Zeta potential helps to measure particle stability > or < 20 mv and has sufficient
electrostatic repulsion for stable nature.

Surface Chemistry and Functionalization

• PVP or tannic acid is used as capping agent. In the biological application, SNPs
were coated with BSA and PEG for stability and have property to flip the surface
with positive and negative charge.
858 S. Paul and C. S. Sasikumar

Measuring SNP Concentration

• Depending on concentrations, the properties of silver nanoparticles also vary.

ICP-MS is used in measuring the concentration of SNPs.

Types of Silver in the Term of Nano

Silver Colloids Silver colloids are available to the market in five types. In that
mesosilver is the purest colloidal silver and others are not true or pure.

NanoXact They are the aggregated spherical nanoparticles that are suspended into
water molecules.

BioPure Silver It is highly concentrated and available in pure form.

OECD Silver This silver was given an Organization for Economic Co-operation
and Development direction. Its definition has been chosen as nano-toxicology
principles with PVP and citrate surfaces.

Custom Silver It has been customized according to the custom organization,

biofunctionalized shells, and suspension media.

Silver Nanoparticles They have high optical efficiencies and tend to cooperate
between the wavelength 550 and 950 nm [30].

Methods of Synthesizing Nanoparticles

Chemical Reduction It is one of the processes used in the reduction of silver

nanoparticles with the help of ionic salts in the appropriate medium in the vicinity
of surfactants utilizing diminishing specialist, e.g. sodium citrate and sodium boro-
hydride [31–34].

Solvothermal Synthesis This is an adaptable low-temperature mechanism; polar

solvents under pressure and at temperature over their building focuses are utilized.
Under solvothermal conditions, the dissolvability of reactants increments fundamen-
tally, empowering response to happen at lower temperature [31–34].

Solgel Technique It is one of the wet chemical strategy/method utilized for the
manufacturing of metal oxides from the available chemicals which represent an
integrated system of discrete patches or polymers. This precursor sol can either be
deposited on the substrate to form a film or casted into a suitable compartment with
fancied shape or used to synthesize particles or powders [31–34].
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 859

Laser Ablation This is the procedure of irradiating so as to expel materials from a

strong surface with a laser shaft. Subsequently, they create nanoparticles [31–34].

Biological Method Biological method follows bottom-up approach with reduction

or oxidation process. As the name subjects, the biological sources such as microor-
ganism and plants are used for the reduction, capping and stabilizing nanoparticles.
The advantages are eco-friendly, cost-effective, faster production, and non-toxic
production with any chemicals [31–34]. The systematic biological pathway has
been indicated in Fig. 5.

Characterization and Application

There are various techniques followed to validate and confirm the synthesis of silver
nanoparticles [35–37].

• Scanning electron microscope, eld emission electron microscope, and trans-

mission electron microscope: Basically used to determine the size and morphol-
ogy of particles.
• X-ray diffraction: To study the crystal structure and size.
• Fourier transform infrared spectroscopy: To identify the functional groups of
biological sample.
• Energy dispersion X-ray spectroscopy: To determine the composition
information.
• Dynamic light scattering: To determine the particle size and is commonly used
in chemicals and pharmaceutical industries.
• Atomic force microscopy: To identify the mechanical properties of sample.

Fig. 5 Biological pathway of silver nanoparticles

860 S. Paul and C. S. Sasikumar

Silver nanoparticles have a strong role in the field of antimicrobial and anti-
inflammatory applications till date. There are other various medical applications
such as wound dressing material, silver impregnated catheters, vascular prosthesis,
ventricle drainage catheters, orthopaedics, and surgical mesh available in the market.
Currently, a lot of research is carried out on nanodrug delivery system; liposomes are
used to extend the life of drug, biochips as nanodevice used in synthetic neuron, and
nanorobots for the microsurgery.

Transdermal Drug Delivery System

The skin is an external barrier that provides us with a complete protection against
bacterial infections, thereby maintaining the homeostasis of the body. Skin loss
occurs frequently as a consequence of blazes, injury, and clutters as the skin is the
main organ in contact with the external factors. Generally, wounds are categorized
into three classes, for example, superficial wound, partial-thickness wound, and full-
thickness wound [38]. The essential guideline of ideal wound healing is to minimize
tissue damage and give satisfactory tissue perfusion, oxygenation, appropriate
sustenance, and moist injury recuperating environment to re-establish its natural
capacity [39]. Traditionally, there are a lot of therapeutic options available to treat
wounds, but it takes prolonged time to heal. Due to recent advancements in the field
of drug delivery, a rapid recovery can be observed against infections. The transder-
mal medication conveyance is a novel medication conveyance framework which has
been as of late created. The bioadhesive patches containing distinctive constituents
of medications are administrated into the skin. It is a non-obtrusive, advantageous,
and effortless technique for medication conveyance; additionally it has significantly
toxic properties, for example, gastrointestinal poisonous quality [40, 41].

Administration of Drug

Drugs that are dermally administered through the skin are categorized as (1) those
applied for local action and (2) for systemic effects. Local action impact incorporates
those connected on or at the surface of the skin, which applies the activity on the
stratum corneum or regulates the function on the epidermis or dermis. The products
that come in these criteria are creams, gels, ointments, pastes, suspensions, lotions,
foams, sprays, aerosols, and solutions. Transdermal drug delivery system (TDS) or
transdermal patches go under the criteria of systemic impact [42]. Transdermal drug
delivery system represents discrete dose type of medication to the general flow
through the skin. It overcomes drawbacks of oral drug delivery system by providing
an end to gastrointestinal lethality and hepatotoxicity [43]. Transdermal patch gives
uniform scattering of medication into target site unlike the oral dosage forms which
forms blood hikes and troughs [44]. Therapeutical applications to the skin to ease the
ailments have been followed since the time of ages and have shown beneficial
outcomes.
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 861

Advantages and Limitation of Transdermal Drug Delivery

Advantages
• It is a convenient method.
• It requires only weekly applications.
• It also acts as an alternative route to administrate drug by avoiding oral dosage
and reducing the toxicity.
• The relatively consistent plasma levels are a good indicator for transdermal drug
delivery.

Limitation
• Local irritation at the site of application may be due to adhesive or other
excipients used in the formulation of film/patch.
• Its molecular weight should be less than 500 Da.

Characteristics of Several Drug Permeation through Transdermal

Transdermal permeation is a slow process of diffusion driven by concentration

gradient between high in delivering system and zero in prevailing system of the
skin. For continuous delivery of drug towards the site, continuous contact of film
with considerable amount of time is required [44]. Transdermal patches are currently
marketed in transdermal delivery system. Functional parts of film are as follows:

• An impermeable backing.
• A reservoir holding active ingredients.
• An adhesive to hold the patch.
• A protective cover that is peeled away before applying it.

Patches fall into two categories: reservoir and matrix system. Formulation of
patches is a complex process. The rate and amount of absorption depends on many
factors such as nature of drugs, concentration in reservoir, or matrix and space
covered by patch. The release of drug also depends on the site covered by patch.
To keep the favourable absorption concentration, large amount of drug is placed in
the film [45–47]. There are various methods to enhance the penetration methods and
are given in Fig. 6 [48].

Transdermal Film

A transdermal patch is defined as an adhesive patch kept over the dermal layer to
release a particular dose of medication released through the skin with fore-ordained
rate of discharge to venture into the circulation system. Today the most widely
recognized transdermal film present in the market is based on semipermeable
membranes that are known as patches [49–51].
862 S. Paul and C. S. Sasikumar

Fig. 6 Various methods used to enhance the skin penetration

Technologies for Development

A number of technologies have been developed to provide rate control release and
skin permeation of drugs. It was classified into four basic approaches [52].

Polymer Membrane Permeation-Controlled TDDS

In this system, drug reservoir has been sandwiched between the drug imperme-
able support overlay and rate-controlling polymeric film. The drugs are allowed
to discharge just through the rate-controlling polymeric film. In the drug supply
compartment, the drug solids are scattered homogeneously in a strong polymer
network, suspended in an unleached viscous fluid medium (e.g. silicone liquid) to
frame a paste like suspension or break down in a releasable dissolvable (e.g. alkyl
liquor) compound to form clear drug solution. The rate-controlling layer can be
either a microporous or a nonporous polymeric film with particular drug perme-
ability. The rate of medication discharge from this TDD framework can be
custom-made by fluctuating the organization of the drug repository plan and
the permeability coefficient and/or thickness of the rate-controlling layer
[52–55].
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 863

Polymer Matrix Diffusion-Controlled TDDS

In this approach, the process of medication supply is framed by homogeneously

scattering the medication solids in a hydrophilic or lipophilic polymer lattice, and the
sedated polymer shape is then formed into medicated discs with a characterized surface
zone and controlled thickness. This drug reservoir-containing polymer disc is then
mounted onto an occlusive base plate in a compartment manufactured from a drug
impermeable plastic backing. Rather than covering the adhesive polymer straightfor-
wardly on the surface of the mediated discs, as demonstrated prior in the main kind of
TDD systems, in this system, the adhesive polymer is connected along the perimeter of
the patch to shape a segment of adhesive edge encompassing the sedated plate [52–55].

Drug Reservoir Gradient-Controlled TDDS

Drug reservoir slope controlled TDDS to beat the non-zero-order (Q versus t½) drug
discharge profiles; polymer matrix drug scattering sort TDD system can be altered to
have the medication stacking level differed in an incremental way, shaping a gradient
of drug reservoir repository along the diffusional way over the multilaminate
adhesive layers [55]. The rate of drug discharge from this sort of drug reservoir
gradient can be expressed by:

dQ/dt ¼ Ka/rDa/ha(t)  Ld(ha).

Microreservoir Dissolution-Controlled TDDS

The drug delivery system can be recognized as a hybrid of the reservoir and matrix
dispersion drug delivery system. In this approach the drug reservoir is framed by first
suspending the drug solids in an aqueous arrangement of water-miscible medication
solubilizer, e.g. polyethylene glycol [55].

Types of Transdermal Films

Single-Layer Drug Adhesive Adhesive layer of system contains the drugs that not
only adhere to other layers but also are responsible for releasing the drugs
[56, 57]. The rate of release follows the diffusion phenomenon (Fig. 7). The rate
of release of drug is expressed as:

dQ=dT ¼ Cr =1=Pm þ 1=Pa :

where Cr is the drug concentration in the reservoir compartment, Pa is the perme-

ability coefficient of the adhesive layer, and Pm is the permeability coefficient of the
rate-controlling membrane.
864 S. Paul and C. S. Sasikumar

Fig. 7 Single-layer drug in

adhesive film

Multiple-Layer Drug Adhesive

It is almost similar to a single-layer adhesive, but in here, there are two layers of adhesive
that are sandwiched with a single layer of membrane in between them. Release of drug
follows the diffusion phenomenon and results in immediate release of drug along with
the adhesive layer (Figs. 8, 56,57]. The rate of release of drug is expressed as:
 
Ä
dQ=dT ¼ K a =r nDa =ha Cr :

where Ka/r is the partition coefficient for the interfacial partitioning of the drug from
the reservoir layer to adhesive layer.

Drug Reservoir in Adhesive

Drug reservoir is immersed in the backing and membrane layer followed by adhesive
layer and release liner (Fig. 9). This drug can be available in many forms such as gels,
solutions, suspension, or dispersed in solid matrix. Release of the drug is controlled by
controlling the membrane (microporous or nonporous) [56, 57]. The rate of drug
release from this drug reservoir system is given by dQ/dT ¼ [Ka/r · Da/ha(t)]A(ha).
where ha is the thickness of adhesive layer and A is the thickness of the
diffusional path.

Drug Matrix in Adhesive

Drug availability nature in this particular system is dispersed homogenously in a

hydrophilic or lipophilic polymer matrix and designed by semisolid matrix having
drug solution or suspension form which is in direct contact with the release liner
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 865

Fig. 8 Multiple-layer drug in

adhesive film

Fig. 9 Drug reservoir in

adhesive patch

[56, 57]. The rate of release of drug is calculated by the following equation: dQ/dT ¼
ACpDp1/2/2 t.
where A is the initial drug loading dose dispersed in the polymer matrix, Cp is the
solubility of the drug, and D is the diffusivity of the drug in the polymer (Fig. 10).

Drug Delivery Routes

Skin Permeation

Anatomy and Physiology of the Skin The skin is the largest organ and receives
about one-third of blood. It is multilayered and is divided into three categories:
epidermis, dermis, and hypodermis [58, 59].
866 S. Paul and C. S. Sasikumar

Fig. 10 Drug matrix in

adhesive patch

Epidermis It is the outer layer of the skin which gives protection from immediate
attacks and also tones the skin.

1. Stratum corneum is otherwise known as horny layer of skin. Eventhough the

layer is flexible, it is impermeable, hence proving the principle barrier for
penetration. The layer constitutes 75 to 80% proteins, 5–15% lipids, and
5–10% ondansetron material.
2. Viable epidermis is found just beneath the stratum corneum. It consists of various
layers such as the stratum lucidum, stratum granulosum, stratum spinosum, and
stratum basale beneath stratum corneum.

Dermis It is the layer found next to epidermis and contains tough connective tissue,
hair follicles, and sweat glands. The continuous function of blood supply is impor-
tant in regulating the body temperature. It provides nutrients and oxygen to the skin
removing toxins and waste products. Dermal concentration permeates very low, and
concentration difference across the epidermis provides essential driving force for
transdermal permeation.

Hypodermis It is a subcutaneous tissue made up of fat and connective tissues. This

layer helps to regulate temperature and provide nutrition and mechanical protection.
During transdermal drug delivery system, drug needs to pass through all these three
layers to reach the circulation, while topical drug delivery penetration through stratum
corneum is only necessary, thus retention of drug in skin layer is desired (Fig. 11).
Drug has been delivered through different routes or pathways according to the
drugs [60]. Drug is administrated and passed through the sweat glands, then
followed by sebaceous gland, or is penetrated through the layers of hair follicles.
Mostly drug that has passed through it is from ointments such as topical delivery
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 867

Fig. 11 Anatomy of the skin

system. But in case of transdermal drug delivery, the drug has been passed through
the stratum corneum (Fig. 12).

• Sweat gland.
• Sebaceous gland.
• Hair follicles.
• Stratum corneum: intercellular route is the major pathway for permeation of most
drugs across the stratum corneum.

Methods of Skin Penetration

Intracellular Penetration Drugs penetrate through the cells of the stratum

corneum. It is mostly used in the hydrophilic medications. As the stratum corneum
hydrates, water accumulates the external surface of the protein fibres. Polar atoms
seem to go through this immobilized water [61, 62].

Intercellular Penetration A non-polar substance passes through the skin by

intercellular penetration route. These particles break down and diffuse through the
non-watery lipid matrix between the protein fibres [62, 63].

Transappendageal Penetration It is also called as the shunt pathway. In this

course, the drug might transverse through the hair follicles, the sebaceous pathway
868 S. Paul and C. S. Sasikumar

Fig. 12 Routes of drug delivery

of the pilosebaceous contraption or the aqueous pathway of the salty sweat organs.
The transappendageal pathway is thought to be of minor significance due to its
moderately smaller range (less than 0.1% of aggregate surface). However, this
course might be of some significance for vast polar compounds [61, 62].
The transdermal permeation can be visualized by a number of series:

• Adsorption of a penetrant molecule onto the surface layers of stratum corneum.

• Diffusion through the stratum corneum and through the viable epidermis.
• Finally through the papillary dermis into the microcirculation.

Properties The quality and potential of a dressing material through transdermal or

skin penetration depend on physiochemical and biological properties [63].

Physiochemical Properties
• Molecular weight should be below or approximately 1000 daltons.
• Drug should have affinity on both lipophilic and hydrophilic phases.
• Low melting point.
• pH range should be between 4 and 6, thus resulting in significant and uniform
distribution off drug.

Biological Properties
• Slow release rate of drug with few mg per day.
• Drugs should have half-life t½.
• Drugs need to be non-irritating and non-allergic.
• Drugs that degrade in gastrointestinal track is an important parameter noted on
transdermal drug delivery system.

Basic Components Required for Transdermal Dressing Material

Polymers It is one of the basic components of transdermal system. Selection of

polymers and designing are vital. There are two categories of polymers: natural polymer,
e.g. zein, gelatin, cellulose, chitosan, etc., and synthetic polymers, e.g. hydrin rubber,
polyisobutylene, silicon rubber, nitrile, neoprene, etc. [49, 50, 55, and].
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 869

Characteristics of Polymer Selection

• Should be stable and non-responsive with the drug moiety.

• Easily accessible, created, and fabricated into desired formulation.
• The properties of polymer ought to be in such a way that the drug should be easily
penetrated through the skin.
• Mechanical properties should be stable, when the high-concentration drug is
substituted.

Release Liners The film is covered by a protective liner until the storage. Outer
covering (release liner) is removed and discarded before the application of films. It is
composed of non-occlusive (paper fabric) or occlusive (polyethylene, polyvinylchloride)
material and release coating layer made up of silicon or Teflon; other materials used as
release liner are polyester foil and metalized laminate [49, 50, 52, 57, 60].

Backing Membrane Backing membrane was designed considering various param-

eters [49, 50, 52, 57]:

• It should be flexible.
• Low water vapour transmission so as to promote skin hydration and thus greater
skin permeability.
• Should be chemical resistant and good tensile strength.
• Non-irritant.

Drugs Drugs selected should be considered with various physiochemical, pharma-

cokinetic, and pharmacological properties for transdermal system development
[49, 50, 52, 57].

Characteristics of Drugs

• Low molecular weight  1000 Da.

• Solubility nature.
• Range of melting point (200  C).
• Lipophilicity, undergo extensive presystematic metabolism, non-ionic, and
non-irritant are considered to be suitable for delivery system.

Penetration Enhancers Incorporation of protein enhancers results in the formulation

and improves the diffusivity and solubility of drugs through the skin [49, 50, 52, 57].

Properties that Need to Be Considered

• Should be non-irritant, non-sensitizing, non-phototoxic, and non-comedogenic.

• Should not have pharmacological activity, as it should not bind to receptors.
870 S. Paul and C. S. Sasikumar

• Should be readily formulated into dermatological preparations.

• Should adhere and equally spread to the skin.

Plasticizers Plasticizers used can be synthetic and natural. Along with brittleness,
ductility, adhesiveness, and strength of the film are also improved. Plasticizers have
been used in many formulations ranging from 5 to 20% (w/w, dry basis). Glycerol,
sorbitol, phosphate, phthalate esters, fatty acid esters, and glycol derivatives such as
PEG 200, and PEG 400 [48, 49, 51, 56, and].

Solvents Various solvents used to prepare drug reservoir are water, methanol,
chloroform, acetone, isopropanol, dichloromethane, etc. [64].

Role of Nanoparticles in Transdermal Wound Dressing Material Generally,

transdermal drug delivery is one of the stimulating areas because the skin naturally
acts as a protective barrier against various external factors. Consequently, to develop
transdermal patches requires standard materials such as polymers, penetration
enhancers, solvents, and drugs with lower molecular weight, size, solubility, and
stability potential [65].
Obviously, in the last few decades, nanotechnology has built a strong foundation
in the use of nanoparticles in consumer products. For instance, titanium oxide, zinc
oxide, and silica nanoparticles have been used in cosmetics, sunscreen cream,
desiccant, and free radical scavengers from almost the 1950s. However, these are
not anticipated to penetrate through the skin but act as an external layer. Thus the
increase of nanoparticle utilization and usage has led its way to transdermal drug
delivery system. There are mainly three nanocarrier categories [66]: (1) solid nano-
carriers have the slowest drug division: metal core, solid lipid, and solid polymeric
nanoparticle; (2) liquid-phase nanocarriers release drug more steadily compared to
solid-phase nanocarriers: micelles and nanoemulsions of lipids; (3) liquid
crystalline-phase nanocarriers are more reliable and synthesized by monolein,
water, and poloxamer. Overall, these resulted in the controversial examination of
toxicity to the environment, skin, eye, and mouth, respectively. Much research was
carried out with in vitro cytotoxicity test with cell lines, namely, vero cell line,
fibroblast (3 T3-L1) cell line, keratinocyte (HaCaT) cell lines, and in vivo and
ex vivo models [67]. Studies showed both upside and downside of nanoparticle-
embedded transdermal patches or dressing material. To the upside, it can easily
penetrate through the skin depending on size, charge, and material. To the downside,
the acute or chronic level of toxicity is still a debatable topic. Hence, limitation
overcomes with substitution of biological or eco-friendly nanoparticles.

Bio-Nano-Based Transdermal Wound Dressing Material The advancement in

polymer science has laid path towards the transdermal delivery system with considerable
flexibility of using natural polymer compared to synthetic and semi-synthetic polymers
to stabilize the release of medicine via the intact skin. In our laboratory, we have
developed biological and eco-friendly transdermal wound dressing material embedded
with bio-silver nanoparticles to boost up the healing process [68, 69]. To illustrate,
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 871

natural polymers such as chitosan and gelatin were used as it is biocompatible,

non-toxic, and biodegradable not only that but also possess various other functions,
viz. cell delivery systems, orthopaedics, wound healing, ophthalmology, bone healing,
antimicrobial, haemostatic, good film-forming property, etc. Exclusively, drug was
prepared with a lot of provisions and silver nanoparticles synthesized with the help of
biological sources; mushroom (G. lucidum) shows synergistic beneficial properties such
as antimicrobial, anti-diabetic, wound healing, anti-inflammatory, and angiogenesis
[67]. Nanosize drug used in transdermal material can be easily transferred and targeted
to specific site and thus portrays the speedy wound healing process.

Characterization and Evaluation of Transdermal Wound Dressing

Material The prepared chitosan-gelatin transdermal patches with bio-silver nano-
particles (Fig. 13) are subject to various physicochemical and biomedical evaluation
tests to meet the essential requirements [70]. Consequently, thickness of the patch,
weight uniformity, folding endurance, percentage moisture content, content uniformity
test, moisture uptake, drug content, shear adhesion test, bioadhesion test (Fig. 14),
oxygen penetration test (Fig. 15), tensile study (Fig. 16), quick stick (peel-tack) test,
probe tack test, microbial penetration test, in vitro drug release studies, in vitro skin
permeation studies, skin irritation study, stability studies, in vivo toxicity, or irritation
study is carried out to determine the uniform distribution of drug through the film and
stability of the film and indicates the capacity of the film to hold the wound exudate
and dispersion of the drug towards the wounded site resulting in the complete
protection against the external factors; duration and percentage of drug diffused
through the diffusion bag and skin are calculated as well as antimicrobial potentiality

Fig. 13 Chitosan-gelatin
transdermal dressing material
872 S. Paul and C. S. Sasikumar

Fig. 14 Bioadhesive properties

and tensile strength of the patch or dressing material [70, 71]. It is also subjected to
analytical characterization techniques to visualize the drug and to determine the size,
percentage, and composition of nanoparticles with scanning electron microscope
(SEM) (Fig. 17), EDAX (Fig. 18), inductively coupled plasma or optical emission
spectrometry (ICP-OES), Fourier transform infrared spectroscopy (FTIR) (Fig. 19),
liquid chromatography-mass spectroscopy, differential scanning calorimeter, small-
angle X-ray diffraction, etc. [72, 73].

Complication of Bio-nanoparticles in Dressing Material Currently in the market,

there are not many nano-embedded transdermal patches especially bio-based trans-
dermal patches are till at the bench side. Furthermore, their aren't enough toxico-
logical assesments available, and it is difficult to develop an analytical method for
drug delivery; sometimes the process of making is time-consuming and difficult, and
the attainted size is not enough to avoid the immune response [74].

Advantages of Bio-nanoparticles in Dressing Material The benefits of using

eco-friendly material and bio-nanoparticles like bio-silver nanoparticles and
chitosan nanoparticles result in the biodegradability nature. There are numerous
processes to prepare the nanoparticles and sometimes can include antibodies
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 873

Fig. 15 Oxygen penetration studies

Fig. 16 Tensile study

874 S. Paul and C. S. Sasikumar

Fig. 17 Chitosan-gelatin transdermal film

in the surface to reach the targeted site; both hydrophilic and hydrophobic
drug can be loaded, and they can avoid the immune response due to their size
[73, 74].

Conclusion

To recapitulate, transdermal patches embedded with nanoparticle drug such as silver

nanoparticles enhance the drug delivery through different skin barriers and reach the
targeted site, thus avoiding various oral and gastrointestinal troubles and also
meeting the required standards in the wound care management. Alternative usage
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 875

Fig. 18 EDAX report of chitosan-gelatin transdermal film

of natural material and bio-silver nanoparticles boosts up the credibility of the wound
dressing material as it is eco-friendly and less to non-toxic to the human system.

Website http://www.adhexpharma.com/
https://www.researchandmarkets.com/r/rewslv
http://leonardino.eu/index.php/nad/
https://axiobio.com/?cmp_id¼11,266,027,574&adg_id¼105,805,492,930&
k w d ¼w o u n d s & d e v i c e ¼c & g c l i d ¼C j 0 K C Q i A h Z T 9 B R D m A R I s A N 2 E -
J2LnOCY71wEewSlEEUJditCUVOQa9R2OOzk7aHT3pyxZ2G1SmkO3
QYaAqW9EALw_wcB.
 876

100.0

95 993.6
1109.5
90 1042.8
1411.5
85 2082.1

80 669.9

75

70

65

60

55

50
%T 1653.9
45 2343.6 1638.8

40 2361.0

35

30

25

20

15

10 3455.5

0.0
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Fig. 19 FTIR report of chitosan-gelatin transdermal film

S. Paul and C. S. Sasikumar
38 Skin Substitute: An Eco-friendly and Nano-Based Transdermal Wound Dressing. . . 877

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Starch Based Bio-nanocomposites : Modern
and Benign Materials in Food Packaging 39
Industry

Shikha Gulati, Sanjay Kumar, Parul Chandra, Atishay Jain,

Lavanya Ahuja, Kanchan Batra, and Nandini Sharma

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 882
Conventional Food Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Metals and Alloys in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885
Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886
Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 887
Shortcomings of Conventional Food Packaging Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 888
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891
Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891
Why Starch Is Used as a Packaging Material? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
Different Types of Starch-Based Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 894
Thermoplastic Starch (TPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897
Starch Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 898
Modification of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
Chemically Modified Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
Physical Modification of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 901
Enzymatic Modification of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 902
Various Properties of Thermoplastics and Composites Needed for Food Packaging (Fig. 12) . .. 902
Biodegradable . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 902
Barrier Property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903

S. Gulati (*) · S. Kumar

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
P. Chandra · A. Jain · L. Ahuja · N. Sharma
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India
K. Batra
Department of Zoology, Kalindi College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 881

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_96
882 S. Gulati et al.

Mechanical Property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905

Thermal Property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 905
Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 907
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908

Abstract
As we know, nowadays there is a drastic shift going on in various industries
especially “food packaging industry” to contribute for sustainable development by
changing their methods. There are some requirements like recyclability, consumer
acceptability, nontoxicity, antimicrobial property, antioxidant property, and flexibility
which are important to maintain our environment safe and ensure the safety and
better quality of food and are discussed in this chapter. Conventionally, food is
packed in petroleum-based plastic, but due to its nonrenewable aspect, it has proved
to be hazardous for the ecosystem. So, the food packaging industry is now trying to
shift to various methods that are eco-friendly and promote sustainable development.
These methods mainly focus on maintaining our environment’s safety and ensuring
the quality of the food packaged. As a result, scientists moved on to a new avenue,
which is biopolymers for food packaging. Biopolymers play an important role in
making our ecosystem safe. Numerous sources can be used in the production of
biopolymers such as biodegradable films that include polysaccharides, proteins, and
lipids. Among polysaccharides, starch due to its low cost and abundance in nature is
of significant importance. Starch has various advantages that are helpful as food
packaging material such as low thickness, flexibility, and transparency. But these
show some drawbacks too, such as the poor mechanical properties and water vapor
permeability. The following chapter focuses on the modification of starch film with
various nanocomposites to increase the efficiency of starch film and also highlights
the current advances in the applications as well as future perspectives of starch-based
bio-nanocomposites for food packaging.

Keywords
Nanocomposites · Bionanotechnology · Food packaging · Starch
bionanocomposites · Biodegradable polymers · Environment-friendly

Introduction

Food packaging is important as it ensures that food is protected and maintained until the
end of its shelf life. If the packaging is not given much importance, the quality and safety of
food will be compromised; hence food packaging is essential. Environmental issues are
becoming increasingly important in different parts of the world as a result of which
consumers are demanding bio-based packaging materials as an alternative to materials
produced from nonrenewable resources [1]. Petroleum-based plastic is widely used in a
various range of applications such as packaging and automobile parts. These conventional
methods which include synthetic polymers show various properties such as thermal
properties, rheological properties, gas and water barrier properties, lightweight, easy to
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 883

manipulate, and cost-effective. Six to 8% of total world oil production is consumed as raw
material, as well as the oil required for energy for plastic production. The amount of
petroleum used to make plastic not only contributes to the depletion of fossil fuel, but also
the overall price of petroleum is influenced by the rate of consumption, contributing to the
current rise in raw material costs. Petroleum-based plastic is not limited to packaging
materials but also includes agriculture, aerospace, automobile, constructions, sports,
domestic, and many more. The production of plastic has grown continuously, approxi-
mately more than 300 million tons per year (Plastics Europe, 2015) [2]. Various synthetic
polymers are used for food packaging such as plastic, glass, paper, metals, and alloys. The
aforementioned substances are non-biodegradable, non-recyclable, and synthetic poly-
meric materials that are raising serious concerns in environment-related issues.
Bioaccumulation is shown in the organism due to phthalates-based plasticizers and
BPA. However, some invertebrate species, especially mollusks and crustaceans, tend to
portray a large number of concentration factors, as compared to vertebrates. Angiosarcoma
of the liver among factory workers is caused due to exposure of carcinogenic vinyl
chloride which is the monomer of PVC plastic. Due to environmental pollution problems
of petroleum-based plastic, now the researchers are contemplating the replacement of
petroleum-based plastic with environment-friendly biodegradable polymer for food pack-
aging materials; these materials, in comparison to fossil fuel-based, are less harmful to the
ecosystem, but the packaging material derived from a natural biodegradable polymer is
more expensive than a nonbiodegradable synthetic polymer. The presence of oxygen and
nitrogen in natural polymer leads the polymer to biodegrade which is absent in synthetic
polymer [3]. In the last few decades of publications, starch-based plastics seem to be the
front-runner in bio-based materials because of their low cost, renewability, and availability.
Starch resists thermoplastic behavior due to intermolecular force and hydrogen bonding.
Plasticizers in addition to water show thermoplastic starch. Starch has some drawbacks,
namely, strong hydrophobic properties, poor mechanical properties, and barrier properties.
Various modifications with nano-fillers increase the various packaging properties of starch
[4]. Amylose (linear with some branched) and amylopectin (branched) are two compo-
nents of starch. Amylose gives strength to films when it is processed, and amylopectin
decreases the tensile strength of films. In this chapter, conventional food packaging
materials and their shortcomings are discussed in detail. To avoid such downsides, the
starch used as a packaging material and its synthesis method are also highlighted in the
chapter. Also, the modification of starch films with various nanocomposites resulting in a
myriad of properties is highlighted in the chapter.

Conventional Food Strategies

Metals and Alloys in Food Packaging

Aluminum
Aluminum is widely used for packaging food materials because the metal and its
alloys are extremely immune to corrosion. What is more important is that they don’t
react or injure the food. Metal packaging protects the food from extreme tempera-
tures, keeps it intact for an extended length, and conjointly protects it from
884 S. Gulati et al.

Fig. 1 Aluminum containers

for food packaging

ultraviolet radiations, oil, vapor, and microorganisms. Once the metal is exposed to
air, the metal develops a layer of aluminum oxide. This film is colorless and
non-flaking. Metal can bear temperatures from
40  C to 350  C, and it ensures
equal distribution of warmth within the food materials (Fig. 1).

Aluminum Foil
Thickness of aluminum foils varies from 0.004 and 0.24 millimeter thick. The time
period of aluminum foil is somewhat around 12 months. The nontoxic nature and
barrier properties of foil create it a helpful material in food packaging. Compared to
the other plastic materials used for lamination applications, it prevents the migration
of water, oxygen, gases, etc. to a larger extent.

Aluminum Cans
Aluminum is widely used for beverage cans and other types of food packaging that
may include foils, cans, and tubes. The food or beverages stored in containers made
of aluminum have the ability to retain their taste for a longer duration of time.
Around 90% of beverages all around the world is sold in cans made of aluminum. In
addition to the barrier properties, it does not modify the organometallic properties of
food and does not react with the components of it.

Steel
The steel used for food packaging applications are mainly of two types; electrolytic
tinplate (ETP) and electrolytic chromium/chromium oxide-coated steel (ECCS)
(Fig. 2):

A) Electrolytic Tinplate (ETP)

ETP is a low-carbon-containing steel sheet or coil which is coated on both

surfaces with tin. The use of tinplate ensures that the stored food is free from
bacterial and other external contaminations. Its shiny surface and the fact that it is
resistant to corrosion make tinplates an ideal choice for the food industry. Tinplate
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 885

Fig. 2 Steel containers to

store food

products have excellent corrosion protection properties, appealing appearance, and

high strength and provide resistance to attack by organic substances for both food
and nonfood packaging products.

B) ECCS (Electrolytic Chromium/Chromium Oxide-Coated Steel)

ECCS (electrolytic chromium/chromium oxide-coated steel) has equal coating

weights on both surfaces of the coil. Electrolytic chromium-coated steel (ECCS),
sometimes also called tin-free steel, is finding increasing use for food cans. A layer
of metallic chromium may also be applied. The function of a chromium coating is to
prevent atmospheric oxidation or sulfur staining of the steel by food materials.

Plastics

Plastics are highly diverse and one of the most common materials used for packaging
foodstuff. Plastics are relatively safer materials for the packaging of food products
especially polyolefin as they do not react with food. Chances of contamination are
difficult (Fig. 3).
Due to plastics’ good barrier properties against water, carbon dioxide, oxygen,
and nitrogen, products retain their flavor, aroma, and nutritional value and are
protected from external contamination. Plastic packaging may consist of single
polymers, e.g., polyethylene terephthalate (PET), polypropylene (PP), high-
(HDPE) and low-density polyethylene (LDPE), polystyrene (PS), and polyvinyl
chloride (PVC).
Plastic materials are made up of large, organic (carbon-containing) molecules that
can be molded into a variety of useful products; they are fluid, moldable, and heat
sealable.
Here are some examples of plastic packaging generally used by the food industry [5]:
886 S. Gulati et al.

Fig. 3 Plastic used in

packing food

A) Polyethylene Terephthalate

PET is the most ordinarily used plastic within the world. The plastic material is
primarily used for food packaging that needs glass-clear quality, e.g., contemporary
salads, fruits, cold meats, snacks, etc. PET could be a terribly powerful and versatile
plastic material with high impact strength.

B) Polypropylene

Polypropylene (PP) is one of the most used thermoplastics globally. It is a robust

material with strong resistance to chemicals, solvents, acids, and alkalis. The mate-
rial is colorless naturally but can be dyed to any other different color. PP is a very
versatile material that is suitable for packaging fresh meat. PP can be recycled into
new raw material as well.

C) Polystyrene

Polystyrene plastic is made from petrochemicals. Polystyrene is commonly used

in food packaging, where it occurs in two forms, rigid and foam. PS is a thermo-
plastic film with good transparency and high tensile strength, but the only problem is
that it provides a poor barrier to moisture and gases.

Glass

Glass is preferred as a potent food packaging material due to its inertness, good
barrier properties toward moisture and gases, and high recyclable nature. Glass
packaging is a type of packaging commonly used in many foods ranging from
heat-treated or pressure-packed solid. Unlike metals, glass does not have free
electrons that can absorb light energy. It is a tough, durable, and chemically inert
material which is being used as a food packaging material for a while now (Fig. 4).
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 887

Fig. 4 Glass containers used to store food

Another reason for its high exploitation is that the chemical integrity of the glass
is quite high. Glass is chemically resistant to all food products, both liquid and solid.
Moreover, it has good design potential as a result of which glass can be made into
different shapes depending on the food to store, making it a preferable food
packaging material.
Glass is extensively preferred as a packaging material due to its properties; it can
be recycled and reused. For example, beer is stored in glass bottles to avoid spoilage.
Besides, since glass is neutral, it does not react with the contents of the food.
The production of glass containers involves heating a mixture of silica or glass
former, sodium carbonate which will act as the melting agent, and limestone/calcium
carbonate and alumina which would act as the stabilizers to high temperatures until
the materials melt into a thick liquid that is then poured into molds. The surface of
glass containers used in food packaging is sometimes coated to provide lubrication
and prevent the effects of scratching. This is done to reduce or prevent any kind of
damage to the containers. Glass coatings also increase and preserve the strength of
the bottle to limit breakage.

Paper

Paper and board are also versatile materials like plastic. Paper packaging can be
made of parchment paper that is generally thin or has the shape of bags to package
foods. Carton board is commonly used in liquid and dry foods, frozen foods, and fast
food. The corrugated board is also used, e.g., in pizza packaging.
Paper and board are made of natural fibers. These fibers can be bleached or
non-bleached. Chemical substances are however needed as additives to achieve
suitable properties that enhance packaging efficiency. They are either added directly
to the pulp or applied to the surface later on.
888 S. Gulati et al.

Fig. 5 Different types of food containers made of paper

Pure cellulose comprises long, ribbonlike molecules of glucose units. These mol-
ecules are held together side-by-side by hydrogen bonds to form “sheets,” which in
turn are piled together in tight layers forming “microfibrils.” The microfibrils group
themselves in bundles and groups of these bundles form the paper fiber [5] (Fig. 5).

Different Types of Paper Employed in Food Industries

Parchment/Baking Paper Made from the acid-treated pulp, and it is impervious to

water and oil (grease resistant); however it is not a good barrier to air and moisture; it
is not heat sealable and is generally used to pack fats (butter) because it is grease
resistant. It is non-sticky.

Kraft Paper Natural kraft is the strongest of all paper and is commonly used for
bags and wrapping. It is having high strength and is eco-friendly. It can also delay the
shelf life of food items. It is accustomed to pack flour, sugar, and dried fruits and
vegetables.

Corrugated Board The corrugated cardboard is formed of two layers of kraft with
a flute paper in the center. Various boxes that are made out of this cardboard can be
single-walled, double-walled, or triple-walled. Although in appearance it may seem
weak and delicate, in reality it is protective in nature. The multiple layers make it
quite rigid. Corrugated paper is eco-friendly, affordable, and convenient. (Fig. 6).

Shortcomings of Conventional Food Packaging Materials

In standard food packaging ways, metals and their alloys, plastics, wood, glass, etc.
are used as packaging materials. Victimization of these materials causes several
issues associated with setting, especially on health. The following mentioned mate-
rials have several shortcomings or disadvantages in terms of packaging of food.
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 889

Fig. 6 Conventional food packaging materials

Metals

Metals like aluminum, tin, steel, etc. are used for packaging. However, the following
limitations of metals make them unsuitable for food packaging:

1. Metal is a corrosive material and will have an effect on the standard of food.
2. Metal is a moderately significant packaging material.
3. The food content is not visible once packaging is done.
4. Due to multistep production method, time taken for creation of packages is
increased.
5. Metals will react with the food material and may be hazardous for health.

Plastics

Plastics are high mass polymers that may be molded into desired shapes like films,
trays, bottles, and jars, through victimization by heat and pressure. They don’t offer a
complete barrier to gases, vapor, and aromas. Plastics as a food packaging material
aren’t thought of as good strategy due to the following reasons:

1. Plastics are leaky to gases that are generated in setting, water vapors, aroma,
monomers, and additives.
2. Food elements can mix with plastics, and it’s proved that food embowered in
plastics could cause diseases like cancer.
3. Plastics have low compressive strength.
4. Plastics lack heat resistance.
5. Main disadvantage is that plastics are nonreusable.
890 S. Gulati et al.

Glass

The shortcomings of glass embrace properties like its weight and vulnerability to
fracture from thermal shock (rapid temperature change) and physical shock. Here are
some additional setbacks of glass as a food packaging material:

1. Glass will cause breakage resulting in loss of merchandise. Also, glass is a

breakable material; therefore it will break down, and the purpose of protecting
food merchandise is contrary to this property of glass.
2. Hermetic seal that’s additional is simply compromised.
3. The multiplied chance of broken glass contaminating the finished product.
4. Color changes of the merchandise due to exposure of sunshine.
5. Expensive food packaging material.

Wood

Wood is an adsorbent material. This suggests that it will adsorb close condensable
vapors below the fiber saturation. Wood won’t be able to satisfy as a good packaging
material as it includes a downside of shrinkage and swelling. Wood doesn’t deteri-
orate itself; there are some agents inflicting wood deterioration. There are two
categories of agents responsible for deterioration, viz., abiotic agents like sun,
wind, water, fire, and chemicals and biotic agents like fungi, microorganisms, and
insects like termites, powderpost beetles, etc.

Fungi as Agent As wood is organic, therefore humans will not digest polyose and
different fiber ingredients of wood; however fungi and insects can digest it and use it
as a nutritional food. Decay fungi wood rotters will use polysaccharides, whereas
stain fungi plainly need straightforward forms like soluble carbohydrates, proteins,
and different substances gift within the parenchyma cell of wood. To boot, the
presence of atomic number 7 in wood is important for the expansion of fungi
in wood.

Insect as Agent Insects drill holes and drive lines into wood. Insects are solely
second to decay fungi within the economic loss they cause to lumber and wood in
commission. Insects are separated into four categories: termites, powderpost beetles,
carpenter ants, and marine borers:

• Termites: There are two kinds of termites – subterranean termites injure wood
that’s untreated, moist, and in direct contact with standing water, soil, and
different sources of wet. Dry wood termites attack and inhabit wood that has
been dried to wet contents as low as 5 to 100 percent. The injury by dry wood
termites is comparative than subterranean termites.
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 891

Table 1 Shortcomings of conventional food packaging materials

Metal Plastics Glass Wood Paper
Corrosive Nonrecyclable Breakable Shrinkage Non-
substance substance waterproof
Nontransparent Low Changes Swelling Easily
compression color pieced
strength
Highly reactive Lack heat Heavy than Deteriorate by agents Very light
resistance others (fungi, insects) to carry

• Powderpost beetles: Powderpost beetles attack hardwood and softwood. They are
known to attack well-seasoned wood as well as freshly harvested and
undried wood.
• Carpenter ant: Carpenter ants don’t go after wood. They tunnel through the wood
and build shelter. They attack most frequently wood in ground contact or wood
that’s intermittently wetted.
• Carpenter bees: They cause injury primarily to unpainted wood by making giant
tunnel so as to get eggs.
• Marine borers: They attack and may apace destroy wood in freshwater and
saltwater.

Paper

Paper as a food packaging material is a sensible choice. Some properties like

waterproof, load bearing, simply pieced, etc. are reasons for paper being a good
packaging material. However, the waterproof property is relatively poor. Though the
carton created of paper is lined, still it is not adequate as it simply leaks the water.
The carton is highly susceptible to many sharp objects in terms of toughness, making
it inappropriate for sharp-edged merchandise as the sharp objects may get hooked
onto it which will compromise the safety of the food packaged. With the exception of
these, in terms of load bearing, the carton is restricted, typically ranging from few
kilograms to many tens of kilograms, and if food substances are too large, then the
purpose of packaging food things is no longer fulfilled (Table 1).

Starch

Environmental awareness is increasing day by day, so many fields are considering

materials which are eco-friendly in nature and that can replace petroleum-based
synthetic materials in packaging field. One of the biodegradable polymers is “starch”
which has now become a very significant polymer. Starch is a biodegradable
polymer, available at a low cost, and it is thermoplastic in nature. It is a natural
892 S. Gulati et al.

polymer having glucose monomers. Starch in the form of granules having the size
between 1 and 100 micrometers is extracted from various plant tissues. It is a
polysaccharide and contains two types of units in its structure named amylose and
amylopectin. Amylose is an unbranched polysaccharide chain which is made up of
α-D glucose units bonded to each other through α-(1–4) glycosidic bonds. Amylo-
pectin is a branched polysaccharide chain which is made up of α-(1–4) D glucose units
that are branched by α-(1–6) glycosidic bonds. The amount of amylose and amylo-
pectin present in starch is around 20%–30% and 70%–80%, respectively [6]. However,
the ratio of these two polysaccharides depends on the starch source as well. Lipids and
proteins are also present in starch, but in very small amount. Starch is obtained from
many botanical sources. Commercial starch is obtained mainly from potato, maize,
wheat, rice, corn, and cassava. Cassava is the cheapest and most abundant agricultural
source of starch and is cultivated throughout Brazilian territory. Nonconventional
starchy sources are taro, banana, plantain, mango, amaranth, quinoa, etc. that are
used for starch isolation. These isolated starches derived from botanical sources are
known as native starch. These nonconventional types of starch are used in encapsu-
lation, film or cover materials, stabilizing agents for emulsion, nanocrystals prepara-
tion, etc. According to the abovementioned concepts, starch is already well known as
green material. As a raw material, starch is used in different applications, for example,
food, pharmaceutical products, plastics, paint, paperboard, etc. It has both upsides like
low thickness, flexibility, and transparency and downsides like poor mechanical
properties and water vapor permeability. However, to improve its functionality, starch
can be modified through chemical, physical, and enzymatic methods (Fig. 7).

Why Starch Is Used as a Packaging Material?

Foods are packed in different packaging materials, such as metals (aluminum, steel,
tin), glass, papers, and other polymers (may be synthetic and biopolymers). There
are four significant functions of good food package; it involves protection, commu-
nication, containment, and convenience to maintain quality as well as safety of any
kind of food products while storing and transporting. Shelf life is a term which
always comes in our mind whenever packaged foods are discussed, so as to extend a
product’s shelf life by preventing unfavorable conditions like spoilage, microbes,
chemical contamination, light, moisture, oxygen, and any external force. These
above properties are exhibited by plastics polymers such as low-density polyethyl-
ene, high-density polyethylene, polyvinyl chloride, as well as biopolymers such as
polysaccharides, lipids, and proteins. But to meet the increasing demand for sus-
tainability and environmental safety, natural or biopolymers are extensively used and
studied for food packaging.
Among all polysaccharides starch is one of the most significant and extensively
used in food packaging because in starch, other polymers like lipids and proteins are
also present in small amounts. Starch is a relevant food packaging material due to
reasons which are considered below [7]:
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 893

AMYLOSE

AMYLOPECTIN

Fig. 7 Chemical structures of amylose and amylopectin

1. Biodegradable Polymer

The term “bio-based” is defined in European Standard (EN) as “derived from

biomass.” Biodegradable polymers are those polymers which are broken down by
microorganisms like fungi and bacteria into water, naturally occurring gases like
carbon dioxide (CO2), methane (CH4), and biomass. As mentioned earlier, starch is
also a biodegradable polymer, so the issue of environmental contamination is
automatically solved. There will be no negative impact of using starch as a packag-
ing material.

2. Derived from Botanical Sources (Renewable Sources)

Plants synthesize and store starch in their structure as an energy reserve. Starch is
found in seeds and in tubers or roots of plants. Botanical sources like wheat, rice,
potato, pea, corn, and cassava give starch which is used in packaging fields. Most of
the starch produced is derived from corn and cassava. By wet milling processes,
starch can be extracted easily from the abovementioned sources [8] (Fig. 8).

3. Antimicrobial Property

Antimicrobial means impermeable to microorganisms like bacteria and fungi.

Antimicrobial packaging refers to the packaging system in which antimicrobial
agents are used for purpose of preventing microbial growth on food products and
894 S. Gulati et al.

Fig. 8 Botanical sources of starch

hence extending its shelf life. Starch may acquire antimicrobial properties by
incorporating antimicrobial components in a polymer matrix, by gas emissions/
flush through modified atmosphere packaging. Using this packaging has been
encouraged because of the increasing global food-borne outbreaks with relation to
health and safety concerns [9].

4. Edible Property

Starch is derived from botanical sources. Botanical sources are neither toxic in nature
nor hazardous to the environment. By packaging food in starch-based films, there will
be no impact on health of human beings. Starch is edible too, which is a bonus factor.

5. Barrier Property

Food packaging materials should have barrier property. The earth's atmosphere is
constituted by many gases, like CO2, O2, N2, etc., and also contains moisture along
with dust particles. While packaging, it is assured that there is no permeability to
such particles, otherwise their entry will result in spoilage of food products. Starch-
based films as packaging materials have barrier property which is an important
criterion for selection of packaging materials.

Different Types of Starch-Based Films

Starch is a natural chemical compound made up of monomers of glucose. It contains

two polysaccharides (amylose and amylopectin) which may vary in starch supply
level. Like in thermoplastic starch (TPS), it is predicated that cassava is one of the
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 895

most important in supply for starch. It indicates that existence of sugar and totally
different molecular combination correlates with crystalline properties, water absorp-
tion, and mechanical behavior. Several researchers have shown that distinction
between triple kinetic values of starch (represents thermal decomposition effect)
isn’t important. In the study, the starch has smarted the film-forming property. Starch
sources, largely biological science sources, play a decisive role in film options
because of the magnitude of relation of amylose to amylopectin and totally different
structural properties of macromolecules [10]. Different sources like oat starch are a
healthier choice because of their higher performance and better chemical science
properties. All starch films obtained are colorless, clear, and versatile and simply
applicable. Although their surface is swish and slick which is not preferable for
defense, Torres et al. (2011) showed in the study that starch was extracted from
12 varieties from anode region product. To create film, properties like Young’s
modulus, final enduringness, and elongation at rupture rate ought to be there.
There are three stages concerned in biodegradation method wherever films were
determined based mostly on their rate of losing weight. The high proportion of
weight loss is found in starch, whereas low proportion of weight loss is found in
golden potato films. Among 12 sources, cassava is a highly important and widely
used starch supply made in geographic area. Because of low price within the world
market as compared to different sources of starch, usage of cassava is increasing.
Food packaging material shouldn’t be negatively affected by storage and tempera-
ture. Thus, to visualize these properties, associate experiments were done on cassava
that resulted in no adverse effects occurring in film throughout 8 weeks of storage at
a temperature of 25  C.
Starch shows an improved interaction with glycerin indicating more H-bonds
with amylose than amylopectin chains. Films with glycerin are preponderantly softer
and amorphous. Thermogravimetric analysis (TGA) and dynamic mechanical anal-
ysis (DMA) increase the temperature that subsequently softens the films. Waxy
maize films and cassava films each are the same in behavior, once exposed to
wetness with the slight distinction in less porosity of starch films that’s related to
presence of amylopectin chains. Quinoa seed is found in extremely little dimensions
having diameter 3 mm in high chain region of South America. Quinoa seed is among
the simplest sources of starch. Up to 80% starch is obtained from this seed. Amylose
and amylopectin are present around 10–21% and 79–90%, respectively, in quinoa
seeds. Quinoa starch is economical for production of clear perishable starch films. To
supply quinoa clear edible films, molding method is employed. The best conditions
are 2/21% of glycerin, base-forming pH of 7/10, and drying temperature of 36  C for
14 h. A wide range of research has been done on starch films supported by cassava
and maize (high amylose); however there has been quite less analysis regarding films
supported by amylum starch. Distinctive property of amylum starch makes it
effective to be introduced within the food packaging films. Amylum starch is
softened by sorbitol not glycerin because a number of its chemical science properties
are quite like starch and potato starch. The waterproofing ability of sorbitol is higher
than glycerin, though amylum films show less waterproofing strength than artificial
polymers.
896 S. Gulati et al.

These starch-based films are mostly perishable and have a few limitations. The
most serious limitation of perishable films is their hydrophilic character that ends up
reducing their stability after they are exposed to totally different environmental
conditions. A different approach is using oat starch films which contain 1–3% fat
in its natural structure that is precise with respect to the quantity of starch as
compared to different sources. Glycerin is employed to melt the oat starch films
and is slick; however it doesn’t have any cracks or bubbles in it. Lipids and amylose
are naturally warranted in oat starch, the section separation is prevented, and
therefore they contribute to scale back hydrophilic character of a substance. Oat
starch lipid isn’t capable of stopping changes in the mechanical properties caused by
wetness. As mentioned earlier, plants synthesize starch. Fabaceae family of
angiospermic plants is usually selected to extract starch. Rosin dicot genus Ahipa
is widely used in alternate supply for films. Organ roots are wealthy in presence of
starch in rosin dicot genus Ahipa species. This species grows on a small scale in a
chain region of Bolivia and northern Argentina. Ahipa starch has superiority over
other kinds of starch because it includes lower amylose content that is adequate
within the retrogradation range. In this the time and energy required for gelatiniza-
tion of suspension is reduced, making it more efficient. Food packaging materials
ought to have antimicrobial activity that is found in rosin dicot genus Ahipa.
Insecticidal and antifungal character is also found in starch extracted from family
Fabaceae of plants. “Rotnon” with the chemical having formula C23H22O6 is one of
the most necessary characteristics of rosin dicot genus Ahipa. Hence, several
researchers all over the world have found that such starch sources have higher
performance. Food packaging method must meet the wants of higher interaction
between packaging materials and food for the safety and health of humans [11]
(Fig. 9).

Fig. 9 Different types of

starch-based films
Pachyrhiz
US Ahipa
Starch

Sago Cassava
Starch Starch

Starch
Based Films
Quinoa
Maize
Seed
Starch
Starch

Oats
Starch
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 897

Thermoplastic Starch (TPS)

Thermoplastic starch is a material that is synthesized by modifying starch, pre-

cisely by mixing native starch with a plasticizer. This process needs to be carried
out at a temperature well above starch gelatinization temperature. This weakens the
hydrogen bonds present in the native starch leading to a fully amorphous free-
flowing material. During different thermoplasticization processes, water and glyc-
erol in the starch act as a lubricant that facilitates the mobility of polymer chains. It
also slows down retrogradation of TPS products. It will flow at elevated temper-
ature and pressure conditions and can be molded to give both foams and solid
molded articles. However, TPS plasticized with water has poor dimensional
stability and becomes brittle on losing water molecules. TPS properties can be
improved significantly by blending with other polymers, fillers, and fibers. Due to
the environmental problems related to nonbiodegradability of petrochemical-based
plastics, modified biopolymers are now being considered as an alternative to
synthetic polymers for several applications, including packaging for food [12]
(Fig. 10).

Amylopectin

Amylose Native Starch

Plasticized with water Plasticized with Glycerol

Amylopectin Amylopectin

Amylose

Glycerol

Plasticized
Amylose starch

Fig. 10 Native starch conversion to plasticized starch

898 S. Gulati et al.

Starch Plasticizers

Thermoplastic starch plasticizers are generally hydrophilic in nature. These sub-

stances not only reduce the hardness, density, viscosity, and electrostatic charge of a
polymer but also enhance the flexibility of the polymeric chain. Hence the brittle
nature of the native starch can be alleviated or removed by using plasticizers that will
minimize the possibilities of fractures.
Plasticizer molecules penetrate starch granules and destroy the inner gas bonds of
starch in high temperature, pressure, and cutting off. These molecules eliminate
starch–starch interactions as a result of which they are replaced by starch–plasticizer
interactions.
Plasticizer molecules will penetrate starch granules and destroy the inner hydro-
gen bonds of starch [13]. Water is considered to be one of the most effective starch
plasticizers and is needed for gelatinization, but it can however easily migrate from
the polymer and evaporate due to high vapor pressure. Glycerol is another suitable
alternative to water. It is a small molecule with polar nature that can enter starch
water channels. It can reduce intermolecular attractions between the polymers to a
great extent and impart the flexibility and stability that is needed for the preparation
of biodegradable bio-based films.
These days’ glycol, sorbitol, maltose, and xylitol also are getting used as starch
film plasticizers.
Compression molding is being extensively researched for improving the properties
of starch-based plastics, one of the major reasons being an improvement in the
properties of foam containers. The process involves gelatinization, expansion, and
drying. In this way, thermoplastic starch can be molded in different forms, and the
property is exploited by food packaging industries. Thermoplastic starch films gener-
ally need to have starch content greater than 70% to have biodegradable nature and can
be composted then only. Content of plasticizers must not exceed a certain value.

Blends When TPS is mixed with any other thermoplastic, generally in molten form,
the mixture can be regarded as a polymer blend. Starch can form stable blends with
polar polymers [14]. Only biodegradable polyesters such as poly-e-caprolactone
(PCL), polybutylene succinate adipate (PBSA), poly-hydroxybutyrate (PHB), and
PLA are generally used; otherwise the biodegradable nature would be lost. Polyeth-
ylene and polypropylene starch blends are been given importance as compatible
starch blends [15].

Composites The term composite refers to matrix polymers that contain glass, fibers,
talc, or clay particles (fillers) in dispersed form. Polymers with fillers that are nano-
sized (1–100 nm) are named nanocomposites [16]. Avella et al. in 2005 successfully
created starch clay nanocomposites using montmorillonite, potato starch, and poly-
esters for food packaging applications. Thermoplastic starch composites with titanium
dioxide nanoparticles have also been prepared successfully [17, 18].
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 899

Modification of Starch

Starches are often changed to enhance their thermal stability, resistance against acid
and bases, shear, time, cooling, or chilling. The texture of the starch can also be
changed, and they can be modified to enhance their performance according to the
applications. Starch can be modified by chemical, physical, and enzymatic methods
[19] (Fig. 11).

Chemically Modified Starch

Chemical modification involves the alteration of the chemical properties of starch by

adding some new chemicals. The chemical modification doesn’t alter the physical
size or form of the starch molecules. Glucose, the monomeric units of the amylose
and amylopectin, has three hydroxyl groups where chemical modification may be
performed [20].

Acid
hydrolysis
Degradation
Oxidation

Chemical Esterification
modification Substitution
Etherification

Cross-linking Esterification
Modification
of starch
Thermal
Physical
modification
Non-thermal
Enzymatic
modification

Fig. 11 Classification of different methods of starch modification

900 S. Gulati et al.

Methods of Chemical Modification

• Oxidation

The process involves the oxidation of primary or secondary hydroxyl groups of the
glucose monosaccharide that leads to the formation of an aldehyde or carboxyl
compound. A suitable oxidizing agent is used for this purpose.
The efficacy of oxidation depends on the type of oxidant used, source of starch,
and the process conditions. Moreover, the oxidation reaction may cause the weak-
ening of intermolecular bonds.
The oxidized starch has better water solubility, lower viscosity, and retrogradation
tendency in comparison to the non-modified starch.
The oxidation of starch can be carried out by using oxidizing agents such as air or
oxygen (in the presence of catalysts), inorganic peroxides (H2O2), organic peroxides
(NaClO), nitrogenous compounds (HNO3), organic oxidants as well as metal oxides
(CrO3).

• Esterification

Starch can be modified to improve its hydrophobicity through esterification.

This improves starch’s thermoplastic properties. The derivatives of these acids like
anhydrides and oxychlorides are also used sometimes. The high tendency of starch
to get esterified by esterifying agents allows the synthesis of several starch esters,
which are used in both food and nonfood applications. For example, starch acetates
have good transparency, low gelatinization temperature, and high wear resistance
that find their applications in various industries. Esterification improves the prop-
erties of starch such that it can be used as a potential biodegradable thermoplastic
material.

• Etherification

Etherification of starch generally involves the addition of hydroxypropyl group

(hydroxypropylation) and hydroxyethyl group to the starch (hydroxyethylation).
This process is carried out to modify the chemical properties of the starch.
Hydroxyethylation improves the drug binding ability for some anticancer and
other drugs, whereas hydroxypropylation increases the peak viscosity, water binding
capacity, and enzymatic digestibility of starch.

• Cationization

Treatment of starch with various cationic molecules improves the solubility,

stability, dispersibility, and clarity of the starch. This is done by the introduction of
amino, ammonium, imino, phosphonium, or sulfonium groups to give a positive
ionic charge to starch. Examples are dry cationization, wet cationization, and
semidry cationization. This leads to the introduction of cross-links in the starch
that enhances stability.
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 901

Physical Modification of Starch

The physical modification involves the changes in morphology and 3D structure of

starch under the influence of some physical factors like water, temperature, pressure, pH
scale and radiation, supersonic waves, etc. Physical modifications result in changes in
properties of starch like surface properties, water absorption, and swelling capability.
Some major ways are mentioned below:

• Heat Moisture Treatment

In this process application of heat is done in the presence of 22–27% of moisture

content and high temperature above the glass-transition temperature (100–120  C)
for a specified length of time that is 1–24 h. This results in a change in size, shape,
and granular and crystalline structure of starch.

• Radiation Treatment

1) Microwave Irradiation

Application of microwave radiation at different percentages of moisture and

ranges of temperature is carried out in this process which changes the dielectric
constant of starch. Microwave treatment improves the water and oil holding capacity
and solubility. It decreases the peak viscosity and gelatinization and the degree of
relative crystallinity as well.

2) Gamma Irradiation

Gamma radiation can break the amylopectin chains. It can also decrease the
amylopectin-to-amylose ratio. It also causes the radiolysis of starch. This increases
the pasting viscosity and enthalpy change of starch and molecular weight. It
increases the susceptibility of starch to amylase. It also improves properties such
as gelatinization, viscosity, swelling power, and solubility.

• Moisture Treatment

The moisture acts as a plasticizer and anti-plasticizer for starch films for different
properties. It causes a plasticizing effect on linear expansion, tensile modulus, and
water vapor permeability, while an anti-plasticizing effect on mechanical properties,
i.e., tensile strength and toughness.

• Mechanical Treatment
• Milling

It is a form of mechanical treatment. In milling starch is grinded by physical

processes which leads to decrease in the ratio of crystalline structure to amorphous. It
902 S. Gulati et al.

also leads to a sudden increase in surface parameters which is followed by a

subsequent decline.

• Ultrasound Treatment
• Ultra-sonication

Treatment of starch with ultrasonic waves. Results of this treatment showed an

initial increase in the solubility of starch and then a subsequent decrease in both
solubility and viscosity. There is a rise in gelatinization temperature of starch post
ultrasound treatment.

Enzymatic Modification of Starch

Enzymatic modification of starch can change molecular mass, branch chain length
distribution, and amylose/amylopectin ratio by reactions when the enzymes react
with gelatinized starch. Common enzymes used in starch processing include alpha-
amylase, beta-amylase, glucoamylase, and its amylase. These techniques provide us
with starches with altered and required physicochemical properties. The sites that are
prone to enzymatic attack are the less well-organized amorphous regions, whereas
the crystalline regions are more resistant. Glycoside hydrolases like, α-amylases,
pullulanases, glucan-branching enzymes and transglycosylases are the common
enzymes used for this purpose [20].

Various Properties of Thermoplastics and Composites Needed

for Food Packaging (Fig. 12)

Biodegradable

The biodegradable polymer is a polymer that is degraded by microorganisms. This is

biological activity. Various enzymes such as amylases and glucosidase attack the starch
and degrade the polymer. Enzymes attack at a specific site of a polymer for the

PROPERTIES

BIODEGRADABLE BARRIER MECHANICAL THERMAL

CARBON
WATER OXYGEN LIGHT
DIOXIDE

Fig. 12 Different properties of thermoplastics and composites

39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 903

degradation of cellulose. The three diverse classes of enzymes, namely, endocellulases,

exocellulases, and cellobiohydrolases, are present which degrade cellulose polymer to
glucose unit. These three types of biocatalysts are called cellulases. No individual
polymer can degrade the complete polymer. The set of enzymes are essential to degrade
a polymer. The polymers are degraded biologically in two ways: first, enzymatically
degradable polymer and, second, photo-oxidizable (by UV radiation) or thermos-
oxidizable (by heat) polymers. When these polymers are disposed to the environment
after their utilization, they are completely degraded by the organisms available in soil,
sea, and sewage. Microbial growth is influenced by glycerol which promotes swelling,
thereby mass transport of water and hence the microbial growth as well. Biodegradable
materials have been found to some significant use in the field of medicine and its allied
field. The occurrence of biodegradation was evidenced by gel permeation chromatog-
raphy indicating a reduction in molecular weight of TPS after the exposure of the
sample; this confirmed that the rate of biodegradation was improved by the influence of
starch [21]. Table 2 shows degradation of various modified membranes with time.

Barrier Property

As food packaging material, we require moisture barrier property. TPS causes poor
water permeability, but starch has a natural hydrophilic character when it is com-
bined with plasticizer glycerol; the swelling of the network holds a significant
amount of water; this swelling breaks the structural integrity of matrices and leads
to poor barrier property. The complex relationship between polymer matrix and
barrier properties depends on various factors such as the structure of the matrix,
molecular weight, polarity, crystallinity, and type of reinforcement present. Moisture
transfer between food and the surrounding atmosphere will lead to spoilage of food;
hence the resistance against water vapor permeability should be as high as possible.

Table 2 Membrane with respective degradation time

Quantity of
S. no. Membrane degradation Time References
1. Maleic anhydride-compatibilized 91% 42 days [6]
starch–PLA blends
2. Starch films cross-linked with resorcinol 100% 60 days [6]
formaldehyde
3. 30% glycerol-plasticized starch 70% 22 days [6]
4. TPS reinforced with Ss’ 100% 60 days [6]
5. TPS reinforced with 10 wt.% CNFs 100% 40 days [6]
6. TPS reinforced with 10 wt.% acetylated 100% 60 days [6]
CNFs
7. TPS/50% commercial calcium carbonate 35.37% 15 days [6]
composite
8. 50 wt.% CaCO3/TPS composite 61.89% 30 days [6]
9. 50 wt.% eggshell/TPS composite 90% 30 days [6]
904 S. Gulati et al.

ASTM D570-81 standard method of studying water resistance of materials involves

drying before placing weighed (Wi) samples indefinite volume of deionized water at
room temperature for 24 h. Then the samples will be taken out and moisture is
removed before weighing (Wf). The calculation of percentage weight gain is given
by % Weight gain ¼ WfW
W i
i
[21]:
As light can pass through packaging material and can catalyze oxidation reaction,
thus light barrier properties are also required for packaging material [21].

Water Barrier
The nature of starch is like a hydrophilic film. Water vapor permeability depends on the
diffusivity and solubility of the water molecule in the film matrix. The incorporation of
nanostructures leads to mending the pathway of water molecules to traverse the film
matrix. The water vapor permeability coefficient quantifies the water vapor barrier. It
indicates the amount of water vapor that permits in packaging per unit area and time
[22]. Relative humidity and the type of plasticizers that are used influence the water
uptake of TPS film. In Table 3, water uptake of two membranes is given in different
relative humidity conditions.

Oxygen Barrier
At low relative humidity (RH), the oxygen barrier properties of most biopolymer-
based packaging materials are moderate to a good level. But when relative humid-
ity (RH) is increased, the oxygen barrier properties deteriorate exponentially. The
measurement of the oxygen barrier can be done by the oxygen permeability
coefficient (OPC). It is the amount of oxygen that permeates per unit of area and
time through the wall of packaging material (Siracusa et al. 2008). Low OPC
indicates that pressure inside the packaging material drops in such a way that
oxidation is retarded [23].

Table 3 Water uptake of maize starch plasticized with isosorbide and glycerol at different Rh
Water Relative
S. no. Membrane uptake humidity References
1. Isosorbide as plasticizers with maize 22.8% 75% [6]
starch
2. Glycerol as plasticizers with maize 25.7% 75% [6]
starch
3. Isosorbide as plasticizers with maize 8.8% 50% [6]
starch
4. Glycerol as plasticizers with maize 10.4% 50% [6]
starch
5. Isosorbide as plasticizers with maize 4.5% 25% [6]
starch
6. Glycerol as plasticizers with maize 5.5% 25% [6]
starch
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 905

Carbon Dioxide Barrier

Carbon dioxide is also important in food packaging applications; carbon dioxide
permeability coefficient quantifies the carbon dioxide barrier; it indicates the
amount of carbon dioxide that permeates the packaging material per unit area
and time [23].

Light Barrier
The light which contains radiation energy affects the photosensitive products
because it accelerates the photochemical degradation reactions that may deteriorate
such products. Exposure to light causes the polymer to undergo oxidative degrada-
tion leading to the weakening of the polymers [23].

Mechanical Property

The mechanical property of starch-based film was assessed employing a tensile test.
This property of starch depends on its ultimate strength, Young’s modulus and
elongation at break. For the mechanical property of starch-based biodegradable
packaging film, various improvements are developed; these include, first, the addi-
tion of new plasticizers such as urea or form amide that aid in the thermoplastic
process and also increase the flexibility of the final product by forming hydrogen
bonds with starch that replaced the strong interaction between hydroxyl groups.
Second is the addition of synthetic biodegradable polymers like poly(vinyl alcohol)
(PVOH) and polylactide (PLA) to produce materials with properties intermediate to
the two components; resultant blends can be better processed by extrusion or film
blowing and have mechanical properties superior to those of starch alone [24]. Third
is the addition of compatibilizers to lower interfacial energy, and increased misci-
bility of two incompatible faces leads to a stable blend with improved characteristics.
Amylose/amylopectin ratios vary with the starch source with high-amylose starches
that affects the material in two ways. First is increasing strength and ductility.
Secondly, it affects gelatinization processes, which generate the uniform amorphous
thermoplastic by the action of heat and mechanical work in the extruder. The
addition of plasticizers increases the toughness of the starch but decreases the
strength and modulus [24] (Table 4).

Thermal Property

The thermal stability of starch ether depends on the degree of substitution (DS).
With an increase in the degree of substitution (DS), thermal stability increases
[25]. In the case of starch–Ag nanoparticles, thermogravimetric analysis was
utilized to investigate the effect of various concentrations of Ag nanoparticles on
thermal stability and activation energy of starch [26]. In one study starch granules
are divided into three categories: (a) diameter 10–15 μm, (b) diameter 5–9.9 μm,
 906

Table 4 The tensile strength, fracture strain, and Young’s modulus of respective modified membrane
Fracture
S. no. Membrane Tensile strength strain Young’s modulus References
1. Methylcellulose–glucomannan–pectin 72.63 MPa 9.85% – [6]
2. Corn starch and poly(vinyl alcohol) blends with glycerol as 1.8 MPa 113% – [6]
plasticizer (without PVA)
RH, 50%
3. Corn starch and poly(vinyl alcohol) blends with glycerol as 4 MPa 150% – [6]
plasticizer (PVA)
RH, 30%
4. Starch–glycerol–PVA – 230% – [6]
Ratio, 65:35:9 (highest)
RH, 30%
5. Corn starch-based films with the incorporation of citric acid and – – – [6]
carboxymethyl cellulose (CMC)
6. Addition of 10% (wt./wt.) citric acid into starch film 6.57 MPa 66.18% – [6]
7. CMC was incorporated along with 10% (wt./wt.) citric acid 16.11 MPa 59.49% – [6]
8. Bamboo cellulose crystals reinforced thermoplastic starch 2.5 MPa – 20.4 MPa [6]
9. 30% nanocrystal reinforcement into thermoplastic starch 11.9 MPa 7.2% 498.2 MPa [6]
10. Starch nanocomposite films produced by reinforcing acetylated 69.50  1.16 MPa 307%  29% 828.68  5.77 MPa [6]
cassava starch nanoparticles (NPs)
S. Gulati et al.
39 Starch Based Bio-nanocomposites : Modern and Benign Materials in Food. . . 907

Table 5 Membrane with respective degradation time

Maximum degradation
S. no. Membrane temperature (Tmax) References
1. Glycerol-plasticized TPS 309  C [6]
2. Isosorbide-plasticized TPS 304  C [6]
3. 20 wt.% leaf wood fiber-reinforced 336  C [6]
composites
4. 20 wt.% of paper pulp fibers are added 339  C [6]
5. Reinforcement of 0.5 wt.% NPs into 334  C [6]
cassava starch
6. 20 wt.% chitin nanofibers filled starch 288  C [6]

and (c) diameter < 5 μm. The thermal energy of different starch grain used is
determined by gelatinization enthalpy (ΔH) of granules decreased in order a > b > c.
ΔH has been related to crystallinity [27]. Maximum degradation temperature
(TMAX) gives the measure of thermal stability of the membrane given in Table 5.

Conclusion and Future Perspectives

Petroleum-based materials are used as a conventional food packaging strategy.

These strategies also involve the use of metals like aluminum, tin, glass, plastic,
etc. which are hazardous to the environment as well as for our health. Most of these
materials are nonbiodegradable too, so researches are shifted toward the search for
biodegradable material. Biodegradable starch film and certain modifications in
their structural and physicochemical properties can be a suitable alternative for
modern-day food packaging, while it follows a green approach. Starch sources are
mostly botanical so they may not harm the environment in any condition. Cassava,
corn, pea, wheat, rice, potato, oats, etc. are the main source of starch which makes
films used in food packaging strategies. The difference in the starch source shows
different properties of the film used as food packaging material. Modification can
be done by the addition of plasticizers termed as thermoplastic or modified
chemically physically or enzymatically to improve the 3D structure and various
properties such as mechanical, thermal and barrier, etc. The development and
modification of these materials are not cost-friendly. Researchers are now trying
to implement various other properties such as antioxidant and antibacterial prop-
erties [28]. In the case of developing antioxidant films, two critical concerns are
important for researchers in this field. First, reduction in the value of the difference
in accessing and reporting antioxidant capacity to get a standardized result. Sec-
ond, for accessing antioxidant capacity, realistic consideration should be taken into
account such as food simulant (solvent) rather than utilizing water or antioxidant
species. Focused research is needed in the development of these materials in such
a way that they show maximum properties and satisfy the condition of cost-
effectiveness [29, 30].
908 S. Gulati et al.

Important Websites

https://www.azonano.com/article.aspx?ArticleID¼1832
https://www.understandingnano.com/nanocomposites-applications.html
https://www.sciencedirect.com/topics/chemical-engineering/nanocomposites
https://www.britannica.com/science/nanoparticle/Nanoparticle-applications-in-
materials
https://www.britannica.com/science/nanoparticle
https://euon.echa.europa.eu/food-packaging
https://www.britannica.com/topic/food-preservation/Packaging
https://www.nanowerk.com/spotlight/spotid¼51119.php

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Wrinkle-Resistant Fabrics: Nanotechnology
in Modern Textiles 40
Shikha Gulati, Sanjay Kumar, Sanah Kumar, Vidhi Wadhawan, and
Kanchan Batra

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
Conventional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
Formaldehyde-Based Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
Non-formaldehyde-Based Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
Nanomaterials in Anti-wrinkling Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
Titanium Dioxide (TiO2) Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
Silver (Ag) Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Zinc Oxide (ZnO) Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Chitosan Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
Silica (SiO2) Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
Multifunctional Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
Environmental Impact of Use of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 926
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 927

Abstract
Nanotechnology is a growing interdisciplinary branch of science that deals with the
utilization of matter at an atomic/molecular/supramolecular scale for diverse pur-
poses. The reason for its impact in wide areas is due to the high effectiveness of
nanomaterials. Owing to the small size (<100 nm) of nanoparticles, different
physical and chemical properties have been observed. These properties make

S. Gulati (*) · S. Kumar

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
S. Kumar · V. Wadhawan
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India
K. Batra
Department of Zoology, Kalindi College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 911

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_97
912 S. Gulati et al.

them advantageous in developing novel technologies or materials having specific

desirable properties. The applications of nanotechnology in the textile industry are
vast and extensive. By surface coating or surface modifications, nanoparticles can
be employed in developing textiles having unique qualities such as durability,
water-resistance, wrinkle-resistance, and high tensile strength. Additionally, nano-
technology can be used to combat the disadvantages of traditional methods that lead
to loss of tensile strength, decrease in abrasion resistance, loss in functionality, etc.
Not only this but nanotechnology also provides nontoxic and inexpensive alterna-
tives to such traditional methods. This chapter encompasses the recent advances and
preexisting methods in the application of nanotechnology in the textile industry
while focusing on the novel technologies developed to fabricate wrinkle-resistant
textiles. Cotton fabric contains cellulosic fibrils and hydrogen bonds, which break
due to water absorption and their reformation may result in wrinkling or the
formation of creases. Various methods have been hitherto developed, which impart
wrinkle-resistant characteristics to fabrics. Wrinkle-free, easy-care treatments and
durable press (DP) finishing are given to produce much required high-end apparel.
Some traditional methods include the utilization of formaldehyde and
non-formaldehyde resins in the cross-linking of fibers, and hence providing DP
Finishing. But the use of formaldehyde resins has proven to be hazardous and these
have other limitations as well, since these may make the fabric stiff or uncomfort-
able. These limitations can be overcome by employing nanomaterials in finishing
processes. A precise comparison has been made between traditional protocols used
for the production of wrinkle-free fabrics with that of the technologies utilizing
nanomaterials. The effectiveness of a variety of nanoparticles for different sets of
fabrics has also been overviewed for the development of this technology. In
conclusion, this chapter aims to understand the current innovations as well as the
future potential of nanoparticles in the revolution of the textile industry.

Keywords
Nanotechnology · Nanomaterials · Modern textiles · Wrinkle-resistance · Cross-
linking · Resins · Nontoxic

Introduction

Nanotechnology finds its use in a broad spectrum of fields primarily due to the
versatility of its applications. Initially, the idea of nanotechnology was put forth by
Nobel laureate Richard Feynman, but it was not till the year 1974 that it garnered
much attention when Norio Taniguchi coined the term “nanotechnology.” Nano-
technology includes the use of nanomaterials, nanoparticles, nanorods, nanocrystals,
nanoribbons, etc. [1–4]. Currently, many research institutes all over the world are
working to develop innovations in this field. Nanomaterials have found their use in
the fields of medicine as vehicles of drug delivery, in the textile industry, in
electronics, in cosmetic products, in food packaging, in industrial and purification
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 913

processes like water purification and are also widely used as catalysts, etc. Hence,
due to its myriad of applications, nanotechnology has proven to become quite a
sought-after field, especially in the production of high-end commercial products
such as wrinkle-free textiles [5].
The durable press treatment is used to provide anti-wrinkle-resistant properties to
fabrics that are much in demand, mainly due to the fast pace of modern life (Fig. 1).
Cotton is made up of cellulose which is a linear molecule and is a structural
homopolysaccharide of D-Glucose molecules linked through (β1!4) glycosidic
bonds. Cellulose fibers have a high tendency to absorb water and form hydrogen
bonds with it. When water moves into the amorphous region of the cellulose, the
fibers swell up. Furthermore, this results in the displacement of cellulose chains and
the formation of new hydrogen bonds and causes wrinkling of the fabric [6, 7].
By introducing cross-linking or branching between the chains, we can impart
anti-wrinkle characteristics to it because this holds the chain in place. This can be
achieved by utilization of formaldehyde-based compounds or formaldehyde resins
but these are hazardous to both human health and the environment. Thus, an
alternate method to utilize polycarboxylic acids along with catalysts such as nano-
TiO2 has been put into use. This method of using nanomaterials as anti-wrinkle
agents in fabrics proves to be much safer and also a more effective strategy.
Furthermore, multifunctional finishing can be provided to nano-textiles which
gives them additional properties such as UV protection, water-oil repellence,

Fig. 1 Before and after anti-

wrinkle finishing of fabric

Before After
Anti-Wrinkle Anti-Wrinkle
Finishing Finishing
914 S. Gulati et al.

antimicrobial properties, and flame retardancy as well. On the other hand, the
environmental impact and adverse effects on human health such as carcinogenicity,
cytotoxicity, etc. also have to be taken into account. Hence, alternative green
methods are being applied in the development of nanotextiles that are eco-friendly
and less detrimental to both the environment and human health [5, 8, 9].

Conventional Methods

Manufacturing processes of textile fabrics can usually result in loss of strength and
stability. Textile fabrics are subjected to finishing processes to improve their prop-
erties of shape retention and to be resistant to wrinkling. Durable press and easy-care
finishing are involved in cotton fabrics containing high cellulosic fiber content, but
can also be advantageous to other fabrics as well [7]. Durable press (DP) treatments
involve cross-linking along with various reagents which can be classified mainly as
formaldehyde-based or formaldehyde-free. Formaldehyde reagents have shown
excellent performance in developing wrinkle-resistance, but the treated fabrics
may emit formaldehyde, which has been considered as a carcinogenic substance.
Thus, the focus has shifted toward the use of non-formaldehyde reagents and
nanomaterials along with resins in the finishing processes [10–13].

Formaldehyde-Based Reagents

Reagents involving the use of formaldehyde were first introduced in the 1920s. Early
compounds developed include urea-formaldehyde or melamine-formaldehyde com-
pounds. These compounds have shown excellent DP finishing with cellulosic
fabrics.
Urea-formaldehyde resins are prepared by reaction of urea and formaldehyde in
an aqueous medium (Fig. 2). This results in the formation of N,N0 -dimethylol urea

Fig. 2 Preparation of urea-formaldehyde resin

40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 915

(DMU), which is further stabilized by reacting with methanol to form an ether. DMU
is a highly reactive compound, which can easily form cross-links with hydroxyl
groups present between the cellulosic chains in fabrics. Fabrics that have undergone
such urea-formaldehyde treatment show improved crease recovery, but it is known
that such fabrics also release a high amount of formaldehyde after finishing. Not only
this but such treatments have also resulted in the retention of chlorine in fabrics after
laundering or washing [10].
Melamine-formaldehyde resins were developed to increase the efficiency of
cross-linking of resins. These resins can be synthesized by the reaction of melamine
and formaldehyde, which forms derivatives of methylol melamine (Fig. 3). Tri-
methylol melamine (TMM) and hexamethylol melamine (HMM) are the two most
commonly used derivatives. These can easily form cross-links with the hydroxyl
groups of cellulosic chains. Treated fabrics show decreased chlorine retention and
more stability in the case of hydrolysis, as compared to the activity of urea-
formaldehyde treated fabrics. The disadvantage of melamine-formaldehyde com-
pounds is the high amount of formaldehyde released from fabrics and the high cost
of such finish [11].
Other cross-linkers synthesized included derivatives of dimethylolethyleneurea
(Fig. 4). One of the main cross-linkers developed was dihydroxydimethylolethyleneurea

Fig. 3 Structure of melamine-formaldehyde resins

Fig. 4 Structure of DMDHEU

916 S. Gulati et al.

(DMDHEU). It reacts similarly to urea-formaldehyde and melamine-formaldehyde

resins, to form cross-links between the hydroxyl groups of cellulosic chains.
DMDHEU treatments have shown excellent DP finishing and relatively less release
of formaldehyde was observed from the treated fabrics, as compared to other
treatments [14].

Non-formaldehyde-Based Reagents

Due to the loss of strength and release of formaldehyde from fabrics treated with
formaldehyde reagents, the focus has shifted to formaldehyde-free reagents. Early
reagents included dimethyl dihydroxyethylene urea and the current reagents applied
are polycarboxylic acid derivatives and other acids.
N,N0 -Dimethyl-4,5-dihydroxyethylene urea (DMeDHEU) is a formaldehyde-free
reagent synthesized by the reaction of urea derivatives and glyoxal and is also termed
as dimethylurea glyoxalate (DMG). The efficiency of cross-linking of DMeDHEU
of hydroxyl groups with cellulosic chains is very low and the DP finishing is
unsatisfactory. Not only this but the reagent is expensive as compared to
formaldehyde-based reagents [10, 11].
A large variety of polycarboxylic acids (PCAs) have been employed as DP finish
reagents, as an alternative to formaldehyde-based compounds for the wrinkle-
resistant finish (Fig. 5). Some of the most common examples include 1,2,3,4-
butanetetracarboxylic acid (BTCA), citric acid (CA), succinic acid (SA), and malic
acid (MLA). Other acids employed in such processes are maleic acid (MA) and
itaconic acid (ITA). The mechanism of action of polycarboxylic acids involves the
formation of an anhydride intermediate of acids, and the esterification of this
intermediate with the hydroxyl groups present on cellulosic chains of fabric. A
major disadvantage of utilizing PCAs in anti-wrinkle finishing is the low efficiency
of esterification reactions of PCAs and cellulose in cross-linking. Hitherto, several
studies have been conducted to improve the reaction efficiency by employing
catalysts along with a combination of PCAs in finishing processes [8].
BTCA is considered to be one of the most efficient formaldehyde-free reagents in
DP finishing and has proven to show excellent performance in providing anti-
wrinkle finishing to fabrics. This performance was achieved by employing a catalyst
such as sodium hypophosphite (SHP) in crosslinking with cellulose. SHP is respon-
sible for reducing the temperature required for anhydride formation and provides
good wrinkle recovery to the fabric. BTCA also has its limitations due to the loss of
tensile strength of treated fabrics and the high cost of the catalyst. Aromatic PCAs
such as 3,30 ,4,40 -benzophenonetetracarboxylic acid (BPTCA) were synthesized and
conferred improved tensile strength retention, but their performance was unsatisfac-
tory due to low cross-linking efficiency [11, 14].
Other PCAs such as CA are inexpensive and renewable formaldehyde-free
reagents which could have been ideal if they did not result in the yellowing of
fabrics. This yellowing occurs due to the dehydration of CA and the formation of
unsaturated acids. The use of glycol derivatives along with CA treatment resulted in
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 917

Fig. 5 Structures of polycarboxylic acids

a decrease in yellowing, but also led to a decrease in DP finishing. Employing

nanoparticles such as nano-TiO2 as a co-catalyst with CA has shown to improve the
wrinkle-resistance of fabrics. Not only this but SHP along with CA treatment has
shown improvement in DP finish [15].

Nanomaterials in Anti-wrinkling Finishing

Conventional methods used in providing wrinkle-resistance to fabrics have been

successful to an extent, but they have various limitations including loss of strength,
water absorbance, comfortability of fabrics along with the release of harmful sub-
stances from the treated fabrics after finishing, such as formaldehyde. Nanomaterials
are employed as co-catalysts along with various polycarboxylic acids and sodium
hypophosphite (SHP) as catalyst to enhance the crosslinking efficiency of the
reagents. These provide multiple functionalities such as water repellence, anti-
bacterial properties, strength retention, and wrinkle resistance in the treated textiles.
918 S. Gulati et al.

Chitosan

Titanium-
Carbon
dioxide
Nanotubes
Nanoparticle

Nanoparticles
used to confer
Wrinkle-
resistance to
Fabrics

Silver Silica
Nanoparticle Nanoparticle

Zinc oxide
Nanoparticle

Fig. 6 Nanoparticles conferring anti-wrinkle finishing in fabrics

Nanoparticles (Fig. 6) like titanium dioxide (TiO2), silicon dioxide (SiO2), silver
nanoparticles (Ag), and so on are involved in anti-wrinkle finishing [7] (Table 1).

Titanium Dioxide (TiO2) Nanoparticles

Researchers have employed TiO2 nanoparticles as a co-catalyst with SHP catalyst

and PCAs, under UV radiation to improve the wrinkle-resistance properties of cotton
fabrics. SHP as catalyst has shown to significantly improve the performance of
finishing processes. Despite this, SHP has some major limitations as it is expensive
and poses a high threat to the environment. So instead of this, TiO2 nanoparticles can
act as preferable catalysts due to their large surface area and can provide a sufficient
number of active sites for the cross-linking reaction to take place easily. Not only this
but ultrafine and small-sized forms increase the chemical reactivity of catalysts
[16, 17].
Wrinkle-resistant finishing involving DMDHEU and TiO2 has been studied
and an increase in the wrinkle recovery angle (WRA) has been observed. This
increase in WRA is attributed to the fact that TiO2 can restrict the movement of
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 919

Table 1 Nanoparticles in anti-wrinkle finishing

Fabrics Reagent
Nanoparticles tested used Advantages Disadvantages References
TiO2 Cotton DMDHEU Increase in WRA; Insignificant [18]
reduced release of effect on
formaldehyde; tensile and
Multifunctional tearing
finishing strength
(UV Protection)
TiO2 Cotton BTCA Increase in WRA; Decrease in [16, 21]
softer fabrics tensile and
tearing
strength
TiO2 Cotton BTCA- Increase in WRA; – [20, 23]
SHP multifunctional
finishing
(UV protection);
Safe fabrics
TiO2 Cotton CA-SHP Increase in WRA; Decrease in [22, 23]
softer fabrics tensile and
tearing
strength;
yellowing of
fabrics
Ag Cotton BTCA- Increase in WRA; Slight decrease [24, 25]
SHP multifunctional in tensile
finishing strength
(Antimicrobial);
no yellowing of fabrics
CNT Cotton BTCA- Increase in WRA – [26]
SHP
ZnO Cotton MA-SHP Increase in WRA – [27]
Multifunctional
finishing (antibacterial
and self-cleaning)
ZnO Cotton BTCA- Increase in WRA; – [28]
SHP multifunctional
finishing
Chitosan A. pernyi BTCA- Increase in WRA; Yellowing of [30, 31]
silk SHP multifunctional fabrics
finishing
(antibacterial)
SiO2 Cotton BTCA- Increase in WRA Decrease in [33]
SHP tensile strength

cellulosic chains and is responsible for enhancing the self-catalyzation of

DMDHEU. The use of catalyst has also shown a reduction in the release of free
formaldehyde but a decrease in tensile strength of the treated fabrics has also been
observed [18].
920 S. Gulati et al.

Fabrics treated with BTCA show higher WRA as compared to that with other
reagents, but these results were still unsatisfactory. TiO2 nanoparticles were
employed along with BTCA/SHP treatment of fabrics, and have shown a significant
increase in WRA in both dry and wet conditions. Not only this but these nano-
particles also increase the effectiveness of SHP and, hence, increase the cross-linking
efficiency. Such fabrics were also found to be softer as compared to untreated
fabrics. By treating the fabrics with a range of concentrations of the nanoparticles,
it was found that an increase in the concentration of nano-TiO2 could lead to
reversible cross-linking and reduce the wrinkle resistance properties of treated
fabrics. Despite the excellent performance of the nanoparticles, a reduction in tensile
strength of treated cotton fabrics was also observed [16, 19–21].
Citric acid and SHP treated fabrics also show an increase in the WRA, which can
be further increased by employing nano-TiO2 in the process. Similar action of TiO2
nanoparticles of restricting the chain movement, as seen with other acids, was
observed here. The mechanism of cross-linking is assumed to be by proton or
electron attack, due to the photocatalytic ability of nano-TiO2 particles. Further
increase in WRA can be observed by increasing the concentrations of CA, but an
increase in the concentration of TiO2 can have the opposite effect on WRA, after a
certain level. Fabrics treated with CA often show a yellowing after finishing, mainly
due to the production of unsaturated acids. Neither SHP nor TiO2 has shown any
significant decrease in yellowing. Tensile strength of fabrics has also been decreased,
possibly due to an increase in cross-linking, which makes the fabrics brittle [22].
An increase in WRA has been noted in the finishing of fabrics with both BTCA
and CA along with nano-TiO2, but BTCA has proven to be a more promising
reagent. This can be attributed to the higher WRA observed with BTCA, which
may be due to the presence of an additional carboxylic group. However, the tensile
strength of CA-treated fabrics has been observed to be higher than that of those
treated with BTCA [23].

Silver (Ag) Nanoparticles

Silver nanoparticles (AgNPs) are employed in imparting wrinkle-resistant character-

istics to fabrics because of their unique properties. Cotton fibers when treated with
colloidal silver nanoparticles which are combined with 1,2,3,4-butanetetracarboxylic
acid (BTCA) in the presence of sodium hypophosphite (SHP) as catalyst displayed
increased wrinkle recovery. This is because this treatment results in cross-linking of
cellulose chains through hydroxyl group which further gives rise to less absorption of
water and also makes the structure more closely packed. This method was proposed by
Montazer et al. In addition to the durable press treatment, antimicrobial finishing can
also be provided to the fabrics which is an added advantage [24].
The method of green synthesis of silver nanoparticles was put forth by Hebeish
et al. in which silver nanoparticles were synthesized under the reducing influence of
sugar and stabilizer polyethylene glycol (PEG). They then combined silver nano-
particles with 1,2,3,4- butanetetracarboxylic acid and sodium hypophosphite catalyst
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 921

and concluded that as the concentration of silver nanoparticles increased, the WRA
increased. But this was observed only till the concentration of silver nanoparticles
reached 100 ppm. After this, no further increase in the WRA was observed [25].

Carbon Nanotubes

Carbon nanotubes (CNTs) have unique properties such as high conductivity, stabil-
ity, and strength, which provide a potential for growth in the textile industry. CNTs
and carboxylated CNTs have been studied for their ability to provide crease-
resistance in fabrics. The strength and anti-creasing properties can be improved by
penetrating CNT into the cellulosic chains of the fabric [19]. Similar to other
nanomaterials, it is believed that better WRA can be achieved by cross-linking of
CNTs with cellulosic chains with the help of a cross-linking reagent such as
polycarboxylic acids. One of the research involved the use of succinic acid and
SHP as a catalyst along with CNTs to enhance cross-linking efficiency. Cross-
linking reduces the flexibility of cellulosic chains and restricts their movement,
thus increasing the WRA [7]. A study has been conducted to compare the WRA of
CNT-embedded fabrics and cross-linked fabrics at different concentrations of CNT.
The WRA of cross-linked fabrics was found to be higher than that of CNT-embedded
and raw fabrics at CNT concentration <1500 ppm. However, the WRA of
CNT-embedded fabrics was observed to increase significantly on increasing the
concentration of CNT above 250 ppm. Further research is required to gain a better
understanding of the ability of CNTs in providing anti-wrinkling properties [26].

Zinc Oxide (ZnO) Nanoparticles

For displaying wrinkle-resistant characteristics, cotton fabric is treated with maleic

acid (MA), sodium hypophosphite, and zinc oxide nanoparticles and it was observed
that as the concentration of MA increased by 6%, the WRA also increased. This is
because when treated with MA, there was an increase in the cross-linking of
cellulose chains which increases the wrinkle recovery angle. Furthermore, the
treatment of cotton with Zinc oxide nanoparticles in addition to MA increases
wrinkle resistance. Untreated cotton has a WRA of 260.2 degrees whereas when
treated with 6% maleic acid, it increases to 320.2 degrees. Additionally, this treat-
ment can also be used to confer self-cleaning properties and antimicrobial functions
to the fabrics [27].
In another study, cotton was treated with zinc oxide nanoparticles, 1,2,3,4-
butanetetracarboxylic acid and disodium hydrogen phosphate. As the concentration
of BTCA increases, the WRA also increases. This is because BTCA reacts with the
hydroxyl group of cellulose chains present in amorphous regions and makes cova-
lent bonds that do not break on bending. More and more permanent covalent bonds
are formed which results in a further increase in the WRA of the fabric. The recovery
angle also depends on the concentration of zinc oxide nanoparticles and it increases
922 S. Gulati et al.

as the concentration of ZnO nanoparticles increases. This can be chalked up to two

reasons, the first being that ZnO nanoparticles may catalyze cross-linking of cellu-
lose chains with BTCA and the second reason could be the strong interaction of ZnO
nanoparticles with cellulose chains which further restricts the movement of these
chains and hence causes an increase in the WRA. Using this treatment, cotton fabrics
can be assigned multifunctional properties like wrinkle resistance, antibacterial
functions, antistatic effect, bending rigidity, and retaining of tear strength for up to
10 washing cycles [28].
A separate study showed that when ZnO nanoparticles were used in conjunction
with an acrylic binder, the WRA of cotton fabrics improved significantly as com-
pared to the case where only the ZnO nanoparticles were used for coating the cotton
fabric. The untreated cotton fabric showed a WRA of 105 degrees, the fabric treated
only with ZnO nanoparticles showed a WRA of 108 degrees and the fabric treated
with ZnO nanoparticles and acrylic binder showed a recovery angle of 111
degrees [29].

Chitosan Nanoparticles

Chitosan is considered highly functional as a nanoparticle, as it has a high surface

area to volume ratio. Chitosan nanoparticles, along with cross-linking reagents, can
be employed in providing anti-wrinkle properties to fabrics and have shown satis-
factory results. The binding of cellulosic chains and chitosan nanoparticles can occur
by intermolecular inclusion interaction, which restricts chain movement and
increases resistance to wrinkling of the fabric. Research has been conducted to
study the impact of chitosan nanoparticles along with BTCA and SHP catalyst on
the properties of Antheraea pernyi silk. An increase in WRA was observed on
increasing the concentration of BTCA as well as that of SHP. On treating the silk
fabrics with a nano-chitosan dispersion solution or hydroxypropyl chitosan (HCS)
nanoparticles, a further increase in WRA was observed. This can be attributed to the
enhancement of cross-linking reaction of BTCA, HCS nanoparticles, and silk fibers.
Nano-chitosan can reduce the movement of chains by entering the amorphous region
of silk fibers. Despite their satisfactory performance, these nanoparticles have certain
disadvantages due to the yellowing observed in the treated fabrics. This yellowing
can be associated with the color of chitosan nanoparticles. Another study has been
conducted on the performance of nano-chitosan in providing wrinkle resistance to
Mulberry silk fabrics, and satisfactory results have been obtained on employing an
appropriate mass fraction of nano-chitosan [30, 31].

Silica (SiO2) Nanoparticles

According to a study by Li-Zhi Gao et al. finishing of silk fabrics with nano-silica
(nano SiO2) along with the usage of silane coupling agent (KH570) conferred both
wrinkle-resistant properties and UV protection. Wrinkling is caused in silk fabrics
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 923

because the intermolecular bonds in silk are weak and break easily and the molecular
chains then form new hydrogen bonds among themselves. To resolve this issue,
cross-linking agents/finishing agents are used which hold the bonds between the
chains in place, and hence, wrinkle-resistance is improved. Nano-silica particles are
considered excellent finishing agents because they have a high specific surface area,
are chemically inert, thermally stable, and exhibit good mechanical properties.
Nano-silica displays the presence of multiple hydroxyl groups which can form
hydrogen bonds, thus increasing the wrinkle resistance of silk fabrics. The WRA
of nano-SiO2 and KH570 treated silk was found to be 270.6 degrees, which shows an
increment of 16.5% as compared to that of the water-treated sample. The cross-
linking between nano-SiO2 and silk fibers might hold the silk molecular chains in
place and restrict their relative movement, thus improving the wrinkle-resistant
properties by a significant amount. Other studies have used other cross-linking
agents such as vinyltrimethoxysilane (Tsukada et al), 2-hydroxypropyl methacrylate
(HPMA) (Yang et al), and some reactive and crosslinking dyes (Nan Yan et al).
HPMA and cross-linking dyes enhance the anti-wrinkle properties of silk fabrics but
vinyltrimethoxysilane is not as good as them in this aspect [32].
In another study, a coating of nano-silica was applied to cotton fabrics in addition
to cross-linking agent 1,2,3,4- butanetetracarboxylic acid and catalyst sodium hypo-
phosphite. BTCA and SHP catalyst cause cross-linking of cellulose chains which
hold them in place and thus improves their anti-wrinkle properties. Not only this but
silica nanoparticles move into the amorphous region of cotton fiber with ease and
adhere to the fiber structure causing betterment of crease-resistant property of cotton
fiber. Furthermore, it was seen that an increase in the concentration of nano-silica
resulted in a higher WRA of the fabric [33].

Multifunctional Finishing

In addition to wrinkle resistance, many other useful properties can be conferred to

fabrics through multifunctional finishing (Fig. 7). This provides an added advantage
as consumers these days are looking for multiple characteristics all combined in one.
Furthermore, this also significantly reduces the cost of production, by cutting down
the number of stages involved in the production of textiles. Durable press treatment
can be used in conjunction with a variety of other properties such as UV protection,
flame retardancy, antimicrobial functions, and water-oil repellency. The aforemen-
tioned properties have been discussed below [8, 11].
Chitosan is used along with easy-care finishing agents in one bath to confer
antimicrobial properties against both gram-positive and gram-negative bacteria. One
of the methods of preparing fabrics that display antimicrobial properties in addition
to wrinkle resistance is by formulating a methoxy polyethylene glycol-N-chitosan
graft polymer which is further utilized along with cotton, citric acid, and sodium
hypophosphite. The other option is to utilize chitosan along with N-(2-hydroxy)
propyl-3-trimethyl ammonium chloride (HTCC) in presence of poly-carboxylic
acids. When cotton is treated with BPTCA, the benzophenone group is photoactive
924 S. Gulati et al.

Flame
Retardancy

UV Multifunctional Antimicrobial
Protection Finishing Functions

Water-oil
Repellency

Fig. 7 Multifunctional properties conferred to fabrics

and this imparts crease-resistance, antimicrobial function, and UV protection. Silk

fibroin and TiO2 amalgamated with glutaraldehyde when employed with cotton
fabrics, imparted both UV protection and wrinkle resistance to them.
Flame retardancy can be provided by the usage of phosphorus and nitrogen-
containing compounds. One way to impart flame retardancy is by the utilization of
tetrakis (hydroxymethyl) phosphonium chloride (THPC). Another method is to use
hydroxyl-functional organo-phosphorus oligomers (HFPO) along with a bonding
reagent like methylol amines. The limitation of these methods is that there is a
release of formaldehyde which is hazardous for human health and the environment.
Hence, a better method was proposed by Wu and Yang in which polycarboxylic
acids were treated with sodium hypophosphite and this confers durable flame
retardancy to fabrics along with crease resistance.
Water and oil repellence can be imparted in integration with wrinkle resistance by
the utilization of fluorocarbon resins and fluorinated coatings. Alternatively, a
perfluoroalkyl containing multi-epoxy compound (PFME) and citric acid can be
used to provide the same. Otherwise, a hydroxyethyl sulfone (consisting of acrylate
monomer) can be used as perfluorinated acrylate copolymer to provide properties of
hydrophobicity and oleophobicity.
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 925

Environmental Impact of Use of Nanomaterials

Despite of all the benefits of application of nanomaterials in textiles as well as other

sectors, the toxic or harmful impact of nanomaterials on human health and environ-
ment has become an increasing concern. The actual toxic impacts of such treated
textiles can be understood by examining their life cycle. Exposure to nanoparticles
during the fabrication processes may pose a threat to human health due to contact
with skin. Not only this, but textiles having undergone finishing processes involving
nanoparticles may accidentally release those nanoparticles during washing, abrasion
or usage. These nanoparticles may end up in soil, water bodies or may be in direct
contact with humans, depending on the use of the developed textiles (Fig. 8). These
particles may cause toxicities in plants or animals, which may be consumed by
humans, and also harm the environment [34–38].
Nanoparticles have a large surface area, which makes them highly reactive in free
form. This property can be both advantageous and disadvantageous, as on the one
hand these can be easily altered to reduce toxicity, while on the other hand these can
react with other toxic compounds and pose a higher threat. Aggregated nanoparticles
in water bodies can be removed by sedimentation techniques. Nanomaterials released
from textiles are majorly carried by sewage water and accumulate over the surface of
water bodies. Nanoparticles such as silver (Ag), titanium oxide (TiO2), and zinc oxide
(ZnO) are considered to be the most harmful types. Dissolution of alumina, silver, and
zinc oxide nanoparticles has shown an increase in toxicity of water bodies, whereas a
reduction in toxicity is observed on the dissolution of silicon dioxide nanoparticles.
Metal and metal oxide nanoparticles exhibit high toxicity toward micro-organisms or
the organisms at lower trophic levels such as bacteria, algae, fungi, etc. even at low
concentrations. Studies have indicated the high toxicity of silver nanoparticles in
aquatic organisms such as zebrafish, daphnids, and clams [37, 38].

Preparation of
Life span of Product is Effects on
Nanoparticles Product
Nanoparticle Disposed Human
and Transportation
Treated and Health and
Application to and Storage
Textiles Recycled Environment
textiles

Release of Nanoparticles from Treated Textiles and

Contact with Humans and Environment

Fig. 8 Life-cycle of nanomaterials in textiles

926 S. Gulati et al.

Owing to their small size, nanoparticles can easily enter body cells. Exposure of
nanoparticles to the human body can be through a variety of pathways, such as oral,
ingestion, inhalation, or absorption. The exposure can be by direct or indirect contact
with the body. Direct exposure occurs by wearing or using the treated textiles, while
indirect exposure occurs through sources like air, water, and food. Nanoparticles of
concentrations of 50 μg/m3 can be absorbed by the body. The most common routes
are by inhalation or through the skin. Nanoparticles may travel through the respira-
tory tract and reach the lungs and other internal organs. Studies have shown that
nanoparticles may accumulate in the liver, spleen, or kidneys. Some of the symptoms
include inflammation, pulmonary damage as well as DNA damage [36, 37].
The harmful effects of treated textiles have not been researched extensively. No
regulations are in place for the application of nanomaterials in textile fabrication.
The need for the future is the development of environment-friendly methods or green
synthesis of nanoparticles to reduce levels of toxicity, along with a better knowledge
of the release of nanoparticles from treated textiles [39, 40].

Conclusion

Nanotechnology is a growing field with multiple avenues in the future of the textile
industry. With the growth of modern science, novel technologies are being devel-
oped to enhance the performance of existing methods. Nanomaterials pose as
promising agents in developing textiles having a variety of functionalities including
wrinkle-resistance, flame retardancy, UV protection, water-oil repellency, antimicro-
bial functions, and so on. Finishing processes of textiles utilizing nanomaterials
confers them with such unique properties. Recent innovations in nanotechnology
have led to the development of sustainable and environment-friendly textiles. In
recent years, research has been focused on imparting anti-wrinkle properties to
produce smart textiles. Since the 1900s, formaldehyde-based reagents have been in
use to provide durable press finishing to fabrics. Due to their toxic effects, novel
technologies are being developed utilizing nanomaterials as catalysts. Successful
performance has been observed with the use of nano-TiO2, AgNP, etc. in improving
the wrinkle recovery of fabrics. Despite the positive aspects of nanomaterials, their
toxicological impact on both humans and the environment must be taken into
consideration. The bottom line is that this field has enormous untapped potential
for further development in the future.

Important Websites

1. https://www.britannica.com/topic/textile/Finishes-improving-performance
2. https://www.britannica.com/technology/nanotechnology
3. https://www.azonano.com/article.aspx?ArticleID¼5501#:~:text¼Antiwrinkle%
20cotton%20fabric%3A%20For%20cotton,during%20the%20fabric%
40 Wrinkle-Resistant Fabrics: Nanotechnology in Modern Textiles 927

20finishing%20process.&text¼Many%20companies%20use%20fabrics%
20coated,stockings%2C%20socks%2C%20and%20undergarments
4. https://textile-future.com/archives/20042
5. https://www.fibre2fashion.com/industry-article/1651/functional-nano-finishes-
for-textiles
6. https://www.nanotex.com/

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 Part XII
Consumer Nanoproducts for Cosmetics
Consumer Nanoproducts for Cosmetics
41
Reshu Virmani and Kamla Pathak

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 932
Nanotechnology-Based Delivery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 933
Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934
Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 935
Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 935
Nanostructured Lipid Carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 936
Nanosponges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 936
Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 936
Nanocapsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 937
Nanodiamonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 937
Nanopigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 937
Nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 938
Nanocosmetic Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 938
Nanoform Shampoos and Conditioners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939
Nanoform Hair Color Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939
Nanoform Toothpastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 940
Nanoform Anti-wrinkle Creams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 942
Nanoform Anti-cellulite Creams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 942
Nanoform Skin Whitening Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 945
Nanoform Moisturizers and Cleansers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 945
Nanoform Deodorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
Nanoform Soaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
Nanoform Sunscreens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
Nanoform Perfumes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
Nanoform Nail Polishes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952
Nanoform Lipsticks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953
Nano-Based Hair Growth and Removal Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953
Miscellaneous Nanocosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955

R. Virmani
School of Pharmaceutical Sciences, MVN University, Palwal, Haryana, India
K. Pathak (*)
Faculty of Pharmacy, Uttar Pradesh University of Medical Sciences, Etawah, Uttar Pradesh, India

© Springer Nature Singapore Pte Ltd. 2022 931

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_58
932 R. Virmani and K. Pathak

Safety Assessment of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955

Regulatory Aspects of Nanocosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958
Web References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 959
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 959

Abstract
A cosmetic formulation that carries actives or other nanostructured ingredients,
which has superior properties regarding its performance if compared with conven-
tional products, is termed as nanocosmetic. In the cosmetic industry, nanoparticles
are present in shampoos, conditioners, toothpastes, anti-wrinkle creams, anti-
cellulite creams, skin whitening creams, moisturizers, face powders, aftershave
lotions, deodorants, soaps, sunscreens, makeup in general, perfumes, and nail
polishes. The first company to introduce a nanotechnology-based cosmetic was
Lancôme, the luxury division of L’Oréal, in 1995, with the launch of a face cream
composed of nanocapsules of pure vitamin E, to combat skin aging. Thereafter,
other international companies started research investments to develop nano-
cosmetics. The cosmetic industry utilizes nanotechnology primarily due to higher
penetration capacity of actives in skin layers. However, larger and more effective
development of this technology is expected in the future to clearly observe its real
benefits and the safety of products. Furthermore, the possible risks in using
nanoparticles include possible toxicity and absence of biocompatibility of the
materials used. Thus, regulations become necessary to ensure that this technology
is within the current legislations. The write-up aims to elaborate all the related
aspects of nanocosmetics including the successful commercial products.

Keywords
Nanocosmetics · Nanocarriers · Skin care products · Hair care products ·
Nanonail lacquers · Nano-perfumes · Regulatory aspects · Safety assessment

Introduction

The main objective of nanocosmetic products is proposed for application to the body
skin and face, with photoprotection and antiaging action. These products are capable
of penetrating into the inner layers of the skin, potentiating the effects of the active.
Nanocosmetic may be defined as a “cosmetic preparation which has actives or other
nanostructured components that feature superior properties in terms of its perfor-
mance than conventional cosmetic preparations.” Nanoparticles are present in var-
ious cosmetic preparations such as sunscreens, perfumes, shampoos, moisturizing
cream, soaps, deodorants, anti-wrinkle creams, anti-cellulite creams, skin whitening
creams, perfumes, conditioners, toothpastes, face powders, aftershave lotions, and
makeup, in general. Owing to the widespread use of these products, it is essential to
carefully choose the nanocarrier/nano vehicles to be incorporated in the cosmetic
41 Consumer Nanoproducts for Cosmetics 933

preparation. Therefore, the cosmetic products, which are intended to remain on the
skin without absorption, such as sunscreens, are formulated in a manner to meet this
attribute. When a deeper penetration is expected, then penetration enhancer of good
quality should be used. The first products that assured to fight against wrinkles were
limited to exfoliate the stratum corneum. In the 1970s, there were cosmetic prepa-
rations whose formulations contained ingredients that could penetrate the skin, but
only into the superficial layer, i.e., stratum corneum. But with advancements, in the
1980s, alpha-hydroxyl acids emerged, with penetration ability slightly higher than
the preparation used earlier in 1970s. In 1990, appeared the liposomes, small vesicles
composed of oil and water that reached deeper in the skin, but not to the basal layer.
Nanocosmetics offer several advantages such as controlled release of the active,
protection from chemical or enzymatic degradation, and prolongation of residence
time of the active cosmetic ingredient(s) in the stratum corneum [1–2].
In 1995, Lancôme the luxury division of L’Oréal introduced a nanotechnology-based
cosmetic preparation with the launch of a face cream composed of nanocapsules of pure
vitamin E, to overcome skin aging. After Lancôme, other international companies
started to invest in research to develop nanocosmetics laboratories. Meanwhile, compa-
nies such as Chanel, Garnier, Revlon, Estee Laudar, Christian Dior, Anna Pegova,
Procter & Gamble, Revlon, Derma zone Solution, Skinceuticals, Shiseido, and Johnsons
& Johnsons developed products in this line. O Boticário, Brazil, was the first company
to develop and market a nanocosmetic preparation. Nano serum which is used as an
antiaging cream is applied in the area of the eyes and forehead and around the mouth.
The nanostructure composition includes active ingredients as vitamin A, C, and K and a
product for whitening of the skin. In 2005, Comucel French laboratory invested
14 million dollars in their cosmetic plant and launched VitActive Nano peeling Reno-
vator Microdermabrasion, Lift serum Antiaging, and Antiaging 65+ Advanced System
antiaging cosmetics based on nanotechnology. Brumas de Leite used for body hydration
launched in 2007 by Natura was a nano system with a particle size of active 150 nm.
This chapter aims to describe the nanotechnology-based delivery systems and different
nanocosmetics that have been developed as commercial products or are under investi-
gation, their limitations/ disadvantages, and the related regulatory aspects.

Nanotechnology-Based Delivery Systems

Nanotechnology is one of the scientifically proven emerging fields which is considered

as versatile model that exhibits complex and remarkably unique properties of matter at
nano level. Currently nanomaterials are being widely used for delivery of actives in
cosmetic formulations and are being researched for the future opportunities. While these
systems offer many advantages, most importantly due to their nanosize, their optical
transparency improves their cosmetic appeal. Thus, nanomaterials are being widely used
in the development of advanced skin care preparations, specifically targeting the hair
follicle and shaft. Various types of nanotechnology-based delivery systems that are
frequently applied in cosmetics are presented in Fig. 1.
934 R. Virmani and K. Pathak

Fig. 1 Types of nanotechnology-based delivery systems used in cosmetics

Fig. 2 Behavior of nanoemulsion on the skin

Nanoemulsions

Nanoemulsions are considered as one of the promising pharmaceutical vehicles that

have potential to become the future of cosmetics. In nanoemulsion, two immiscible
phases are mixed together with the help of emulsifying agents resulting in globules
with the mean diameter ranging from 50 to 1000 nm. Because of the nanosized
particles, it shows good penetration into the dermis layer of the skin (Fig. 2).
41 Consumer Nanoproducts for Cosmetics 935

Nanoemulsions are preferred as the advanced nano systems in the cosmetic world as
they have a higher surface area and free energy; are free from coalescence, creaming,
flocculation, and sedimentation; can be formulated in different formulations like
foams, creams, liquids, and sprays; are nontoxic and nonirritant and easily applicable
on the skin; and do not damage healthy human and animal cells [3].

Liposomes

Liposomes are self-closed vesicles of colloidal dimensions, in which phospholipid

bilayers sequester part of the solvent, in which they freely float, into their interior.
Mezei and Gulasekharam in the early 1980s reported the efficacy of liposomes in
topical drug delivery. Liposomes are used in different cosmetics owing to their
biocompatible, biodegradable, nontoxic, flexible, and encapsulation behavior [4]
(Fig. 3). They can encapsulate hydrophobic and hydrophilic compounds and can
protect them from external environment [5]. Thus, they are used to deliver vitamins
and other essential molecules for regeneration of epidermis [6]. Phosphatidylcholine
is the main ingredient of liposome which has softening and conditioning properties;
thus, it is widely used in moisturizers, lotions, creams, shampoos, and conditioners.
Liposomes increase the physical and chemical stability of other active ingredients
like vitamin A, E, and K, carotenoids, and CoQ10 when dispersed in water.

Solid Lipid Nanoparticles

Solid lipid nanoparticles are nanometer-sized lipid droplets having a solid lipid
matrix and surfactants for stabilization purpose. Solid lipid nanoparticles (SLN)

Fig. 3 Behavior of liposomes on the skin

936 R. Virmani and K. Pathak

are considered as promising nanocarrier for active ingredients used in cosmetics due
to their advantages. For example, their UV blocking potential is used in sunscreens
for photoprotection, controlled release of drug from their shell, protection of labile
drug from chemical degradation, occlusive behavior (help to increase water content
of skin), and improving penetration of active moieties into the stratum corneum
[7]. SLNs can be used for the controlled delivery of coenzyme Q10 and retinol as
cosmetic agents over a prolonged period of time as they can remain stable for
long time.

Nanostructured Lipid Carriers

Nanostructured lipid carriers (NLCs) are the second generation of SLNs and are
formulated by mixing a predefined ratio of solid lipids with liquid lipids and have
distorted structure [8]. This type of structure creates spaces in which the active
compounds can be accommodated, thus increasing the occlusion factor, loading
capacity, and level of skin adherence properties. NLCs are superior to SLNs as
they enhance the stability and prevent dehydration by making a thin film on
the surface due to the adherence of particles on the outer skin layers [9].
The cosmetic applications of NLCs are also addressed as nanobeads or nano
pearls.

Nanosponges

Nanosponges are polymeric, porous, and highly cross-linked systems. The average
diameter of a nanosponge is 500 nm. These sponges are used as nano delivery
systems in cosmetics and dermatology as they have smooth texture, are free flowing,
enable high entrapment efficiency, can solubilize poorly water soluble active,
improve bioavailability, and can provide prolonged release of active moiety in a
diffusion-controlled manner. The size and entrapment efficiency of nanosponges are
dependent on solubility of the active, polymer characteristics, cross-linking property
of the polymer used, temperature, plasticizer concentration, and emulsification speed
of the process [10].

Nanocrystals

Nanocrystals have a size range of 100 nm to 1 μm and are formed by clustering of

several hundreds to tens of thousands of atoms. Dermal penetration through nano-
crystals is increased by (i) increasing concentration gradient between formulation
and skin as higher saturated solubility of tiny particles causes higher drug diffusion
into the skin, (ii) increasing the rate of dissolution due to increased surface area of
nanosized particles, and (iii) increasing adhesion to the skin due to their smaller
size [11].
41 Consumer Nanoproducts for Cosmetics 937

Nanocapsules

Submicroscopic nanocapsules are polymeric capsules which are surrounded by a

watery or oily core. These are used as cosmetics to protect sensitive actives,
decrease unwanted odors, and remove incompatibility between formulation com-
ponents. An anti-wrinkle lotion containing vitamin A nanocapsules was formu-
lated that gradually released the active moiety with time. Nanocapsules are also
used to reduce the penetration of UV filter – octyl methoxycinnamate – in the skin.
These are used as a sunscreen carrier for octyl salicylate, octyl methoxycinnamate,
and benzophenone-3. They form a preservative layer on the skin surface which
retards the permeation of the actives in sunscreen to the viable layer. On the basis
of incorporated material, various types of nanocapsules for cosmetic purpose are
formulated.

Nanodiamonds

Nanodiamonds are also considered as one of the novel approaches in the cosmetic as
well as healthcare industries wherein these are used as carriers for topical preparation
for the treatment of many skin diseases. In this technology, diamond core is
surrounded by various functional groups attached to the surface which helps in
the stabilization of the drug molecules by removing the attached bonds. Change in
the hybridization state of carbon from SP3 to SP2 is responsible for stability of the
surface. Nanodiamonds offer various advantages such as ant scarring property and
wound healing property. Hydrophobic property of nanodiamond surface can be
increased by addition of fluorine molecule. Fluorinated nanodiamond molecule has
Teflon (CF2 ¼ CF2) surface and diamond core which is also known dialon frag-
ments. Dialon rapidly diffuses in organic solvents and has many pharmaceutical as
well as cosmetic applications [12].

Nanopigments

Titanium dioxide and zinc oxide are the two nanopigments which are used as
sunblocking agents in sunscreen formulations. Because of small particle size, they
give transparency to the product without leaving a white film on the skin and
improve spread ability, thus improving consumer acceptance. Their presence also
does not show any side effects (irritation and contact allergy), improve durability of
the formulation, and show antibacterial properties under UV light irradiation. These
are used in different sunscreens to protect the skin against broad-spectrum sun
ultraviolet radiation including UVA, UVB, and UVC [13].
For lipsticks, gold and silver nanopigments are prepared to give new colored
pigments. These nanopigments are safe and harmless and show good pigment
dispersion. Instead of natural yellow color, gold in this tiny size (nanometers)
exhibits red color. Like gold, silver shows yellow color instead of silver color in
938 R. Virmani and K. Pathak

nanometer size [14]. Both are nontoxic and have high disinfecting and stability
abilities, thus greatly used in cosmetic industries. Many other pigments and nano-
particles are also used in cosmetics.

Nanofibers

These are the particles having dimension less than 100 nm and a theoretically
unlimited length. Nanofibers are small porous solid nanomaterials having diameters
of 5–500 nm and large surface area per unit mass. This large surface area provides
appropriate active sites for reactions. By suitable structural modification, mechanical
strength and flexibility of nanofibers can be improved. Nanofibers are used in
various biomedical areas such as drug and gene delivery, artificial blood vessels,
and artificial organs. These are also used as cosmetic skin care masks for skin healing
and skin cleansing. They improve the drug efficiency and penetration of active
ingredients into the skin due to small interstices and high surface area [15].

Nanocosmetic Products

Nanocosmetics are one of the most promising and attractive areas where nanotech-
nology is used to provide different types of unique cosmetic product. In spite of few
difficulties, certain nanocosmetics have been converted into commercial products
which are now available in the market for use. Some commercial nanocosmetic
products are presented in Fig. 4.

Fig. 4 Nanocosmetic products

41 Consumer Nanoproducts for Cosmetics 939

Nanoform Shampoos and Conditioners

Shampoos are used for cleaning and washing the hairs. In shampoos, various
nanomaterials are incorporated to enhance resident contact time of shampoo with
the scalp and hair follicle, allowing active ingredients to form a protective layer or
film, preventing trans follicular water loss. After washing the hairs with hot water,
the cuticle layer is opened, exposing the hydrophobic emulsion layer, whose main
work is to permit external water absorption and prevent internal water loss. In
traditional shampoos, due to hydrophobic properties, silicone accumulates on the
scalp rather than penetrates into deep layer of hairs. However, when silicone oil is
incorporated into shampoo which was prepared by adding nanomaterials in the
preparation, it can quickly diffuse into hair fibers due to its small size and improve-
ment in hair moisture, lubrication, and gloss achieved after application of the same
[16]. The main advantage of using this formulation is that it does not harm the cuticle
of the hair fibers, but relatively its nanosize allows for penetration into the hydro-
phobic emulsion layer of shampoo.
In contrast to shampooing, whose main goal is to cleanse the hair, Seracin derived
from silkworm has been added in the shampoo for conditioning purpose as cationic
nanoparticles which is responsible for reintroducing the materials necessary for
proper growth, gloss, texture, and health of damaged cuticles [17]. Cationic nano-
emulsions with a droplet diameter of less than 100 nm can significantly improve dry
hair, even after repeated application of shampooing [18]. The cationic emulsion is
applied on the hairs for nongreasy appearance and shine and to reduce brittleness.
Cosmetic preparation containing nanoparticles of silicates, hydroxides, carbonates,
phosphate, and oxides was able to control the grease of hair. Chitin and zinc
nanofibril complexes were also used to reduce hair flakes which can be measured
by the corneocyte count; and sebum can be measured by milligrams of superficial
lipids per centimeter2 of surface of the skin both in vitro and in vivo [19]. Incorpo-
ration of nanomaterial into the cosmetic formulation improves the properties of
ingredient deposited into the hair and directly impacts amino acid synthesis and
keratin formation in order to repair the damaged cuticle and cortex. Thus, nano-
materials help to improve hair cosmesis by endorsing increased contact between
active ingredients and the hair shaft and also by enhancing the quantity of added
active ingredients reaching the target site.

Nanoform Hair Color Products

Hair color products are applied on the hairs that are based on alkali or oxidation that
can leave the hair thinner and dry after use. There are various approaches by which
different permanent hair color products are prepared by using different ingredients
such as color precursor which gets oxidized by the application of hydrogen peroxide,
but these types of reactions can damage hair. The hair color products are also
associated with hypersensitivity reactions and increased risk of non-Hodgkin’s
lymphoma and multiple myeloma [20]. Beside this, hair color has many limitations
940 R. Virmani and K. Pathak

such as its weak interaction with hair, ultimately staining other contacting surfaces
(i.e., combs, brushes, clothing, scalp). The cosmetics industry is continually in
search of new dyes and precursors, as a substitute to permanent hair dyes. In ancient
days, Greeks and Romans made quantum dots within hair shaft using a process of
litharge, slaked lime and water, to blacken hair. More recently, an alkaline solution of
chloroauric acid having a molar mass of 339.7 g/ml was allowed for the preparation
of gold nanoparticles inside human hair [21]. The nanoparticles provide a long-
lasting, water-resistant color without demolition of the keratin fibers. Lastly, carbon
nanotubes are used to enhance the attraction of carbon black for hair fibers. Carbon
black is widely used as a pigment in a variety of cosmetic formulations for coloring
of white or gray hair. The smaller size and increased surface area/volume ratio of
carbon nanotubes result in increased attraction and interaction with hair for a long-
lasting effect.
Hair follicles provide an interesting target of cosmetic interest. As mentioned
above, by changing the particle size, it is possible to target specific sites within the
hair shaft. For example, topical liposome entrapped melanin can be used for hair
shaft targeting [22]. Thus, these kinds of new developments in nanotechnology are
giving new dimensions and opportunity for hair dye applications by increasing its
lasting effect while restricting the toxicity problems. By using nanotechnology
approach, scientists have developed a natural and non-damaging hair surface engi-
neering technique for making hair coloring formulations that do not use any chem-
ical reactions but instead rely only on physical forces acting at a very close range.
Most hair care preparations are formulated by using surface active agents or
polymeric coating of micro- and nanoparticles for modification of hair and its
enhancement and protection. Halloysite clay nanotubes formed by rolled sheets of
aluminosilicate kaolin assemble on the surface of hair forming a robust multilayer
coverage. Prior to the application, clay nanotubes were loaded with selected dyes or
drug allowing for hair coloring or medical treatment. This technique, which employs
a very safe, biocompatible, and inexpensive material, is abundant with respect to the
species of source of hair and additives in solvent, making it viable as an excipient for
conventional medical and veterinarian formulations [23].

Nanoform Toothpastes

There are three main toothpaste ingredients that may be made of nanosized particles.
First is hydroxyapatite, a lattice of calcium found naturally in teeth and bones. It
helps prevent tooth pain associated with sensitivity, coats the teeth, and slips into the
tiny cracks in the tooth. It breaks down in response to acid before the enamel does,
thus protecting the teeth from decay and cavities. Hydroxyapatite also provides a
source of calcium and phosphate ions which, combined with fluoride, help to
remineralize the tooth surface [24] (Fig. 5). Silver nanoparticles are proven to have
antibacterial properties, reducing the risk of gum disease and bad breath caused by
bacteria in the mouth. Its distribution in toothpaste remains largely limited to
manufacturers based in Asia.
41 Consumer Nanoproducts for Cosmetics 941

Fig. 5 Remineralization of tooth surface

Titanium dioxide is an intensely white pigment with a high refractive index,

which means it scatters light to create a very white product [25]. Titanium dioxide is
widely used in toothpaste, but often the particles used are not small enough to be
defined as nanoparticles. Some of the marketed examples of nano toothpaste are
given in Table 1.
A randomized double blind clinical trial was aimed to compare the efficacy in
reducing dentin hypersensitivity of a dentifrice formulation containing nano-
hydroxyapatite with a fluoride dentifrice and a placebo. The application of nano-
hydroxyapatite in gel toothpaste fluoride-free was an effective desensitizing agent
providing relief from symptoms after 2 and 4 weeks [26].
Similar study was conducted to evaluate and compare the effects of three different
desensitizing agents (15% nanohydroxyapatite crystals, 5% novamin, and 8% pro-
argin) on dentinal permeability and tubule occlusion in vitro. Scanning electron
microscope was used to evaluate the effect of these commercially available
desensitizing toothpastes. The qualitative analysis showed no occlusion of the dentinal
tubules in Group A (control group), and Group B (nanohydroxyapatite) showed 98.1%
tubule occlusion. Group C (Novamin) and D (Proargin) showed 83.1% and 69.1%
tubule occlusion, respectively. While all the three desensitizing agents were effective
in the dentine tubule occlusion, the efficacy of nanohydroxyapatite toothpaste was
greater compared to the other desensitizing agents [27].
A number of popular brands still do not contain nanoparticles. Since July 2013,
EU cosmetics regulation demanded that all nanoparticles be labeled on the ingredi-
ent list. Despite publishing guidance on assessing safety, there are no formal testing
requirements in the legislation. Research into the safety of nanoparticles in tooth-
paste and other everyday products is ongoing. Widely used silver nanoparticles are
an area of particular concern, with studies showing that this substance could make its
way from the mouth to accumulate to other organs of the body.
942 R. Virmani and K. Pathak

Table 1 Examples of nano toothpastes

Product Manufacturer Origin Active
Coral White Mint Coral LLC USA Golden seal (Hydrastis canadensis)
Toothpaste extract, ginkgo (Ginkgo biloba)
Nano silver nano Nano well USA Nano silver fluoride
biotechnology
toothpaste
Nano silver toothpaste Trucare’s USA Nano silver fluoride
ACE silver plus nano Hanil Korea Aminocaproic acid, precipitated
toothpaste Pharmaceutical calcium carbonate xylitol, green tea
Co. extract
M Plus Medical Nano Sangi Apagar Japan Nanohydroxyapatite
hydroxy apatite
toothpaste
Plus White Xtra Fort Lauderdale Florida Sodium monofluorophosphate (0.15%
Whitening Gel w/v fluoride ion)
Toothpaste

Nanoform Anti-wrinkle Creams

Antiaging creams are mostly moisturizer-based cosmetics that are marketed for
making the consumer look younger by reducing, masking, or preventing signs of
skin aging. Collagen plays an important role in skin rejuvenation and wrinkle
reversal effect, and its quantity in the skin decreases along with age. Antiaging
products are the main cosmeceuticals in the market currently being made using
nanotechnology. L’Oréal has employed nanotechnology in products such as
Revitalift anti-wrinkle cream which instantly retautens the skin and reduces the
appearance of wrinkles. Application of retinol can increase epidermal water content,
epidermal hyperplasia, and cell renewal while enhancing collagen synthesis
[28]. The advantages of using this include reduction in the appearance of fine lines
and wrinkles and lightening of lentigines. Lancôme introduced Hydra Zen Cream to
renew the skin’s healthy look which contains nano-encapsulated triceramide. Some
of the marketed nano anti-wrinkle creams are listed in Table 2.

Nanoform Anti-cellulite Creams

Cellulite is a term for the formation of lumps and dimples in the skin. Cellulite can
affect both men and women, but it is more common in females, due to the different
distributions of fat, muscle, and connective tissue. Several therapies have been
suggested for removing cellulite, which can be classified into (i) energy-based
devices, (ii) injectable therapies, and (iii) topical therapy [29]. Topical agents,
combined with vigorous massage, were the earliest attempts to treat cellulite.
Methylxanthines (aminophylline, theophylline, and caffeine) and retinoids have
been the most extensively evaluated ingredients used in topical formulations for
cellulite. Table 3 shows topical anti-cellulite preparations which may be divided in
41 Consumer Nanoproducts for Cosmetics 943

Table 2 Examples of nano anti-wrinkle cream

Nanomaterial/
Product Manufacturer Origin nanotechnology Active
Olivenol Dr. Theiss/ Homburg/ Solid lipid Olive oil
Augen Mediphara Saar nanoparticles
pflege cosmetics
balsam
Soosion Soosion – Solid lipid Olive oil
facial lifting nanoparticles
cream
Phyto NLC Sireh Emas Malaysia Solid lipid Olive oil, propylene glycol
active cell nanoparticles
repair
Cutanova- Dr. Rimpler Germany Lipid-based Coenzyme Q10,
Cream Nano nanoparticles polypeptide, hibiscus
repair Q10 extract, ginger extract,
ketosuga
Intensive Dr. Rimpler Germany Lipid-based Coenzyme Q10,
Serum Nano nanoparticles polypeptide, mafane extract
repair Q10
Cutanova Dr. Rimpler Germany Lipid-based Coenzyme Q10, TiO2,
Cream Nano nanoparticles polypeptide, ursolic acid,
vital Q10 oleanolic acid, sunflower
seed extract
24K Nano Orogold USA Lipid-based Cyclopentasiloxane,
Ultra Silk nanoparticles dimethicone/vinyl
Serum dimethicone crosspolymer,
PEG/PPG-20/15
dimethicone
Iope Amore France Seletinoid Butylene glycol, squalene,
Supervital Pacific diisostearyl malate,
Extra Moist propanediol
Eye Cream
Chantecaille Chantecaille – – Rosemary leaf extract
Nano Gold
Energizing
Cream
Cell Act Cell Act Switzerland – Cyclopentasiloxane,
DNA Filler ethylhexyl palmitate,
Intense myristyl myristate
Cream
Nanosphere DermaSwiss Switzerland Nanosphere Palmitoyl oligopeptide, rara
Plus Swiss apple (Uttwiler
Spatlauber)
Eye Tender Kara Vita USA Q10 (vitamin C Argireline ®, Matrixyl™
and E) 3000, Pepha ®-Tight,
Tyrostat™-09, Velvet
Veil™
Revitalift USA L’Oreal Nanosomes Pro-retinol A
Double
Lifting
944 R. Virmani and K. Pathak

Table 3 Topical anti-cellulite preparations divided on the basis of their mechanism of action
Formulation
Mechanism of action Agents strength
Reduce lipogenesis and promote Methylxanthines (aminophylline, Caffeine used
lipolysis theophylline, theobromine, and caffeine) in
1–2%
Restore the normal structure of Retinol 0.3%
dermis and subcutaneous tissue
Prevent free radical formation or α-Tocopherol
scavenge free radicals Ascorbic acid
Ginkgo biloba
Vitis vinifera
Increase the microcirculation flow Ginkgo biloba 1 to 3%
Pentoxifylline Used
Centella asiatica transdermally
Ruscus aculeatus 2 to 5%
Carica papaya 1 to 3%
Ananas sativus 2 to 5%
Vitis vinifera 2 to5%
Glechoma hederacea 2 to 7%
Cynara Scolymus 2%
Melillotus officinalis 2 to 3%
Hedera helix 2 to 5%
2%

four major groups according to their mechanism of action. These treatments include
agents that increase the microcirculation flow, reduce lipogenesis and promote
lipolysis, restore the normal structure of dermis and subcutaneous tissue, and prevent
free radical formation or scavenge free radicals.
Only two agents, aminophylline and retinoids, have been critically evaluated
[30]. Methylxanthines are hypothesized to improve cellulite by stimulating lipolysis
and inhibiting the enzyme phosphodiesterase, which increases the concentration of
cyclic adenosine monophosphate. Retinoids, on the other hand, are thought to reduce
cellulite by increasing dermal thickness, increasing angiogenesis, synthesizing new
connective tissue components, and increasing the number of active fibroblasts. For
both agents, there have been several peer-reviewed publications with promising data,
but the studies have been small with no long-term follow-up. Overall, certain
formulations can improve collagen production and reduce skin laxity, but they are
rarely effective on cellulite, which requires extensive fat, collagen, and connective
tissue remodeling [31]. Alternative or supplemental therapies include grape-seed
extract or Gingko biloba. These agents have been applied topically, orally, and by
injection, but none of them have proven effective.
Creams are said to tighten the skin, which makes the skin appear smoother and
firmer. They also add moisture, which can reduce the appearance of cellulite. As with
all topical treatments, the main challenge of these therapies is for the active ingre-
dients to reach their target in sufficient concentration to have a therapeutic effect.
Nanotechnology-based topical products offer solution to this challenge, and hence
41 Consumer Nanoproducts for Cosmetics 945

Table 4 Examples of nano anti-cellulite cream

Product Manufacturer Origin Active
Anti-Cellulite Nano Stherb Cosmetics Thailand Horse chestnut extract, pure retinol
Cream Internatinal Co., extract, barley extract
Ltd.
B-Tight Cellulite Maelys Israel Pink pepperslim, ecoslim, red
Removal Cream grapefruit oil
B-Flat Cellulite Maelys Israel Cetearyl ethylhexanoate, glycol
Stretch Marks stearate
Firming Cream
Lipofeme nano Extratos da terra Brazil Oil of Camellia sinensis, safflower
shower anti-cellulite oil
Glymedplus anti- Glymed plus Canada Caffeine, peppermint, methyl
cellulite massage nicotinate
cream
Tuel shape shifter Tuel Australia Methyl nicotinate, niacinamide
cellulite minimizing
cream
Murad Firm and Tone Murad Australia Cat’s claw extract, horse chestnut
Serum tree extract, tiger’s herb, cayenne
pepper

many formulations have been commercialized. Some marketed nano anti-cellulite

creams are listed in Table 4.

Nanoform Skin Whitening Products

To reduce the dark spots caused by acne or age spots, skin-lightening creams can be
used. Skin whitening creams contain ingredients that act to slow the production of
melanin in the skin’s outer layer. Skin bleaching agents act to reduce the action of the
enzyme, tyrosinase, which controls the rate of melanin production in the skin
(Fig. 6). The gold standard ingredient in skin-lightening creams is hydroquinone
although since 2001 its use has been banned in Europe as an ingredient in cosmetics.
This is prescribed in a concentration ranging from 4% to 8%, while 2% can be found
in over-the-counter products. Occasionally it may be formulated with corticosteroids
such as hydrocortisone. Many alternative skin-lightening products are available.
Other ingredients that may be present in skin-lightening creams include kojic acid,
arbutin, vitamin C, azelaic acid, glycolic acid, niacinamide, retinol, topical steroids,
and tranexamic acid.

Nanoform Moisturizers and Cleansers

Solid lipid nanoparticles, liposomes, and nanoemulsions are widely used in mois-
turizing preparations due to their extended effects. These are considered as one of the
946 R. Virmani and K. Pathak

Fig. 6 Mechanism of nanoform skin whitening cream

best products in the treatment of itching, redness to the skin, atopic dermatitis, and
other skin-related disorders [32]. Barreto et al. isolated a product from A. sislana
which is formulated as micellar nanoparticles of polysaccharide-enriched fraction.
The micelles-based nanocosmetic formulation prepared by nanoemulsification pro-
cess showed better clinical moisturizing efficiency. Various researchers reported that
the in vivo clinical testing of moisturizing cream verified that 0.5% fraction of total
nanoemulsion formulation can increase the water content of the stratum corneum by
10.13% compared to the vehicle and 19.28% compared to baseline values. Besides,
the formulation was able to maintain skin barrier function after 5 h of a single
application [33].
In New Jersey, the Tri-K Industries has launched a new nanotechnology-based gel
formulation for an extensive range of skin care preparations developed by Kemira
(patent company). The gel commercially known as Kemira nanogel revealed to be a
unique nanoemulsion carrier system to create submicron emulsion containing micel-
lar nanoparticles of bioactive component. The main benefit of the gel is to minimize
water loss from the skin and produce new skin cells and quick penetration of active
moiety into the skin. These characteristics have been suggested to be useful for
sunscreen and moisturizing and antiaging preparations of the cosmetic segment. Few
commercial products of nano moisturizers and cleansers are exemplified in Table 5.
A Malaysian company, SHE Empire Sdn. Bhd., has introduced its “Micellar
Series” launched by a brand, Naturel Kiss, which employs micellar nanotechnology-
based cosmetic segment. The leading brand uses nanotechnology in most of the
cosmetic products being developed by research and development [34]. The second
implementation of nanoemulsion technology system in micellar-based cosmetic for-
mulation patented by L’Oreal was developed as micellar nanoparticle dispersion
which was fully loaded with oily layer which can be improved by using a surfactant
composed of polyethylene oxide and polypropylene block copolymer. The nanotech-
nology micellar-based cosmetic preparation that has been formulated is fluid makeup
remover, makeup removing gel, and eye lotion. These cosmetic segments are dis-
persed with micellar nanoparticles of oils having molecular weight of more than
 41

Table 5 Examples of nano moisturizers and cleansers

Nanomaterial/
Product Manufacturer Origin nanotechnology Active Category
Allure Body cream Chanel France Nanoemulsion Marine extracts, hyaluronic acid, shea Moisturizer
butter
Vitacos Vita-Herb Nona-Vital Skin Vitacos Florida Nanoemulsion Niacinamide, adenosine, ceramide Moisturizer
Toner Cosmetics
Precision-Solution Destressante Coni Beauty Malaysia Nanoemulsion – Moisturizer or
Solution Nano Emulsion Peaux skin hydration
Sensitivity
Phyto-Endorphin Hand Cream Rhonda Grapevine, Nanosuspension Butyrospermum parkii (shea butter), Softens and
Consumer Nanoproducts for Cosmetics

Allison Texas C10-30 cholesterol/lanosterol esters smoothes the

skin
Iope Supervital Extra Moist Softner Amore France Nanosuspension Squalane suspension, retinol Moisturizer for
Pacific drug and rough
skin
Fresh as A Daisy Body Lotion Kara Vita USA Nanoemulsion Ethyl hexyl palmitate, glycerin, fragrance, Moisturizing
C11-13 isoparaffin, steareth-21, steareth-2 body lotion
Hydralane ultra moisturizing day Hydralane Paris Nanospheres Hyaluronic acid Deep
cream Paris moisturizing and
hydration
Nano Salt moisture Key Salvona Spain – – Moisturizer
Coryse Salome Competence Cokararyse Paris Nanospheres – Moisturizing
Hydration ultra-moisturizing cream Salome cream
947
948 R. Virmani and K. Pathak

400 and average particle diameter < 100 nm [35]. Bioderma, Garnier, Park Avenue,
Laroche-posay, Chanel, L’Oréal, and other international and local brands claim their
nanotechnological micellar facial cleanser cream to be the most efficient product.

Nanoform Deodorants

The tendency of conventional deodorants is to mask bad odors rather than eliminate
them. Nano silica which is 1/50000th of human hair derived from beach sand with
copper compound has both antibacterial and anti-odor functions. Silver nano-
particles are also used in deodorants and other cosmetics, mainly as an antimicrobial
agent. While the claims are tall, the efficiency of these preparations needs real-time
assessment. Some marketed nanoform deodorants are listed Table 6.

Nanoform Soaps

Cleansing is also necessary to remove oil (which may include bacteria) from the skin
surface that is acquired by incidental contact or by intentional application (medica-
tions or makeup and other cosmetic products). Silver nanoparticles are used as skin
disinfectant and decontamination. Nano Cyclic, Inc. produces Nano Cyclic cleanser
pink soap which is a scientifically balanced blend of nano silver and natural
ingredients and claims that it kills harmful bacteria and fungi, fights acne, and
diminishes age spots and sun-damaged skin.
EVOLUT soap is used for cleansing, inflammation elimination and restoration of
health problem in oily skin and in the regeneration of the body’s skin problem area.
The product is considered as an effective remedy for acne and severe skin inflam-
mation. The main constituents of EVOLUT soap are cocamidopropyl betaine (coco-
nut oil), vegetable glycerin, kokoglyukozid (cocoa butter and sugar), sorbitol,
sodium stearate, water, sodium lauryl sulfoatsitat, sodium laurate, hydrogenated
castor oil, silver nanoparticles, organic orange oil, essential oil tangerine, lemon
essential oil. EVOLUT soap is designed specifically to eliminate the inflammation
and prevent their reemergence. Silver nanoparticles in the composition of anti-
bacterial soaps perform recovery functions and protect the skin. Table 7 enlists
nanoform soaps that are available commercially.

Nanoform Sunscreens

Sunscreens made with the minerals zinc oxide and titanium dioxide generally score
well in EWG’s ratings, because they provide strong sun protection with few health
concerns and don’t break down in the sun. Mineral sunscreens are superior to
chemical sunscreen, as depicted in Fig. 7. However, mineral sunscreens are
famously white and chalky and therefore less appealing for everyday use. To create
sunscreens that are both useable and effective, manufacturers often use nanosize
41 Consumer Nanoproducts for Cosmetics 949

Table 6 Examples of nano deodorants

Product Manufacturer Origin Active
Tropical breeze on Geodeo Canada Australian tea tree oil, grapefruit seed
deodorant honey dew extract, and aloe
Sure antiperspirant Sure UK Aluminum zirconium
deodorant invisible solid trichlorohydrex gly 16%
Right Guard Henkel USA Butane, Cyclomethicone,
Antiperspirant Hydrofluorocarbon 152a, PPG-14
Deodorant Aerosol, Butyl Ether, Isobutane,
Sports Fresh Disteardimonium Hectorite, Propane,
Pentane, Propylene Carbonate,
Parfum (Fragrance), aluminum
zirconium trichlorohydrex glycerine
Deodorant Citrus Weleda New York Citrus medica Limonium (lemon)
peel oil, limonene, linalool, geraniol,
citral, farnesol
Crystal Body Deodorant Crystal body Delhi Ammonium alum, citric acid
Stick deodorant

Table 7 Examples of nano soaps

Product Manufacturer Origin Active
Bastide Artisanal Provence Bastide – Sodium palmate, sodium palm
Soap kernelate
HuaShen fragrant soap HuaShen EU New York Organic calendula, coconut oil
International
Bar Soap, Rosemary Mint A LA Lancaster Virgin organic olive oil, organic
Masion Ave, coconut oil, grass-fed goat’s milk
Ardmore
Maximum Strength Neem Organix UK Olea europaea (olive) fruit oil,
oil soap, Fragrance Free south Cocos nucifera (coconut) oil,
Elaeis guineensis (palm) oil,
Melia Azadirachta (neem) seed
oil
Le Cadeaux Fresh Milled ProNature France Lemon trees in the orchards of
Bar Soap Earth Sicily, rosemary mint
Basis Sensitive Skin Bar Vitacost Canada Chamomile and Aloe vera
Soap Cleans Plus
Smoothes

versions of these minerals to increase clarity and SPF. The smaller the particles, the
better the SPF protection and the UVA protection. Manufacturers must strike a
balance: Small particles provide greater transparency, but larger particles offer
greater UVA protection. The form of zinc oxide most often used in sunscreens is
larger and provides greater UVA protection than do the titanium dioxide products
that appear clear on skin. Some studies indicate that nanoparticles in large doses can
harm living cells and organs. But a large number of studies have produced no
950 R. Virmani and K. Pathak

Fig. 7 Types of sunscreen creams

evidence that zinc oxide nanoparticles can cross the skin in significant amounts. A
real-world study tested penetration of zinc oxide particles of 19 and 110 nanometers
on human volunteers who applied sunscreens twice daily for 5 days [36]. Researchers
found that less than 0.01 percent of either form of zinc entered the bloodstream. The
study could not determine whether the zinc in the bloodstream was insoluble
nanoparticles, so the European regulators concluded it was most likely zinc ions,
which would not pose any health risk. Other FDA- and EU-sponsored studies
concluded that both zinc oxide and titanium dioxide nanoparticles did not penetrate
the skin [37]. A study by Italian researchers focused on the potential for nano-
particles to cross damaged skin and found no evidence this actually happens.
Titanium dioxide and, to a lesser extent, zinc oxide are photocatalysts – when they’re
exposed to UV radiation, they can form free radicals that damage surrounding cells.
Nanoparticle sizes of these minerals are more affected by UV rays than larger
particles are.
Sunscreen manufacturers commonly employ surface coatings that can dramati-
cally reduce the potential for photoactivity, with data suggesting that they reduce UV
reactivity by as much as 99 percent [38]. In sunscreens, problems may arise if
particles aren’t treated with inert coatings, if the coatings aren’t stable, or if manu-
facturers use forms of zinc oxide or titanium dioxide that aren’t optimized for
41 Consumer Nanoproducts for Cosmetics 951

stability and sun protection. However, tests of living skin from human volunteers
and animal tests suggest that these hazards are not a concern for human safety,
because the free radicals generated by nanoparticles on the skin are quenched by the
skin’s own antioxidant protections [39].
Nanoparticles can cause lung damage when inhaled. For many reasons, it is
dangerous to inhale nanoparticles. The International Agency for Research on Car-
cinogens (IARC) has classified titanium dioxide as a possible carcinogen when it is
inhaled in large doses. The lungs have difficulty in clearing small particles, so the
particles may pass from the lungs into the bloodstream. Insoluble nanoparticles that
penetrate the skin or lung tissue can cause extensive organ damage. Nanoparticles in
lip sunscreens can be swallowed and damage the gastrointestinal tract, although
there are no studies to suggest consumers swallow enough zinc oxide or titanium
dioxide for this to pose a concern.

Nanoform Perfumes

Ethanol forms the base for traditional perfumes available in the market, since it is the
solvent for aromatic substances. Unfortunately, people prone to allergies or with
sensitive skin who use ethanol-based perfumes may suffer from skin irritation and
inflammation because ethanol is a solvent with defined irritating potential. As an
alternative to alcohol compositions, there are perfumes in a solid state (solid
emulsions, gels, and pomades) and perfumed oils. However, their main disadvantage
is that they leave greasy and slippery spots on the perfumed surfaces. Some
examples of perfumed products found in the literature are water based and are called
“alcohol-free perfumes” (emulsions, microemulsions, liposomes, and micelles)
[40]. Yet from a technological perspective, the introduction of lipophilic systems
to water without a cosurfactant (ethanol, among others) is very difficult, with respect
to thermodynamic stability. It requires the use of solubilizers of essential oils which
can be polyols (glycols and glycerin) or surfactants. An interesting solution for the
water-based perfumes without alcohol seems to be nanoemulsions that have a much
lower amount of surfactant (approx. 5–10%) that allows maintaining adequate
stability of the system [41]. Clear appearance and low viscosity make nanoemulsions
even more popular with the cosmetic industry. In the case of perfume products,
nanoemulsions can be not only a medium for a fragrance composition, but they also
increase chemical stability of the compounds in the composition (protection against
oxidation).
Alcohol-free perfumes based on micro- and nanoemulsions are already present in
the patent literature [42]. Nanoemulsions turned out to be a solution for solving
problems related to the oxidation and low bioavailability of fragrances, and they
could be applied as nano-encapsulated fragrance systems, in the perfume industry. In
a research, stable oil-in-water nanoemulsions compatible with selected fragrance
compositions, without ethanol, polyols, and ionic surfactants, were developed. The
nano-perfume systems were obtained with a low-energy method (phase inversion
composition; PIC), as well as with an ultrasound (US) high-energy method, taking
952 R. Virmani and K. Pathak

into account the possibility of moving from the laboratory scale to an industrial
scale [43].
Currently known applications of nanotechnology in perfume production and
application are predominantly based on nano-encapsulation methods (coating of
nanoparticles with different substances). Nanotechnology enables reduction of costs
of perfume compound manufacture while at the same time making it possible to
produce purer and completely natural perfume compounds. This can be achieved by
using nanoparticles such as gold-palladium that can replace expensive and poten-
tially toxic reagents that promote oxidation of aromatic primary alcohols to alde-
hydes, which is one of the crucial processes in the perfume production.
Another nano-encapsulation procedure proposes the use of Manzo, nanoparticles
coated in natural enzymes in the process of manufacturing expensive perfume
compounds. There are no unwanted or harmful residuals. Further, the acquired
scent compounds are of higher purity and can be labeled as completely natural
since they are derived from reaction catalyzed by enzymes from natural organisms.
This procedure could replace expensive extraction of perfume compounds from
natural materials or their expensive purely chemical synthesis. Nano-encapsulation
can also help improve the attributes and performance (durability, stability) of
fragrances that can be negatively affected by the environment (light, air). Applica-
tion of nano-encapsulation in fragrance products enables more efficient (prolonged)
and time-controlled release of the scents. Release of scents can be time-controlled by
stimuli such as diffusion, pressure, or temperature sensitivity. Table 8 lists some
commercial nanotechnology-based perfumes.

Nanoform Nail Polishes

Pigment powders are commonly used for coloring of the polishes. These pigment
particles are added to the polish and dispersed by different process engineering
techniques to obtain adequate distribution of the particles in the highly viscous
carrier media. The resulting product is a colored nail polish containing usually
micrometer-sized and solid particles with good colloidal stability [44]. Reports
demonstrate usage of nanoparticles in nail polishes and mention that nail polishes
containing nanoparticles can dry to a very hard state and improve toughness and
resistance against damage and that silver nanoparticles can treat fungal toenail
infections. Recently, integrated nanocarbon materials are reported resulting in rein-
forcements of the polish. The pulsed laser ablation in liquid technique for fabrication
of nanoparticle-polymer composites and the ultrafast laser lithography for polymer-
ization in resins and photoresists were also reviewed. In a report by Lau et al., a
top-down synthesis route to fabricate nanoparticles directly in an already completely
finished nail polish was detailed. It was based on adding a color effect based on
metallic nanoparticles, solely, thus minimizing the number of chemicals affecting the
nails polish’s functionalization [45]. Even though “Goldfinger” is already known,
the authors claim to fabricate “(nano-) Goldfinger.”
41 Consumer Nanoproducts for Cosmetics 953

Table 8 Examples of nano-perfumes along with manufacturing details

Product Manufacturer Origin Active
Nano scent oriental Abdul Samad Birmingham –
weather Al Qurashi
Wild Stone Hydra Wild Stone India Lily, basil, jasmine, geranium
Energy Eau De Parfum base
SKINN Womens Eau de Titan Hosur, India Ethyl hexyl methoxy cinnamate,
Parfum butyl methoxy benzoylmethane,
Ethyl hexyl salicylate
Premium Eau De J.K. Helen India and Dilute ethanol, oils of lavender,
Cologne Curtis USA thyme, rosemary, petitgrain
Trance from Fastrack Fasttrack from India –
Titan
SKINN Mens Titan Hosur, India Lavender oil, lemon, aromatic
Fragrances Verge Company Accord (rosemary and basil oils)
Allure Parfume Bottle Chanel France Sparkling mandarin, rose
Allure Eau Parfume Chanel France Honeysuckle, water lily,
spray magnolia, mandarin, passion fruit

Nano Labs Corp. (a nanotechnology research and development company) was

awarded a provisional patent for its original nanonail polish and lacquer having
advantages that it dries to a very hard state and resists shock, cracking, scratching,
and chipping and its elasticity offers superior ease of application without cracking.
Some marketed examples of nanoform nail polish are given in Table 9.

Nanoform Lipsticks

Different nanoparticles can be incorporated into lipstick and lip gloss which will
soften or soothe the lips by preventing transepidermal water loss. Korea Research
Institute of Bioscience and Biotechnology holds a patent that describes preparation
of pigments exhibiting wide range of colors using gold or silver nanoparticles by
mixing in various compositional ratios and whose color can be maintained for a long
period of time [46]. Silica nanoparticles used in lipsticks improve the homogenous
distribution of pigments. Once applied, they prevent the pigments from migrating or
bleeding into the fine line of lips. Nanoscale gold particles give lipstick an intense
red color, with the added benefit of being a treatment of Alzheimer’s disease.

Nano-Based Hair Growth and Removal Products

Cosmetics based on nanotechnology are very useful as they allow higher permeation
into the pores of hair with prolonged effects. Fullerene nanomaterials can create new
hair growth and formation of new hair follicle within the dermis in murine and
human skin due to the ability of fullerenes to scavenge free radicals, inhibiting the
954 R. Virmani and K. Pathak

Table 9 Examples of nanonail polish

Product Manufacturer Origin Active
Nanonails – fast All Brazil Citral (geranial), melaleuca
nail recovery Chemistry
effect
SOS Nail Podal Nano Brazil Styrene/acrylate copolymer, di-isobutyl
Cosmetics glutarate, panthenol, tocopherol, di-isobutyl
succinate
Gelly Hi Shine Barry London Nitrocellulose, acetyl tributyl citrate
M Cosmetics
Diamond Luxe Models Own UK Nitrocellulose
Heart Red
Silk Barry London Nitrocellulose
M Cosmetics

Table 10 Examples of nano hair growth products

Product Manufacturer Origin Active Category
Hair growth factor Nanogen UK Hyaluronic acid, Hair growth
treatment serum hydrolyzed lupine protein factor serum
Terapia capilar Extratos da Brazil Coceth-7, Chlorphenesin, Hair growth
tônico nano hair terra d-limonene, citrulline, factor
Keratin hair Nanogen UK Keratin Hair growth
thickening fibre factor
sprayer
Capillary growth Kollob Brazil Arginine, babosa Hair growth
vitamin pump kit cosmeticos factor

oxidative stress associated with hair follicle apoptosis and aging [47]. The US FDA
approved two hair loss treatments of minoxidil and finasteride. Minoxidil encapsu-
lated in solid lipid nanoparticles showed good skin penetration without dryness,
irritation, and burning [48]. However, finasteride encapsulated into topical liquid
crystalline nanoparticles was proposed to maintain high skin retention in the scalp
which permits lower dosing frequency and reduces different side effects like mood
disturbances, gynecomastia, and erectile dysfunction. Moreover, different hair grow-
ing ingredients like hinokitiol, gylcyrrhetinic acid, and 6-benzylaminopurine loading
in poly (lactic-co-glycolic acid) nanoparticles showed a 2–2.5-fold higher scalp-pore
permeability and enhanced hair growth by accelerating the transition from the
telogen to anagen phase of the hair cycle [49]. In other studies, a significant higher
degree of hair growth was reported by using hair cleansing shampoo or hair tonic
infused with nanocapsules containing hinokitiol. Some marketed examples of nano-
form hair growth products are given in Table 10.
Recently, a patent was issued for the development of nanoparticles capable of
removing unwanted hair. The patent claims that the topical application of plasmonic
nanoparticles, localized to target structures within the hair follicle, can be activated
by light to localize thermal damage [50]. Taken together, these results suggest that
41 Consumer Nanoproducts for Cosmetics 955

topically applied nanomaterials are successful carriers for hair-altering ingredients,

representing a potentially new therapeutic opportunity for hair loss and hair removal.

Miscellaneous Nanocosmetics

There are still many more preparations which have gained attention in cosmetic world;
these include aftershave lotion, face powder, hair shiner, eye cream, mascara, lotion,
foundation creams, serum, and hair polish. Some of the miscellaneous commercial
nanocosmetic preparations are given in Table 11. Furthermore, many patents have
been granted on a variety of nanocosmetics. Some of these are listed in Table 12.

Safety Assessment of Nanoproducts

The application of nanotechnology to products regulated by the FDA, including

cosmetics and over-the-counter drugs (OTCs), provides health and other benefits to
consumers. A number of international expert bodies have finalized their assessments
and found nanomaterials to be safe for use. For example, the European Union
(EU) Scientific Committee on Consumer Safety (SCCS) published their recommen-
dations on the nanoforms of ZnO in 2012 and TiO2 in 2013 concluding that both,
within certain specified conditions, are safe for use in sunscreens. Similarly, Health
Canada revised its sunscreen monograph in 2013 specifically concluding both nano
zinc oxide and nano titanium dioxide are permitted ingredients. The Australian
Therapeutic Goods Administration in their 2013 opinion reviewed the literature
and the work of other international regulatory agencies and again affirmed its 2006
conclusion that neither TiO2 nor ZnO nanoparticles are likely to cause harm when
used as ingredients in sunscreens. In 2012 the FDA said it was not aware of any
evidence that demonstrates a safety concern from the use of micronized TiO2 in
sunscreens. Similarly, FDA stated that available literature indicates nano ZnO used
in sunscreens does not penetrate into or through human skin to produce adverse
health effects when applied topically. Quoting FDA, “In sum, the evidence available
does not suggest that use of TiO2 or ZnO nanomaterials in sunscreens presents a
public health hazard.” FDA goes further and points out that contrary to the hypo-
thetical risk, “The public health benefits of regular sunscreen use are well-
established.”

Regulatory Aspects of Nanocosmetics

Cosmetic preparations are not regulated as rigorously as pharmaceutical preparation

by any drug regulatory authority agency across the world. Manufacturer is respon-
sible for providing the safety profile of newly launched cosmetic product. Cosmetic
industry is associated with biotechnology, nanotechnology, and herbal technology
for its various added advantages; these interdisciplinary technologies make it very
Table 11 Manufacturing details of few miscellaneous nanocosmetics
956

Nanomaterial/
Product Origin Manufacturer nanotechnology Active Category
Clearly It! USA Kara Vita Nanosphere Origanum and salicylic acid Lotion
Aenel Lotion N USA – Nanoparticle Organics Lotion
Arouge Deep nanomoisture Care Japan Zenyaku Kogyo Co., Nanoparticle Organics Lotion
Set Ltd.
Nano-in Deep Cleaning China Nano-Infinity Nano micelles Zinc oxide Lotion
Nanotech Co., Ltd
Diorskin Extreme Fit France Christian Dior Nano- Stretch – Foundation
NetworkTM
Diorskin Forever – Extreme Wear France Dior Nano-stretch – Foundation
Flawless Makeup FPS 25 NetworkTM
Dual Finished Pressed Compacts USA Colorescience Nanotechnology Vitamins incorporated in mica Foundation
mica vitamins
Alusion Alumina Powders Australia Advanced Nanoparticles Aluminum oxide Powders
Nanotechnology
Limited
Nano Gold 24 Hour Cream Deutschland Joyona International Nanoparticles Gold Cream
Marketing Ltd.
Eye Tender USA Kara Vita Nanospheres Bioactives and peptides Eye cream
Enlighten Me! USA Kara Vita Nanospheres Hydroquinone, kojic acid, glycolic Lightening
acid cream
Nano-mascara Norway Nano concept – – Maskara
Mesosilver Antifungal Spray USA Purest Colloids, Inc. Nanoparticle Silver Disinfecting
spray nourish
Nourish USA Bellapelle Fullerene Fullersome Serum
Pureology Nano Works Shine Luxe USA Pureology Nanoparticles Mica mirrors Hair Polish
Pureology Nanowax USA Pureology Nanoparticles Nanoparticulate polymer resin made Hair care
R. Virmani and K. Pathak

from orange peel wax

41 Consumer Nanoproducts for Cosmetics 957

Table 12 A cross section of patents on nanotechnology-based cosmeceuticals

Publication
Title Publication number date Applicant
Cosmetic composition containing EP2583665A2 April Act Co., Ltd
retinol stabilized by porous 24, 2013
polymer beads and nanoemulsion
Multiactive microtargeted EP20110798597 April17, NY Derm LLC
antiaging skin cream polymer 2013
technology
Semipermanent mascara and US20130068242A1 March Cry Baby Culture
method of applying 21, 2013
Topically administered, skin- US20130059769A1 March Eva Turley
penetrating glycosaminoglycan 7, 2013
formulations suitable for use in
cosmetic and pharmaceutical
applications
Biodegradable, biocompatible, US20130034638A1 February Inis Biotech LLC
and nontoxic material sheets 7, 2013
consisting of said material and the
use thereof in food,
pharmaceutical, cosmetic, and
cleaning products
Metal oxide nanocomposites for US20130022655A1 January BASFSE
UV protection 24, 2013
Oil-in-water-type emulsion US20130011348A1 January TomikoTakakura
sunscreen cosmetic composition 10, 2013
Synthetic collagen threads for US20130018415A1 January Rebeccah Brown
cosmetic uses including skin 17, 2013
wrinkle treatments and associated
methods
Deodorant composition WO201210122A1 August IliosSrl
2, 2012
Preparation of cationic EP 2254545A2 December BASFSE
nanoparticles and personal care 1, 2010
compositions comprising said
nanoparticles
Geltechnology suitable for use in US20100266649A1 October Avon Products, Inc.
cosmetic compositions 21, 2010
Nanocrystals for use in topical EP2099420A1 September Abbott Gmb H &
cosmetic formulations and 16, 2009 Co. KG
thereof method of production
Nanodiamond UV protectant US20090220556A1 September International
formulations 3, 2009 Technology Center
Nanoparticle compositions US20090175915A1 July Avon Products, Inc.
providing enhanced color for 3, 2009
cosmetic formulations
Nanocomposite pigments in a WO2008079758A1 July Avon Products, Inc.
topical cosmetic application 3, 2008
Cosmetic pigment composition EP 1909745A1 April Korea Research
containing gold or silver 16, 2008 Institute of
nanoparticles
(continued)
958 R. Virmani and K. Pathak

Table 12 (continued)
Publication
Title Publication number date Applicant
Bioscience and
Biotechnology
Antimicrobial silver WO2006026026A2 March AcryMed, Inc.
compositions 9, 2006
Long-lasting coatings for US 6955834B2 October The Proctor &
modifying hard surfaces and 18, 2005 Gamble Company
processes for applying the same
Nail polish compositions US20050220730A1 October Martinez Francisco
comprised of nanoscale particles 6, 2005
free of reactive groups
Use of nanoscale deodorants EP 1239823B1 June Cognis Deutschland
16, 2004 Gmb H & Co.KG
Cosmetic compositions US20030064086A1 March Danuvio Carrion
comprising nanoparticles and 13, 2003
processes for using the same
A controlled delivery system for WO2002060399A1 August Salvona LLC
hair care products 8, 2002
Antimicrobial body care product WO2000078281A1 December Bernhard Hanke
28, 2000

challenging and difficult. At the initial stages of birth of nanomaterials, none of the
regulatory agencies emphasize on the properties of nanomaterials as compared to
traditional cosmetic and pharmaceutical preparations. Royal Society of Sciences has
taken the initiative for the nanomaterials to be treated as new chemical moiety. The
Food and Drug Administration, USA, TGA, NICNAS (Australia), and EMEA
(EU) have taken initiative for the regulation of nanocosmetics which includes
classification and definition and for the regulation designing for the industry. The
nanomaterials used in the cosmetic industry differ from nanomaterials used by other
industries in various aspects which primarily include their shape and molecular
structures followed by their mode of use and specific interactions with the living
world and the environment. These nanomaterials are now being extensively used in
sunscreen creams, fairness creams, antiaging formulations, hand and body lotions,
colored makeup, and so on.

Conclusion

From the above study, it can be concluded that nanocosmetic formulations are
preferred because of its nanosize and good penetrability. The demand for nano-
cosmetic formulations is increasing day by day as scientists are continuously putting
their best efforts to give the safe cosmetic preparations to the consumers. The
application of nanotechnology to cosmetic products regulated by the FDA, including
cosmetics and over-the-counter drugs (OTCs), provides health and other benefits to
41 Consumer Nanoproducts for Cosmetics 959

consumers. A number of international expert bodies have finalized their assessments

and found nanomaterials to be safe for use, but still rigorous procedure must be
adopted for regulations of cosmetic preparations like that of pharmaceutical prepa-
rations. On the basis of patents and available literature, knowledge-based investiga-
tions of recent cosmetic products must be done for a beautiful and healthier skin.

Web References

http://nanopinion.archiv.zsi.at/en/nanotechnology-your-toothpaste.html
https://www.cosmeticsdesign.com/Article/2011/05/16/Nano-nail-polish-product-to-
be-expanded-in-the-European-market
https://www.ewg.org/sunscreen/report/nanoparticles-in-sunscreen/
https://nanogloss.com/nanotechnology/applications-of-nanotechnology-in-
perfumes/
https://www.nanowerk.com/nanotechnology-in-cosmetics.php
https://scholar.google.co.in/scholar?q¼C.M.+Hussain,+Handbook+of+Polymer
+Nanocomposites+for+Industrial+Applications,+Elsevier+(2020).&hl¼en&as_
sdt¼0&as_vis¼1&oi¼scholart
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nanomaterialsnanotechnology/
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https://scholar.google.co.in/scholar?q¼C.M.+Hussain,+Handbook+of
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Nanocosmetics: Opportunities and Risks
42
Ambika and Pradeep Pratap Singh

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 964
Nanomaterials/Nanocarrier Used in Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 965
Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 965
Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 966
Nanocapsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 966
Niosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 967
Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968
Application of Nanomaterials/Nanocarriers in Different Types of Cosmetic Products . . . . . . . . 968
Skin Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 968
Lip Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 971
Hair Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 973
Oral Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 974
Toxic Effect of Nanotechnology in Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 975
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 976
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 976

Abstract
Cosmetics are substances used to enhance the “appearance” of the human body.
Globally millions of consumers use cosmetic products on daily basis. Cosmetic
products can be used to treat conditions such as photoaging, hyperpigmentation,
wrinkles, and hair damage. Due to the daily application of cosmetic products,
they are required to ensure quality, safety, and performance at high level.

Ambika
Department of Chemistry, Hansraj College, University of Delhi, Delhi, India
P. Pratap Singh (*)
Department of Chemistry, Swami Shraddhanand College, University of Delhi, Delhi, India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 963

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_59
964 Ambika and P. Pratap Singh

Recently, nanotechnology has been employed in the field of cosmetics.

Nanotechnology-based cosmetic products offer several advantages such as
enhanced color, transparency, solubility, etc. Various types of nanomaterials
employed in cosmetics include niosomes, liposomes, fullerenes, solid lipid nano-
particles, etc. However increased use of nanotechnology in cosmetic products has
raised concern about the possible penetration of nanoparticles through the skin
and potential hazards to the human health. This chapter aims to discuss different
nanoparticles used in various classes of cosmetic products and their associated
risks caused by nanoparticles on exposure.

Keywords
Nanocosmetics · Nanocarriers · Liposomes · Nanoparticles · Niosomes

Introduction

Cosmetics is a huge market worldwide. A large number of consumers use cosmetic

products on daily basis. A variety of cosmetic products are available to treat various
problems associated with hygiene and beauty such as photoaging, hyperpigmentation,
wrinkles, hair damage, etc. [1]. However, daily application of cosmetic products
requires to ensure quality, safety, and performance at high level. Many of the ingre-
dients found in cosmetic products that claim to promote enhanced skin absorption may
in fact be unstable when applied to the skin and, therefore, unable to absorb beneath
the surface layer of the skin [2]. Nowadays it is believed that the smaller particles are
readily absorbed into the skin and repair damage easily and more efficiently as
compared to bulk analogues [3]. Thus, there is an urgent need of a technology
which can produce smaller particles for enhanced absorption of cosmetics.
Nanotechnology is the science which deals with the materials of nanosize.
Various types of nanomaterials have been employed in different fields of research
and development [4–21]. Recently, nanotechnology has been employed in the field
of cosmetics. Nanocosmetics are the cosmetics consisting of nanomaterials. The
nanoparticles have unique chemical and physical properties due to the smaller size
and high surface area-to-volume ratio as compared to their bulk counterpart. It is
claimed that the use of nanomaterials in the cosmetics can offer several health
benefits due to which various problems can be retarded effectively [22]. These
cosmetic products offer several advantages such as enhanced color, transparency,
solubility, etc. Different types of nanomaterials employed in cosmetics include
nanosomes, liposomes, fullerenes, solid lipid nanoparticles, etc. These nano-
materials are used in the cosmetic industry for the preparation of different products
such as sunscreens, anti-aging creams, toothpastes, hair growth promoters, mineral
cosmetics, etc., for numerous benefits. However, nanotechnology-based cosmetics
may pose severe toxicity due to the change in the physicochemical and structural
42 Nanocosmetics: Opportunities and Risks 965

properties of engineered nanomaterials with decreased size. This chapter aims to

discuss different nanoparticles used in various classes of cosmetic products and their
associated risks caused by nanoparticles on exposure.

Nanomaterials/Nanocarrier Used in Cosmetics

There are several types of nanomaterials which have been employed in the formu-
lation of nanocosmetics; few of them have been discussed below (Fig. 1).

Liposomes

Liposomes are the spherical-shaped vesicles with particle sizes ranging from 30 nm
to several μm (Fig. 2). They are generally prepared from cholesterol and phospho-
lipids with one or more lipid bilayers surrounding aqueous units. Recently, lipo-
somes have attracted the attention of researchers due to their biocompatibility,
biodegradability, low toxicity, property to trap compounds with enhanced stability,
and targeted delivery of molecules [22, 23]. Liposomes possess hydrophobic and
hydrophilic properties due to which they can be employed to encapsulate various
molecules used in cosmetics industry [24].

Fig. 1 Various
nanomaterials/nanocarriers
used in the preparation of
cosmetic products
966 Ambika and P. Pratap Singh

Fig. 2 Structural
representation of liposomes

Fig. 3 Schematic
representation of
nanocapsules

Nanoemulsions

Nanoemulsions are a colloidal particulate system employed as nanocarrier for drug

molecules with size varying from 10 to 1000 nm. They can exist as oil-in-water (o/w)
or water-in-oil (w/o) form, where the core of the particle is either oil or water,
respectively. They are prepared from natural surfactants, are nontoxic, and are safe
for use. They have small-sized droplets having large surface area resulting in
enhanced absorption. It can be formulated in a variety of formulations such as
foams, creams, liquids, and sprays. They offers several advantages as nanocarriers
which include enhanced solubility of compounds, increased stability, bioavailability,
controlled drug release, and enhanced shelf life of the product [25].

Nanocapsules

Nanocapsules (NC) are spherical-shaped nanocarriers which are prepared from

polymeric membrane with size ranging from 50 to 300 nm. The cosmetic agents
are seated in a cavity which is entrapped by the polymeric membrane (Fig. 3).
Nanocapsules are generally used in cancer therapy and diagnosis. Their main
advantages are, namely, sustained release, incremental drug selectivity and
effectiveness, improvement of drug bioavailability, and alleviation of drug
toxicity [26].
42 Nanocosmetics: Opportunities and Risks 967

Niosomes

Niosomes are stable and biodegradable vesicles prepared from nonionic surfactants
consisting of both hydrophilic and hydrophobic terminals. The size of niosomes
ranges from 100 nm to 2 μm in diameter. They can be used in skin care applications
and cosmetics due to several advantages like enhanced skin penetration, target-
specific compound delivery, increased bioavailability, biodegradable, biocompati-
ble, nontoxic, low production cost, and easy storage and handling. They are
employed in various cosmetics products like conditioner, shampoo, moisturizing
cream, skin-whitening creams, anti-wrinkle creams, and lipsticks [27].

Solid Lipid Nanoparticles

Solid lipid nanoparticles (SLNs) are colloidal drug delivery nanocarrier system with
size ranging from 50 to 1000 nm. They are prepared from solid biodegradable lipids
with low toxicity dispersed in water or in aqueous surfactant solution. They possess
unique properties such as small size, large surface area, UV-resistant property, high
drug loading, etc. They offer several advantages such as improved performance of
pharmaceuticals, enhanced stability of the encapsulated ingredients, and improved
penetration of active compounds [28].

Dendrimers

Dendrimers are nanosized, three-dimensional, highly branched macromolecules

with low polydispersity index (Fig. 4). They contain large number of external groups
suitable for multifunctionalization. Dendrimers have been employed in host-guest
interaction and self-assembly processes as an ideal delivery vehicle, due to their
chemical stability, low cytotoxicity, and solubility [22, 29].

Hydrogels

Hydrogels are three-dimensional, polymeric networks which can absorb large vol-
ume of hydro fluids in comparison to their own mass [11, 30]. Various properties of

Fig. 4 Schematic
representation of dendrimers
968 Ambika and P. Pratap Singh

hydrogels such as mechanical properties, water absorption capacity, etc. depend on

their three-dimensional network structure [31, 32]. They possess enhanced network
porosity, high water retention, elasticity, etc. [33]. They can be synthesized using
polymer either from natural or synthetic origin. The polymer-based hydrogels have
been employed in various fields such as wastewater treatment, biomedical materials,
hygiene, agriculture, etc. [34–37].

Fullerenes

Fullerenes are a type of carbon nanomaterial with size approximately 1 nm in

diameter. They possess strong antioxidant activity and brightening effect. They are
used in formulation of skin rejuvenating cosmeceutical products due to their free
radical scavenging activity [38, 39].

Application of Nanomaterials/Nanocarriers in Different Types

of Cosmetic Products

Nanocarrier can be employed to enhance the quality and effect of nanomaterials/

nanocarriers used for the formulation of different types of cosmetic products. Few of
the applications of these nanomaterials have been discussed below.

Skin Care

The skin is the largest organ which plays an important role and offers a protective
barrier against harmful external environment. It regulates body temperature, water
balance, protects against radiations and microorganisms, etc. Skin cleansers, sun-
screen, moisturizers, skin-whitening agents, etc. are some of the common skin care
cosmetic products used to improve the functioning and quality of skin. The skin care
products (e.g., topical sunscreens) can retard the degradation of skin collagen and
elastin by reacting with the free radicals produced by the exposure of skin with
ultraviolet rays, smoking, pollution, stress, etc. [40]. Different nanocarriers such as
nanoemulsion, liposomes, nanoparticles (NPs) have been utilized for enhanced
transdermal delivery of active components [41]. Different type of active components
(organic and inorganic compounds) which can reflect, scatter, or absorb the UV rays
may be used for the formulation of sunscreens. Some common inorganic and organic
compounds used in cosmetic formulations include titanium dioxide (TiO2), zinc
oxide (ZnO), silicon dioxide (SiO2), benzophenones, avobenzone, meradimate,
methyl anthranilate, p-aminobenzoic acid (PABA), cinnamates, salicylate deriva-
tives, etc. [42, 43]. Inorganic compounds are preferred over organic compounds for
the formulation of skin care products, due to their various properties such as absence
of skin irritation and sensitization and limited skin penetration with a broad spectrum
protection. ZnO and TiO2 have been employed for the formulation of sunscreen
42 Nanocosmetics: Opportunities and Risks 969

products as inorganic physical sun blockers. TiO2 is more effective in UVB and ZnO
in the UVA range; the combination of these particles assures a broadband UV
protection [44]. However, the microsized TiO2 and ZnO are naturally opaque
which can leave a chalky residue over the skin. This can be eliminated by utilizing
the TiO2 and ZnO NPs without reduction in their UV-blocking efficiency [44]. Sim-
ilarly, nanoencapsulation of ZnO NPs and octocrylene in poly-styrene-co-methyl
methacrylate (PMMA/PS) NPs can be employed to prepare new sunscreens with
efficient solar protection factor (SPF) and low cytotoxicity on human dermal fibro-
blasts [45]. Various naturally occurring compounds isolated from different plants
displayed enhanced sunscreen effects. Moreover, the stability and skin protective
effects of these bioactive compounds can be enhanced by their incorporation into
different nanomaterials [46, 47]. Different phytochemicals like Aloe vera, curcumin,
resveratrol, quercetin, vitamins C and E, genistein, and green tea catechins have been
converted into nanoparticles and were incorporated into gels, lotions, creams, etc. for
their enhanced delivery in skin care [48]. Bioactive compounds isolated from
Schinus terebinthifolius Raddi have been utilized in sunscreens with enhanced
antioxidant and sun-blocking activities [49].
Various nanocarriers like NPs, nanoemulsions, neosomes, and SLNs can be
incorporated into cosmetic bases for skin nourishment due to their property to
form thin film of humectants to retain moisture for longer time. The antiaging
nanocosmetics which generally consists of liposomes, nanocapsules, nanosphere,
and nanosomes can enhance the rejuvenation of skin, renewal of collagen, and lifting
and firming of the skin [50]. Liposomes, niosomes, SLNs, and nanoemulsions are
broadly used in nanoencapsulation of organic component of the sunscreen that can
improve its photostability, skin retention and UV-blocking ability [51]. Recently,
liposomes have been employed for the encapsulation of sun-blocking agents. For
example, skin photoprotective agents from Punica granatum L seed oil nano-
emulsion can be used to protect human erythrocytes from oxidative damage and
DNA against UVB-induced damage in human keratinocyte (HaCaT) cell line
[52, 53]. Recently, a broad-spectrum liposomal sunscreen is reported to block the
development of UV-triggered cutaneous lupus erythematosus (CLE) skin lesions by
a reduction in lesional tissue damage and the inhibition of the typical IFN-driven
inflammatory response [54]. Ammonium glycyrrhizinate-loaded ultra-deformable
liposomes have been employed as a potential topical drug delivery system for anti-
inflammatory therapy [55]. Lipo/octyl p-methoxycinnamate system formulation has
been prepared by the inclusion of octyl p-methoxycinnamate system in liposomes
and cyclodextrins. The above formulation displayed enhanced in vivo skin protec-
tion and water resistance [56]. Allantoin has been incorporated in conventional
liposomes and in new argan oil-enriched liposomes for the improved accumulation
of drug in the skin and deeper tissues resulting in the softening and relaxing effect on
the skin [57]. The elastic liposomes composed of egg phosphatidylcholine and
cholesterol loaded with benzophenone-3 (BP-3) displayed enhanced in vitro SPF
as compared to free BP-3 molecule [58]. Surfactant-based elastic vesicles have been
developed for the encapsulation of water-insoluble drug resveratrol with high effi-
ciency and fast release pattern [59]. Similarly, resveratrol and a binary mixture of
970 Ambika and P. Pratap Singh

surfactants consisting of colloidal carriers have been developed for the enhancement
of the drug loading with improved antioxidant, anti-inflammatory, and anti-
wrinkling activity and skin protective effect, after UVB irradiation [60]. In a similar
fashion, a dendrimer-resveratrol complex can be used to enhance the resveratrol
solubility in water, stability, skin penetration, and cream dosage forms [61].
Lipid carriers (SLN, nanostructured lipid carrier (NLC), nanostructured poly-
meric lipid carriers (NPLC), NC) can be employed as an effective alternate to
formulate chemical UV filters such as BP-3 by reducing their skin penetration.
The comparison of percutaneous absorption and cutaneous bioavailability of BP-3
loaded into the above lipid carriers demonstrated that NPLC and NC can signifi-
cantly reduce BP-3 skin permeation with high SPF [62]. Stable SLN containing the
chemical UV filter octyl methoxycinnamate (OMC) and another SLN possessing
20% of the OMC content replaced by the botanical urucum oil have been developed.
The above formulations exhibited no significant change in SPF on reduction in
concentration of chemical UV filter with no induced toxicity responses in the skin
[63]. A new sunscreen formulation composed of hybrid SLN-silica particles loaded
with octyl methoxycinnamate has been developed. Further, these silica NPs on
incorporation into a hydrogel displayed enhanced encapsulation efficiency, physi-
cochemical stability, and semi-solid properties suitable for topical application
[64]. Recently, SLN-safranal formulations have been prepared by the incorporation
of safranal (UV-blocking agent) into SLN as nanocarriers for topical delivery with
enhanced skin hydration properties [49]. Sunscreen mixtures have been incorporated
into the novel topical delivery systems such as SLN and NLC, as ultraviolet
protector enhancers. The nature of lipid and UV wavelength can affect the
UV-protective efficiency of the lipid particles [65]. A cost-effective NLC or
SLN-based formulation for the enhancement of amorphous heptapeptide DEETGEF
delivery into skin displayed enhanced protection against UV irradiation and
decreased DNA damage in UVA-irradiated skin [66]. Encapsulation of UVA filter
and antioxidant α-tocopherol with lipid-based NPs, SLNs, and NLCs displayed
enhanced photostability of formulations, but it does not enhance the photoprotection
of the cosmetics. However, the addition of the antioxidants to the formulation results
in the enhanced photostabilization and reduction of UV filter concentrations along
with protection of the skin against reactive oxygen species [67]. Nanostructured lipid
carriers and renewable vegetable resources-based lipid nanocarriers have been
constructed using rice bran oil and raspberry oil. The above NLC displayed sun-
screen activities with higher antioxidant and UV-protective properties [68]. A stable
kenaf seed oil-NLC (KSO-NLC)-based sunscreen demonstrated enhanced photo-
protective effect with high SPF value [69]. UV protection formulation has been
developed using pumpkin and kenaf seed oil to prepare NLCs loaded with Uvinul
T150 and Uvinul A Plus Granular. Spherical amorphous NLC structure with encap-
sulated UV filters displayed high entrapment efficiency, drug loading, antioxidant
activities, and UV absorption properties [70]. Similarly, efficient photoprotective
nanostructured formulations with UV protection and antioxidant activity have been
developed by the encapsulation of various vegetable oils (pomegranate seed, wheat
germ, blackcurrant seed, sesame seed, carrot root, raspberry seed, and rice bran) and
42 Nanocosmetics: Opportunities and Risks 971

their combinations in new NLCs as carriers. Pomegranate seed oil-based cream

displayed enhanced UV protection. Also, NLCs prepared by the combination of
pomegranate seed oil with wheat germ oil demonstrated the best entrapment effi-
ciency and photoprotection. The encapsulation of all vegetable oils into NLCs
exhibited enhanced antioxidant activity as compared to their free oils [46]. NLCs
have been prepared using bocaiuva almond (BAO) and pulp (BPO) oils and cetyl
palmitate, for the entrapment of avobenzone (AVO) and octocrylene (OCT). Both
NLC-BAO and NLC-BPO displayed enhanced entrapment efficiency (EE) for UV
filters (AVO and OCT). A twofold enhancement in the SPF has been observed in
NLC-BAO, co-loaded with the UV filters, after its incorporation into a hydrophilic
cream base SPF 14. However, NLC-BAO, without AVO and OCT, exhibited SPF of
this cream base to 27.7  0.8. Thus, NLC-BAO can be used as a potential
replacement of organic filters [71]. Encapsulation of naringenin into NLCs based
on vegetable oils has been employed for the formulation of safe and efficient
polyphenol-rich sunscreens with enhanced, photostable, anti-UV, and antioxidant
performance of the vegetable nanocarriers [72]. A NLC formulation consisting of
6% titanium dioxide has been developed to enhance the photostability of all-trans
retinoic acid and alleviate its skin photosensitivity [73]. A mixture of chemical
sunscreens (ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine,
and ethylhexyl methoxycinnamate) were incorporated into NLCs to prepare a
photoprotective formulation with an increased SPF. NLC with carnauba wax
displayed 45% higher SPF values, as compared to the bees wax NLC [74].
Niosomal carriers are suitable for the transdermal delivery of numerous pharma-
cological agents and have been used to prepare various skin care formulations.
Niosomes could be applied topically, acting as controlled release systems as they
fuse with the lipids of the stratum corneum [75]. Photoprotective niosomes
containing sunscreens (octyl methoxycinnamate, diethylamino hydroxybenzoyl
hexyl benzoate and phenylbenzimidazole sulfonic acid), nonionic surfactants, cho-
lesterol, and stearylamine (positive-charged lipid) have been developed as potential
nanostructures to be used against solar radiation. The above system displayed no
toxicity against macrophages and skin-compatible pH that reduces allergies
[76]. Different flavanoids such as quercetin, morin, festin, myricetin, rutin, and
breviscapine were loaded in niosomes to improve their solubility, stability, and
penetration. Quercetin displayed considerable whitening and antioxidant capacities.
The solubility and photostability of quercetin have been enhanced remarkably by
employing niosomes. Moreover, quercetin-niosomes displayed sustained release and
improved transdermal penetration, with skin retention, as compared with quercetin
solution [77].

Lip Care

The lip care nanocosmeceutical products include lip balm, lipstick, lip volumizer,
and lip gloss. Lip cosmetic products are prepared by blending wax, oil, and
coloring agents, antioxidants, preservatives, and perfumes [78]. Generally, lip
972 Ambika and P. Pratap Singh

care products are employed to hydrate or protect the lips. Recently, nanotechnol-
ogy has attracted the attention of researchers and scientists for the development of
nanocosmeceuticals. Nanomaterials have been employed as pigments or fillers to
promote controlled release of active compounds in cosmetic products. The
nanocosmeceuticals can be incorporated into lip care products for increasing lip
volume, delineating and filling lip wrinkles, and to improve lip hydration with
uniform distribution and long shelf life [79, 80]. For example, lipsticks with
homogenous distribution of pigments, transfer resistance, breathability, film
brightness, softness with increased the stay time can be prepared by the utiliza-
tion of silica NPs [81]. A nanocompound of high elasticity, such as Fillderma lip
volumizer (Sesderma), which contains low molecular weight hyaluronic acid
(nanosomes), mimetic peptides, niacinamide, and collagen has been used to
moisturize, soften, and protect lips [82]. The lipstick adherence can be enhanced,
while the fine lines of lips can be reduced by the application of vitamin
E-filled nanocapsules alongside alpha-hydroxy acids [79]. Lip volumizer
loaded with liposomes improve volume, lip contour wrinkles, outlines and
hydrates the lips. W/O olive nanoemulsions can be utilized as lipstick base
formulation [83].
The color of the lipsticks may be due to organic or inorganic pigments like
dyes, heavy metals (Pb, Cu, Cd, Hg, Ni, Sb), etc., which may pose severe toxic
effects to human beings [84–86]. Recently, various nanomaterials-based syn-
thetic and metal particles are used for effective lip protection and enhanced
coloration for lip care products. Nanocolorants are advanced nanocompounds
which have the advantages of both pigments and dye. These compounds can
modify optical properties and generate bright colors in the absence of heavy
metals [87]. As lips are highly sensitive, so application of synthetic and metallic
NPs-based lip care product requires special attention. Recently, gold and silver
nanopigments have been utilized as coloring agents in lipsticks [88]. Nowadays
natural colorants have attracted the attention of researchers for their application
in pharmaceutical and cosmetic products due to their lesser side effects as
compared to their synthetic analogues. The natural contents of the herbs enrich
the body with nutrients and other useful minerals [89]. They possess different
biological activities, like antioxidant, antimicrobial, and food-preserving capa-
bility [90–93]. Natural colorants are comparatively less stable, which may be
attributed to their sensitivity towards pH, heat, and light. Encapsulation can be
used to increase the stability of these pigments [94, 95]. Recently, emulsion
systems have been developed consisting of natural colorants extracted from
plant roselle for the preparation of lip care formulations. Alpha-hydroxy
acid (AHA) is the main active compound isolated from Roselle which can be
employed for effectively minimizing the wrinkles, fine lines, and dryness
of lips [96]. The encapsulation of the plant betalains, a source of natural
pigments, enhances their stability and can be efficiently used in the lip care
products [97].
42 Nanocosmetics: Opportunities and Risks 973

Hair Care

Hair care products include shampoos, conditioning agents, hair gels, hair serums,
leave-on products, hair growth stimulants, styling products, hair color, etc. However,
extensive use of chemical-based hair products may result in dandruff, scalp redness,
thinning of hair, hair loss, etc. Recently, nanotechnology has attracted the attention
of researchers and scientists for the development of new and effective hair care
solutions. Nanotechnology has become a promising drug delivery system which can
be used to enhance the permeation into the hair pores with sustained effects for better
hair growth and disease treatment. The properties of the hair care products can be
enhanced by the utilization of different nanocarriers like liposomes, nanoemulsion,
nanospheres, niosomes, microemulsion, etc. [98]. Shampoo is used for hair cleaning
and conditioners are employed to improve the hair texture and health by providing
nourishment. For example, silicone oil nanoemulsion has been incorporated in
shampoos to obtain maximum resident contact time with the scalp and hair follicle,
which in turn prevents transfollicular water loss by the formation of a thin protective
film [98]. Repairing of damaged hair cuticles and restoring gloss and texture can be
performed by the incorporation of different active compounds, such as sericin, into
conditioning agents as cationic NPs [99]. Recently, phytochemicals from rice and
artichokes are used to enhance the hair growth, color, and appearance and to protect
hair from UV-induced degradation [100]. Curcumin-based liposomes displayed
enhanced penetration of the curcumin to the hair growth [101]. Similarly, follicle
penetration and hair growth enhancement can be effectively obtained by the appli-
cation of a curcumin-based cyclodextrin complex [102]. The combination of poly-
arginine and oleic acid-modified NPs in size range of 140–143 nm demonstrated
enhanced skin penetration of follicular or nonfollicular cell pathways [103].
Hair grease can be controlled by the utilization of compounds containing NPs of
oxides, hydroxides, carbonates, silicates, and phosphates of titanium, calcium,
magnesium, etc. [104]. Shampoos rich in zinc and chitin nanofibrils can effectively
reduce the hair flakes and sebum, ameliorating the hair shine and manageability
[105]. Fullerene nanomaterials can significantly affect the hair growth and hair
follicle numbers within the dermis in murine and human skin. The enhanced activity
could be attributed to the free radical scavenging ability of fullerenes to inhibit the
oxidative stress associated with hair follicle apoptosis and aging [106]. Nanocapsules
containing hinokitiol have been included in shampoo and hair tonic. The in vivo hair
growth of the above two preparations demonstrated comparable results to minoxidil
(MXD) solution [107]. Hair loss can be effectively treated by using SLN prepared
from semi-synthetic triglycerides stabilized with a mixture of polysorbate and
sorbitan oleate loaded with 5% of MXD. SLN suspensions displayed an efficient
skin penetration similar to commercial solutions without corrosive potential
[108]. Formulations based on MXD NPs have been prepared for the delivery of
MXD into hair bulbs via the follicles in C57BL/6 mice. The MXD NPs displayed
higher therapeutic efficiency as compared to commercially available MXD
974 Ambika and P. Pratap Singh

[109]. Finasteride (FIN) has been used orally in the treatment of androgenetic
alopecia and some other pilosebaceous unit (PSU) disorders. Different vesicles
(liposomes and niosomes) could efficiently deliver FIN to the PSU [110]. Similarly,
FIN-loaded spherical-shaped ethosomes (FES) displayed enhanced permeation
across rat skin and frontal scalp skin of human cadaver in comparison to
unencapsulated FIN. These results demonstrated the ability of FES to permeate
across the stratum corneum to reach the PSU of the hair follicle [111]. Encapsulation
of FIN into topical liquid crystalline NPs exhibited high skin retention in the scalp
and a lower dose frequency with minimum significant side effects [112]. Hair-
growing ingredients have been encapsulated in poly(lactic-co-glycolic acid)
(PLGA) nanospheres for their delivery to hair follicles. The above formulation
exerted 2.0- to 2.5-fold higher scalp-pore permeability as compared to the control
samples resulting in significantly enhanced degree of hair growth [113].
Hair discoloration is a huge problem in recent times. Various hair coloring agents
are used for the coloration of hairs such as permanent hair dyes, temporary dyes, metal
salts, natural dyes, etc. Permanent hair dyes constitute two components: primary
intermediates and couplers. p-Phenylenediamine (PDA) is one of the common primary
intermediates used in permanent hair dye [114]. These hair dyes may lead to contact
allergy and bladder cancer risk in consumers [115, 116]. Encapsulation of PDA into
hyaluronic NPs displayed reduced toxicity and increased cell viability in comparison
to free PDA [117]. PDA-incorporated NPs have been prepared by the ion-complex
formation between the cationic groups of PDA and the anionic groups of
poly(γ-glutamic acid) (PGA). These NPs displayed reduced toxicity as compared to
free PDA against HaCaT human skin keratinocyte cells. Furthermore,
PDA-incorporated NPs showed reduced apoptosis and necrosis reaction at HaCaT
cells [118]. Functionalized carbon nanotubes have been claimed to dye hair black by
forming a surface coating [119]. Hair treatment and coloring can be effectively
performed by coating hairs with nanotubes loaded with drugs or dyes. This method
offers sustained long-lasting drug delivery directly on the hair surface and in cuticle
openings. Dye can be encapsulated inside the clay nanotubes which avoids the direct
hair contact with dye. Encapsulation offers the loading of water-insoluble dyes from an
organic solvent and to store the formulation in dried form for a long time and finally
can be used on hair as an aqueous nanotube suspension. The above formulation having
halloysite nanoclay can be loaded with different dyes/drugs for enhanced hair color
and treatment efficiency with sustained release [120]. A hair-dyeing methodology
using lead salts has been developed involving the formation of PbS nanocrystals
within the hair during blackening. The PbS nanocrystal growth inside a hair can be
controlled by the composition and supramolecular organization of keratins [121].

Oral Care

Oral care is important for maintaining healthy teeth, gums, and tongue. These
cosmetic hygiene products such as toothpastes and mouthwashes are used by the
consumers of all age and income groups on daily basis for the prevention or
42 Nanocosmetics: Opportunities and Risks 975

reduction of tartar, plaque, and gingivitis. Sometimes, whitening agents are also
added to the mouthwash to whiten the teeth. These oral care products have also been
modified involving nanotechnology for enhanced efficiency and performance. Var-
ious nanocarriers like dendrimers, NPs, and hydrogels have been utilized for the
preparation of oral care products. Early carious lesions can be remineralized by the
utilization of toothpastes consisting of CaCO3-based NPs and 3% nanosized sodium
trimetaphosphate as compared to conventional toothpaste without nano-additives
[122]. Hydroxyapatite (HA) NPs can act as a remineralizing agent and can be
employed as a new synthetic enamel biocompatible material to repair early carious
lesions [123]. The microhardness values in human enamel can be significantly
enhanced by using toothpaste prepared by utilizing HA NPs in comparison to
toothpaste without HA [124]. Various nano-whitening agents have been employed
in oral care products. Recently, TiO2 nanotubes have been also used as an effective
tooth whitener. Very low concentrations of H2O2 in combination with TiO2 nano-
tubes displayed improved whitening [125]. HA NP toothpaste can be used for teeth
whitening and brightness [126]. A combination of HA NPs and TiO2 incorporated in
toothpastes can result in better protection and whitening [127]. Similarly, HA NPs
can be employed as strong desensitizing agents as compared to NovaMin and Pro-
Argin [128]. HA NPs and fluoride-containing toothpaste can significantly prevent
demineralization and assist the formation of fluoridated apatite, which is more
resistant to acid attack [129]. However, demineralization of enamel induced by
acidic products can be effectively prevented by oral care products such as toothpaste,
mouthwash, containing HA and Zn NPs as compared to fluoride toothpaste which
reduces the risk of gingivitis and periodontitis [130–133].
Different metal (Ag, Au, Cu, Zn, TiO2, ZnO, etc.) NPs have been used in the
formulation of oral care products due to their antimicrobial activity. Streptococcus
mutans is one of the main pathogens known to be involved in carious lesions
[134]. For example, Ag NPs are incorporated into toothpastes and mouthwash that
act as potent microbicide [135]. Mouthwash containing low concentration of ZnO
NPs displayed high antibacterial activity against Streptococcus in the mouth
[136, 137]. Mouthwash containing Ag/ZnO NPs can be employed as an effective
antimicrobial agent which may be attributed to the synergistic antibacterial effect of
Ag NPs with ZnO NPs in combination [138]. Also, Ag/ZnO NPs displayed
enhanced antimicrobial activity against S. mutans in comparison to mouthwash
containing ZnO NPs, chlorhexidine 0.2%, and sodium fluoride 0.05%. Thus, the
Ag/ZnO NPs-based mouthwash could be an effective alternative in plaque control
instead of chlorhexidine 0.2% [137].

Toxic Effect of Nanotechnology in Cosmetics

Nanotechnology has attracted the attention of scientists and researchers which may be
attributed to the requirement and applications of nanomaterials in various industries
including agriculture, business, medicine, and public health. Since nanotechnology has
become an inevitable part of our daily life, the side effects related to nanotechnology
976 Ambika and P. Pratap Singh

cannot be overlooked. The use of nanomaterials in cosmetic products is of major

concern. Nanomaterials may pose huge risks to humans and the environment which
may be attributed to their smaller size and large surface area-to-volume ratio
[139, 140]. The health risk associated with nanoparticles depends on the route and
extent of exposure. The most common routes of exposure to NPs include inhalation and
ingestion. For example, the workers are susceptible towards the toxicity of nano-
materials during their production in the absence of appropriate safety devices. The
NPs can easily enter the bloodstream via skin or inhalation and can travel to various
organs leading to toxicity. The long-term exposure and high dose of these NPs in the
vital organs may result in their dysfunctioning [141]. Regular exposure of sun care
products prepared from ZnO and TiO2 NPs may impose severe toxicity such as cyto-
and genotoxicity [44]. Carbon nanotubes may pose various toxic effects on the body due
to their unique physical and chemical properties. CNT-induced toxicity is related to
surface modification, degree of aggregation in vivo, and NP concentration.
CNT-induced associated toxicities include hepatotoxicity, lung toxicity, and cardiovas-
cular toxicity [142]. Carbon fullerenes possess bactericidal properties, genotoxicity, and
toxicity towards the vascular endothelial cells [143–145]. These NPs may be released
during the manufacture, use, or disposal and can pollute the environment (water, air, and
soil) by interfering with the normal cycles. Also, the NPs have the potential for
biomagnification. Thus, it is very important to observe special care while dealing with
nanomaterials and their products.

Conclusions

Nanotechnology is one of the most promising and revolutionizing fields that offer
huge opportunities for the development of the cosmetic sector. Various types of
nanomaterials such as liposomes, microemulsions, nanoemulsions, niosomes, etc.
have been employed in cosmetics. These nanomaterials provide additional advan-
tages in relation to the high loading capacity, efficient adsorption, as well as targeted
release and the possibility of achieving synergistic actions, higher stability, and
longer shelf life. Sunscreens, lip care products, toothpastes, mouthwashes, hair
dyes, hair growth promoters, etc. are some of the cosmetic systems where nano-
materials have been employed for their formulations. However, increased use of
nanotechnology in cosmetic products has raised concern about the possible pene-
tration of nanoparticles through the skin and potential hazards to the human health.
Thus, health of consumers and the environment should be considered while design-
ing the cosmetic products based on nanotechnology.

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Role of Nanotechnology in Cosmeceuticals
43
Mahtabin Rodela Rozbu, Samiha Nuzhat, and
Paulraj Mosae Selvakumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
Current Nanotechnology in Cosmeceuticals: Synthesis and Applications . . . . . . . . . . . . . . . . . . . . 987
Synthesis and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 987
Nanodiamonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 987
Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
Nanosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
Nanoliposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 990
Metallic Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
Polymeric Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
Silica Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 992
Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
Micellar Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
Nanopigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Solid Lipid Nanoparticle (SLNs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
Buckyball . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
Impacts of Nanotechnology-Based Cosmeceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
Environmental Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 998
Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
Sustainability of Nanotechnology in Cosmeceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
Works Cited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001

Abstract
Cosmetics are one of the most primitive tools for beautification holding huge
significance from both historical and co-current perspectives. Like the other gradul
additions in the cosmeceutical industry, nanotechnology-based approaches, being a
growing technological sector of recent times, are often adopted in cosmeceutical
production. Addition of such modern approaches offers a more environment friendly,
user friendly and low cost alternative for cosmeceutical industries. Even evidence has

M. R. Rozbu · S. Nuzhat · P. M. Selvakumar (*)

Science and Math Program, Asian University for Women, Chittagong, Bangladesh

© Springer Nature Singapore Pte Ltd. 2022 985

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_60
986 M. R. Rozbu et al.

proved that some nanomaterial mediated processes incorporated with cosmeceutical

productions have drastically reduced negative health impacts caused by different
cosmeceutical products. Synthesis and applications of a wide variety of nano-
materials have been found specifying to the context of the cosmeceutical industry.
Some of the widely used nanomaterials in the cosmetics industry are nanodiamonds,
nanoemulsions, nanosomes, nanoliposomes, metallic nanomaterials, polymeric
nanomaterials, silica nanoparticles, nanocrystals, micellar nanoparticles, nano-
pigments, byckyball and so on. All these different types of nanoparticles have
different synthesis mechanisms based on their applications. Their applications are
also quite broad due to the huge variety and multiple purposes of different cosme-
ceutical products. Considering all these aspects of nanotechnological application in
cosmeceuticals, this chapter aims to explore synthesis, applications and sustainability
concerns of different nanomaterials and nanoparticles in the cosmeceutical industries.

Keywords
Nanoparticles · Nanomaterials · Nanotechnology · Cosmeceuticals ·
Nano-cosmeceuticals · Cosmeceutical Industry · SLNs · Nanoemulsion ·
Nanosomes · Sustainability

Introduction

Arguably enough, cosmetics is an essential part of human evolution and advance-

ment. Invented to enhance and take care of face, body, and human appearance,
cosmetology forms a huge industry in the modern era. With the surge of technology,
innovation in nanoscience and nanotechnology swiftly ventured its way into cos-
metology. Cosmetic industry adapted various applications of nanotechnology in
their process since the beginning of nanotechnological innovations. With increasing
research and remarkable development of nanomaterials and nanoparticles, the use of
nanotechnology in the field of cosmeceuticals gradually increased, giving rise to
nano-cosmeceuticals [23, 27]. So, what is nano-cosmeceuticals exactly? Nano-
cosmeceuticals, an emerging field as we know it, is the cosmetic formulation that
uses nanomaterials as a delivery mechanism to enhance the performance of bioactive
components present in cosmetics. The major classes of nano-cosmeceuticals consist
of moisturizers, sunscreens, cleansers, anti-aging products, and hair, nail, and skin
care formulations [10, 27]. Nanotechnology-based applications in cosmeceutical
industries are so vast that from UV-protective sunscreens to makeup, deodorant,
and many more, nanoparticles are fundamental aspects in cosmetic production. In
this regard, nanotechnology-based applications include utilization of metallic nano-
materials, nanoemulsions, nanosomes, polymeric based nanoparticle, silica nano-
particle, micellar nanoparticle, nanopigments, solid lipid nanoparticle, nanocrystal,
buckyball, fullerene, nanodiamonds, and so on. Despite having several beneficial
properties of these nanotechnology-based applications, there are controversies asso-
ciated with its sustainability and negative impacts.
43 Role of Nanotechnology in Cosmeceuticals 987

This chapter aims to critically analyze some of the major properties, mechanisms,
and impacts of nanotechnology applications in cosmeceuticals. In doing so, this
chapter essentially explores widely used nanotechnology concepts that are relevant
to cosmetology. Additionally, it covers nano-cosmeceutical associative advantages
and risks toward the sustainable health and environment sector.

Current Nanotechnology in Cosmeceuticals: Synthesis

and Applications

Treating wrinkles, hair damage, dark spots, and many other dermatology issues, the
cosmetic industry aims to deliver products to diminish unwanted body/facial dete-
rioration. Hence, the presence of improved and customized cosmetic products
establishes the growing cosmeceutical industry [23]. One such example is the
incorporation of nanotechnology in the field of cosmeceuticals, to further enhance
the functional chemistry and bioactivity of the compounds present in cosmetic
products. Although nano-cosmeceuticals is an emerging field, cosmetics have uti-
lized nanoparticles since the beginning of cosmetology (most commonly gold and
silver nanoparticles). The primary function of nanomaterials is to act as dispersion or
carrier for the bioactive compounds present in cosmetics. However, the size, mass,
and soluble properties of nanomaterials can be made to have innovative changes, in
order to create better eco-friendly non-toxic, biocompatible products.

Synthesis and Applications

The establishment of an efficient delivery system using various nanomaterials

requires optimum size and characterization. Nanodiamonds, nanoemulsions, nano-
liposomes, nanosomes, metallic nanomaterials polymeric-based nanoparticle, silica
nanoparticle, micellar nanoparticle, nanopigments, solid lipid nanoparticle, nano-
crystal and buckyball, and fullerenes are some of the common nanomaterials used in
present cosmetics. This chapter overviews the synthesis and significant applications
of some of the widely used nanoparticles/nanomaterials in cosmeceuticals.

Nanodiamonds

Nanodiamonds are another novel delivery innovation of nanotechnology (Fig. 1).

Significant in various drug delivery applications in the fields of biomedicine, the
innovative properties of nanodiamonds found its way into cosmeceuticals as well.
Nanodiamonds are non-poisonous, making them a prominent choice for most
cosmeceuticals applications. Having purity, size selectivity, better retention of
aggregation, colloidal stability, and surface functionality, nanodiamonds tend to be
advantageous over other nanoparticles, used for delivery purposes [2]. The synthesis
of nanodiamonds usually comprises of three main mechanism:
988 M. R. Rozbu et al.

Fig. 1 Structure of nanodiamonds: (a) carbon backbone, (b) arrangement of atoms in crystal
structure. (Drawn using PowerPoint (a) and ChemSketch (b))

1. Detonation nanodiamond (DND)

2. Ultrasonic cavitation method
3. Pulsed-laser irradiation

Detonating trinitrotoluene (TNT) and hexogen (RDX) mixture, followed by

chemical purification and exposure toward high-energy electron beams and then
heated 800 degrees Celsius, results in nanodiamonds [2]. The structure, purity,
shape, and size depend on the synthesis conditions and the heat capacity of the
cooling medium (air, water, etc.) in the detonation chamber. Effectively, higher
cooling capacity of the medium yields larger diamonds. In order to remove metal
contamination, after synthesis, the nanodiamonds require to be autoclaved in boiling
acid for about 1–2 day period [2]. Finally, the synthesized and purified detonated
nanodiamonds are characterized using X-ray diffraction and various other charac-
terization techniques, necessary to acknowledge the shape and size of the product.
Ultrasonic cavitation of graphite suspended in organic liquid at atmospheric pressure
and room temperature yields nearly about 10% of nanodiamonds. An acoustic cavitation
is created under high pressure and temperature that slowly expands upon the shock
waves present [2]. Then together with the presence of liquid ethanol and hexane, under
acoustic cavitation and tensile energy differences, nanodiamonds are obtained [2, 40].
Pulsed laser irradiation of graphite is another synthesis technique of nano-
diamonds. Femtosecond laser pulses on graphite surfaces induce a phase transfor-
mation of carbon graphite to sp-bonded carbine, resulting in nanodiamonds [2].
With remarkable properties such as hardness, chemical inertness, optical proper-
ties, and functionalizing flexibility, nanodiamonds have major implications in skin
care due to particular adsorption qualities [2, 45]. Moreover, it is a promising filling
for dental care based on its strength and biocompatibility [2]. Furthermore, as an
effective component for hair, nail, toothpaste, etc., nanodiamonds are great bubbling
agents and can even enhance the durability of the cosmetics’ chemical compositions
[2, 45]. Having numerous advantages and applications across various cosmeceutical
products, the popularity and use of nanodiamonds is therefore increasing rapidly.
43 Role of Nanotechnology in Cosmeceuticals 989

Fig. 2 Schematic diagram of an oil-in-water nanoemulsion system. [9]

Nanoemulsions

Nanoemulsions are spherical colloidal dispersions. Generally composed of two

immiscible liquids, a stable structure forms with aid of surface-active agents iden-
tified as emulsifiers (Fig. 2). Drugs or active cosmeceutical agents are contained in
the internal phase of nanoemulsions (Fig. 2) [9].
Emulsions of nano-droplets of one liquid with another effectively form nano-
emulsions that can have various structures depending on the synthesis mechanism
[5]. For instance, by means of mechanical shearing, colliding large droplets into
smaller forms, nanoemulsions can be synthesized. With a typical size range of
20–500 nm, nanoemulsions are deliberately kept small to enhance higher activity,
stability, suitability, and shelf life of the product [5, 47].
Nanoemulsions primarily protect vitamins, antioxidants, and other active com-
pounds present in cosmetics.

Nanosomes

Nanosomes are lipid soluble entities composed of a phosphatidylcholine

(PC) membrane [5]. It usually consists of a polar and hydrophobic cavity for
encapsulating both water-soluble and oil-soluble compounds (Fig. 3).
The synthesis of nanosomes depends on several material properties and process
factors such as bubble size, interfacial forces and pressure, architect of decompression
nozzle, rate of decompression, nature, and charge distribution of the compound that is
encapsulated within the PC or phospholipid membrane [5, 13, 36]. In accordance,
mathematical modeling helps to determine the optimal size of the nanosome
necessary [5].
Similar to nanoemulsions, nanosomes also act as a protecting agent of active
ingredients in cosmetics and enhance lightness and transparency of the cosmetic
products [5].
990 M. R. Rozbu et al.

Fig. 3 Schematic representation of nanosome. (Created using BioRender.com)

Fig. 4 Schematic
representation of
nanoliposome. (Created using
BioRender.com)

Nanoliposomes

Nanoliposomes are spherical vesicles with a phospholipid bilayer (Fig. 4). These
nanocarrier systems, 30 nm to varying micrometers are artificially constructed,
containing aqueous centers [5, 31]. The main difference between nanosomes and
nanoliposomes are that nanosomes are typical liposomes that are encapsulated and
consist of nanoparticles in their membranes, unlike nanoliposomes.
Microfluidization, extrusion, and sonification are some of the significant meth-
odologies used in the synthesis of nanoliposomes.
Depending on the physicochemical properties of the media where the vesicles are
dispersed, the synthesis of nanoliposomes is tailored. Moreover, shelf-life, size,
polydispersity, toxicity, and concentration of aqueous centers are some of the
significant factors that dictate synthesis of particular nanoliposomes for various
cosmetic products [33].
43 Role of Nanotechnology in Cosmeceuticals 991

Fig. 5 Application of metal

nanoparticles. [12]

The application of nanoliposomes in the field of cosmetics is huge. The encap-

sulation of saffron in nanoliposomes is one significant example. Saffron that can act
as a sunscreen, when encapsulated in nanoliposome, may have significant sun
protective effect in less concentration [28].
The use of nanoliposomes based on particle size improves hydration, making the
skin soft and elastic [5]. It works when a flexible film of nanoliposomes forms
externally on the skin surface, a substitute of the hard film that forms when toxic and
dirt deposits on skin [5].

Metallic Nanomaterials

Metallic nanomaterials in cosmeceuticals usually tend to be oxides or pure metals

such as gold, copper, and silver, some of the common metal nanoparticles. Metallic
oxide nanoparticles have specific density and size, which gives them particular
chemical and physical properties. [5] (Fig. 5).
There are several applications for metallic nanoparticles in various arenas such as
biomedicine, electronics, cosmetology, and many more [20, 21, 30]. For example,
centered around cosmeceuticals, metallic nanoparticles such as titanium dioxide and
zinc oxide are used for UV protection, whereas silver and gold nanoparticles act as
moisturizing agents, valued for their antibacterial properties [5, 17, 20].

Polymeric Nanomaterials

Polymeric nanoparticles in cosmetics maintain health and physiological properties of

the skin [1, 30]. Polymeric nanomaterials are nanostructures designed as either a
nanosphere or a nanocapsule (Fig. 6).
Nanospheres typically consist of the bioactive compound amid the polymer
network, and nanocapsules consist of polymeric shells (Fig. 6). Polymeric nano-
materials are advantageous for dermatology-related cosmetics mainly because
992 M. R. Rozbu et al.

Fig. 6 Schematic diagram of

polymeric nanomaterials

Fig. 7 Representation of Stober’s method for silica nanoparticle synthesis. [37]

such nanomaterials are able to deliver the bioactive compounds by reducing

cytotoxicity. For example, again for the sunscreen cosmetics, employing poly
lactic-co-glycolic acid or PLGA nanoparticles, when loaded with morin, proved
to have effective photoprotection and remarkable antioxidant properties for the
skin [1].

Silica Nanoparticles

Nonporous silica nanoparticles and mesoporous silica nanoparticles (MSN) are

some of the common silica nanoparticles present in cosmeceuticals [26]. One pri-
marily synthesis of silica nanoparticles is the Stober’s method (Fig. 7). The initial
synthesis of silica nanoparticles involved the addition of excess water to tetra-
alkoxysilane, ammonia, and alcohol (of low molar mass).
43 Role of Nanotechnology in Cosmeceuticals 993

Fig. 8 Different nanocrystal structures. (Created using grain boundary studio v.3)

The type of silicate ester, alcohol, volume ratio of reactants, and reacting envi-
ronment essentially determines the size, shape, and surface properties of the nano-
particles [38, 42, 46, 26]. Furthermore, treating with cationic detergent (CTAB)
followed by a surfactant removal essentially results in MSNs (Fig. 7). Various
cosmetics incorporating the use of silica nanoparticles hence have significantly
different synthesis mechanisms [26].

Nanocrystals

Nanocrystals are an aggregate complex of innumerable atoms in a cluster, altogether

having a size in the nanoscale (Fig. 8) [5].
Nanocrystals are known to support a safe and effective delivery of bioactive
compounds through skin [5, 43]. These nanostructures increase both the dissolution
velocity due to enhanced surface area and saturation solubility, thus increasing the
bioavailability of the chemicals in cosmetics. The prominent application of nano-
crystals is sunscreens (Fig. 9).

Micellar Nanoparticles

Micellar nanostructures can be branched around 20 nm in size, with a well-defined

frequently branched symmetrical structure. These nanoparticles have high density
functional end groups at their periphery with synthetic polymers in layered archi-
tectures. Micellar nanoparticles hold promise and potential in several biomedical
cosmetics applications. They are suitable for multifunctionalization due to the
presence of many external groups [3, 5].
994 M. R. Rozbu et al.

Fig. 9 Three layers of

micellar nanoparticles shown
in different colored layers
(drawn using Biorender.com)

Fig. 10 A schematic representation of the synthesis of nanopigments. [39]

Nanopigments

Nanopigments such as cobalt chromite (CoCr2O4) can be synthesized using the

corresponding metal acetates reacted together in diethylene glycol media and heated
in 180 degree Celsius for approximately 2 h [39]. The precursor solution is then
purified via calcination at 700 degree Celsius for about 3 h, resulting in cobalt
chromite nanopigments (Fig. 10). Various other nanopigments although having
different synthesis mechanisms are essentially used as UV filters in cosmeceutical
formulations.

Solid Lipid Nanoparticle (SLNs)

SLNs are submicron colloidal carriers, usually about 50 to 1000 nm in size. These
nanoparticles are composed of lipids and dispersed in surfactant of water or aqueous
solution [16] (Fig. 11).
Hydrocarbons or organic additives in combination with cosmetic active agents in
aqueous dispersions are melted at high temperatures when adjusted to a required
particle size in a homogenization procedure and later cooled down, forming solid
nanoparticles known as solid lipid nanoparticles (SLNs). SLNs have a significant
application as a waxing agent. Demonstrating minimal toxicity, acting as UV
blockers as well, SLNs were observed to provide enhanced skin hydration, making
them conventional cosmeceutical agents [10, 16].
43 Role of Nanotechnology in Cosmeceuticals 995

Fig. 11 Solid lipid

nanoparticle

Fig. 12 Buckyball or
fullerene

Buckyball

Buckyball, C60, or buckminsterfullerene, a type of fullerene, can effectively

scavenge radical oxygen species and act as cytoprotective agents, making them
an attractive compound for skin rejuvenation cosmetics. There are several syn-
thesis mechanisms for the production of buckyball, necessary in various appli-
cations across cosmeceuticals. One such method resulting in bulk production of
buckyball follows the combustion synthesis, where a hydrocarbon and oxygen
reacts together under low pressure yielding approximately 95% pure buckyballs
[6, 15] (Fig. 12).
The application of various nanomaterials and nanotechnology in cosmeceuticals
is therefore significantly promising. However, more ground research and observation
is necessary to understand or identify any possible consequences; such nanoscience
may hold in terms of health and environmental implications.
996 M. R. Rozbu et al.

Impacts of Nanotechnology-Based Cosmeceuticals

Cosmeceutical products are mostly synthesized with an aim to correct, perfume, or

protect external body parts like hair, nails, skin, eyes, etc. Currently, benefits of
cosmeceutical products are not limited to these only. Instead, a huge variety of positive
inclusions are assured while synthesizing cosmeceutical products. In this regard,
nanotechnology-based approaches are often utilized to design various advantageous
characteristics in cosmeceutical products. There are several product-specific direct
beneficial applications of nanotechnology in cosmeceuticals. There are also several
co-benefits of these nanotechnology-based applications. At the same time, benefits of
such nanotechnology-based cosmeceuticals are often suppressed by controversies, since
researchers suggest several negative outcomes nanotechnology-based cosmeceuticals
may bring about. This is why successful risk governance and safety assessment of
nanotechnology application is an ethical challenge in this regard. Considering the
potential positive and negative impacts and controversies of nanotechnology in
cosmeceuticals, some of its major impacts have been discussed in this chapter.

Environmental Impacts

Though several environment-friendly properties of nanotechnology-based applica-

tions are compared with other products, its corresponding environmental risks are
mostly caused when nanoparticles and nanomaterials are exposed to environmental
components like water, air, soil, and so on due to uncontrolled industrial waste
disposal. Since nanotechnology-based cosmeceutical products often contain antimi-
crobial agents, these nanomaterials and nanoparticles can kill beneficial microbes in
our environment. Even when these products reach the sewage system, they cause
dysfunction of biological treatment killing the useful bacteria used in the treatment
process [32]. A commonly found cosmeceutical ingredient, nano-titanium dioxide
(TiO2), commonly used in sunscreen and skin thickening or whitening creams, is
found toxic for some animals and microorganisms [25]. Moreover, this nano-chemical
bypasses the basic waste treatment process which causes ecotoxicological effects in
the long term. Nano-zinc oxide can also have similar impacts, as it may also kill
beneficial bacteria, and even exposure of nano-zinc oxide at the slightest amount may
even cause significant threat [35]. Similarly, many other nanotechnology-based ingre-
dients are found to have antimicrobial effects (Fig. 13).
Another cosmeceutical antioxidant nanoagent, fullerene, is responsible for ner-
vous system damage of several organisms when this is exposed to the environment
[29]. It is also found that nanoparticles bind with contaminating substances easily
increasing stability of the contaminating substances. It may cause large-scale pollu-
tion nearby the nanoparticles using industries [41]. Besides, nanoparticles and
nanomaterials commonly used in cosmeceutical industries have biomagnification
and bioaccumulation properties. The proof of nanoparticle biomagnification is found
from simple microbial food chains to large-scale terrestrial food chains that will
surely have dreadful impacts [19]. The more the environment is exposed to
43 Role of Nanotechnology in Cosmeceuticals 997

Fig. 13 Schematic representation showing antimicrobial effects of TiO2 nanoparticles

nanoagents, the more chances of environmental degradation. Such environmental

risks can be minimized largely, if cosmeceutical industries ensure well-controlled
industrial waste disposal.
Despite the environmental risks of nanotechnology applications in cosmeceuticals,
there are several environment-friendly characteristics of nanotechnology-based
cosmeceuticals. So far, most of the nanoparticles and nanomaterials used in cosmetics
industries are regarded as the safest alternatives of many of the formerly used
hazardous chemicals [7]. Even nanotechnology-based process modifications in cos-
metics industries, for example, introducing nanocarriers, nanomedicinal properties,
etc., often minimize its environmental hazards [8]. At the same time, nanotechnology-
based applications are found useful in resource and energy savings. Therefore, its
suitable applications in cosmetics industries are also hoped to promote resource
efficiency in such industries [14]. However, unless these nanotechnology-based prod-
ucts are exposed uncontrollably in the environment, there is almost no chance of
nanotechnology-mediated environmental degradation. Otherwise, several environ-
ment hazards may occur. To prevent such hazards, the industrial regulatory authorities
should be conscious to ensure proper nanotechnology-based product labeling and
testing so that its toxicity remains out of the harmful range. At the same time,
environmental safety assessment of the products is also necessary.
998 M. R. Rozbu et al.

Health Impacts

Most of the elements present in the cosmeceutical products are found not to be
harmful for human health. Instead, there are proven examples suggesting many of
the products’ beneficial health impacts. To discuss the health benefits of nano-
cosmeceutical products, sunscreen can be regarded as a noteworthy example. Tita-
nium dioxide (TiO2) and zinc oxide (ZnO) are two major ingredients used in
sunscreen. These two are efficient ultraviolet ray blocking agents and protect the
skin from UV ray-mediated skin cancer [8]. Antibacterial and antifungal properties
of several cosmeceutical products minimize skin issues and acne problems and
prevent dirt accumulation in the skin. Nanoparticles like nano-gold, nano-silver,
and cubosomes moisturize and nourish the skin [8]. Besides, as antioxidants are
often present in cosmeceutical products, such products help to prevent skin wrinkle
formation. In this regard, nanocarriers of cosmeceutical products ensure smooth
transportation of antioxidants in different dermal layers [4]. In addition to it,
nanoemulsions, another common cosmeceutical ingredient, increases drug penetra-
tion in the skin, and thus, it increases drug efficiency and reduces skin diseases
[8]. Apart from these, utilization of nanocrystal technology in toothpaste is found to
be helpful in preventing enamel damage of teeth [34]. Also, nano-cosmeceuticals
present in oil, shampoo, and conditioners help to nourish the scalp and protect scalp
skin damage [22]. There are many more examples of nanotechnology-based cosme-
ceutical applications that help to improve human health conditions.
However, as nano-sized nanomaterials and nanoparticles used in cosmeceutical
products come to direct contact with human epidermis, these compounds may be
absorbed by respiratory system, digestive organs, eye membranes, and skin pores
[7]. By getting into contact with different body organs, these materials often cause
inflammation, cellular breakdown, imbalance, oxidative stress, and many more issues.
In this regard, the penetration potentials of the nanomaterials and nanoparticles are
associated with the size of the particle. Even nanotechnology-based products may
change their physicochemical properties at different stages for which even if they are
found to be non-toxic at the preliminary stage, their toxicity may arise during the final
stages of products’ life cycle [44]. Therefore, there are chances that nanotechnology-
based cosmeceuticals may exhibit harmful impacts even if they are found to be harmless
during product manufacturing. Some widely used cosmeceutical and nanotechnology-
based products like titanium dioxide do not penetrate through the skin. However, its
health hazard potential is quite controversial, as it forms free oxygen radicals which may
cause damage to skin cells [7]. Besides, nano-medicinal applications in cosmeceutical
products are designed to help smoothen skin, but it may form tumors crossing bound-
aries of blood vessels and brain tissues. Such applications are often noticed in case of
cosmetic surgeries which can be the reason for tumors or cancer formation in later terms
[8]. Another commonly used cosmeceutical nano-reagent, fullerenes, is also regarded to
have toxic effects on humans, though there is not much research that discovers its direct
impacts on the human body. In most of the cases, regular exposure to such
cosmeceuticals is responsible for microbial dysfunction [35]. Therefore, health impacts
of nanotechnology-based cosmeceutical applications are often regarded as controversial
(Fig. 14).
43 Role of Nanotechnology in Cosmeceuticals 999

Fig. 14 Human health-

related positive and negative
impacts of nanotechnology-
based applications in
cosmeceuticals

Others

Impacts of nanotechnology-based applications in cosmeceutical industries are not

only limited to environment and human health. Rather its impacts are noticed in the
economic and business sector, industrial process designing, and advanced research
sectors. Cosmeceutical industry, being one of the first few industries adapting
nanotechnology, is yet an emerging field for nanotechnology-based research.
There are yet many scopes to modify the process more suitably and effectively.
This is why it can be considered as a modern research arena with industrial,
environmental, and health-related significance. Besides, nanotechnology-based
researches to improvise the country’s industrial sectors in terms of cosmeceutical
industries are often regarded as a useful inclusion for economic growth [24]. Even in
most of the cases, nanotechnology-based approaches are more cost-effective and
more sustainable than other traditionally adopted approaches. Significant contribu-
tion in improvising this sector will help to gain economic profit as well. Thus,
different sectors can be benefitted as an impact of nanotechnology-based applica-
tions in cosmeceuticals.

Sustainability of Nanotechnology in Cosmeceuticals

As discussed earlier, impacts of nanotechnology are yet controversial for which

sustainability of nanotechnology-based applications cannot be confidently assured.
However, there are several properties of nanotechnology-based applications that can
be modified to ensure sustainability of nanotechnology in the cosmeceuticals industry.
It is because co-currently discovered properties of nanotechnology implications in
cosmeceuticals indicate huge potentials of nanotechnology-mediated sustainability in
the future, though it requires advanced experimental research and collaborations
1000 M. R. Rozbu et al.

among the stakeholders. In this regard, the concept of “Green Nanotechnology” can be
quite relevant, as it ensures environmentally sustainable applications of nanotechnol-
ogy. Green nanotechnology incorporates a variety of green chemistry principles and
zero waste concepts [18]. Besides, green nanotechnology is also energetically sustain-
able and environment friendly. Therefore, there is almost no possibility of health risk
or occurrence of environmental hazards under a sustainable green nanotechnology
scheme (Fig. 15).
However, in the case of the cosmeceuticals industry, nanotechnology-based
sustainability can have far-reaching positive outcomes. Being one of the very first
nanotechnology utilizing industry, cosmeceutical industries have more opportunities
to incorporate green nanotechnology-based applications at the earliest. Unfortu-
nately, there are several challenges associated with this, such as increased cost,
limited commercial set up, insufficient nanotechnology-based knowledge, and so
on. Realizing the knowledge gap, sustainability of nanotechnology-based applica-
tions in the cosmetics industry cannot yet be predicted. This solely depends on how
the researchers approach in advancing nanotechnology-based knowledge and how
much cost savings the cosmeceutical industry can ensure by adopting
nanotechnology-based approaches.
It is understood that there is a huge lack of data, research, and information
regarding nanotechnology-based cosmeceutical applications. Furthermore, the
unusual traits of such compounds makes it even more difficult to determine its
reactivity and toxicity. Therefore, Yapar et al. [44] suggest to close information
gaps, setup monitoring scopes, review, design, and regulate relevant applications in
terms of nanotechnology-based applications in cosmeceutical industries. This is
hoped to guide future researchers and industrialists to approach nanotechnology-
based cosmeceutical applications at an industrial level.

Fig. 15 Requirements for

green nanotechnology-based
applications. [11]
43 Role of Nanotechnology in Cosmeceuticals 1001

Websites https://cosmeticsinfo.org/nanotechnology
https://www.dermatologytimes.com/view/nanotechnology-and-cosmeceuticals-
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https://www.fda.gov/cosmetics/cosmetics-science-research/cosmetics-nano
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Nanobiotechnology-Based Anti-aging
Products 44
Rex Jeya Rajkumar Samdavid Thanapaul,
Mosae Selvakumar Paulraj, and Daniel S. Roh

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
Main Text . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
Nano-cosmetics on the Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
Safety and Efficacy of Nanobiotechnology-Based Cosmetic Products . . . . . . . . . . . . . . . . . . . . 1006
Commercial Nanobiotechnology Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1008
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1027
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1027
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1028

Abstract
Nanobiotechnology is one of the fast-growing domains in the personal care sector
and has played a major role in the arena of developing anti-aging products. The
anti-aging products offered based on nanobiotechnology has a significant
increase in their bioavailability levels with diverse and prolonged therapeutic
effects. A large number of nano-based topical cures for anti-aging have become
widespread. The present chapter figures out the therapeutic benefits and the
potential side effects of various nano-biotechnology-based anti-aging products
commercially available in the market.

R. J. R. Samdavid Thanapaul (*) · D. S. Roh (*)

Division of Plastic and Reconstructive Surgery, Department of Surgery, Boston University School
of Medicine, Boston, Massachusetts, USA
e-mail: [email protected]; [email protected]
M. S. Paulraj
Science and Math Program, Asian University for Women, Chittagong, Bangladesh
Panaiyaanmai - Centre for Self reliance and Sustainable Development, Munnetram Green Industry,
Kadayam, Tenkasi, Tamil Nadu, India

© Springer Nature Singapore Pte Ltd. 2022 1005

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_62
1006 R. J. R. Samdavid Thanapaul et al.

Keywords
Nanobiotechnology · Anti-aging · products · cosmetics

Introduction

The integration of nanotechnology into cosmetic formulations is known as the latest

and newest available technology. Nanoscale ingredients are used by cosmetic man-
ufacturers to provide better UV protection, deeper penetration of the skin, durable
efficiencies, increased color, improved finish, and much more. Nanotechnology-
based cosmetic formulations help to boost the efficiency of bioactive components
[1, 2]. The therapeutic effects are enhanced in various cosmetic qualities and
performance areas by the smaller nano-size of cosmetic bioactive components that
have been integrated with nanocarriers [3]. Table 1 explains the benefits of various
nanobiotechnology based carriers used in antiaging products. Nanobiotechnology
will be the key to cosmetics of the next generation. Several nanobiotechnology-
based products have been reported in the areas of colors, transparency, solubility,
textures, and durability to improve cosmetics' operations and properties [4–11].

Main Text

Nano-cosmetics on the Skin

The deterioration of the skin is due to several factors. Time, heat, toxic materials,
waste, ultraviolet, and infrared radiation are the most critical factors. The potential
routes to the skin are intercellular, hair follicles, and transcellular routes, via distri-
bution of the active cosmetic nanoingredients. Nano-cosmeceuticals for the skin,
hair, or nails need nanocarriers when used to combat the effects of aging.
Nanobiotechnology-based materials [12–17] are used to strengthen the skin barrier
while avoiding the skin’s surface water loss due to the small particles’ occlusive
properties, which improve skin moisturization. This approach helps smaller cos-
metic nanoparticles, which are readily absorbed into the skin, quickly repair the
damage and facilitate improved product efficacy [18].

Safety and Efficacy of Nanobiotechnology-Based Cosmetic Products

The safety of nanobiotechnology-based cosmetic products are improved with the

areas of concern that are explicitly addressed, and the release of drugs more
regulated. The constant reduction in particle size creates concern about protection
and performance. The effects of the nano-cosmetic products are not limited to these
drawbacks. Nano-components improve the penetration of the drug into the skin and
confer the administered agent with superior pharmacodynamic profiles. Besides,
44 Nanobiotechnology-Based Anti-aging Products 1007

Table 1 Benefits of various nanobiotechnology-based carriers used in antiaging products

Types of
nanocarriers Benefits References
Carbon nanotubes • Biodegradable [19]
• Biological stability and versatility
• Can be used in hydrophilic and lipophilic medicines
• Hydrophobic core provides an environment that is protein
affable
• Reactive to stimulus
Cubosomes • Possess the biodegradability of lipids [20]
• Return bioactive agents with a controlled and targeted
release
• The high internal surface area with various modalities for
drug loading
Gold • Accumulating in cancer cells [21, 22]
nanoparticles • Chemically inert
• High stability due to the bond of gold sulfur
• No photo-bleaching or blinking
• Non-toxic
• Show the effect of cytotoxicity
Dendrimers • Biofriendly [23]
• Controlled degradation
• Molecular weight and size can be checked
• Structure-friendly to function
Liposomes • Better efficiency [24, 25]
• Biodegradable and biocompatible
• Enhanced reliability
• Impact of site avoidance
• Reducing toxicity
• The capability of dermal layer penetration
Nanoemulsions • Do not show sedimentation, creaming, or flocculation [26, 27]
problems
• Improved absorption rate
• It can be formulated in foams, creams, sprays, and liquids
• Non-inspiring
• Non-toxic
• Suitable for the delivery of hydrophilic and lipophilic drugs
Nanospheres • Easy cell and tissue penetration [28]
• Protection of drugs from enzymatic and chemical
degradation
• Release controlled
• Targeting of the site
• Toxicity reduction
Nanostructured • Easy preparation and scale-up [29]
lipid carriers • Enhanced drug release
• Greater capacity for drug loading
• Low toxicity
• Physically stable
• Systemic low toxicity
Niosomes • Biocompatible [30, 31]
• Biodegradable
(continued)
1008 R. J. R. Samdavid Thanapaul et al.

Table 1 (continued)
Types of
nanocarriers Benefits References
• Controlled delivery of drug products
• Delivery of targeted drugs
• Have a base of water
• Improved therapeutic performance of drugs
• Increase in oral availability
• Increased penetration of the dermal
• No special conditions required for the handling and storage
of surfactants
• Non-immunogenic
• Non-toxic
• Osmotic active
• Stable and reliable
• Used on parenteral, oral and topical routes
Solid lipid • Controlled release of active substances and increased [32, 33]
nanoparticles bioavailability of trapped bioactive substances
• Enhanced drug penetration
• Facilities to upgrade on a big scale
• Improved stability and excellent biocompatibility of
unstable active ingredients
• Occlusive properties improve hydration of the skin
• Versatility of application

some nano-cosmetic materials are directly cytotoxic with induced cellular stress and
damages components in the cell, such as DNA and protein, causing tissue inflam-
mation, while other nanomaterials can produce unintended harmful effects on the
environment. While nano-cosmeceuticals have many advantages over conventional
cosmeceuticals, some accompanying inconveniences remain.
Nanobiotechnology has a significant influence on the efficacy of skincare and
antiaging products, amid health concerns. Nevertheless, nanoparticles are still not
well known for long-term health threats. Nanobiotechnology-based cosmeceuticals
promise to overcome traditional cosmeceuticals’ disadvantages. Table 2 shows the
advantages and disadvantages of nanotechnology-based antiaging products. Repre-
sentatives try to oppose physiological processes including photography, wrinkles,
photoaging, and hair damage. In the case of nano-cosmeceuticals, nanomaterials can
be used widely as transdermal drug supply systems in cosmetics.

Commercial Nanobiotechnology Products

Nanobiotechnology-based cosmetics are produced by harmonizing nano bioscience

and beauty. Many cosmetic retailers produce nano-particulate antiaging cosmetics.
Applied to nanobiotechnology cosmetics products that are trending and marketable in
local and international markets, nanoparticles are one of the latest fields in the market.
Table 3 shows the various types of nano-based antiaging products with their key
ingredients and benefits. This chapter discusses the various nanobiotechnology-based
44 Nanobiotechnology-Based Anti-aging Products 1009

cosmetics already accessible on the world market. The usage of nanobiotechnology on

cosmetic products will successfully distribute active compounds such as vitamins,
anti-inflammatory agents, antioxidants, and anti-infective agents that are usually
correlated with their embedded active substances’ smart releasing properties.

Table 2 Advantages and disadvantages of nanotechnology-based antiaging products

Nanotechnology-based antiaging Advantages • Enhanced efficiency
products • Occlusive characteristics
• Performance in large entrapment
• Release under control
• Stability Physical
• Targeting of site
• Transportation of the key
ingredient
Disadvantages • Environmentally and humanly
damaging
• Fewer particulates can be
susceptible
• No health protection controls
• Recommended drug trials
• Tolerance

Table 3 Nanobiotechnology-based commercially available antiaging products

Manufactured
Name of the and marketed
product by Key ingredients Benefits
Advanced Night Estée Lauder Water(aqua), bifida ferment Reparation of the skin
Repair Protective lysate, methyl gluceth-20,
Recovery Peg-75, Bis-Peg-18, methyl
Complex ether dimethyl silane,
butylene glycol, propanediol,
Cola acuminata (kola) seed
extract, hydrolyzed algin,
pantethine, caffeine, lecithin,
tripeptide-32,
ethylhexylglycerin, Sodium
RNA, bisabolol, Glycereth-
26, squalane, sodium
hyaluronate, Oleth-3
phosphate, caprylyl glycol,
Lactobacillus ferment, Oleth-
3, Oleth-5, Anthemis nobilis
(chamomile), yeast extract
\faex\extrait de levure,
choleth-24, hydrogenated
lecithin, ceteth-24, tocopheryl
acetate, ethylhexyl
methoxycinnamate, hexylene
(continued)
1010 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
glycol, carbomer,
triethanolamine, trisodium
edta, Bht, xanthan gum,
phenoxyethanol, Red
4 (Ci 14700), Yellow
5 (Ci 19140) <Iln39632>
Ageless Facelift cream Coenzyme Q10, Antiaging,
I-Wen Naturals tetrahexyldecyl ascorbate, antioxidant, decrease
glycan booster peptide, matrix of wrinkles
peptide (tripeptide-29),
hydrolyzed oat proteins,
cranberry seed oil
Ameizii Nano Ameizii Nano-gold, peptide, peptide Repair, hydrate, and
Gold Foil Liquid molecules, hyaluronic acid, promote skin
deionized water. whitening
Anti-Age Simply Man Ginseng extract, avocado oil, Treatment of the
Response Cream Match mineral salts Niosomes wrinkle
(pomegranate seed oil,
purified yeast extract,
ribonucleotide
monophosphates
Bepanthol- Bayer Provitamin B5, vitamin E, Antiaging and anti-
Protect Facial HealthCare madecassoside, Glycerin, pollution
Cream Ultra lactate, and glycine, vitamin moisturization
B3, ceramides
C-Vit Liposomal Sesderma Ethyl ascorbic acid, Ginkgo Hydration stimulates
Serum biloba extract, quercetin and the production of
pterostilbene collagen and
promotes skin
elasticity and firmness
Capture Totale Dior Hyaluronic acid, floral complex Removes wrinkles
of longoza, white lily, Chinese and dark spots and
peony, Chinese jasmine has a sunscreen glow
effect
Clear It! Complex Kara Vita Lecithin, complex origanum, Anti-acne
Mist lyphazomes
Chantecaille Chantecaille 24-karat gold and silk, 24-karat gold
Nano Gold bionymph peptide stem cell nanoparticles are
Energizing extract, tripeptide, pullulan/ bound to silk
Cream algae extracts, anti-fatigue microfiber, a natural
complex, butcher’s broom, protein that is
Centella, marigold, Plantago moisturizing,
extract, microalgae extract, antioxidant, and anti-
vitamin E/white inflammatory. These
tea/cornflower extract, borage elements reach the
and evening primrose oil, cellular level where
jasmine/narcissus/mimosa they act as the ultimate
flower waxes
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1011

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
force of healing and
preservation
Chantecaille Chantecaille Bionymph peptide stem cell Prevents aging,
Nano Gold extract, Matrixyl™ 3000 promotes collagen,
Energizing Eye tripeptide, anti-puffiness reduces
Serum complex, 24 K gold and silk, inflammation, and
raspberry stem cell extract, repairs cell growth
lycoskin, antiwrinkle
hexapeptide
Clinicians Clinicians Deionized water, sunflower oil, It nourishes the skin
Complex Complex squalane, glycerine, and prevents
Liposome Face & phospholipids, sodium photoaging
Neck Lotion hyaluronate, tissue respiratory
factors, super oxide dismutase,
cetearyl alcohol, ceteareth-20,
sorbitan, stearate, glyceryl
stearate, octyl
methoxycinnamate, Ppg-15,
stearyl ether, stearic acid,
tocopheryl acetate (vitamin E),
polysorbate 20, dimethicone,
magnesium aluminum silicate,
carbomer, tetrasodium edta,
potassium hydroxide, citric
acid, diazolidinyl urea,
methylparaben, propylparaben
Coni Hyaluronic Coni Beauty Water, Citrus aurantium amara Hydration of the skin
Acid & flower distillate, propylene
Nanoemulsion glycol, phenoxyethanol,
Intensive chlorphenesin, methylparaben,
Hydration Toner glycerin, butylene glycol, yeast
extract, Avena sativa (Oat)
kernel extract,
ethylhexylglycerin, tranexamic
acid、glycosyl trehalose
Hydrogenated starch
hydrolysate, panthenol、
sodium hyaluronate,
methylisothiazolinone,
iodopropynyl butylcarbamate,
hyaluronic acid oligomer,
xanthan gum, styrene/acrylates
copolymer, Peg-60,
hydrogenated castor oil,
fragrance
Coryse Salome Coryse Salome Nanospheres Moisturized cream
Competence Paris
Hydration Ultra-
Moisturizing
Cream
(continued)
1012 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Cutanova-Cream Dr. Rimpler Aqua, squalane, Cannabis Fine lines smoothing,
Nanorepair Q10 sativa seed oil, glycerin, support skin and
C14-22 alcohol, dimethicone, aging restructuring
alcohol, C12-20
alkylglycoside,
cyclopentasiloxane,
galactoarabinan, ubiquinone,
Acmella oleracea extract,
hydrolyzed wheat protein,
hydrolyzed soy protein, Zea
mays oil, tripeptide-1,
tocopherol, carotene, cetyl
palmitate, cetearyl alcohol,
inulin lauryl carbamate,
xanthan gum, dimethicone
crosspolymer, polyglyceryl-3
methylglucose distearate,
hydrogenated palm glycerides
citrate, tetrasodium edta,
caprylic/capric triglyceride,
phenoxyethanol,
methylparaben, ethylparaben,
butylparaben, propylparaben,
isobutylparaben, parfum
Cutanova Cream Dr. Rimpler Aqua, squalane, dimethicone, UV protection,
Nanovital Q10 Cannabis sativa seed oil, antiaging therapy,
cyclopentasiloxane, glycerin,
octyldodecanol, Helianthus
annuus seed extract, cetearyl
alcohol, titanium dioxide,
arachidyl alcohol, ubiquinone,
hydrolyzed wheat protein,
hydrolyzed soy protein, Zea
mays oil, panthenol, ursolic
acid, ole anoic acid,
tripeptide-1, tocopherol,
sodium lactate, carotene,
arachidyl glucoside, cetearyl
glucoside, behenyl alcohol,
inulin lauryl carbamate,
dimethicone crosspolymer,
xanthan gum, caprylic/capric
triglyceride, cetyl palmitate,
aluminum tristearate,
aluminum hydroxide,
tetrasodium edta,
hydrogenated palm glycerides
citrate, polyglyceryl-3
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1013

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
methylglucose distearate,
phenethyl alcohol, alcohol,
phenoxyethanol,
methylparaben, ethylparaben,
butylparaben, propylparaben,
isobutylparaben, parfum
Decorte Moisture Decorte Water (aqua), butylene glycol, Hydrates, improves,
Liposome Eye glycerin, glycosyl trehalose, and lightens the
Cream hydrogenated lecithin, sensitive eye skin
alcohol, hydrogenated starch
hydrolysate, Ginkgo biloba
leaf extract, Lagerstroemia
speciosa leaf extract, oyster
extract, palmitoyl
pentapeptide-4, Panax
ginseng root extract,
polyglutamic acid, sodium
hyaluronate, tocopheryl
nicotinate, carbomer,
cholesterol, hydroxypropyl
methylcellulose, polysorbate
20, sodium hydroxide,
methylparaben, fragrance
(parfum)
Decorte Moisture Decorte Water (aqua), butylene glycol, Moisturizer
Liposome Face glycerin, squalane,
Cream hydrogenated lecithin,
triethylhexanoin, Akebia
trifoliata stem extract,
Asparagus officinalis stem
extract, Fagus sylvatica bud
extract, Impatiens balsamina
flower/leaf/stem extract, royal
jelly extract, Vitis vinifera
(grape) leaf extract, alcohol,
carbomer, cholesterol,
dimethicone, hydroxypropyl
methylcellulose, sodium
hydroxide, xanthan gum,
methylparaben,
phenoxyethanol, fragrance
(parfum)
Eusu Niosome Eusu Extracts of Indian gooseberry Skin whitening
Makam Pom particles, makhampom extract
Whitening Facial
Cream
(continued)
1014 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Eye Contour Euoko Rose moss, Asiatic It depends on the
Nanolift pennywort, lupine technology of
lipopeptides, sweet black tea, nanocapsules.
Eyeliss, Rhodiola, sugar beet, Nanocapsules are
ceramide-2, hyaluronic acid, raised and seven
dermaxyl fighters with fine
lines, wrinkles, and
puffiness are joined
instantly and longer.
This offers
immediate and long-
term fluidity, adds
more radiance to the
eye area, and reduces
the presence of dark
circles and puffiness
Eye Tender Kara Vita Argireline ®, Matrixyl™ 3000, It contains
Pepha ®-Tight, Tyrostat™-09, nanospheres,
Velvet Veil™, olive fruit oil, provides 13 bioactive
Canadian Willowherb™ agents, including
extract, green tea extract, proven, wrinkle-
squalane, shea butter, reduction peptides, to
tocopheryl acetate (vitamin stimulate fibroblasts,
E), hyaluronic acid, alpha build collagen, and
bisabolol, lyphazomes lighten the skin
Hydralane Ultra Hydralane Paris Marine collage nanospheres Hydrating and deep
Moisturizing Day moisturizing
Cream
Intensive Serum Dr. Rimpler Q10 (Vitamin C And E) Fights signs of aging,
Nanorepair Q10 Nanoliposome serum antiwrinkle
Iope Supervital Amore Pacific Phyllostachys bambusoides Face lines, blandness
Extra Moist Eye juice, cyclopentasiloxane, and low elasticity are
Cream dimethicone, glycerin, removed
butylene glycol,
cyclohexasiloxane, alcohol,
water, PEG-75, PEG-10
dimethicone, biosaccharide
gum-1, squalane, niacinamide,
acetyl glucosamine,
hydrolyzed Phyllostachys
bambusoides, hydrolyzed
Camellia sinensis leaf, Glycine
soja (soybean) seed extract,
Nelumbo nucifera flower
extract, Opuntia coccinellifera
fruit extract, hesperidin,
caffeine, theanine, kaempferol,
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1015

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Camellia sinensis flower
extract, natto gum, beta-glucan,
sodium hyaluronate,
tocopherol, phytantriol,
epigallocatechin gallate,
disteardimonium hectorite,
lauryl PEG-9
polydimethylsiloxyethyl
dimethicone, polysilicone-11,
propanediol, dimethiconol,
dimethicone/vinyl dimethicone
crosspolymer, stearyl behenate,
polyglyceryl-3 methylglucose
distearate, hydroxypropyl
bispalmitamide mea, inulin
lauryl carbamate, polysorbate
20, PEG-15 pentaerythrityl
tetra (laureth-6 carboxylate),
sodium chloride, poloxamer
407, Ammonium
acryloyldimethyltaurate/Vp
copolymer, 1,2-hexanediol,
disodium edta,
ethylhexylglycerin,
phenoxyethanol, fragrance
Kerstin Florian Kerstin Florian Vitamin C, beeswax, shea Moisturizer
Rehydrating butter, hyaluronic acid,
Liposome Day vitamin E, dimethicone
Crème
Lancoˆme Lancoˆme Avobenzone 3%, octisalate Formulated with
RenergieMicrolift 5%, octocrylene 7% water, nanoparticles made
dimethicone, glycerin, of colloidal silica and
hydrogenated polyisobutene, soy protein for the
beeswax, poly C10-30 alkyl nearest face lifting
acrylate, sucrose stearate, effect
Saccharomyces/xylinum/
black tea ferment, sodium
polyacrylate, hydrolyzed
linseed extract, hydrolyzed
soy protein, hydrolyzed
hyaluronic acid, sodium
hydroxide, sodium benzoate,
Red 4, stearic acid,
phenoxyethanol, adenosine,
acetyl tetrapeptide-9,
PEG-100 stearate, palmitic
acid, silicam chlorphenesin,
(continued)
1016 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Yellow 5, dimethicone/vinyl
dimethicone crosspolymer,
dimethiconol, limonene,
benzyl alcohol, linalool,
caprylyl glycol, acrylates/
C10-30 alkyl acrylate
crosspolymer, geraniol,
disodium stearoyl glutamate,
disodium edta, citronellol,
aluminum starch
octenylsuccinate, coumarin,
glyceryl stearate, fragrance
Lancôme Soleil Lancoˆme Vitamin E, Moringa extract, Revitalizing,
Soft-Touch Anti- Edelweiss extract, free of antiaging
Wrinkle Sun sulfates SLS and SLES,
Cream SPF 15 formaldehyde, formaldehyde-
releasing agents, phthalates,
mineral oil, retinyl palmitate,
coal tar, hydroquinone,
triclosan, and triclocarban, and
contains less than one percent
of synthetic fragrances
LR Nano Gold LR Zeitgard Aqua (water), caprylic/capric Protection of skin
Day & Silk Day triglyceride, butylene glycol, against UV rays and
Cream dicaprylyl carbonate, Olus the premature aging
(vegetable) oil, cetearyl of the skin caused by
alcohol, ethylhexyl light
methoxycinnamate,
diethylamino hydroxybenzoyl
hexyl benzoate, sodium
stearoyl glutamate,
dimethicone, hydroxide
tocopheryl acetate, carbomer,
silica, cyclodextrin, perfume
(fragrance), glycogen,
titanium dioxide, xanthan
gum, phenoxyethanol,
tocopherol, dimethicone
crosspolymer, fibroin,
ethylhexylglycerin,
triethoxycaprylylsososetine,
acctosidosos, arctisidososos,
arctosidososos, arctosidosos,
seed extract, gold, acetyl
hexapeptide-20, hexylene
glycol, fructose, glucose,
sucrose, urea, dextrin, alanine,
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1017

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
glutamic acid, aspartic acid,
hexyl nicotinate, limonene
Lumessence Eye Aubrey Aqua, glycerin, Rosa Antiwrinkle, firming
Cream Organics rubiginosa (Rosa mosqueta)
seed oil, Camellia sinensis
leaf oil, Avena sativa (oat)
kernel extract, Oenothera
biennis (evening primrose)
oil, Laminaria digitata
extract, Secale cereale (rye)
seed extract, Butyrospermum
parkii (shea) butter*,
carrageenan, hydrogenated
lecithin, sodium PCA, Citrus
grandis (grapefruit) peel oil,
Lavandula angustifolia
(lavender) flower, sodium
benzoate, Citrus grandis
(grapefruit) extract, potassium
sorbate, ascorbic acid, citric
acid, proline, tocopherol,
glycine, lysine, tocopheryl
acetate, xanthan gum
Mayu Niosome Laon Cosmetics Ginseng Whitening and
Base Cream moisturizing
Nano antiaging PHYTOMO Not available The product of daily
cream use is strong, smooth
skin. The skin is
gradually reduced to
fine lines and wrinkles
caused by drying out.
Nano Anti-Aging Nano by Not available Nano cream that
Serum Saurina treats aging and
improves skin
elasticity, based on
semi-light texture
Nanocream Sinerga Combination of vegetable- Wet wipes
based substances, lipoamino
acids, and palm glycerides, for
microemulsions with very low
interfacial energy. It is
indicated for very fluid O/W
emulsions with low droplets
size (100–300 Ƞm).
Nanoemulsions made using
(continued)
1018 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
nanocream show
extraordinary stability,
sharply defined particle size,
and low viscosities
Nano Gold Chantecaille 24-K gold and silk, Matrixyl™ Ever thin, pure gold
Firming 3000 tripeptide, apple stem nanoparticles are
Treatment cells complex, microalgae connected to firm and
Dunaliella salina extract, tone silk microfibers
palmitoyl dipeptide 5 And while giving you
6, Imperata cylindrica extract, amazing anti-
vitamin E/white tea extract/Co inflammation, cure,
Q10, jasmine/narcissus/ and age-defying
mimosa flower waxes strength
Nano-Lipobelle Mibelle Combination of defined Antiwrinkle,
H-AECL Biochemistry, vitamins and polyunsaturated antiaging
Switzerland. fatty acids
Nano-Lipobelle Mibelle 5% of coenzyme Q10 and Anti-aging, anti-
H-EQ10 cream Biochemistry, 10% of vitamin E acetate in a inflammatory
Switzerland nanoemulsion
Nanolipid CLR Water, Ribes nigrum (black Revitalizing,
Restore CLR Chemisches currant) seed oil, Copernicia antiaging
Laboratorium cerifera (carnauba) wax,
Dr.Kurt Richter decyl glucoside, solid lipid
GmbH nanoparticles containing 27%
blackcurrant seed oil
Nanosphere Plus DermaSwiss Deionized water (aqua), Antiaging and
glycerin, butylene glycol, antiwrinkle.
saccharide isomerate, Nanosphere Plus
hydrolyzed collagen, serum has been
hydrolyzed elastin, allantoin, explicitly developed
carbomer, sodium hyaluronate for the regeneration
(hyaluronic acid), a-lipoic and preservation of
acid, Malus domestica fruit skin cells by natural
(apple) cell culture, stem cells. The use of
polysorbate-20, palmitoyl the cells of a rare
oligopeptide, palmitoyl Swiss apple.
tetrapeptide-7, xanthan gum, Nanosphere Plus
lecithin, phenoxyethanol, protects longevity
lactic acid, Passi ora edulis and combats
(passion fruit) flower extract, chronological aging
urea, Rosa centifolia (rose)
flower extract, acid-
hydrolyzed vegetable protein,
jojoba esters,
ethylhexylglycerin
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1019

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Nanovital Vitacos Arbutin, oriental herb extracts Skin moisturizing,
Vitanics Crystal Cosmetics of Lonicera japonica flower, elastic, and lightning
Moiture Cream ginseng, Glycyrrhiza glabra, effects
Angelica acutiloba fruit,
Morus alba root, ceramide,
ursolic acid, allantoin,
Dl-panthenol, hyaluronate
Natural NOW Solutions Water (aqua), Aloe Maintenance of
Progesterone barbadensis leaf juice, healthy feminine
Liposomal Skin glyceryl stearate SE, glycerin, balance
Cream stearic acid (vegetable
source), cetearyl alcohol,
caprylic/capric triglyceride,
cetearyl alcohol and cetearyl
glucoside, Helianthus annuus
(sunflower) seed oil,
Simmondsia chinensis
(jojoba) seed oil, natural
progesterone (USP grade),
phenoxyethanol and
ethylhexylglycerin, xanthan
gum, Rosmarinus officinalis
(rosemary) leaf extract,
potassium sorbate, panthenol,
retinyl palmitate (vitamin A),
Daucus carota sativa (carrot)
seed oil, tocopherol (vitamin
E) (soy-free), Panax ginseng
root extract, Serenoa
serrulata (saw palmetto) fruit
extract, Chamomilla recutita
(Matricaria) flower Extract,
citric acid, Cymbopogon
exuosus (lemongrass) Oil
Niosome+ Lancome Not available Foundation cream,
clear and white skin
tone
Niosome+ Lancome Not available Removes wrinkles
Perfected Age
Treatment
Nuvoderm Nano Nuvoderm Deionized water, glycerin, Reduces signs of
Gold Anti-Aging methyl glucoside phosphate aging, including fine
Lifting Serum proline lysine copper lines and wrinkles.
complex, gold powder, coffee Promotes the
seed (Coffea arabica) extract, development of
Aloe barbadensis leaf juice, collagen and elastin.
Cucurbita pepo (pumpkin)
seed extract, hyaluronic acid,
(continued)
1020 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
carbomer, triethanolamine,
phenoxyethanol, caprylyl
glycol, potassium sorbate,
hexylene glycol
O3+ 24K Gold O3+ Nano Gold Particles, Optic Makes skin glow and
Gel Cream Caviar, Berries shine
Olivenol Anti Dr. Theiss/ Aqua, PEG-8 beeswax, Olea Antiwrinkle and skin
Falten Medipharma europaea fruit oil, Triticum tightening
Pflegekontrat Cosmetics vulgare germ oil, Persea
gratissima oil, Prunus
amygdalus dulcis oil,
glycerol, methylpropanediol,
perfume, caprylyl glycol,
carbomer, disodium edta,
phenylpropanol, ascorbyl
palmitate, lecithin,
tocopherol, hydrogenated
palm glycerides citrate,
sodium hydroxide, linalool,
limonene, citronellol,
eugenol, benzyl salicylate,
geraniol
Orogold 24K Orogold Cyclopentasiloxane, Restores moisture
Nano Ultra Silk dimethicone/vinyl loss, reduces
Serum dimethicone crosspolymer, wrinkles and fine
Peg/Ppg-20/15 dimethicone, lines, and keeps skin
tetrahexyldecyl ascorbate, healthy
Helianthus annuus
(sunflower) seed oil, Prunus
amygdalus dulcis
(sweet almond) Oil, Triticum
vulgare (wheat germ) germ
oil, Sesamum indicum
(sesame) seed oil, gold,
Laminaria japonica
(seaweed) extract, Chlorella
vulgaris extract, Laminaria
digitata (kelp) extract,
Helichrysum arenarium
(everlasting) extract, Citrus
aurantifolia (lime) peel
extract, Rosmarinus
officinalis (rosemary) leaf
extract, yeast, parfum, benzyl
salicylate, linalool
Phyto-Endorphin Rhonda Allison Aqua (water), Butyrospermum Softens and smoothes
Hand Cream parkii (shea butter), C10-30 the skin
cholesterol/lanosterol esters,
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1021

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
caprylic/capric triglyceride,
Bellis perennis (daisy) flower
extract, glycerin, palmitic
acid, stearic acid, cetearyl
olivate, sorbitan olivate, Vitex
agnus castus (Monk’s pepper-
casticin) extract, glyceryl
stearate, alcohol denatatured,
lecithin, D-alpha tocopherol,
cetearyl alcohol, polysorbate
60, ascorbyl tetraiso-
palmitate, cyclodextrin,
myristic acid, retinyl
palmitate, Zea mays (corn) oil,
Simmondsia chinensis
(jojoba) seed oil, Olea
europaea (olive) fruit oil,
Lavandula angustifolia
(lavender) oil, Glycine soja
(soybean) oil, Citrus
aurantium dulcis (sweet
orange) peel oil, Prunus
amygdalus dulcis
(sweet almond) oil, Cananga
odorata (ylang ylang) flower
oil, Pelargonium graveolens
(geranium) flower oil, Vanilla
planifolia fruit oil, Rosa
damascena flower oil, Aloe
barbadensis (Aloe vera) leaf
juice powder, citric acid,
allantoin, sodium hydroxide,
potassium sorbate, cetyl
alcohol, squalane, xanthan
gum, calcium gluconate,
gluconolactone, sodium
benzoate, caprylyl glycol,
phenethyl alcohol, trisodium
ethylenediamine disuccinate
Phyto NLC Sireh Emas Purified water, propylene Skin rejuvenation,
Serum glycol, unsaponifiables olive hyperpigmentation,
oil, PEG-8 beeswax, hydrating, and
dimethicone, Cucumis firming of the skin
sectivus extract, Citrus
medica Limonum peel extract,
sodium cocoamphoacetate,
Prunus, Armeniaca oil,
Curcuma xanthorrhiza (SFE
(continued)
1022 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
extract), polyacrylamide and
C 13-14 isoparaffin and
laureth-7, phenoxyethanol
and ethylhexyglycerin, and
capryly glycol
Precision- Chanel Almond extract combined Moisturizer
Solution with micelles
Déstressante
Solution Nano
Émulsion Peaux
Sensitivity
RevitaLift Anti- L’Oreal Formula 917038/10, aqua/ Pro-Retinol A, an
Wrinkle and water, cyclohexasiloxane, effective antiwrinkle
Firming Face and glycerin, paraffinum agent encapsulated in
Neck Contour liquidum/mineral oil, nanosomes, enriches
Cream propanediol, myristyl RevitaLift
myristate, Shorea robusta formulation. Deep
seed butter, stearic acid, within the epidermis,
palmitic acid, Peg-100, nanosomes penetrate
stearate cera alba/beeswax, through the wrinkles
glyceryl stearate, Peg-20,
stearate acrylamide/sodium
acryloyldimethyltaurate
copolymer, cetyl alcohol,
phenoxyethanol, stearyl
alcohol hydrolyzed soy
protein isohexadecane,
caprylyl glycol, glycine soja
protein/soybean protein,
parfum/fragrance,
acrylonitrile/methyl
methacrylate/vinylidene
chloride copolymer,
triethanolamine, polysorbate
80, retinyl palmitate,
pentaerythrityl tetra-Di-T-
Butyl
hydroxyhydrocinnamate,
acetyl trifluoromethylphenyl
valylglycine, myristic acid,
pentylene glycol, sorbitan
oleate, sodium cocoyl
glutamate, faex extract/yeast
extract, ethylhexylglycerin,
sodium benzoate, isobutane
phenethyl alcohol, benzyl
salicylate, benzyl alcohol,
potassium sorbate, benzyl
benzoate, Centella asiatica
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1023

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
extract, linalool, hexyl
cinnamal, citronellol,
Limonene, geraniol, alpha-
isomethyl ionone, salicyloyl
phytosphingosine, tocopherol
RevitaLift L’Oreal Aqua/water, glycerin, RevitaLift is a unique
Double Lifting cyclohexasiloxane, alcohol dual-action treatment
denat, isocetyl stearate, that straightens the
butylene glycol, lithium skin instantaneously
magnesium sodium silicate, and fights wrinkles
Peg-100 stearate, Peg-20 effectively. It
stearate, stearic acid, stearyl contains the
alcohol, linalool, cera alba/ nanosomes
beeswax, geraniol, glyceryl Pro-Retinol A
stearate, glycine soja protein/
soybean protein,
triethanolamine,
isohexadecane, Helianthus
annuus seed oil/sunflower
seed oil, silica, coumarin,
limonene, citral, citronellol,
acetyl trifluoromethylphenyl
valylglycine, polymethyl
methacrylate, polysorbate
80, polyurethane-2,
acrylamide/sodium
acryloyldimethyltaurate
copolymer, cetyl alcohol,
butylphenyl methylpropional,
benzyl salicylate, retinyl
palmitate, methylparaben,
chlorhexidine digluconate,
caprylyl glycol, ethylparaben,
benzyl alcohol, Ci 14700/Red
4, Ci 17200/ Red 33, parfum/
fragrance, alpha-isomethyl
ionone, hydroxyisohexyl 3-
cyclohexene carboxaldehyde,
sodium dehydroacetate,
phenoxyethanol,
chlorphenesin
Rovisome ACE Rovi Cosmetics Encapsulated antioxidative Antiaging, wrinkle
Plus International vitamins reduction
GmbH
Russell Organics Russell Vegetable oils and organic Rejuvenate and
Liposome Organics floral water blended with hydrate. It
Concentrate liposomes, superoxide strengthens, softens
dismutase, beta-glucan from and softens the skin;
oats
(continued)
1024 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Sircuit Addict Sircuit Skin Hamamelis virginiana (witch Revitalizing, anti-
Firming Cosmeceuticals hazel) water, Glycine soja aging.
Antioxidant Inc. (soybean) protein, glycerin,
Serum aqua (water), alcohol denat.,
tocopheryl acetate (D-alpha),
polysorbate 20, ergothioneine
(L), Polygonum cuspidatum
(giant knotweed) extract,
phenyl T-butylnitrone (spin
trap), Epigallocatechin
gallate, Camellia oleifera
(green tea) leaf extract,
Peumus boldus leaf extract,
Cassia angustifolia seed
polysaccharide, Vitis vinifera
(grape) seed extract,
Saccharomyces/xylinum/
black tea ferment, Glycine
soja (soybean) oil,
Macadamia ternifolia seed
oil, Lavandula angustifolia
(lavender) oil, Rosa
damascena flower oil,
Jasminum officinale (jasmine)
oil, Citrus aurantium dulcis
(orange) peel oil, Cananga
odorata (ylang ylang) flower
oil, Citrus grandis (grapefruit)
peel oil, Aleurites moluccana
seed oil, Santalum
austrocaledonicum
(sandalwood) wood oil,
Buddleja davidii meristem
cell culture, wine extract,
glutathione (L), carnosine (L),
carnitine (L), glucosamine
HCI (D), whey protein,
superoxide dismutase,
xanthan gum,
hydroxyethylcellulose, citric
acid, phytic acid, potassium
sorbate,
hydroxyethylcellulose
Soleil Soft-Touch Lancoˆme Not available It contains
Anti-Wrinkle Sun nanocapsules which
Cream SPF 15 contribute to
effectively preserving
the young skin. SPF
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1025

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
15 provides excellent
sun protection. It
contains exclusive
ingredients to ensure
a durable impact.
Soosion Facial Soosion Solid lipid nanoparticles Antiwrinkle cream
Lifting Cream
SLN Technology
Surmer Crème Isabelle Aqua, Aleurites moluccana Intensely hydrating
Legère Nano- Lancray seed oil, squalane,
Protection dimethicone, glycerin,
cetearyl alcohol,
octyldodecanol, arachidyl
alcohol, cyclopentasiloxane,
polyglyceryl-3 methylglucose
distearate, Ximenia americana
seed oil, hydrogenated
coconut oil, titanium dioxide,
propylene glycol, behenyl
alcohol, Cocos nucifera fruit
juice, Helianthus annuus seed
oil, Magnolia biondii bark
extract, cetyl palmitate,
Tephrosia purpurea seed
extract, inulin lauryl
carbamate, arachidyl
glucoside, Aleurites
moluccana nut oil, caprylyl
glycol, dimethicone
crosspolymer, tocopherol,
Salix alba bark extract,
xanthan gum, aluminum
tristearate, aluminum
hydroxide, Camellia sinensis
leaf extract, Citrus grandis
fruit extract, propolis extract,
Morinda citrifolia fruit
extract, carotene, tetrasodium
edta, Gardenia tahitensis
flower, Chamomilla recutita
extract, glutamylamidoethyl
Indole, Thujopsis dolabrata
branch extract, sodium
benzoate, potassium sorbate,
Zea mays oil, butylene glycol,
alcohol, phenoxyethanol,
parfum, Ci 42053
(continued)
1026 R. J. R. Samdavid Thanapaul et al.

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
Surmer Masque Isabelle Aqua, cetearyl alcohol, Weak and dehydrated
Crème Nano- Lancray glycerin, octyldodecanol, skin, wrinkles and
Hydratant squalane, Aleurites fine lines reduction
moluccana seed oil,
hydrogenated coconut oil,
Ximenia americana seed oil,
cetyl palmitate,
cyclopentasiloxane, arachidyl
alcohol, Aleurites moluccana
nut oil, Cocos nucifera fruit
juice, Magnolia biondii bark
extract, Salix alba bark
extract, Tephrosia purpurea
seed extract, Citrus grandis
fruit extract, Camellia
sinensis leaf extract, Gardenia
tahitensis flower, Propolis
extract, Chamomilla recutita
extract, Thujopsis dolabrata
branch extract, Helianthus
annuus seed oil, tocopherol,
Calophyllum inophyllum seed
oil, Zea mays oil, carotene,
butylene glycol, behenyl
alcohol, cetearyl glucoside,
inulin lauryl carbamate,
caprylyl glycol, arachidyl
glucoside, dimethicone
crosspolymer, xanthan gum,
polyglyceryl-3 methylglucose
distearate, alcohol,
glutamylamidoethyl indole,
tetrasodium edta,
phenoxyethanol, parfum, Ci
42053
Tony Moly Nano Tony Moly Nano-gold ingredient, silky Whitening of the skin
Gold BB Cream amino acids reduces wrinkles and
SPF 50 PA+++ prevents UV rays
Vital Marie Louise Water, butylene glycol, Nutrition and
Nanoemulsion glycerin, absorbyl glucoside, miniaturization
Α-VC dimethicone, squalane,
behenyl alcohol, stearic acid,
butyl alcohol, arginine, Ppg-5-
Cetheth-10 phosphate, retinyl
palmitate, alpha-arbutin,
vitamin A oil, tocopherol,
ceramide 1, ceramide
2, ceramide 3, alcaligenes
(continued)
44 Nanobiotechnology-Based Anti-aging Products 1027

Table 3 (continued)
Manufactured
Name of the and marketed
product by Key ingredients Benefits
polysaccharides, bittern,
stearyl glycyrrhetinate,
phytosteryl macadamiate,
hydrogenated lecithin, lecithin,
Glycine soja (soybean) sterol,
lecithin, superoxide dismutase,
sodium citrate, xanthan gum,
phytic acid, neopentyl glycol
dicaprate, Peg-100
hydrogenated castor oil,
hydroxyethylcellulose,
caprylic/capric triglyceride,
tricaprylin, Bht, polymethyl
methacrylate, polysorbate
80, methylparaben,
propylparaben
Zelens Fullerene Zelens Retinol and dimethylmethoxy Fullerene C-60 is a
C-60 Night chromanol, synthetic natural microscopic
Cream vitamin E, argireline (acetyl carbon type with
hexapeptide-8), AH8 significant
(Or AH3 Or argireline) Freeze antioxidant properties
24:7, Avetone And Athena
7 Minute Lift

Conclusion

In the era of modern cosmetic distribution networks, nanobiotechnology has been used
to supply the products by different carriers. Nano-biomaterials have been used in
antiaging formulations for more than a decade with promising improvements and
benefits over traditional formulations. Currently, the nano-based biomaterials are com-
monly used in nearly every major cosmetics industry. Consequently, the market for
nanobiotechnology-based topical antiaging products has increased, and there is still
scope for the protection of intellectual property for new and enhanced antiaging
products. This chapter discussed in detail about the usage of nanobiotechnology-based
materials for the efficient supply of cosmeceutical ingredients in antiaging products.

Important Websites

1. https://www.happi.com/issues/2015-09-01/view_anti-aging%2D%
2Dcosmeceutical_corner/how-nanotechnology-enhances-anti-aging-product-
efficacy/
2. https://www.news-medical.net/health/Nanotechnology-Against-Aging.aspx
1028 R. J. R. Samdavid Thanapaul et al.

3. https://www.nanowerk.com/nanotechnology-in-cosmetics.php
4. http://sustainable-nano.com/2020/03/20/nanotechnology-for-younger-healthier-
skin/

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Nanocosmeceuticals: Novel and Advanced
Self-Care Materials 45
Shikha Gulati, Sanjay Kumar, Rachit Wadhwa, Shweta Lamba, and
Kanchan Batra

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1032
Major Classes of Cosmeceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1034
Progress in Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1037
Nanotechnology-Based Cosmeceuticals: Novel and Advanced Self-Care Materials . . . . . . . . . 1037
Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Cerium Oxide (CeO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1040
Fullerenes/Buckyballs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1041
Gold Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1041
Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1042
Nanocapsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1043
Nanostructured Lipid Carriers and Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1044
Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045
Silica Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1046
Silver Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1046
Titanium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1046
Zinc Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1047
Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1047
Routes of Exposure to Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1048
Regulations for Nanocosmeceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
Demerits of Nanocosmeceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1051
Conclusion and Future Outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1052
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053

S. Gulati (*) · S. Kumar · R. Wadhwa · S. Lamba

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
K. Batra
Department of Zoology, Kalindi College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 1031

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_99
1032 S. Gulati et al.

Abstract
Nanotechnology has been gaining interest by the day in the field of research and
development. It comes with a baggage of solutions in order to overcome certain
drawbacks of the traditional technology and formulation of products. Over the years,
the cosmeceutical industry, which includes cosmetics combined with pharmaceutical
ingredients to exhibit therapeutic effects on the skin, has become one of the fasted
growing self-care industries which comes with attractions like skin care and anti-
aging solutions. The increasing popularity of nanoparticles in the cosmeceutical
industry is due to their minute size and extremely high surface area-to-volume
ratio. In modern times, consumers are actively investing in cosmeceuticals for
appearance enhancement. So, their common problems like wrinkles, dandruff, hair
damage, photoaging, hyperpigmentation, etc. are required to be addressed profi-
ciently. In this regard, nanotechnology has been playing a very important role by
providing active ingredients with therapeutic benefits. The application of nanotech-
nology has also increased transparency, and its fusion with Cosmeceuticals has
served as an efficient replacement and as novel nanocarriers such as liposomes,
nanoemulsions, solid lipid nanoparticles, nanocapsules, nanospheres, etc. for the
conventional drug delivery systems. The processes of skin penetration, sustainable
drug release, better stability, high entrapment, and targeting have become more and
more efficient and been enhanced with the use of these modern nanocarriers. In this
chapter, the role of nanotechnology in the cosmeceutical industry is discussed. The
applications and fabrication of novel nanocosmeceuticals are highlighted along with
their advantages over conventional products.

Keywords
Nanotechnology · Cosmeceutical · Drug delivery · Nanocarriers · Nano-
cosmeceutical

Introduction

The product which combines the properties of cosmetics and therapeutic actions is
given a word “cosmeceutical” [1]. They are basically those cosmetic products that
are incorporated with the biologically active ingredient with therapeutic benefits on
the surface applied. These products are utilized for the purpose of appearance
enhancement [2]. Cosmeceuticals are often confused with cosmetics [3]. Cosmetics
clean the skin and make it look more beautiful, while cosmeceuticals contain active
ingredients that change the physical structure and functioning of the skin.
Cosmeceuticals cannot treat skin problems. They enhance beauteousness and are a
non-invasive way to improve the appearance and texture of the skin. They are not
considered drugs, and hence, one does not need any prescription to buy them. The
cosmeceutical industry is developing at a great pace. The reason behind this fast
development is the desire to look beautiful and attractive and the increasing
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1033

consciousness of consumers to shift towards safe and reliable products for their skin
[4]. This industry has seen a decline due to COVID-19, but the impact is not as
severe as witnessed by many other industries. Different cosmeceuticals are in use
since time immemorial. Turmeric was among one of the oldest ingredients to be used
as a cosmeceutical. With the passage of time, different materials were taken into use
as cosmeceuticals much before nanotechnology came into play. Examples of con-
ventional cosmeceuticals include alpha-hydroxyl acids, beta-hydroxyl acids, reti-
noids, antioxidants, and de-pigmenting agents. With the development of technology,
the dark side of these cosmeceuticals was recognized. These have many side effects
like rashes on the body, constant itching, and pain. These cosmeceuticals cannot
penetrate deep inside the body, have a bad odor, and are expensive. Thus, the
intervention of nanotechnology was a great boon for the cosmeceutical industry.
The word “nanotechnology” is derived from two separate terms, namely, “technol-
ogy” and the Greek word “nano” whose literal meaning is “dwarf.” It is a young
technology that basically involves the formulation, production, and development of
particles with superior characteristics and functioning, in the size range of 1 to 100 nm.
This technology opens up huge future prospects in the twenty-first century and is
emerging in various fields of physics, chemistry, ecology, biology and biochemistry,
engineering and their further branches like pharmaceutics and cosmeceuticals, etc. It is
believed that nanotechnology has been exploited for the purpose of dying hair right
back from 4000 BC by Egyptians, Greeks, and Romans [2, 5, 6]. Nanotechnology is
basically based on two approaches which are top-down and bottom-up approaches.
The top-down approach refers to the minimization of larger structures into nano-
structures without compromising their fundamental properties, whereas in the bottom-
up approach, assembling and self-assembling of atomic and subatomic particles is
done to obtain nanosized matter [7]. Talking about the bulk properties of nanoparticles,
they are hard, tough, and flexible. Their novel characteristics also involve their
transparency, hydrophobic nature, and bioavailability. As compared to other macro-
scopic matter, nanoparticles attain a vital property that they have a maximum percent-
age of their ingredient atoms on their surface [8, 9]. Synthesis of nanomaterials is done
in large quantities. Most nanoparticles are composed of crystals or grains, i.e.,
polycrystalline [10]. Over the years, a lot of research has been done for the efficient
synthesis of nanomaterials. Some of the excessively discussed methods include
plasma ionization, electrodeposition, sol-gel synthesis, chemical vapor deposition,
ball milling, etc. [11]. A revolutionary achievement in sciences to be mentioned is
the strength of CNTs, which is 100 times more than that of steel with still retaining
about 16.67% of the weight of steel. Nanotechnology is emerging across various fields
as above mentioned. It has created a huge impact on more industrial sectors, like
nanomedicine, aeronautics, plastic industry, etc. Nanotechnology is contributing and
serving assistance in more branches like energy transformation, chemical gas sensing,
functional polymer fillers, manufacturing of sun blockers, nanotubes, nanowires,
production of textiles, and catalytic processing [8]. Properties like super strength and
resistivity toward corrosion make nanomaterials suitable and superior choice for being
used in power systems in mechanical engineering. Their advanced properties like
super conductance at room temperature, eco-friendly nature, etc. make them utilizable
1034 S. Gulati et al.

for green energy areas such as water, wind, and solar energies, controlling the usage of
fossil fuels [12]. With more advancement, the development of novel tools such as
nano-biosensors, nano-barcode, microarray, biochip, and nanorobots has impacted the
medical sciences sector too. Detection of diseases like cancer, cardiac issues, diabetes,
muscular problems, and skeletal diseases has been eased [13]. Increased food produc-
tion, food preservation, and quality enhancement are some more areas where nano-
technology has created a revolution by providing better nutrition value [14]. Talking of
pharmaceuticals, controlled drug release to secure therapeutic efficacy is another area
in which nanotechnology is assisting by providing new nanoparticles for the target
drug delivery systems. Neurodegenerative disorders such as Alzheimer’s disease,
tumors, etc. can be treated with controlled drug release which secures therapeutic
efficacy is another breakthrough in nanotechnology [15]. Application of nanotechnol-
ogy in various fields have been and are being studied indicating a great potential of
usage for the development and formulation of various novel nanomaterials. Nano-
particles used in the cosmeceutical industry prove to be superior to conventional
sources in many aspects. They allow deep skin penetration and an effective release
of ingredients, which contributes to better pharmaceutical and cosmetic effects.
Attaining a set of advanced properties, nanocosmeceuticals prove to be more efficient
for utilization in classes such as anti-aging, make-up, nails, deodorants, oral care,
sunscreens, and hair care products [16]. In spite of the positive aspects, cosmeceuticals
have various short-term and long-term health hazards [17]. Size, structure, and surface
properties become the cause for the toxicity levels. The lack of prominent regulations
for cosmeceutical products causes a sense of insecurity and safety concerns. Certain
measures like specification and testing of ingredients used must be made necessary in
order to prevent their poisoning effect and to make sure whether they are backed by
science for application on skin or not. In this chapter, we have discussed the influence
of nanotechnology in cosmeceutical industries and the different nanocarriers which
prove to be advantageous over other conventional cosmeceuticals. Major classes of
cosmeceuticals, regulations, along with their setbacks have been thrown a light as
well [18].

Major Classes of Cosmeceuticals

Cosmeceuticals have been divided into four major classes (Fig. 1a). Each class is
further branched for specific applications (Fig. 1b), which utilizes different assets
provided by different nanocarriers.

• Nail Care: Nail care products based on nanotechnology are far better than
conventional nail care products and possess many advantageous properties
[19]. Nanocosmeceuticals based nail care products are more durable, dry rapidly,
have improved toughness, resistant to chip, and are highly elastic which makes it
a cakewalk to use them. They also have antifungal properties for the prevention
from fungal infections [17]. The nail care nanocosmeceutical products include
nail lacquer. Nail issues occur due to poor care of nails. Keeping nails clean and
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1035

Fig. 1a Major classes of

nanotechnology-based
cosmeceuticals

Hair care Lip care Nail care Skin care

Nail Sun
Conditioner Lipstick
lacquer screen

Shampoo Lip gloss Antiaging

products

Hair styling
Lip volumizer
creams Moisturizurer

Hair serum
Lip balm Anti-acne
products
Hair
colour Skin
cleanser
Growth
stimulators

Fig. 1b Different applications in major classes of cosmeceuticals

dry to keep bacteria and other infection-causing organisms from grouping

beneath the nails, cutting nails in a proper shape (straight across with only slight
rounding at the tip), and using a fine-textured file to keep nails shaped and free of
snags are some of the ways to maintain nail health [20, 21].
1036 S. Gulati et al.

• Lip Care: This is one of the most promising classes of cosmeceuticals. Lips are a
significantly vulnerable part of a human body as the skin is so thin, and thus, they
are first to present signs of dryness. In the winter season, dry air and the cold
temperature have a drying result on the skin which makes the lips to clench and
sometimes on stretching leads to pain and bleeding. The nanotechnology-based
lip care products soften the lips, prevent them from drying, and shield them from
external exposure. Lip care nanocosmeceutical products include lip balm, lip
volumizer, lipstick, and lip gloss [18]. Many nanoparticles can coalesce into
lipstick and lip balm which provides a soothing effect to lips by impeding
trans-epidermal water loss, prevents migration of pigments from lips, and main-
tains color for a longer duration [17]. Lip volumizer mostly contains liposomes
which increase lip volume, hydrates, and outlines the lips and fill wrinkles in the
lip contour [20].
• Hair Care: Though hair is not a vital organ of our body, it can be an indicator of
individual health. For example, brittle hair may be a marker for thyroid disease or
nutritional deficiency or thinning of hair may represent hormonal imbalances.
Hair shapes the appearance of a person, and loss of hair can lead to a loss of self-
esteem and induce a feeling of inferiority and helplessness, and thus taking good
care of our hair is important [22]. Nanotechnology-based products of hair include
conditioners, shampoo, hairstyling creams, hair serums, hair color, and growth
stimulators. The unique and intrinsic properties of nanomaterials help in targeting
hair follicle and shaft targeting [17]. Major nanomaterials used in hair care
products are liposomes, nanoemulsion, nanospheres, niosomes, and micro-
emulsion. Nanocosmeceutical hair care products provide smoothness and silki-
ness to hair, remove dandruff, prevent hair fall, repair damaged cuticle, and
promote hair growth [20].
• Skin Care: It is the most important and largest class of cosmeceuticals. Nano-
cosmeceutical skin care products include sunscreens, moisturizers, anti-acne
creams, anti-aging creams, and skin cleansers [17]. Skin is the largest organ of
the human body. It acts as a protective layer, protects from UV radiations,
prevents loss of moisture, and has many other important roles. Hence, it is really
important to take great care of the skin [20, 21]. Cosmeceuticals for skin care
enhance the skin texture and function by stimulating the growth of collagen by
combating the harmful effects of free radicals. They maintain the structure of
keratin in good condition, thus making the skin healthier. ZnO and TiO2 are the
most effective and most commonly used nanoparticles in sunscreens which
penetrate the deep layers of skin, thus protecting it from harmful UV radiations.
Also, these nanoparticles make the product less greasy, less smelly, and transpar-
ent [19, 21]. In moisturizers, liposomes, nanoemulsions, and niosomes are the
most extensively used nanoparticles as they form a thin layer/film of humectants
and are capable of retaining moisture for a prolonged span. All other skincare
products also contain a variety of nanoparticles that helps in collagen removal,
skin rejuvenation, firming, and lifting of skin [19].
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1037

Progress in Nanotechnology

Nanotechnology has opened a new era of technology that has a great impact on all
sectors of human life. The American physicist Richard Feynman introduced the
concept of nanotechnology in 1959, but the developments in this field began with the
establishment of the National Nanotechnology Initiative (NNI) in the year 2000 in
the USA. It jump-started research and development in the field of nanotechnology
which resulted in significant advances in this field, and since then, it has seen no way
back [23]. Nanotechnology is defined as understanding and control of matter at
dimensions between 1 and 100 nanometers. The invention of TEM (Transmission
Electron Microscopy), STM (Scanning Tunneling Microscope) and other types of
equipment which enabled the study of nanoparticles easier provided a much clear
picture and helped in a detailed study on the scope and applications of nanotechnol-
ogy [24]. The most common and widely discussed methods for the synthesis of
nanomaterials are plasma ionization, electrodeposition, sol-gel synthesis, chemical
vapor deposition, and ball milling.
Nanotechnology is now an indispensable part of development. Nanotechnology
gives more efficient and promising results in all fields than before it was not used.
Nanotechnology and nanoscience have fundamental importance to industrial appli-
cations and medical devices, such as diagnostic biosensors, drug delivery systems,
and imaging probes. However, the most significant advances in nanotechnology fall
in the broad field of biomedicine. Nanotechnology has made it possible to find the
cure of many diseases which were earlier did not have any treatment [19].
In the cosmeceutical industry, the use of nanotechnology has led to an efficient
and better performance of cosmeceuticals and has increased their therapeutic effect.
Nanoparticles have immense benefits, but little has been known about their long- and
short-term effects on organisms and the environment. Due to the toxic effects of
nanomaterials, safety concerns are raised regarding its possible dangers. Nano-
cosmeceuticals have various advantages (Fig. 2), providing controlled drug release
from its carriers by various factors that include preparation method, ratio, additives
and polymers, drug composition, and the chemical or physical interactions between
different components [19, 24]. Scientists are still working for breakthroughs in
nanoscience and nanotechnology to make human life easier and more comfortable.

Nanotechnology-Based Cosmeceuticals: Novel and Advanced

Self-Care Materials

There is a wide range of nanomaterials (Fig. 10) which are being used as nano-
carriers for modern cosmeceutical applications.
We have discussed some of the major nanocarriers along with their properties
which make them suitable and efficient for different applications in the field of
cosmeceuticals (Table 1).
1038 S. Gulati et al.

Controlled release

Highly efficient

Physical stability

Efficient transport of active ingredients

Site-specific targeting

Occlusive properties

Fig. 2 Merits of nanocosmeceuticals

Table 1 Some major market applications of various nanocosmeceuticals [19, 58]

Sr. No. Nanocarrier used Application proposed Manufacturer (Company)
1. Nanocapsules Moisturizer Lancome
Lip treatment Lancome
Anti-wrinkle antiaging Euoko
2. Nanocrystals Anti-wrinkle Lancome
Moisturizer Nano-infinity and nanotech
3. Nanospheres Anti-wrinkle Kara vita
Body lotion Kara vita
Anti-acne Kara vita
Antiaging DermaSwiss
Moisturizer Salvona
4. Nanosomes Anti-wrinkle L’Oreal
5. Liposomes Antiaging Dior
Anti-wrinkle Jafra cosmetics
Moisturizer Kerstin Florian, Decorte
Skin-repair Estee lauder’
6. Niosomes Anti-wrinkle Lancome, simply man match
Hair-repair Identik
Moisturizer Laon cosmetics
Shampoo Identik
Skin whitening Eusu
7. Gold nanoparticles Antiaging Chantecaille
Skin repair/moisturizer Ameizii, Orogold
Sunscreen LR Zeitgard
8. Solid lipid NPs Moisturizer Chanel
Antiaging Soosion
Skin treatment SirechEmas
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1039

Carbon nanotube

Fig. 3 Carbon nanotube (CNTs)

Carbon Nanotubes

Carbon nanotubes are basically rolled structure of graphene consisting of sp2

hybridization. Because of its exceptional strength, almost 100 times than that of
steel, it is one of the most vital achievements in the field of nanotechnology. CNTs
are allotropic form carbon having a hollow cylindrical fibrous structure whose walls
are composed of graphene which is rolled at a chiral angle (Fig. 3). The approximate
length of a CNT is around 10s of microns and a diameter between 0.7 and 50 nm
[6, 25]. There are three types of CNTs that are single-walled CNTs, double-walled
CNTs, and multiwalled CNTs. These are extremely light-weighted. Single-walled
CNTs are composed of single self-rolled graphene sheet with a diameter ranging
from 1 to 2 nm, double-walled are made up of two concentric nanotubes, while
multiwalled CNTs are composed of layered tubes of graphene, and their diameter
ranges from 2 to 50 nm.
Methods for the synthesis of CNTs can be names as saline solution method, flame
synthesis method, chemical vapor deposition method, laser ablation, and the arc
discharge method [27].
CNTs are also being used for cancer treatment. A number of carbon nanoparticle
patents, namely, hair colorants and cosmetic compositions (WO2005117537A3 and
WO2006052276A2), have been filed in the cosmeceutical industry [28, 29].

Dendrimers

The word “dendrimer” is derived from two Greek words, “Dendron,” which means
tree, and “Meros,” meaning part (Fig. 4). These are unimolecular and well-dispersed
hyperbranched tree-like structures with a high density of functional groups at
terminals and the size of about 20 nm in dimension. They show multifunctionalities
due to the presence of various external groups [13, 30, 31]. It is comprised of three
1040 S. Gulati et al.

Fig. 4 Structure of dendrimers

different parts, i.e., closely packed surface, core moiety, and branching units. The
first ever dendrimer was formulated in 1958, was called Newkome dendrimer.
Dendrimers serve the purpose of target delivery of the active constituents to the
liver and macrophages [32]. The fusion of both hydrophobic and hydrophilic
medicines can be done with the help of dendrimer because of its versatility [33].
In cosmeceutical products such as sunscreen, shampoos, anti-acne creams, hair
gels etc., dendrimers are being utilized [34]. Dendrimers are more stable than
liposomes, and hence, they do not decompose into the skin. Dendrimers assist
drug skin permeability upon interaction with skin bilayer. This is very productive
for cosmetic delivery, and hence, it is utilized for skin and hair treatment
[16, 35]. Moreover, companies such as L’Oreal, Unilever, and Wella The Dow
have filed patents for the application of dendrimers in their products.

Cerium Oxide (CeO)

Cerium oxide NPs are another type of inorganic nanoparticles which prove to be
important in the field of cosmeceutical applications. They possess features like good
transparency in the Balmer range, a bandgap of about 3.2 eV, and hence are suitable
for cosmetic applications such as UV filters in sun-blocking creams. CeO does not
offer any known toxicity. Its hybrid with other chemicals, CeO provides exceptional
protection from UV radiations. It showed better physical UV defense than TiO2
nanoparticles according to the statistics provided by Radical Status Factor (RSF).
RSF value given by CeO-based and TiO2 based sunscreens were 57.8 and 8.4,
respectively, showing the superiority of CeO over TiO2 NPs. CeO acts as an ideal
inorganic UV filter which is especially effective for the UVA range [36]. Ca2+-doped
ceria particles show a tremendous amount of shielding against UV radiations and can
find application in sunscreens. Mn+-doped cerium dioxide was produced with the
help of chemical methods also to be utilized as a UV filter [37].
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1041

Fullerenes/Buckyballs

Fullerenes, informally known as buckyballs, are another type of nanomaterials that

serve valuable applications in biomedical industries. Fullerene was discovered for
the first time in 1985 when Krato et al. [38] were conducting an experiment
involving the vaporization of graphene. Their basic structure can be defined as
hollow balls consisting of 32 faces of hexagons and pentagons along with 60 vertices
(60 carbon atoms), comprised of carbon rings clustered together (Fig. 5). Their
exceptional antioxidant properties make them an ideal ingredient for their applica-
tion in sunscreens and antiaging creams. One of the setbacks of fullerenes is that it
causes cell dysfunction and also the death of cells in some cases [39].
Talking further about their cosmeceutical applications, their scavenging capaci-
ties against radical oxygen species make them suitable for the preparation of skin
rejuvenation cosmeceutical formulations [40]. Although their applications were
limited initially due to their hydrophobic nature resulting in insolubility in aqueous
solutions, they brought great revolutions in nanocosmeceutical applications [41].

Gold Nanoparticles

Gold nanoparticles offer antimicrobial properties which make them suitable for
applications in deodorant, antiaging products, facial creams, and moisturizing
creams [13]. Their size falls in the range of 5 to 400 nm, and the determination of

Fig. 5 Structure of
Fullerenes
1042 S. Gulati et al.

their properties is carried by their assembly along with the interparticle forces of
attractions [42]. Their synthesis is carried out using bottom-up methods with the
application of a matrix in order to prevent the formation of clusters. There is vast
variation in the shape of different gold nanoparticles, including triangle, cube, rode-
like, star, branched, shelled, etc. Their color varies from purple to red and to blue and
maybe black. Some major highlights of gold nanoparticles include the absence of
cytotoxicity, biocompatibility, inert nature, high stability, and availability [43–46].
Due to their disinfecting properties, they are used in toothpastes. Coming back to
cosmeceutical application, their ability to be able to deliver active agents through the
skin makes them attractive to the cosmetic industries for drug delivery [16].

Liposomes

Liposomes consist of two layers of coaxial vesicles in which man-made bilayer of

lipids or natural non-toxic products (phospholipids) surround the aqueous volume
(Fig. 6). The size of these structure lies between 20 nm and 2 μm. They are
compatible with delivering both hydrophilic and hydrophobic compounds. It
assists in the systematic delivery of cosmetics with the attachment of liposomal
bilayer with the plasma membrane. They also serve assistance for the preparation
of cosmetics due to their efficiency in active ingredients, easy synthesis, and
provision for regular penetration of agents into the cells over a specified period
of time. Liposomes could save the medication from metabolic degradation by
encapsulation.
Liposomes have shown utilization in sunscreens, hair treatment, and antiaging
creams, but with development in inorganic pigments, liposomes were then bound to
the transportation of sensitive agents such as vitamins and fragrances. Certain limita-
tions such as loosely held constituents, low loading capacity, instability, etc. made
liposomes less useful for commercialization. Liposomes having a good adsorption

Fig. 6 Structure of
Liposomes
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1043

capacity, biocompatibility, etc. were still considered as a safe option due to the
presence of natural ingredients in their composition [47, 48].

Nanocapsules

Nanocapsules serve the purpose of containing cosmetic agents in a cavity that is

located inside their core (Fig. 7). The cosmetic agents are encapsulated by a
polymeric membrane which is either be synthetically or naturally composed
[49]. Nanocapsules are one of the primary carriers used for controlled drug release,
preventing harmful effects at the site of delivery [16]. Nanocapsules, with their
sensory properties, have created an impact in amplification of the efficiency and
quality of the products as well as they tend to protect the ingredients from being
decomposed due to the encapsulation [13].
Hinokitiol (HKL) comprised nanocapsules were synthesized with the help of an
emulsion-diffusion method which served application into two types of products,
namely, shampoos and hair tonics. The results, with comparison, inferred the
effectiveness of the hair tonic for growth [50]. According to the development
study of nanocapsule suspensions by interfacial deposition which incorporated a
coenzyme Q10, properties of these nanocapsules favored dermal application. Prep-
aration of a semisolid consisting nanocapsule suspension, loaded with coenzyme
Q10, inferred its scope for cosmetic preparations in topical application [51].

Fig. 7 Structure of
nanocapsules
1044 S. Gulati et al.

Nanostructured Lipid Carriers and Solid Lipid Nanoparticles

Nanostructured lipid carriers (NLCs) are also known as second-generation lipid NPs
[52]. There are three types of NLCs developed, multiple, amorphous, and imperfect.
Their size falls in the range of 10–1000 nm. Some of the properties which make them
suitable for their utilization in nanocosmeceuticals are that they have increased skin
hydration and penetration and minimal side effects and they are commendable UV
barriers [53]. One of the first cosmetics which incorporated NLCs were NanoRepair
Q10 cream and NanoRepair Q10 serum. These were introduced in the market in
2015. By now, there exist more than 30 number of cosmetic products which use
NLCs [54, 55].
The establishment of solid lipid NPs took place in the 1990s. Their size ranged
from 50 to 1000 nm. SLNs are oily droplets of lipids that are stabilized with the
use of surfactants (Fig. 8). The core of SLN is oily in nature as well and has a
single layer surrounding it. These are composed of physiological lipids dispersed
in an aqueous solution of surfactants. To bypass the toxicity problems during their
preparation, biocompatible compounds are used [54].
These are capable of meticulously transporting cosmetic agents, preventing their
destruction, into the stratum corneum due to their penetration abilities. They are
extensively used in cosmeceutical and pharmaceutical due to their low toxicity.
Some of its major applications involve sunscreens, because of their UV-resisting
nature. Their solid structure at room temperature makes them more stable from
liposomes [56].

Fig. 8 Structure of solid lipid nanoparticles

45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1045

Nanoemulsions

These are micro-emulsions of size ranging from 20 to 200 nm [57]. These are one of
the most advanced nanoparticulate systems for cosmeceuticals. The nanoemulsions
mainly consist of oil, emulsifying agents, and aqueous phases (Fig. 9). Three types
of nanoemulsions can be formed: (a) oil in water nanoemulsion in which oil is in the
continuous aqueous phase, (b) water in oil nanoemulsion in which water droplets are
in the continuous oil phase, and (c) bi-continuous nanoemulsions. These are trans-
parent and exhibit various properties like they are thermodynamically stable and
have low viscosity, high interfacial area, and high solubilization capacity [58]. The
extremely small particle size provides higher stability and higher suitability to carry
out active ingredients. The low viscosity value leads to great spread ability
[17]. They are majorly used as target drug delivery systems. They help in deep
penetration and rapid transportation of the active ingredient and provide hydration to
the skin [57, 58]. The problems like sedimentation, flocculation, creaming, etc.
which are associated with the use of macromolecules do not occur when nano-
emulsions are used. Thus, nanoemulsions are much effective and safe than
macromolecules.

Quantum Dots

Quantum dots (QDs) are man-made nano-sized crystals that can transport electrons.
Their size ranges between 1 and 10 nm. These can be synthesized from different
materials, most common being zinc sulfide, lead sulfide, cadmium selenide, and
indium phosphide [59]. When UV light falls on these nanoparticles, the light of
various colors is radiated out. These nanoparticles have found several applications in
composites, solar cells, and fluorescent biological labels. The extremely small size of

Fig. 9 Structure of
nanoemulsions
1046 S. Gulati et al.

these dots allows them to go anywhere in the body making them suitable for different
biomedical applications like medical imaging, biosensors, etc. [60]. They protect the
skin from UV radiation. They do have toxic effects on the body, and to reduce the
toxicity, these are coated with a protective layer of polymers. They are not much
preferred as their toxicity levels are high as compared to other available nano-
carriers.

Silica Nanoparticles

These nanoparticles are a combination of silicon dioxide and oxygen and are mostly
spherical. They have particle sizes up to 200 nm. These are the most important type
for drug delivery and have a high potential in medicinal use due to their biocom-
patibility, low toxicity, and biodegradability. Silica nanoparticles are of three types,
namely, solid, nonporous, and mesoporous. Out of the three types, the mesoporous
type is best for drug delivery systems. Their porous structure allows for high drug
loading of drugs with poor water stability. Mesoporous silica nanoparticles (MSNs)
have a large surface area and pore volume that have attracted considerable attention
for their application in drug delivery and biomedicine. The major applications
include protein adsorption and separation, nucleic acid detection and purification,
drug and gene delivery, and many more. These nanoparticles are not much harmful
and are thus highly preferred for being used in cosmeceutical products.

Silver Nanoparticles

These are nanoparticles of silver having the size in the range 1 nm–100 nm. These
have unique optical, chemical, biological, and thermal properties. The smaller the
size of the nanoparticle, the greater the surface and the more the reactivity [61]. Silver
NPs have great antibacterial and antifungal properties. Thus, the most common
application of silver nanoparticles is for antimicrobial coatings, and many textiles,
keyboards, wound dressings, and biomedical devices contain silver nanoparticles
that release silver ions in a considerably small amount continuously to protect
against bacteria [62]. They can cause certain harmful effects on human health if
they enter the human body like abnormalities in the liver, spleen, and lung, as well as
toxicity in the muscle, but even then, they are widely used because the skin
penetration ability of these nanoparticles is quite low.

Titanium Dioxide

These are micro-sized titanium dioxide particles having a diameter of less than
100 nm. These nanoparticles are bright and have a refractive index approximately
equal to 2.4 which makes them suitable for the industry dealing with toothpaste,
pharmaceuticals, coatings, papers, inks, plastics, food products, cosmetics, and
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1047

textile [63]. They have self-cleaning and anti-fogging (ability to prevent fogging on
the surface by inhibiting the condensation of water on the surface) properties. Some
of the methods of synthesis of these nanoparticles are sol-gel technique,
solvothermal, hydrothermal electrochemical process, etc. The efficiency of these
particles as a UV filter is proven in the prevention of skin cancers and sunburns
[64]. These are always used in the coated form (coated with alumina and silica) in
cosmeceuticals because they are photoreactive and results in an increase in reactive
oxygen species known to be implicated in cellular damage.

Zinc Oxide

These are nanoparticles of zinc oxide having a diameter of less than 100 nm.
These particles are commonly spherical. Common preparation methods of these
nanoparticles mainly include the chemical precipitation method, sol-gel method,
solid-state pyrolytic method, solution-free mechanochemical method, and bio-
synthesis method [65]. These nanoparticles are highly absorbent due to wide
bandgap, and that is why the most common use of these nanoparticles is in
sunscreens. These nanoparticles are harmless to a human body up to a concentra-
tion of 100 μg/ml. These nanoparticles are chemically and thermally stable and
have antibacterial properties. These are among the most reliable nanoparticles as
they have low levels of toxicity, and also on doping it with iron, the toxicity can be
decreased.

Nanocrystals

These are micro-sized crystals comprising tens of thousands of atoms having

dimensions in the range of 10–400 nm [58]. The three main principles that can be
used for producing nanocrystals are milling, precipitation methods, and homogeni-
zation methods, as well as a combination of these. They show physical and chemical
properties in between bulk solids and molecules. They are used as a drug delivery
system for drugs that are poorly soluble in water and are very effective for oral drug
delivery. The extremely small size of these crystals leads to the increased surface
area which ultimately leads to an increased dissolution velocity [66]. They allow
reliable and efficacious passage through the skin. Various properties of nanocrystals
provide several advantages, which include the potential for passive and active
targeting of drugs, higher solubility than conventional particles, possibility of
administering a drug through different administration routes (oral, intravenous,
intramuscular, pulmonary, ocular, dermal), possibility of formulating a drug under
different pharmaceutical dosage forms (tablets, capsules, suspensions, ointments,
etc.), and many more. These do have some disadvantages like uniform and accurate
dose cannot be achieved, these are difficult to handle and transport, etc. Nanocrystals
have given a great contribution in improving the bio-availability of the drugs [67]
(Fig. 10).
1048 S. Gulati et al.

Nanocry- Cerium
stals dioxide

CNTs Dendrim-
ZnO
ers
TiO Fullerene

Silver NANOCARRIERS Gold

Silica NPs Liposome

Quantum Nanocap-
NLCs
dots sules

Nanoem-
SLNs
ulsions

Fig. 10 Different types of nanocarriers for cosmeceuticals

Routes of Exposure to Nanoparticles

Increasing production and use of nanoparticles in the personal-care industries has led
to a greater number of people getting exposed to them. The exposure of the
NP-based cosmeceuticals takes place through several varying routes (Fig. 11);
thus, there is a need to determine these exposure routes [21]. The extent of harm
that these nanoparticles can cause also depends on the route through which they
enter the body and the thoroughness of exposure to such particles. Nanoparticles can
enter the human body mainly through three routes: inhalation, ingestion, and dermal
routes [19].

• Inhalation: According to the National Institute of Occupational Health and

Safety, inhalation is the most common route of exposure to airborne nano-
particles. During production, NPs escape to the environment and are inhaled by
the workers while customers can get exposed to these particles by using products
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1049

Fig. 11 Routes of exposure

DERMAL
INHALATION
ROUTES

INGESTION

like deodorants, sprays, powder, etc. [21]. The inhaled NPs enter the pulmonary
tract and reach the lungs causing interstitial inflammation and epithelioid granu-
lomatous lesions, and in rare conditions, these particles may travel via nasal
nerves reaching the brain and gaining access to the nervous system, blood, and
other organs [17, 19].
• Ingestion: This route of exposure can be taken up intentionally or accidentally.
Intentional ingestion may take place via hand and mouth transfer of nanoparticles
and unintentionally by ingesting the NPs from cosmeceuticals applied on mouth
or lips (lip care, lipstick, lip balm, etc.) unknowingly [58]. The majority of NPs
that enter via ingestion rapidly move out of the body through urination and
excretion, but sometimes a fraction of NPs may migrate to organs. Several studies
conducted on animals concluded that when NPs enter via ingestion, the target
organs are the liver, spleen, heart, pancreas, and bone [19, 21]. The harm caused
to the organs depends on the type of nanoparticle ingested. For example, when
studied on mice, the gold nanoparticles caused a reduction in body weight, RBCs,
and damaged spleen, whereas copper nanoparticles caused toxicological effects
and severe internal injuries to organs [17].
• Dermal Routes: Skin is the largest organ of the human body, and a majority of
cosmeceuticals are applied to the skin. The skin prevents many nanoparticles
from penetrating the body, but the NPs having a size less than 10 nm can easily
penetrate via the skin into the body [17]. The penetration through skin takes place
in three ways: intracellular, transcellular, and transfollicular. There are possibil-
ities that nanoparticle penetration could be affected by skin barrier alterations
1050 S. Gulati et al.

such as scrapes, wounds, and dermatitis conditions [58]. NPs may directly enter
into the blood and reach various organs causing damage and leading to dysfunc-
tion of the organs. Fullerenes are one of the most widely used nanoparticles in
cosmeceuticals, but the toxicity they can cause remains less known [19].

Regulations for Nanocosmeceuticals

Over the years, many challenges have been hurdled in the regulation of nanoparticle
systems in the nanocosmeceutical industries.

• Food and Drug Administration (FDA)

Food and Drug Application agency of USA, i.e., FDA, works for the regulation of
various branches of products assisted by the Federal Food, Drug, and Cosmetic Act.
However, there is no direct control of the FDA over cosmetics and cosmeceuticals.
For the time, there is no such standard approval required for the cosmetic products,
but assurance for the safety of products becomes the duty of the manufacturers.
Although, in 2006, the FDA, with the help of an internal task force, worked towards
the regulation of NP-based products. It was an important step in order for the safe
and effective progress of the cosmeceutical and pharmaceutical industries [68]. Cer-
tain amendments were made in the year 2007 followed by the issuance of guidelines
for the safety of FDA-regulated items which use nanotechnology. Two of the three
guidelines were associated with nanoparticles-based cosmetics. The first guideline
focused on the regulation of nanotechnology-based products, based on the particle
dimension and the dimension-dependent phenomena. The safety measures for the
usage of nanocosmeceuticals were addressed in the second guideline. Although,
revealing the name of the nano-cosmeceutical used in a product wasn’t made
mandatory by the FDA [68].

• European Union (EU)

According to EU regulations, nanomaterials are bio-persistent, synthetically

synthesized materials with size in the range 1 and 100 nm. It is mandated that all
the nanomaterials must be prefixed with “nano” for indication.
It states a few protocols such as product specification, toxicity, safety profile, and
side-effects are to be informed 6 months before the release of the nanocosmeceutical
in the market, requirement of premarket approval for different cosmeceutical
products.

• India

Funds were raised judiciously by the Government of India for nanotechnology

providing adequate set-ups in different universities, academic societies, laboratories,
start-ups, and R&D units. Situated in the national capital, the Council of Scientific
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1051

and Industrial Research, Indian Council of Medical Research, Department of Sci-

ence and Technology (DST), and Department of Biotechnology played a key role in
the research systems of the country. Prevention and control over health hazards are
looked up by the Ministry of Health and Family Welfare. Furthermore, the Com-
mittee of Nanotechnology works actively for the regulation and standardization of
nanomaterial-based products.

Demerits of Nanocosmeceuticals

• Ecological Hazards

Nanomaterials offer versatile applications and scope for development in various

fields, but with these assets, there are a few long-term/short-term drawbacks to them
as well (Fig. 12). The use of cosmeceuticals tends to increase the toxicity of water,
air, and soil due to their release or disposal in them. The nanomaterials which are
antibacterial in nature could result in contaminating the water which is meant to be
reused by interfering with the beneficial bacteria.
The reactive nanomaterials having a small size and charge used for the production
and consumption of cosmeceuticals with the production of ROSs activates the
pathways spreading toxicity.

• Health Hazards

Their harmful effects are not limited to the environment only; they are equally
harmful to the human body as well (Fig. 13). While using nanocosmeceuticals,
nanoparticles may enter into the human body in three ways: inhalation, ingestion,
and dermal route [58]. They may reach different parts of the body and harm them.
When they enter via inhalation, they may affect the respiratory tract and cause harm
to the lungs and heart. When they enter through ingestion, they may cause damage to

Reactive due to small

Toxicity Harmful to ecology
size

No requirement of
Lack of regulation Cost of production
clinical trials

Fig. 12 Demerits of nanocosmeceuticals

1052 S. Gulati et al.

Fig. 13 Harmful effects of

nanoparticles on human body Neurological Disorders

Lungs Inflammation

Cardiovascular Problems

Pancreatic dysfunction

the liver and pancreas and eventually lead to digestive problems. When they
penetrate through the dermal route, they can be detected in blood and urine and
may cause infection [58]. Industries where products containing nanoparticles are
manufactured or used release their chemical wastes into the environment causing
harm to the environment. These chemical wastes get dissolved in water, threatening
aquatic life, and this water is then consumed by terrestrial animals. In this way, these
nanoparticles reach animals. Over a period of time, these particles get accumulated
in their body and may cause various diseases and reduce the life span of animals.
Specifically talking, lipid-based nanomaterials offer wide utilization in different
industries such as food, medical, and pharmaceutical because of their low toxicity,
biocompatibility, and biodegradability. However, ingested lipids and encapsulated
bioactive components might get biologically modified due to the very small size of
the nanoparticles, leading to adverse effects on the human body’s health. One of the
setbacks of Fullerenes is that it causes cell dysfunction and also the death of cells in
some cases [39]. Carbon nanomaterials such as fullerenes and CNTs cause brain
damage to aquatic species [46].
Nanoparticles exhibiting poor stability tend to cause tumors and can be said to
have more noticeable toxicity. The chemical composition of the nanoparticles
absorbed on the human skin also determines the toxicity factor.

Conclusion and Future Outlooks

Cosmeceuticals are taking pace in the sector of the personal care industry, attracting
consumers with a range of products and treatments for aging skin, acne, hair care,
nail care, etc. The intervention of nanotechnology has played a vital role in the
expansion of cosmeceuticals. Nanoparticles, exhibiting exceptional characteristics,
45 Nanocosmeceuticals: Novel and Advanced Self-Care Materials 1053

make them compatible and useful in various industries creating an impact on their
growth. One of the most utilized and suitable nanoparticles used in cosmeceuticals
are CNTs, fullerenes, dendrimers, gold, silver, and QDs. Serving the purpose of skin
penetration and target-specific sustainable drug delivery through different routes of
exposure, nanocosmeceuticals have proved to be very efficient with constant devel-
opment, and they offer a wide scope of applications in the future. There are a few
demerits and risks associated with them which limit their utilization to some extent.
Regulation authorities play an important role in maintaining safe and secure usage of
nanocosmeceuticals.
Not only as nanocarriers, but nanoparticles provide diverse utilization in a variety
of fields. Over 20 countries are actively working on the development of NP-based
products, cosmetics being one of the leading ones. In the near future, can expect
various novel nanotechnology-based cosmeceuticals easily available all over. Various
research organizations are working on formulating safe NP-based products which do
not cause side effects and harm the ecology and hence do not require regulations.

Important Websites

1. https://www.sharecare.com/health/cosmeceuticals/how-cosmeceutical-differ
ent-from-drugs
2. https://www.nanowerk.com/nanotechnology-in-cosmetics.php
3. https://www.nanoshel.com/Nanoparticles-in-Cosmetics
4. https://www.dermatologytimes.com/view/nanotechnology-and-cosmeceuticals-
good-bad-and-dangerous
5. https://www.understandingnano.com/nanotechnology-skin-care-cosmetics.html
6. https://www.fda.gov/cosmetics/cosmetics-science-research/cosmetics-
nanotechnology
7. https://www.azonano.com/article.aspx?ArticleID¼3100
8. https://www.ncbi.nlm.nih.gov/books/NBK544223/
9. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5750557/
10. https://www.intechopen.com/books/recent-advances-in-novel-drug-carrier-
systems/
11. https://www.cosmeticsdesign.com/Article/2015/04/16/Weighing-the-pros-and-
cons-of-nano-ingredients
12. www.fda.gov/ForConsumers/Consumer Updates/ucm241820.htm
13. https://www.fda.gov/cosmetics/cosmetics-laws-regulations/cosmetics-us-
law#Product_Both_Cosmetic_and_Drug

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Advancing of Zinc Oxide Nanoparticles
for Cosmetic Applications 46
Ravi Chauhan, Amit Kumar, Ramna Tripathi, and Akhilesh Kumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
Preparation of ZnO Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Structure Analysis of ZnO Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
Features of Human Skin and Role of ZnO Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
Structure of Skin Blockade Characteristics of Human . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
Permeability of Human Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1063
Light Interaction with Human Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Ultraviolet Attenuation of ZnO Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
Effectiveness and Safety on Sunscreen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
Toxicity of ZnO Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065
Applications of Inorganic ZnO Nanomaterial in Cosmetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1066
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070

Abstract
In this chapter, authors incorporate the use of zinc oxide (ZnO) nanoparticles in
cosmetic formulations to introduce products with advanced benefits taking cue from
the existing research and publications. As evident from the past research and
publications, the vesicles do not penetrate the stratum corneum, the outermost layer
of human skin. The nano-sized personal care products formulations have tendency to
either speed up or retard the absorption of ingredients into the skin albeit to a minimal
scale. ZnO insoluble nanoparticles with excellent UV filters are present in latest
sunscreens/sunblocks, and these nano constituents do not penetrate human skin. It
passes the safety parameters through tests/analysis of cytotoxicity, genotoxicity,
photo-genotoxicity, general toxicity, and carcinogenicity studies. This may incline

R. Chauhan · A. Kumar · R. Tripathi (*)

THDC Institute of Hydropower Engineering and Technology, Tehri, India
A. Kumar (*)
Department of Physics, Govt. Girls P. G. College, Rajajipuram, Lucknow, India

© Springer Nature Singapore Pte Ltd. 2022 1057

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_100
1058 R. Chauhan et al.

the study towards weighted benefits of UV-induced skin aging and cancer compared
to vague concerns. It would open gamut of applications of ZnO nanoparticles in the
field of cosmetics. Given the growing commercial and scientific interest, this chapter
will highlight the effectiveness, safety, and toxicity of ZnO nanoparticles in sun-
screen formulations.

Keywords
ZnO nanoparticles · Skin blockade characteristics · UV attenuation · Safety and
toxicity · Cosmetic application

Introduction

Technologies and inventions play remarkable role in human life making it healthy
and sustainable; this could be proved from various recent material developments and
breakthrough in product applications. One such concept is being discussed here by
incorporating use of ZnO nanoparticles in cosmetic products. Prolonged exposure to
unfavorable radiations from wavelength ranging from UVA-2, 320–340 nm; and
UVA-1, 340–400 nm together with certain UVB radiations may prove detrimental
due to biological and metabolic reactions [1, 2]. Radiation fall in varying wave-
lengths from UVC 100–290 nm (filtered off by stratospheric layer of space due to
shorter wavelength in making of ozone) to UVB 290–320 nm absorbed by strato-
spheric ozone. The radiations are sometimes favorable in synthesizing vitamin D
(cholecalciferol) but for short-term exposure. Our concern restricts to the wavelength
which finally breach down to the human skin causing skin redness (erythema) and
lethal cancerous effect due to actinic keratosis and skin cancer from epidermal cells.
Some other ill effects in the list includes loss of skin elasticity, due to UVA
producing reactive oxygen species (ROS) that activate different matrix of meta-
lloproteinase, which damages collagen and other dermal matrix proteins [3, 4].
There are existing examples of protection against the skin cancer but the scientific
study of this has been restricted to the case of actinic keratosis and squamous cell
carcinoma. Evidence for the other banal types of cancer, i.e., basal cell carcinoma
and malignant melanoma is inconclusive [5].
Sunscreens are required to have protection against both UVA and UVB radiations
[6], the relevant developments have been observed only in last decennia where the
use of ZnO nanoparticles are used preferably above organic ingredients as physical
sun blockers [7]. The reason to use unconventional ZnO nanoparticles over organic
counterparts are loaded with benefits, and some of them are listed below:

Absence of skin irritation and sensitization

Inertness of ingredients
Limited skin penetration
Broad spectrum protection [8]
Help in reducing the opaqueness without affecting their UV blocking efficacy [9]
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1059

The nanomaterials safety and acceptability are of concern due to their tendency of
being more bio reactive than normal bulk due to the presence of all three external
dimensions in the nanoscale [10], this is attributed to the fact that increase in surface
area to volume ratio with decrease in diameter. This compels the cautious study on
safety of application of nanoparticles in cosmetics [11–13]. Use of sunscreen is for
the protection of human skin against the harmful effects of sun radiation which
should not otherwise effect in negative form due to the applications of nanoparticles,
where as recent studies are restricted to toxicological and skin penetration
[14, 15]. This study should also incorporate physiochemical properties of sunscreen
ingredients absorbed by human skin in presence and absence of light. This would
balance the boon and bane of these nanoparticles formulations which seems to be in
limited presence. Applications of nanomaterials are in existence from last 30 years
[16, 17], and it has formed a big family of products which have consolidated their
presence due their physiochemical properties [18] harbinger being the cosmetic
industry [19]. A nanomaterial defined by European Union (EU) is as “an insoluble
or bio-persistent and intentionally manufactured material with one or more external
dimensions, or an internal structure, on the scale from 1 to 100 nm” [20].
The nanomaterials-based cosmetics override the advantage of microscale cos-
metics as they gain long-lasting effect and increased stability. High surface area
supports effective transport of ingredients through the skin [21], and this advantage
is well recognized apart from new color elements (e.g., in lipsticks and nail pol-
ishes), transparency (e.g., in sunscreens), and long-lasting effects (e.g., in makeup).
Current application predominates in skin care and UV filters. For an instance in
1986, an antiaging product containing liposome was introduced by Christian Dior
and named it as Capture TM. Over the years, their applications of Nanomaterials
found increased presence in cosmetic products of renowned brands [22], and this
could be observed by moves of certain brands like L’Oréal which ranks sixth in the
USA in the number of patents in nanotechnology [23] has poured in huge cash in the
research and development of nanomaterials. It uses tin oxide (TiO2), zinc oxide
(ZnO), silica, carbon black in some of their formulae [24]. Shiseido (another brand)
uses nano-TiO2 and nano-ZnO in wet-based formulae (e.g., emulsions) but does not
use them in aerosols due to the risk of inhaling [25]. It collates the fact that world
famous brands have started use of nanomaterials in their products [26].
Still road ahead have the bumps of safety concerns which has been raised by
World Health Organization (WHO), nongovernmental organizations, political insti-
tutions, and other agencies. European commission came up with latest guidance on
use of nanomaterials in cosmetics [27], and similar approach has been made by Food
and Drug Administration for the application in industrial products [28]. There are
restrictions related to testing on animals in countries of Europe for toxicological data
(EC Cosmetic Regulation No. 1223/2009) and therefore, alternative methods like
ex-vivo, in-vitro methods are used for evaluation.
In the early part of 2020, the European Union Observatory for Nanomaterials
(EUON) [29] announced that all companies that manufacture, use, or import nanoforms
should have a REACH registration compliance (REACH is a regulation of the
European Union and stands for Registration, Evaluation, Authorization, and Restriction
1060 R. Chauhan et al.

of Chemicals). This was for end user awareness on safer use and application. Non-
compliance is declared ultra vires. Based on the latest guidance framework of NMs, the
EC asked the Scientific Committee on Consumer Safety (SCCS) for a priority list of
nanomaterials used in cosmetics for the purpose of risk assessment. In this chapter,
effectiveness, safety, and toxicity assessment process followed by the recent status and
advances regarding production, characterization, and application in cosmetic of ZnO
nanomaterials is presented.

Preparation of ZnO Nanomaterials

For preparing ZnO nanoparticles, three solutions were prepared differently. Solu-
tion (1) was prepared by dissolving 0.2725 g of ZnCl2 (1/10 M, 20 ml) in methanol.
Solution (2) was prepared by dissolving 0.4 g NaOH (1/10 M, 100 ml) in methanol; a
definite concentration of thioglycerol in methanol (1/10 M, 50 ml) was prepared as
third solution (3). Solution (2) was slowly added to Solution (3) with continuous
stirring. The resulting solution was stirred for almost 1 h and then Solution (1) was
added to it. After 3 h of constant stirring, a milky white colored solution of zinc oxide
was obtained in the range of nanometers using following chemical reactions:

ZnCl2 þ 2NaOH ¼ ZnðOHÞ2 þ 2NaCl ð1Þ

ZnðOHÞ2 ¼ ZnO þ H2 O ð2Þ

Thioglycerol is used as the capping agent, because it seizures the agglomeration

of ZnO nanoparticles during precipitation or to achieve the stability and elude the
coalescence. Size selective precipitation was carried out using acetone as a
non-solvent. The organic solvents were allowed to evaporate at room temperature
to obtain ZnO in white powder form. The white powder of ZnO was palletized into a
disc using polyvinyl alcohol (PVA) as binder.
The X-ray diffraction of the sample at room temperature is taken by a powder
X-ray diffractometer (Rigaku Miniflex-II). The scanning electron micrograph of the
sample is taken by a scanning electron microscope (FEI Quanta 200).

Structure Analysis of ZnO Nanomaterials

Structure analysis (Fig. 1) shows the X-ray diffraction (XRD) pattern of ZnO
nanoparticles. The broadening of the diffraction peaks is primarily due to the finite
size of the nanocrystallites and is quantitatively analyzed by the Debye–Scherrer
formula [30].

L ¼ 0:9λ=B Cos ð3Þ

46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1061

Fig. 1 SEM and XRD (inset)

pattern of ZnO nanoparticles

where L is the average size of the particle, λ is the wavelength of X-ray radiation, B
is the full width at half maximum (FWHM), and θ is the diffraction angle. According
to the data in Fig. 1 and above formula, the average particle size of the material is
found to be 50 nm. The scanning electron micrograph (SEM) of the sample is shown
in the inset of Fig. 1, which demonstrates the formation of ZnO nanoparticles.

Features of Human Skin and Role of ZnO Nanoparticles

Structure of Skin Blockade Characteristics of Human

The skin with a total area of 20 square feet is the outer covering and largest organ of
the human body. The skin protects human from microbes and the other elements; it
helps to regulate the human body temperature and also allows the sensations of
touch, heat, and cold. Human skin has mainly three layers: the epidermis, the dermis,
and the hypodermis (deeper subcutaneous tissue).
The epidermis is the outermost, water-resistant layer of human skin, creates skin
tone, and it protect against transcutaneous penetration of chemicals which is pro-
vided by the upper epidermal layer. Epidermis has five sub-layers as shown in Fig. 2;
the sub-layers of the epidermis include:
Stratum basale: It is also known as stratum germinativum and is the deepest layer
of the epidermis, which is adjacent to the basement membrane by hemidesmosomes
and separated from the dermis by the basement membrane (basal lamina). In this layer,
cuboidal to columnar shaped mitotically active stem cells are found that are constantly
producing keratinocytes, and it also contains melanocytes.
1062 R. Chauhan et al.

Fig. 2 The epidermis, basic the stratum corneum (SC), contains three layers, the stratum basale, the
stratum spinosum, and the stratum granulosum. Pathways for cutaneous penetration include (a) the
paracellular, (b) transcellular, (c1) the transappendageal route, includes the transport along hair
follicles, (c2) sweat pores, and (c3) sebaceous glands

Stratum spinosum: Here the prickle cell layer (eight to ten cell layers) contains
irregular, polyhedral cells with cytoplasmic (spines) processes, which extend outward
and contact nearest cells by desmosomes. Dendritic cells can be found in this layer.
Stratum granulosum: It contains diamond-shaped cells (three to five cell layers)
with keratohyalin granules and lamellar granules. In keratohyalin granules, keratin
precursors eventually aggregate, crosslink, and form bundles and lamellar granules,
keep the cells stuck together due to the glycolipids which secreted to the surface of
the cells and work as glue.
Stratum lucidum: It contains eleidin, clear intercellular proteins, which are a
transformation product of keratohyalin with two to three cell layers and present in
thicker skin found in the palms and soles.
Stratum corneum: It is the uppermost layer with 20–30 cell layers, made up of
keratin and horny scales made up of dead keratinocytes, which secrete defensins
(a part of our first immune defense). The densely packed stratum corneum structure
consists of dead corneocytes embedded within lipid region [31], and the stratum
corneum consists of approximately 15 layers of corneocytes, mainly filled with
keratin, water, and various enzymes are surrounded by a cell envelope.
This cornified envelope, densely cross-linked proteins with a chemically
bound lipid monolayer, functions as a mechanical and permeability barrier,
decreases the dividing of substances into corneocytes and functions as a skin
barrier. Furthermore, corneodesmosomes are interconnecting the corneocytes and
important for the SC cohesion and integrity. The intercellular lipids (ceramides,
long-chain and short-chain free fatty acids, and cholesterol) form two lamellar
phases with repeated distances of 6 and 13 nm. Within the lamellae, the lipids are
structured in semicrystalline lattices. The crystalline packing and the lamellar
phases are also important for the skin barrier function. Besides the im-
portance of SC for skin barrier function, other factors contributing to the same
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1063

purpose are tight junctions (the junctions between keratinocytes in the stratum
granulosum), skin-related immune factors, and hair follicle (sebaceous) gland
secretions.

Permeability of Human Skin

Permeability of human skin is very low due to the stratum corneum, the outermost layer
of the skin, is an effective barrier to most inorganic nanosized particles and external
substances, which are not able to penetrate and diffuse through the skin. This protects
the body from foreign particles that comes into contact with internal tissues. However,
sometimes it is desirable to allow particles entry into the body through the skin.
Penetration through the stratum corneum may occur via different pathways shown in
Fig. 2, i.e., the transappendageal route that includes the transport along sweat pores, hair
follicles, and skin (sebaceous) glands; the transcellular SC route; and the paracellular SC
route. Due to the highly impermeable character of the cornified envelope, the trans-
cellular route seems to be of minor importance when compared with the paracellular
route. In the paracellular route, transport of substances may be facilitated by liquid
domains created by the unsaturated moieties of the ceramides in the 13 nm lamellar
phase. This gives the tortuous pathway alongside the corneocytes as shown in Fig. 2a.
Hydrophilic pore diameters range from >5  104 nm (sweat ducts) to 0.5–7.0 nm and
20–30 nm for inter-corneocyte pathways. Diseased skin, however, is often characterized
by a reduced barrier function as a consequence of altered tight junctions or changes in
lipid composition and organization. Other skin damaging factors such as skin flexing
motions, erosions, and ulcers may also facilitate the penetration of compounds that are
normally not able to pass through the skin barrier. Due to certain unwanted local and
systemic reactions particularly for NPs smaller than 5 nm are influenced by surface
coatings and particle’s geometry. Moreover, UVB induced disruption of the skin barrier
may also lead to an increased epidermal permeability that is possibly associated to
defective lipid lamellar layers in the SC. Liu et al. also reported alterations in SC
integrity resulting from daily sun exposure. Finally, SC thickness partly determines a
particle’s chance to reach viable skin cells. This thickness is different for different parts
of the body and varies with age, gender, and skin type.
In the penetration process, size of the particle play a very important role. Particles
size less than 40 nm in diameter have been successful in penetrating the human skin.
Researchers studied that the permeability of skin depends on different shapes of
nanoparticles, i.e., spherical particles have a better ability to penetrate the skin
compared to oblong particles because spheres are symmetric in all three spatial
dimensions. Different materials at nano-range are also having skin’s permeability
limitations for example; gold nanoparticles less than and equal to 40 nm in diameter
have shown to penetrate into the epidermis. Titanium oxide, zinc oxide (important
ingredients in sunblock), and silver nanoparticles are ineffective in penetrating the
skin past the stratum corneum. Cadmium selenide quantum dots have proven to
penetrate when they have certain properties.
1064 R. Chauhan et al.

Light Interaction with Human Skin

Various wavelengths of the solar spectrum interact in a different way with various
skin parts. The skin (depth) penetration is dependent on the type and concentration of
absorbing compounds. The visible and the long-wave part of UVA can penetrate
deep into the dermis, while UVB and short-wave UVA reach only the upper dermal
skin layer [32]. A theory of skin optics has been studied by Van Gemert et al. [33]. It
reviews the absorption and scattering experimental data in the UV-visible light range
(260–800 nm) for SC, epidermis, and dermis, which showed that the involved skin
layers have equal refractive indices [34]. Both the absorption and scattering coeffi-
cient seems to be higher for the SC in comparison to the epidermis and dermis. Main
chromophores of the horny layer affecting the absorption (of mostly 280–300 nm)
are tryptophan, tyrosine, and urocanic acid [32].

Ultraviolet Attenuation of ZnO Nanoparticles

Different microscopic sized wurtzite ZnO particles, coated and uncoated, have been
used as sunscreens materials (average size is approximately 0.1–10.0 μm) for many
years. ZnO occurs naturally in the Earth’s crust, and it exists in two main crystalline
forms: wurtzite and zinc-blende. The wurtzite structure is the most common and
stable form. The optical refractive indices vary between 2.3 and 2.0 of varying angle
spectroscopic ellipsometry in the 375–900 nm range. ZnO is a wide band and n-type
semiconducting material. Energy band gap of wurtzite is 3.22 eV and for zinc-blende
is 3.32 eV of ZnO have been detected at 77 K.
Ultraviolet (UV) attenuation is the result of both reflection and scattering of UV
radiation and visible light. UV attenuation characteristics of ZnO nanoparticles are
effective in UVA absorption. In addition to size-related optical particle characteris-
tics, the ability of particles to attenuate ultraviolet radiation is determined by the
surrounding environment. When the particles are smaller than 100 nm, the new
optical features appear. In semiconductors of small and large NPs compared with the
Bohr radius of excitons, electrons energy levels are no longer regarded as continuous
bands but should be interpreted as discrete energy levels. It affects the band gap
width and the blue spectral shift of absorption results in threshold point. When the
particles become smaller than the optimal light scattering size (approximately half
the wavelength), visible light will be transmitted and the particles appear transparent.
This solves the unwanted cosmetic opacity of inorganic sunscreens and makes the
application of nanoparticles commercially attractive. ZnO particles in the range of
200 nm and less than that are virtually transparent. Therefore, the reduction of the
particle size will reduce the UVA absorption capacity and transfer it to the UVB
region [35]. However, high interaction energy can also lead to NPs aggregation,
which depends to some extent on the surrounding conditions, such as pH and ionic
strength [36]. This affects their size and band gap width demonstrated by Kolár et al.
that the dependence of the band gap energy on the age of NP in colloidal suspensions
of quantum-sized particles and linked it to the increased particle size, up to 365 days,
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1065

the band gap energy is reduced by about 0.05 eV [37]. The smaller band gap reduces
the energy required to overcome the band gap corresponding to the higher wave-
length. The average size of ZnO nanoparticles in sunscreens will change uniformly
over time [38], resulting in the loss of the UV attenuation characteristics of specific
nanoparticles. Mie theory is an analytical solution to the Maxwell equation of
electromagnetic wave scattering, which is often used to calculate the relationship
between ultraviolet attenuation efficiency and particle size. It is important to note
that the Mie theory is actually applicable to the Nano-particles having size, roughly
equal to the wavelength single, spherical, particles that scatters light [39]. The micro-
sized and nano-sized sunscreen ZnO particles are actually nonspherical and exhibit
anisotropy.

Effectiveness and Safety on Sunscreen

According to the recommendations of the US Food and Drug Administration (FDA),

the protection factor against UVA should be at least one-third of the overall sun
protection factor. In addition to the optical properties related to the size of nano-
particles in the skin, sunscreen formulations may affect the sunscreen efficacy of
nanoparticles [40]. Since micron TiO2 is the most effective in the UVB range and
micron ZnO is the most effective in the UVA range, the combination of these two
oxides ensures the necessary broadband UV protection. In human SC, the resulting
particle size of higher UV absorption and scattering and lower UV transmission
improves UV attenuation. The reduction in the size of micron-sized ZnO enhances
the UVB absorption of the two particles at the expense of UVA-1 absorption, and the
UV protection becomes unbalanced. The solution to this problem may be a combina-
tion of various ZnO micron-sized particles (200 nm or less to maintain transparency)
and nano-sized TiO2. Research in this field shows that further optimization can
combine two levels of ZnO particles (dispersed in isononyl methacrylate) with the
slightly white 35 nm TiO2 NP to provide better UVB protection. To ensure the
recommended balanced UVA/UVB protection, the ZnO dispersion should preferably
contain small nano-sized and large micro-sized particles. According to this study,
130 nm total ZnO particles instead of 20 nm primary particles affect UVA-1 protec-
tion. Papers focusing on NP size optimization related to UV attenuation are rare,
especially when it comes to particle-particle, particle-skin, and skin-particle-light
interactions. These interactions are important because they affect the UV attenuation
ability of sunscreens. The research of Popov et al. solved this problem [41].

Toxicity of ZnO Nanoparticles

Most of the people use zinc oxide nanoparticles-based sunscreens seasonally for
many hours due to its intrinsic UV-absorbing properties. In the range of
200–400 nm, particles reflect and scatter light, making the sunscreens appear
white. However, in the range of 40–100 nm, ZnO NPs absorb and scatter UV
1066 R. Chauhan et al.

radiation and largely absorb visible wavelengths, making the sunscreens appear
transparent. Due to semiconducting properties of zinc oxide nanoparticles, approx-
imately 10% part of the absorbed UV radiation can generate free radicals on the
surface of metal oxides in the presence of water. This photocatalytic activity is
reciprocal of nanoparticle size. Coating or doping is used to reduce the metal
oxide semiconductor activity when used in sunscreens. Many researchers’ studies
that on healthy human skin ZnO nanoparticles present in sunscreens do not penetrate
the stratum corneum.
Zinc oxide is an essential ingredient of many enzymes, sunscreen as ultraviolet
(UV) light filters, cosmetics, photographic catalyst material with excellent UV absorp-
tion and reflection properties. Impact of zinc oxide on biological functions depends on
its morphology, particle size, exposure time, concentration, pH, and biocompatibility.
ZnO nanoparticles are more toxic and partially soluble in neutral solutions on contrary
to acid environments. It induced significant cytotoxicity in a size-dependent manner
and also may cause neurotoxicity and probably reaches the brain by olfactory system.
The influence of ZnO nanostructures, such as nano-plate, nano-rod, and nano-flower,
on various human cancer cells were studied by examining reactive oxygen species
(ROS) and genotoxicity. They can also be cytotoxic and genotoxic to multiple types of
human cells. The cytotoxicity and genotoxicity of zinc oxide nanoparticles are usually
related to their photocatalytic activity. In particular, the light-induced reaction of zinc
dioxide has attracted a lot of attention and has proven useful in environmental
applications such as organic waste and wastewater treatment processes [42, 43].
Monteiro-Riviere et al. confirmed the occurrence of invalid test results based on
NP-dye interactions and showed that the results strongly depend on these interac-
tions [44]. Changes in physicochemical particle properties may also play a role in the
toxicity problems caused by different particle treatments where the photo-reactivity
of ZnO seems to be lower, but it exhibits instability during irradiation
[45]. Mahalakshmi et al. reported the photocatalytic degradation of carbofuran in
an aqueous solution using Degussa [46]. In the case of ZnO, the oxidation rate of
coated and uncoated particles was found to be extremely low. Unfortunately, there is
a lack of accurate data on radiation status and dose indicators. The results on the
light-induced genotoxicity of ZnO are quite different [47]. In most of the mentioned
studies, NPs have been correctly characterized; however, no attempt has been made
to structure and correlate the obtained toxicity data with specific NP physical and
chemical properties. The inherent cytotoxicity and genotoxicity of ZnO NPs
(100 nm) are frequently reported [48]. Kocbek et al. [49] emphasized the importance
of long-term exposure in toxicology studies. Their research shows that some soluble
ZnO particles can stimulate the production of ROS in keratinocytes.

Applications of Inorganic ZnO Nanomaterial in Cosmetics

Nanomaterials can be used in the cosmetics industry in various forms and types as
shown in Fig. 3. The fact is that due to the advancement and development of research
and development in the cosmetics industry, more and more nanostructures are being
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1067

Fig. 3 Use of nanomaterials in various cosmetic applications

tested in cosmetics. The future goal is clear to find out the safest and suitable
nanomaterials for cosmetic applications at low cost. In addition, it must be men-
tioned that “The European Union aims to promote the development and verification
of alternative methods that follow the 3Rs (Replacement, Reduction and Refine-
ment) principles and provide protection equal to the level of protection achieved
through animal testing, while using fewer animals, causing less suffering, or
avoiding any use of animals” In view of the restrictions, the need to introduce
nonanimal substitutes is particularly important for the safety assessment of cosmetic
ingredients/products, because safety data can only be generated by alternative
methods, which means that 3R substitutes are effective and are usually limited to
1R (i.e., Replacement of animal testing). In view of this, the SCCS considered all
available scientific data, as well as the testing and marketing restrictions that came
into effect under Regulation (EC) No. 1223/2009. The latter statement is the first to
appear, because the diversity of nanomaterials in cosmetics is huge, but ethics must
be observed.
Inorganic nanoparticles are nontoxic, hydrophilic, biocompatible, and highly
stable compared to organic nanoparticles. Their major difference apart from the
aforementioned is that inorganic nanoparticles are synthesized from inorganic ele-
ments (Ag, Au, Ti, etc.), while the organic ones are synthesized from polymers. One
of the most widely used inorganic nanoparticles for sunscreens is ZnO, and in
nanoscale, it has a higher sun protection factor (SPF) which makes it more efficient
and has a better cosmetic result due to its transparency. Generally, in the market,
companies use terms such as “transparent” or “invisible” when using nanoscale
ZnO. It is reported that nanoscale ZnO shows much better than most products with
nano-dimensions [50]. Due to its UVA and UVB absorption capacity, micro-ZnO is
used as an ingredient in sunscreens. ZnO nanoparticles have been widely used in
1068 R. Chauhan et al.

sunscreens as UV filters starting from 20 nm. They show better dispersion and leave
a better cosmetic effect. For the analysis of ZnO in cosmetics, a combination of
scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) is con-
sidered an effective method. Regarding their safety, the health damage caused by
inhalation of high-concentration ZnO nanoparticles has been reported [51]. However,
the different exposure routes of ZnO concentrations in typical sunscreen formula-
tions are considered safe, because there is neither proof of penetration into the viable
epidermis nor toxicity issues [52]. ZnO nanoparticles also have good UV blocking
properties. Generally, there are three types of ultraviolet radiation in sunlight,
namely UV-A (320–400 nm), UV-B (290–320 nm), and UV-C (250–290 nm).
UV-A radiation is the main concern, because it accounts for 95% of total solar
radiation. The contribution of UV-B radiation is 5%, while UV-C radiation has no
significant effect because it is absorbed by ozone on the earth’s surface.
In addition, UV-A rays are considered to be more harmful than UV-B because
they are about 100 times stronger than UV-B and can penetrate deep into the skin. In
view of the above UV levels, it is important to prevent such harmful radiation, as
exposure is known to cause human skin cancer. Generally, ingredients with
UV-resistant properties are added to cosmetics to protect the skin. To protect the
skin from UV-A radiation, ZnO nanoparticles provide effective UV-protective mate-
rial. In general, ZnO nanoparticles show effective absorption than dispersing UV-A
rays. In addition, due to the high photocatalytic activity of ZnO, active oxygen will
be produced, thus oxidizing ingredients in cosmetic formulation. In this regard, there
are few reports on the combination of ZnO nanoparticles solution and the combina-
tion of silica coating on the surface of ZnO nanoparticles to avoid unnecessary
photoactivation. The synthesis of silica-coated ZnO nanoparticles by microwave-
assisted corridor and its photocatalytic activity was confirmed. ZnO nanoparticles
coated with silica are identified by XPS, FT-IR, HRTEM, CHN basic analysis and
possible zeta measurement. FT-IR and XPS analysis clearly confirmed silica coating
on zinc oxide nanoparticles. The HRTEM micrograph shows a continuous dense
silica coating of 3 nm thick on the surface of the ZnO nanoparticles. Furthermore, by
measuring the zeta capacity of silica-coated ZnO nanoparticles and SiO2, silica
coating on ZnO nanoparticles is confirmed. In both cases, the zeta potentials are
highly correlated. The photocatalytic activity of ZnO nanoparticles that are not
sealed and coated with silica was tested with photodegradation of methylene blue
(MB) solution. Non-synthetic ZnO nanoparticles showed high photocatalytic activ-
ity, and MB concentration decreased rapidly with increased UV radiation time. On
the other hand, when high Si content (22.7%) is used to cover the surface of ZnO
nanoparticles, these silica layers effectively inhibit the photocatalytic activity of ZnO
nanoparticles. In addition, nanoparticles coated with silica also show excellent UV
protection and visible light. Regarding surface coating of ZnO nanoparticles to
reduce photocatalytic activity, Fangli et al. reported the properties of zinc nano-
particles induced by zinc aluminate. Zinc oxide nanoparticles coated with zinc
aluminate are prepared by performing Al2O3 precipitation on the precursor basic
carbonate of zinc (BCZ) of zinc oxide. ZnO-coated nanoparticles were confirmed by
TEM analysis, which showed that a similar layer was formed on the surface of the
46 Advancing of Zinc Oxide Nanoparticles for Cosmetic Applications 1069

zinc oxide nanoparticles, and the composite particle size was approximately
50–60 nm. HRTEM analysis clearly shows that the thick outer layer of aluminum
oxide is 4–5 nm. In addition, XPS confirmed the presence of alumina coating and
indicated the presence of Zn, O, and Al. In addition, XRD and lattice edge data show
that coating is a ZnAl2O4 component composed of zinc-based carbonate and
aluminum-based carbonate. Using castor oil as an oxidizing agent, the lubricating
activity of zinc aluminate coated zinc oxide nanoparticles was measured by conduc-
tivity measurement (CDM) scale. During the measurement of photocatalytic activity,
the sample containing castor is ZnO nanoparticles: growth, structure, and use under
250 W UV light irradiation. Therefore, it has been proven that coating of zinc
aluminate can effectively reduce the regenerative activity of zinc oxide nano-
particles. In addition, zinc oxide nanoparticles coated with zinc aluminate not only
absorb high ultraviolet absorption but also enhance its apparent brightness.

Conclusion

As we learnt that ZnO particles can be manufactured using different methods, the
sol-gel method being most prominent and favorable because of its pros like envi-
ronment friendly; handling; cost-effective (commercially viable); reliability and
repeatability. Also, the in-depth review confirmed that their application depends on
the process control of their physical and chemical properties which are size, shape
dispersion, shape, surface state, crystal structure, organization on the carrier, and
dispensability. So it clarifies that the method of synthesis will definitely affect the
qualitative results. That means scientific deliberations would bring favorable results
pre- and post-manufacturing (product development). Attention would be suitable at
stages of type and concentration of precursor, the type of capped molecule, and type
of solvent, reaction time, and reaction temperature.
Looking towards future aspects [53] as there are existing instances of variety of
applications ZnO with varying shapes and sizes, there is still room for quality in
physiochemical structures giving more options of their favorable applications with
changes in thickness, size, width, and no use of organic solvents.
Cosmetic applications of ZnO nanoparticles require non-photocatalytic properties
which may be obtained by silica or other molecules through their surface coating.
Toxicity towards human skin is also a concern. Aqueous solutions of high-quality
Zno nanoparticles with natural pH and physiological temperature would be required
in biological field applications. This is because of the compulsion of sensitivity of
biomolecules towards above two mentioned parameters.
Additional benefits of nanosize, ease of transportations within tissues and mem-
branes, transfusion through membrane walls, response towards biomedical mole-
cules make them perfect candidate for biomedical medicinal applications.
Conceptually we need to take cognizance of the balance or relationship between
physiochemical properties and relevant qualitative results. This affects potential of
electronic and chemical interactions adjustments and biological and chemical sens-
ing properties.
1070 R. Chauhan et al.

Though the global demand of zinc oxide nanoparticles are dominated by UVA/B
filters in sunscreens and cosmetics, they also ride on lot of other benefits like
anticorrosion, antifungal, photochemical, catalytic, electrical, antibacterial, ultravi-
olet filtering, and photovoltaic properties. Its cosmetic and non-cosmetics use can go
beyond powders, creams, ointments, etc., due to their UVA and UVB blocking
abilities.
Deliberations in synthesis technique could open up gamut of applications satis-
fying commercial feasibility. This could be synthesized into nanorods, nanocables,
nanoneedles, nanowires, nanotubes, etc., with new electronic, visible, and functional
properties.
Dominance of ZnO nanoparticles is observed in multinationals branded high-
tech chemical firms engaged in cosmetics and sunscreens, followed by their
applications in automotive, paint, biomedicine, and last but not the least academics
and research.

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Utilization of Consumer Nanoproducts
for Cosmetics and Their Impacts 47
Shashi Chawla, Divyanshi Thakkar, and Prateek Rai

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1074
Types of Nanoproducts Used in the Cosmetic Industry (Fig. 1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1075
Nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1075
Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1075
Nanocapsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1076
Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1077
Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1078
Cubosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1078
Bucky Balls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1079
Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1079
Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080
Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1081
Niosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1082
Polymerosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
Zinc Oxide and Titanium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1083
Cosmetic Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
Hair care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
Nail Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
Lip Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
Deodorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
Perfumes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
Commonly Used Nanoparticles in Cosmetics and Efficacy of Herbal Nanocosmeceuticals . . . 1090
Health, Safety, and Environmental Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1090
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091

S. Chawla (*) · D. Thakkar · P. Rai

Department of Chemistry, Amity Institute of Applied Sciences, Amity University Uttar Pradesh,
Noida, India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1073

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_101
1074 S. Chawla et al.

Abstract

Nanoproducts have gained the utmost attention all over the world fundamentally
due to their high surface to mass ratio, high reactivity, and enriched applications
of use. The nanoscale versions of ingredients used by the cosmetic industry for
lip, skin, nail, and hair care provide enhanced color and finish quality, better UV
protection, site-specific targeting, longer-lasting effects, deeper skin penetration,
transparency, solubility, etc., with high benefit to cost ratio. Products like UV
filters in sunscreens and moisturizers are expected to have high Sun Protection
Factor (SPF) and their quality can be restored with the use of nanoparticles of
ZnO, TiO2, etc., which reflect and absorb UV rays. Buckminsterfullerene (C60)
has the property to act as a scavenger for free radicals so it is used in facial
creams. This chapter mainly focuses on the application, benefits of nanoparticles
in the cosmetic industry, and their effect on human health and the environment.

Keywords
Nanoproducts · Cosmetics · Benefits · Health concerns · Environmental concerns

Introduction

Nanomaterials are a class of compounds in which the size of the particles is

measured in nanometers. Nanotechnology has proven to be promising in various
fields of science, engineering, and medical science. Over a period of few years,
nanotechnology has developed many applications in different industries. The cos-
metics industry is considered the most recognized industry for the use of nanotech-
nology. The nanoparticles made up of gold and silver are being used in face creams
and nail paints for a long time. The cosmetic industry has numerous applications of
nanoparticles in various types of cosmetic products like skincare, lip care, hair care,
nail care, perfumes, deodorants, etc. The most common applications in the field of
skincare include UV protection creams that are used for the protection of our skin
from sun rays. The majorly used nanoparticles in such applications are niosomes and
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1075

liposomes [1]. Nanomaterials synthesized from different class of substances like

organic, inorganic, polymeric, carbon-based, etc., can be used in the manufacturing
of cosmetics. The cosmetic composition is formed by mixing oil and water, making
emulsions out of them. They increase the size of the particle from 50 nm to 100 nm
because of the aqueous makeup which makes them easier to penetrate [2–8].

Types of Nanoproducts Used in the Cosmetic Industry (Fig. 1)

Nanocrystals

Brief Description
Nanocrystals are clusters of hundreds of atoms, sizes of which range between 10 nm
and 400 nm.

Properties
Nanocrystals are reported to be chemically and physically stable [8]. Their properties
such as bandgap, charge conductivity, crystalline structure, and melting temperature
can be tailored by controlling their size and surface area. By dispersing the nano-
crystals in water, they can have a foamy nature which can be used for the treatment of
skin ailments. By controlling the size as well as the surface area of the nanocrystals, the
properties like structure, melting point, charge, etc., can also be controlled [2, 9–12].
Factors helping in skin penetration of nanocrystals:

(a) Concentration gradient helps in increasing the saturation solubility which leads
to better skin penetration.
(b) The large size of nanocrystals leads to quicker solubility.
(c) Solubility can be increased by small-sized nanocrystals.

The increased loading capacity of nanocrystals can lead to more retention in the
skin [8, 13].

Hydrogels

Brief Description
Hydrogels are polymers, generally having a three-dimensional structure.

Fig. 1 Nanocrystals, hydrogels, and nano-capsules used in the cosmetic industry

1076 S. Chawla et al.

Properties
On combining with any biological fluid or even water, they swell [8]. They can swell
without dissolution because of the crossovers between their molecular masses
[13, 14]. There are many characteristic features of hydrogels and they can be
modified or replaced as these changes can prevent any mutilation [15]. Hydrogels
are usually pH-sensitive materials, because they have cosmetic molecules, for
example, at pH 4, the compounds have drugs that penetrate through the skin, and
at pH 6, the skin penetration increases.

Uses
Applications of hydrogels extend to facial marks, antiwrinkle creams, etc. [14, 16–
22]. Depending on the need for new products, specific modifications can also be
made in the foreseeable future [15].

Nanocapsules

Brief Description
Nanocapsules are very small particles that are composed of polymer and surround a
core, generally made up of liquid and fat content [8, 13]. The diameter value of
nanocapsules is about 115 nm. As the core of the nanocapsule is usually made up of
water or oil, it can dissolve octyl salicylate using acetyl trimethyl ammonium
chloride [23]. The core of the nanocapsule has a high carrying capacity and has a
very low content of the polymer [24].

Preparation
The preparation of nanocapsules includes an enclosing technology and they have
major application in targeted drug delivery [2].

Uses
Nanocapsules, like any other nanoparticle, have applications in cosmetics and
dermatology. They can be applied to release the longing active substances, protect
them from oxidizing, and reduce unpleasant odors [25]. The small structure of
nanocapsules helps the release of active agents in a controlled environment
[15]. Nanocapsules are used as the sole ingredient in preparing many active com-
pounds such as UV protectors. Applications of nanocapsules also extend to anti-
wrinkle creams and sunscreen lotions [24] (Fig. 2).

Fig. 2 Nano-emulsions, dendrimers, and cubosomes used in the cosmetic industry

47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1077

Nanoemulsions

Brief Description
Nanoemulsions are made up of a two-phase system, in which water, oil, etc., are
present and they form the usual contents of makeup. Their size ranges from 50 nm
to 100 nm and they usually disseminate in the liquid phase [24]. The small
size of these nanoemulsion capsules helps in the proper delivery of drugs and
optical activity [1]. The small size of droplets is reported to help improve skin
absorption [26].

Preparation
Based on their composition, nanoemulsions can be classified as:

(a) Oil in water

(b) Water in oil
(c) Bicontinuous [6, 28].

There can be two methods, based on which nanoemulsions can be prepared

(a) High energy: It is a mechanical process, in which pressure is applied. Production

is done on small scale.
(b) Low energy: This is based on the physicochemical process, like surface
tension [29].

Properties
Many properties of nanoemulsions can be generated just by combining oil and water
and applying mechanical stress on them. The properties like better carrying capacity
and higher stability are because of small proportions. They also help in providing
thermal strength and can carry hydrophilic as well as hydrophobic molecules
[8, 13]. Nanoemulsions are mostly transparent and exhibit other important properties
like kinetic energy, high contact area, solubility, etc. [14, 27]. These biodegradable
tissues can help provide antiwrinkle creams. When nanoemulsions are formed, they
are contained by nonpolar hydrocarbon chains [26]. The unique texture of nano-
emulsions makes them very valuable.

Uses
There are several uses of nanoemulsions in the production of cosmetics, some of
them include the production of bath oils, body creams, antiwrinkle or antiaging
creams. It is reported that nanoemulsions are used in moisturizing the skin. Another
example is palm oil esters because they are moisturizing and nonirritant to the skin.
Olive oil can be used as an application in the field of cosmetics. Another application
of nanoemulsions is sunscreens produced by mechanical valves. The developments
in the sector of nanoemulsions also include improving skin conditions because of the
presence of lipids [26].
1078 S. Chawla et al.

Dendrimers

Brief Description
Dendrimers are highly bifurcated structures and are widely used in cosmetic prod-
ucts. They are composed of a single molecule and tiny structures [29]. The outer
shell of dendrimers is reported to be hydrophobic and its core is said to be hydro-
philic, due to which they have symmetrical branching. The size of the dendrimers
usually ranges from 2 nm to 20 nm [27, 30–32]. These are branched with carbon-18,
at the inner shell and polyethylene glycol, at the outer shell [33].

Properties
Dendrimers are even more stable than liposomes and due to this, they do not easily
decompose when applied to the skin. Some compounds like indomethacin and 5-FU
show increased skin absorption. This happened due to the addition of amines,
another nanoceramic to aqueous formulations when they were used on a rat for
experimentation purposes [23]. Many functional groups are attached to it so that it
can perform many functions at a time [8]. Dendrimers that attract cations can reduce
skin infections of cosmetic formulation which contains anionic emulsifiers.
Dendrimers have many properties such as solubility, biodegradation, and biocom-
patibility. The most common functional groups of dendrimers are carbylamines,
carbohydrates, and ethers. They disperse exceedingly and also have a low cost of
manufacturing and many companies manufacture it in bulk [26]. Some of the
examples of dendrimers include 5 DSA and CMS [33].

Uses
Targeted drug delivery uses the rarest end of a dendrimer[15]. Dendrimers can be
used in sunblock cream, shampoos, antiacne lotions and can be utilized in the
formation of hair, skin, and nail treatment [15]. Dendrimers are also extensively
used in spray gels, lotions, shampoos, and deodorants [14].

Cubosomes

Brief Description
Cubosomes are self-assembled liquid structures arranged in random form and the
size of which is very small [27]. The ratio of the structure is very small. It is also heat
resistant and can also carry hydrophilic and hydrophobic molecules [8].

Properties
Cubosomes are not soluble in water because of their cubic structure which is responsible
for lipid deposit on them [14]. These are usually emulsifiers and are crystalline
[27, 34]. They have sufficient internal surface area, easy preparation technique has
biodegradable lipids, and the potential of encapsulating hydrophobic, hydrophilic, and
amphiphilic compounds, targeting the bioactive agents [15]. These are biodegradable
and thermodynamically very stable and have a pasty appearance. They are found to be
biocompatible [33].
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1079

Uses
Currently, cubosomes have many appealing applications in the cosmetic industry. Soon,
the cosmetic industry can do major developments using cubosomes. Skincare, haircare,
and cleansing mechanism are some of the applications of cubosomes [13] (Fig. 3).

Bucky Balls

Brief Description
Buckminsterfullerene, Carbon-60, is used as a nanomaterial with a diameter of about
1 nm.

Preparation
They are nanoscale materials produced as a side product during the manufacturing of
nanomaterials.

Properties
Generally, it is utilized for its ability to behave like a free radical attractor [8]. The
antioxidizing power of fullerene is even more than vitamins.

Uses
They give a brightening effect and also result in controlled melanin production.
Their applications involve creams responsible for a healthy and fresh look and for
cleaning the dark circles around the eyes [15].

Carbon Nanotubes

Brief Description
Carbon nanotubes are cylindrical, hollow shells that are synthesized by rolling a
graphene sheet with sp2 hybridized carbon. Their diameter ranges from 0.7 nm to
50 nm. The nanotubes have an arrangement that they form a DNA-like
structure [33].

Preparation
Carbon nanotubes are prepared by arc discharge, laser ablation, fame synthesis, etc.
[27]. However, even in unmodified conditions, carbon nanotubes localize with
certain cytoplasmic vacuoles and can cause skin infections [23].

Fig. 3 Buckyballs, carbon nanotubes, and solid lipid nanoparticles used in the cosmetic industry
1080 S. Chawla et al.

Uses
The applications of carbon nanotubes include cosmetic products like hair coloring
and cosmetic composition and amino-based carbon nanotube colors that can be
applied on hair [27].

Advantages
The advantages of carbon nanotubes include cosmeceuticals like fat-based carbon
nanotube colors which can be used in hair [1].

Solid Lipid Nanoparticles

Brief Description
Lipid-based nanoparticles are primarily of two types, namely, solid lipidnano-
particles (SLNs) and nanostructured lipid carriers (NLC) [4]. Solid lipid nano-
particles are formed from solid lipid and have a diameter of less than 1μm
[25]. These are first-generation lipoidal drug carrier systems [35].

Preparation
Raw materials such as lubricants are often used to make solid lipid
nanoparticles [25].

Properties
Physiological and biocompatible lipid make up this system when scattered in
water or any other aqueous solution. This system has a waxy core that is covered
by an outer layer that can capture anything important for properties. The popu-
larity of solid lipid nanoparticles in cosmeceutical fields has increased due to the
use of biocompatible ingredients which cause morbid issues [25]. Solid lipid
nanoparticles are employed in cosmetic products because they penetrate the skin
and ensures proximity with the stratum corneum because they have small pro-
portions and are said to be occlusive, which makes it a skin hydrating reagent
[35]. They also resist UV rays which makes them a good reagent to act as
sunscreens due to which they form a constituent in sun-protecting products.
They have improved photoprotection and fewer reactions on the skin. An alter-
native to liposomes and emulsions for carrier systems, solid lipid nanoparticles
are used due to their solid matrix [1]. It does not have any trouble when produced
in bulk [27]. The release of active substances can be controlled whereas the
bioavailability of captured bioactive agents is increased. It has a large variety of
applications [27].

Uses
Solid lipid nanoparticles are used in perfumes as well as creams as they have
modified-release patterns [35, 36].
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1081

Fig. 4 Liposomes, niosomes, polymerosomes, zinc oxide, and titanium dioxide used in the
cosmetic industry

Advantages
Despite having so many advantages, there are drawbacks like having poor drug
loading capacity due to partitioning effects and sometimes, even excess release can
also take place [27] (Fig. 4).

Liposomes

Brief Description
Liposomes are two-layered structures with concentric tubes which generally enclose
a double layer of fatty substances that can be both natural or synthetic and are
regarded as toxin-free products. The shape of liposomes is spherical and it has one or
more layers that contain two layers of fatty substances and encloses a watery core.
The diameter ranges between 50 nm and 100 nm. Liposomes are very stable and
have a plane sheet-like structure which is formed rapidly when it comes in contact
with an aqueous layer.

Preparation
The synthesis of liposomes can be summed up in three stages. The first stage is the
hydration of lipid, the second is designing the structure of the liposome, and the third
concludes by the removing of active substances that are not enclosed in the lipo-
some. The chemical and physical aspects of liposomes can easily be classified after
the preparation of the liposome [25]. Liposomes are divided into many small parts,
some of which also include nanospheres [38].

Properties
Properties of liposomes include:

(a) Liposomes can carry aqueous, amphiphilic, and fatty substances. This is possible
because of their biphasic character.
1082 S. Chawla et al.

(b) The determination of the position of the bilayer depends on its ability to dissolve
a compound. The compounds which are less soluble in water have minimal
storage capacity in such compounds [37].

The reason why liposomes are used in a variety of cosmetics is because of their
biodegradation capacity and ability to enclose cavities [27]. Liposomes can have an
advantage in terms of skin absorption because they can change shape [23]. Owing to
their exceptional chemical properties, liposomes can act directly on the skin which
results in the replacement of the lipids present in the stratum corneum [25].

Uses
For skin, sheltering of active substances is done by liposomes, and in the branch of
cosmetology, the researchers are still finding their other applications. Some of the
molecules, for example, astaxanthin, have helped to prevent spots and wrinkles on
the skin by nascent oxygen. But there is a limitation to astaxanthin that it requires
an organic solvent because the direct use on skin can be harmful. After all, it is
highly lipophilic. There are many uses of astaxanthin in the cosmetic industry
[39]. Liposomes are used to treat disorders related to skin, scalp, underarms, and
foot odor. This is possible because liposomes can bind to microorganisms
[40]. Liposomes have many applications in the cosmetic industry. They are
designed to deliver active substances in the epidermis; this is required for absorb-
ing the active ingredients in the skin layer. Sunscreens that use liposome-based UV
filters are very useful because they prevent getting easily removed from the skin.
Liposomes can also prevent dryness and replenish the skin due to their lipid
formulation [37]. The applications of liposomes extend to cosmetics because
phospholipids have some fatty acids which are esterified and are also present in
vegetables [15]. Liposomes have some limitations like they can be very leaky at
times, have very little capability of carrying, minimized reproducibility, and are
less commercial [40].

Niosomes

Brief Description
Niosomes are prepared by coagulant substances, like polyoxymethylene alkyl ethers
and cholesterol mixtures, etc. Several other types of ethers are used [27], which are
insoluble in water with a fatty layer such as lipids. The aftermath of the process
includes homogenization reduced vesicle size which is then separated of a drug
which is usually un-entrapped. The factors affecting the properties of niosomes
include preparation, temperature, technique, and composition.

Properties
Niosomes also have improved stability, high purity, and low cost of production [37].
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1083

Polymerosomes

Brief Description
Polymersomes are composed of self-composed block copolymers which usually
having two layers and comprise artificial vesicles with an aqueous hole in the center.
Their size varies from 5 nm to 50 nm or more. They have a watery and fat-soluble
inner core which is two layered. This makes them very useful for lipophilic and
hydrophilic drugs. Their hydrophobic part acts as a protein surrounding [27]. Using
polymersomes is a proficient way to protect and encapsulate different sensitive
molecules such as RNA fragments, DNA, enzymes, peptides, proteins, and drugs [15].

Properties
Varied properties of different block copolymers prepare polymersomes with different
characteristics like membrane thickness, permeability, and stimuli sensitiveness [33].

Uses
The main uses of polymersomes include functioning as an envelope and act as a
shield to sensitive molecules [27].

Zinc Oxide and Titanium Dioxide

Brief Description
Titanium dioxide is made by the combination of two crystals-rutile and anatase,
which are then used to make personal care products.

Properties
When ZnO was tested on the stratum corneum, there was no absorption taking place
on the skin, but when TiO2 was used, it showed absorption at deeper levels [23].

Uses
Zinc oxide and titanium dioxide are widely used in many applications of nano-
particles. Zinc oxide as well as Titanium dioxide are utilized for the function of
protection against UVA and UVB rays. Two kinds of filters are used to make
cosmetic makeup easier, one of which includes dispersions and the second is
inorganic filters [41]. Titanium dioxide, when dipped in carnauba wax, enhances
the SPF factor [2]. Titanium dioxide and zinc oxide can be used in many
sunscreens protection creams as it scatters and reflects UV light [42]. Titanium
oxide is more harmful as it penetrates the epidermis layer of the skin and the skin
appears to be loose. This is the reason why the effects of nanoparticles are
considered to be hazardous sometimes [24]. Investigations and experiments
were also done on zinc oxide and it was reported that zinc oxide proved to be
toxic to organisms [43].
1084 S. Chawla et al.

Cosmetic Products

Skin

Skin is regarded as the most important part of the human body. As we know, the
main function of the skin is to provide a shield against the external environment [4].

Structure of Skin
The skin has three coatings or layers, of which the first is called the epidermis. It is
the outermost layer, which is visible to us. Epidermis also has four distinct layers, the
innermost is called the stratum basale, followed by stratum epidermis, stratum
granulosum, and stratum corneum [37]. The second layer is called the dermis and
is situated deep below the epidermis layer. The third layer, which is located under the
dermis, is called the subcutaneous tissue, which is mainly made up of fat [44].
Skin portrays a vital role in the body of a human and optimizes itself depending
upon external conditions.

Some of the Major Functions Are

• It restricts the release of important body fluids, and it also prevents the entry of
toxic substances inside the body.
• It helps in maintaining body temperature and tries to keep it around 98.6  F.
• If any toxic substance enters the body, it tries to secrete it through sweat.
• It helps provide a sheet to decrease the penetration of harmful radiations of
the sun.
• It protects the body from extreme climatic conditions.
• It helps absorb vitamin D in our bodies.

Penetration of Nanoparticles in the Skin

The three major optimum ways of penetration of nanoparticles inside the skin are
intercellular, transcellular, and trans appendageal [4]. These methods help us to
deduce the mechanism involved in skin penetration through the stratum corneum
[37]. There are many properties like skin penetration, toxicity, etc., that can be
influenced by the size, shape, coating, and purity of nanoparticles [4]. Flexible
structures like that of liposomes have been discarded during penetration, while
particles like solid lipid nanoparticles were found to be included in the process of
penetration. The skin penetration using very fine particles like TiO2, ZnO, and
quantum dots was also included [41]. But, after some time, it was seen that TiO2
cannot penetrate through pig skin so the chances of it penetrating through human
skin were unlikely [6].

Penetration of Quantum Dots

There are two types of quantum dots known to us. The basic structure of quantum
dots has two layers, spherical and ellipsoid, and they can be cationic anionic or
neutral. Their skin penetration can occur in 8–24 h and they have been reported to
produce spectra of samples [41].
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1085

The use of dendrimers and polymers was also explored, in which polymers were
found to be of smaller size and therefore are easily soluble based on their structure.
Polymers were found to be very stable, which was not the case with lipid vesicles as
they do not bifurcate in the skin. While using dendrimers, enhanced skin absorption
was seen when used on rat skin [6].

UV Radiation and Its Effects on the Skin

Particular attention was devoted to the UV component of the electromagnetic
spectrum, in the wavelength of 100–400 nm, which are classified as follows:

• UVC is regarded most dangerous portion and can cause immense damage to the
skin, but they are protected by the ozone layer of the atmosphere and it helps
prevent them from reaching the earth’s surface.
• UVB is absorbed by the ozone layer and is in the troposphere, but it can cause
damage to DNA causing skin tumors.
• UVA causes the maturation of skin and is the reason why photosensitive reactions
take place. They have high penetration ability and can cause damage to the
epidermal layer of the skin.

Skin tumors are caused by the exposure of skin to UV radiation due to solar
radiation. They also cause mutilations in the skin [44].
Usage of nanomaterials should be done safely as there can be risks involved
associated with the process [45] (Fig. 5).

Applications
Many antiaging creams, regeneration creams, sunscreens, and some vitamins like
vitamin A, E, and C are extracted from liposomes that have proven effective for the
skin. Many methods are used to increase their penetration in the skin, as some
nanoparticles like niosomes and liposomes show limited penetration in the skin have.

Fig. 5 Application of nanoproducts

1086 S. Chawla et al.

Some aids like folic acid, composed of vitamin B-9, are used to improve hair and
condition of the skin. It is used as it provides a barrier for the skin. Vitamin K-1 acts
as an antioxidant that helps in antiaging effects which showed penetration in the
dermis layer of the skin [26]. The cosmetic products were seen fighting harmful
reactions of free radicals when used in a developed form [15].
In antiaging creams, some nanoparticles were used such as nanocapsules, nano-
spheres, and nanosomes. These nanoparticles were reported to regenerate skin,
lifting and moisturizing the skin as well [33].

Antiaging creams: In winters, skin dryness is a general problem that leads to the use
of creams that forms a thin film of an oily layer, helping in moisturizing.
Moisturizers are also useful for preventing water loss and restoring the functions
of the stratum corneum [15].
Skin cleansers: Skin cleansers are used for removing oil, dirt, makeup, and dead skin
cells. For this, metallic nanoparticles can be considered, which act as a skin
disinfectant and are also used to moisturize skin [15].
Creams: An emulsion such as oil in water or water in oil is used as creams and can be
applied to the skin directly. Creams were initially having an orange color and are
generally odorless and smooth. The formation of creams was seen to be homog-
enous without any lumps. Creams were found to be at a pH of 6.8–7 which means
they are neutral [46].

Hair care

The health of a person can be estimated by the hair condition of the individual. The
hair is composed of carbon, oxygen, nitrogen, hydrogen, and sulfur, combined in
certain portions. The most common compound in hair is keratin. It is strong and hard
and makes up for the fibrous layer in the hair. Zinc and chitin have the responsibility
to provide fibrous structure to the hair [14].

Structure of Hair
• Hair shaft
The top part of the hair is called the hair shaft and it emerges from the scalp and
is majorly made up of dead cells. It is made up of three parts: cuticle, cortex, and
medulla
• Hair follicles
They are the part of the hair that reaches into the skin, which is usually the
epidermis layer. The thickness of this part usually depends on the active sites of
the skin.

Hair Problems
Hair damage: Hair damage is caused by various agents, like genetic or due to any
external sources. The damage caused by the hair shaft is due to the routine in our
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1087

daily life which causes some harmful effects on the hair. Some of the causes can
also be damages caused by chemical, physical, and heat.
Hair greying: It can be reduced through hair dyeing.
Alopecia: It can be caused due to increased applications of hair products and is
known to make our hair cells dead.
Dandruff: Dandruff problem is caused due to the drying of the scalp, but there can be
several factors leading to dandruff. They are common in men and women and are
generally caused when they hit puberty or in the winter season. Some of the major
causes of hair damage can be hair color or the production of melanin. They can
also be caused by more serious problems, such as Alzheimer’s, Parkinson’s, gold
nanoparticles, and graphene [29].
Hair colors: Hair color is made up of two types of pigments, and both of them are
melanin. The two pigments, namely, eumelanin and pheomelanin, give black,
brown, and red color to hair.

Haircare Through Nanocosmetics

Nanocosmetics like niosomes, microemulsions, nanoemulsions, etc., have been
efficient in providing shine, softness, and nongreasiness to the hair. These are
applied to the hair through shampoos, conditioners hair stimulants, and styling
products [26]. They are prepared from nanoparticle colloids and also help us in the
treatment of hair depletion caused by bacteria. The nanoparticle’s composition in
these products should be about 0.15 ppm [2]. Nanoemulsions can be used in the
treatment of hair loss which is usually caused by hormones, genetically, or by some
chronic swelling. It is known to affect the follicle part of the hair and the scalp. The
infusion of these compounds in the nanoemulsions creates reduced side effects and
can also help reduce the source of the problem.

Nail Care

The nail care industry has many applications and is regarded to be the largest
industry [15].

Nail: A nail is composed of multilayered tissue. It is known for making the outer
layer of the nail which provides the nail plate [47].
Nail coatings: There are a variety of nail coatings that can be used. One of them
being flexible plastics or vinyl, commonly known as extensions, on which the nail
polish is applied afterward and has a gel-based coating. This is applied using UV
rays, which prevent cracking in the nail and are used after applying the nail
polish, as a final step. Top coatings are also applied to prevent the nail polish from
cracking. There were also base coats used to protect the skin, but certain
researches revealed that those base coats contained nanoparticles that penetrate
the skin and make the skin under the nail look even worse. Cracking can also be
an after-effect from uneven drying of the solvent of the topmost layer. The nail
1088 S. Chawla et al.

polishes which change color are made up of polymeric matrix and they possess
thermal stability and are capable of many photochemical reactions.
The advantage: The coatings have water-based polymers and emulsions that are
made up of oil and water. These coatings are water and oxygen permeable. [47].
The nail paints contain silver, metal oxides, and antifungal particles. The nail paints
made from nanoparticles have many advantages as they dry fast, they are durable,
and they have elasticity. [26].
Nail polishes provide elegance to the users. It also provides a protective layer on the
nail which provides both toughness and flexibility.
Drawbacks: Many times, bad quality nail paint can lead to staining of the nail which
proves to be very toxic. It is advised by a specialist to remove the nail paint in
5–7 days as they can lead to nail lacquers [46].

Lip Care

The lip care products are lip balm, lipstick, lip gloss, and lip volumizer. The lipstick
types can be lip liquids, pencils, lip balms, roll-ons, etc. [48]. Many nanoparticles
provide a shield to water and are called waterproof lipsticks and lip balms. It also
helps in providing long-lasting effects [15].

Importance of the lip care products: Lip care is considered an essential beauty
regime and involves lip healing properties. Once a lip protective agent is
applied, it prevents bleeding. It is seen that nanogold and nanosilver provide
pigments in lipsticks and are responsible for giving red and yellow color,
respectively. They are considered to be safe pigments; hence, we use nanogold
and nanosilver to large extents. Some silica nanoparticles are used in lipsticks.
They are known to provide pigmentation at a uniform level and also heal
bleeding lips [33]. Lip products cause an increase in volume, matte effect, and
glossiness.

Deodorants

The main purpose of using a deodorant is to reduce body odor. Deodorants are less
irritating than antiperspirants. The use of deodorants has increased in foreign places [49].

Types of Deodorants
Antiperspirant active-containing deodorants: Antiperspirants are used to reduce
the excessive stress in our body with the use of metals like aluminum and
zirconium.
Odor-masking deodorants: These are applied to hide the body odor.
Odor-neutralizing deodorants: These are the deodorants that are used to neutralize
body odor.
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1089

Odor-quenching deodorants: These are the deodorants that are used to hide the
antiperspirant effects.

Esterase Inhibitors
Zinc glycinate: These are the salts that are used to reduce the enzymes caused by the
excessive sweat released from the body.
Antimicrobial active-containing deodorants: These are the deodorants that prevent
underarm odor [50].

Perfumes

The fragrance is an odor or scent that is pleasant to smell. The pleasant fragrances
can be derived from the fragrances like flowers, pine trees, mint, musks, camphor,
etc. Out of these, the fragrance made from flowers is considered to be of more
importance [50].
Production of aroma can be done by the use of nanoparticles such as gold and
palladium and is known to replace toxic or hazardous aromatic products. There is a
procedure called nanoencapsulation, which is used in the manufacturing of
expensive but good quality perfumes. In this process, there are no harmful
by-products [50].
The nanomaterials utilized for the production of aroma have a particle size
smaller than 100 nm. The nanoparticles used in the production are made up of
inorganic metals and their oxides, such as silver, titanium dioxide, silicon dioxide,
iron dioxide, and zinc oxide, and certain organic components such as lipids, proteins,
and carbohydrates [50]
Many types of emulsions are used in the making of perfumes. Some of which are
water-based, that is alcohol-free, and nanodispersions that carry fragrances. Due to
the small droplet size, perfumes are transparent or translucent, but sometimes they
appear milky. Nanoemulsions are also used in the production of perfumes. The type
of nanoemulsions that are used is high energy-based, high pressure-based, ultra-
sonication, low energy-based, spontaneous, etc. [51].

Home Fragrance Products

There are many types of products that can be used in providing freshness to our
homes, toilets, kitchens, etc. The products include scented oils, incense holders,
room fresheners, and lamps [50].

Fragrance for Body

Many scents can do wonders for your well-being. They can improve the condition
of the body and mind. They constitute lavender, which can help induce sleep,
cinnamon can sharpen the mind, pine can alleviate stress, fresh-cut grass can make
one more joyful, citrus can help feel more energized, and vanilla can elevate the
mood [50].
1090 S. Chawla et al.

Fragrance Affects Your Skin

Fragrances can also affect our skin. It causes itchiness redness and, in some cases,
hives. Using expired perfumes can cause burning sensations and rashes. It can be
prevented by using water directly on the skin but in severe medical conditions, one
should consult a doctor [50].

Commonly Used Nanoparticles in Cosmetics and Efficacy

of Herbal Nanocosmeceuticals

The particle size of nanoparticles has an average diameter of 85 nm and consists of

an oxygen complex. Nanoparticles based on polyacrylonitrile can be prepared after
doping them with fluorine. Production of dye uses them. Some studies show that
different nanoparticles cause different kinds of biological effects. The use of titanium
dioxide is reported to be harmful to the body as it causes cell damage and leads to
drastic effects. On the contrary, when the experiments were done with zinc oxide, the
damage of the cells was found to be minimum and the activation of certain things
like caspases did not take place. The results were proven to be highly safe and
provided benefits to the consumers. Moreover, the studies showed that nanoparticles
are not biologically inert. Nanoparticles based on zinc oxide have many applications
such as action against bacterial diseases [53, 54].
Conducted studies help us understand the adverse effects caused by making
cosmetics of synthetic nanoparticles. The use of natural ingredients in the making
of nanoparticles has provided many advantages and is considered safe. They are
found to have a lesser toxic effect on the skin. Consumers are now attracted to
natural substances. The first reason is awareness. People now know the side effects
of using synthetic nanoparticles; hence, they lean towards herbal-based nano-
particles. Now, the use of herbal nanoparticles has increased significantly. The herbal
ingredients used in the sunscreens help them penetrate deeper into the skin for better
protection. Some of the known applications of herbal-based nanoparticles are being
utilized as sunscreens, antiaging creams, etc.
Nanoparticles are utilized in the compositions of herbal-based nanoparticles.
Some of which are nanoemulsions, solid lipid nanoparticles, niosomes, pyrosomes,
ethosomes, etc. Liposomes help us by increasing the deposition of nanoparticles in
the skin which improves the blockage of deposition of nanoparticles in the skin.
Nanoemulsions help by increasing the deposition of fragrances. Solid lipid nano-
particles help us in improving the stability of reactions that take place inside our
body once the herbal nanoparticles penetrate [55]. The herbal extracts from plants
give us protection against irritants and microbial activity, etc. [7, 56–59].

Health, Safety, and Environmental Impacts

Toxicity in humans due to nanoparticles is caused because of some metallic bonds

between silver ions, zinc oxide, and titanium oxides. Toxicity is also caused by the
use of disinfectants we use in drinking water and the preserving agents often used for
47 Utilization of Consumer Nanoproducts for Cosmetics and Their Impacts 1091

storage purposes. This has forced scientists to take adequate tests before the
manufacturing process [59].
In many cases, it is seen that the size of the particle is responsible for the toxicity
in the human body [59–65]. Programs are being conducted that result in maintaining
human health, which helps using the nanoparticles to an optimum sight [30]. The
toxicity of nanoparticles can extend to organisms and eventually reach human beings
via the food chain. This happens because the wastewater accumulates the nano-
particles present in the cosmetic products and ends up getting in the food chain
through biological processes [40].
Some conducted studies provide us information about product safety [66]. The
safety of nanoparticles also depends on the size of the particle, chemical structure,
and composition of the nanoparticle. The size of the nanoparticles mostly ranges to
100 nm. Larger nanoparticles do not penetrate through the skin [39]. There is a
chronic health effect when people use nanoparticles in an excessive amount. The
chemicals we use, cause irritations and may cause adverse health effects [59]. Zinc
and titanium, when utilized in the making of nanoparticles, also cause adverse effects
on the health and environment [42].
Dendrimers based on polymers have also been tested to be toxic for human
beings [38].
Among all the nanoparticles used, the toxicity caused by silver is less. Due to this,
the consumption of silver nanoparticles has increased in cosmetic products [59].
Polymers are usually biodegradable so they have less or no adverse effect on
human health [38].

Conclusion

Due to their unique properties, nanoparticles are playing a huge role in the cosmetic
industry. The nanotechnology we are using right now is helping us with making new
products and enhances the quality of the others. Besides their numerous advantages,
still there are several cons related to the toxicity and other health hazards in the use of
nanomaterials in cosmetics. Seeing these side effects of using synthetic nano-
materials, the focus is being directed to increase the usage of herbal nano-
cosmeceuticals. They have the efficacy of a synthetic nanoparticle with minimal or
zero side effects. In the coming future, the use of these herbal products in the making
of cosmetics will increase rapidly, considering the need of people of consuming safe
and secure products. Also, the proper disposal and handling of nanomaterials are
required to minimize environmental hazards.

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s40820-015-0040-x

Further Reading
Arun Nanda; Sanju Nanda; Tuan Anh Nguyen; Susai Rajendran; Yassine Slimani (2020) Nano-
cosmetics 1st edition fundamentals, applications and toxicity
Khan FA (2020) Applications of nanomaterials in human health. Springer, Singapore
Peppas NA (2000) Principles of polymer science and technology in cosmetics and personal care.
J Control Rel 68:303. https://doi.org/10.1016/S0168-3659(00)00252-2
 Part XIII
Consumer Nanoproducts for Environment
Nanoproducts: Biomedical, Environmental,
and Energy Applications 48
Shikha Kaushik

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1098
Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1100
Nanoproducts: Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1102
Nanoproducts: Environmental Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1104
Nanoproducts: Agricultural Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1110
Nanoproducts: Energy Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1112
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1118
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1119

Abstract
The word “nano,” derived from the Greek word nanos meaning “dwarf,” is now
being extensively used not only by the scientific community but also by a common
man in daily life. Many “nano-” words (nanometer, nanoscience, nanotechnology,
nanoscale) can be easily found in dictionaries, and some recent additions are
nanostructure, nanomaterial, nanoproduct, nanorobot, nanowire, nanodevices,
nanoarrays, and nanotools, and the list is endless. The developments and advances
in the field of nanoscience and nanotechnology have made life uber easy in this era.
Nanotechnology represents an emerging field which deals with the designing,
manufacturing, and application of materials at the atomic and molecular scale.
These materials exhibit novel properties and functions with structural features
having at least one dimension in the nanometer scale (1–100 nm). The important
role and application of nanotechnology in almost every field of science is quite
evident by large number of research papers published in this area.
Nanotechnology paved way to the development of new innovative materials,
systems, and devices which seem to have promising results and potential to tackle
most of the problems the world is facing today. It has benefitted almost every field of

S. Kaushik (*)
Department of Chemistry, Rajdhani College, University of Delhi, New Delhi, India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1097

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_63
1098 S. Kaushik

science including chemistry, biology, physics, material science, engineering, envi-

ronmental science, food and agriculture, medicine, and information technology. This
emerging research field has given new perspectives or solutions to many environ-
mental problems like availability of clean water, nanocatalyst for hydrogen genera-
tion, dental materials, drug delivery systems, antimicrobial nano powders,
nanosensors for detection of pathogens or toxic materials, gas-separation nano-
devices, and many more. In recent years, it has also been applied to medicine and
healthcare for the development of nanodevices to prevent, monitor, and treat lethal
diseases, and promising results are achieved especially in the cancer treatment.
Although the advancements and innovations in this field have significantly improved
the standard of living, nevertheless, there are associated concerns and uncertainties
about its impact on human health. These concerns can be overcome by utilizing the
concepts of green chemistry and green engineering to produce nanomaterials and
nanoproducts, which can significantly contribute toward novel discoveries and
developments without causing detrimental effects on environment and human health.

Keywords
Air remediation · Carbon nanotubes · Catalyst · Energy · Environment · Medicine
and healthcare · Nanofertilizers · Nanoproducts · Solar cells · Wastewater
treatment

Introduction

Nanoscience is a branch of science which deals with the study of molecules and
structures in the nanometer scale, ranging from 1 to 100 nm, and the technology that
utilizes it for manufacturing of materials and devices is called nanotechnology.
Nanotechnology and nanoscience have been widely exploited in recent years in
various fields, ranging from medicine to environmental science. As a comparison
and to help understand how small a nano is, one must know that an average human
hair has a thickness of 60,000–1000,000 nm and, our fingernail grows 1 nm every
second. Also, the diameter of DNA double helix, the genetic material in almost all
living organisms, except few viruses, is 2 nm. The concept of nanoscience and
nanotechnology was first introduced by American physicist and Nobel Laureate
Richard P. Feynman during his talk entitled “There’s Plenty of Room at the Bottom”
at an American Physical Society meeting at the California Institute of Technology
(CalTech), on December 29, 1959 [1]. Although he was the one who gave the vision
of using machines to manufacture smaller machines and devices, down to molecular
level, the term nanotechnology was first coined by Norio Taniguchi, a Japanese
scientist in 1974. He defined nanotechnology as: “Nanotechnology mainly consists
of the processing of separation, consolidation, and deformation of materials by one
atom or one molecule” [2].
Nanotechnology is considered as one of the most promising tool of the twenty-first
century and has revolutionized many aspects of our lives by creating various
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1099

nanomaterials and nanodevices exhibiting potential applications especially in the field

of medicine and environmental science. In the recent times, dictionaries are flooded
with various terms having “nano-“ as a prefix, and it seems important to define these
scientific terms before discussing nanoproducts and their progressive aspects in
biomedical, environmental, and energy sectors. Some of these are as follows:

• Nanoparticles: It is defined as a microscopic particle with a size of 100 nm in at

least one dimension.
• Nanoscale: It refers to 1–100 nm size range.
• Nanoscience: The science that deals with the study of matter at the ultrasmall-
scale to understand their structure-dependent properties which vary considerably
from those at larger level.
• Nanotechnology: It is defined as the designing, manufacturing, and application of
structures and devices by manipulating shape and size at the nanometer scale.
• Nanomaterial: Material that contain at least one nanoscale dimension, internally
or on their surface (externally).
• Nanocomposite: It is defined as multiphase solid structure in which at least one of
the phases has nanoscale dimension.
• Nanostructure: Any structure having one or more dimension in the nanoscale
region.
• Nanoproduct: Any product containing nanoparticles.

There are many promising nanoproducts already existing in the market, for
instance, optical electronics, solar energy convertors, nano filters, clinical diagnos-
tics and medical equipment, fuel nanocells, nanocomposites, etc., and many more
are yet to be introduced. At least about 40 different nanomaterials have been used for
the manufacturing of these nanoproducts; for example, silver nanoparticles are used
in medical supplies and food packaging, as disinfectants, in water filters and
household appliances; titanium dioxide in cosmetics and some food items; and
carbon nanotubes in water treatment, sporting goods, touch screens, and automo-
biles. The aim of nanotechnology is not only to develop new nanoproducts but also
to enhance the properties of the ones already existing in the markets [3]. A TV that
could be easily folded and carried in a pocket, a paint that can protect the surface
from scratches, bone tissue engineering, nanodevices for various biomedical appli-
cations, enhanced food storage capacity and quality, and wrinkle- and stain-resistant
fabric are all being introduced in the market, many thanks to nanotechnology.
Figure 1 shows various nanoparticles/nanomaterials used in biomedical, environ-
mental, and energy sectors.
In the recent years, enormous research has been performed in area of green
nanotechnology. Green nanotechnology employs nanotechnology to develop prod-
ucts that provide solution to the environmental problems, using the concepts of green
chemistry and green engineering. The main goal of green nanotechnology is to make
nanomaterials and nanoproducts that are devoid of toxic ingredients and also do not
have any detrimental effects on the environment and human health. It also encour-
ages the replacement of existing products with new nanoproducts that are more
1100 S. Kaushik

Fig. 1 Various nanoparticles/nanomaterials used in biomedical, environmental, and energy sectors

environmentally friendly. Green nanotechnology minimizes the use of fuel and

energy by consuming less material and renewable sources, wherever possible. It
has been expected that application of green nanotechnological processes and prod-
ucts may contribute significantly toward a sustainable environmental by reducing the
emission of hazardous wastes and greenhouse gases into the atmosphere and hence
can stop affecting human life adversely.

Nanoproducts

Nanotechnology is emerging as one of the most revolutionized field, enabling the

enhancement of functionality of existing material as well as the manufacturing of
new products for numerous industrial, environmental, and biomedical applications.
In the last few years, nanotechnology has shown remarkable progress in the produc-
tion and application of various nanoproducts in almost every field of science.
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1101

Most importantly, it has contributed toward environment protection by saving raw

materials and energy resources and also reduced the level of greenhouse gases as
well as perilous waste. Implementation of various nanotechnological products in the
agricultural sectors has also enhanced the crop productivity and quality, hence
catering the needs of growing population across the world. The top 3 applications
of nanotechnology and nanoproducts that occupy the largest share in the market are
electronics goods, energy and biomedical equipment, and diagnostics tools.
Literature is rich in studies illustrating the role of nanotechnological products
in environmental protection, whether in practical application or in research, and
the advantages these nanoproduct offers to mankind are the prime reason why
markets are flooded with these products. For example, nano coating reduces the
cleaning efforts by keeping the water and dirt away from the object and also
increases its lifespan and durability; nanoparticle addition to a material reduces its
weight which saves energy during transportation; use of a nanocatalyst is a way to
enhance energy and resource efficacy and many more. At the same time, the
assessment of the impacts of these nanoproducts on the environment and society
is quite important in order to assure a sustainable development of this technology
[4]. The main aim of nanotechnology should not only be the development of
nanoproducts, but it should be coupled with the assessment of societal, environ-
mental, and economic aspects so that maximum benefit to the society can be
provided. Different groups have discussed the impacts of nanoproducts on sus-
tainability, including life cycle assessment (LCA), health and safety issues, and
social and economic assessment [5–7].
Soon after the commercialization of nanoproducts, various organizations have
developed nanotechnology databases to provide information about them, and some
important nanotechnology databases are Nanotechnology Consumer Product Inven-
tory (CPI, 2005), nanotechnology-claimed consumer products (2007) available in
Japan, and Nanowerk. An online inventory, the Nanodatabase (www.nanodb.dk),
was established in 2012 by the Danish Consumer Council and Ecological Council
and the Technical University of Denmark’s Department of Environmental Engineer-
ing [8]. This inventory contains the basic information about various nanoproducts
along with their safety assessment according to the NanoRiskCat framework
[9]. The database has registered 4000 products until June 01, 2020. Another data-
base, Nanotechnology Products Database, contains nearly 8000 products in different
categories. In this database, data and statistics about various nanoproducts have been
provided in a categorized form. This database also provides the information about
the highly used nanomaterials in different fields [10].
Different nanomaterials (NMs) are used for the manufacturing of various nano-
technological products which can be classified mainly into four categories:

(i) Carbon-based NMs

(ii) Inorganic-based NMs
(iii) Organic-based NMs
(iv) Composite-based NMs
1102 S. Kaushik

(i) Carbon-Based NMs

These nanomaterials are made up of carbon and can be found in various forms
such as spheres, ellipsoids, and hollow tubes. Carbon-based nanomaterials exhibit
numerous biomedical and environmental applications; these are used for enzyme
immobilization, as biosensors, as drug delivery agents, in diagnostic equipment, and
for bioimaging.

(ii) Inorganic-Based NMs

These are made up of nanomaterials consisting of metals (silver (Ag) or gold

(Au)) or metal oxides such as zinc oxide (ZnO), titanium dioxide (TiO2), and
semiconductors such as silicon and ceramics. These nanoproducts have major
applications in biomedical and pharmaceutical industries.

(iii) Organic-Based NMs

The products constructed from nanomaterials which are made up mainly of

organic matter are termed as organic-based nanomaterials, and these exclude
carbon-based and inorganic-based nanomaterials. The non-covalent interaction
between the molecules allows the organic nanomaterials to adopt numerous self-
assembled forms such as micelles, dendrimers, liposomes, and polymer-based struc-
tures. Dendrimers are branched components which are mainly used for catalysis but
are equally important in biomedicine. They are used in gene therapy and pain
management and as anticancer drugs.

(iv) Composite-Based NMs

This class belongs to the materials made up of combinations of nanoparticles or

nanoparticles with other materials. These may be any combinations of metal-based,
carbon-based, or organic-based nanomaterials with any other metal, polymer, or
ceramics.
In the following section, we shall discuss about various nanoproducts and their
applications in biomedical, environmental, and energy sectors.

Nanoproducts: Biomedical Applications

The intense use of nanotechnology in medicine and healthcare is quite evident from
the growing number of research papers in this field, and different sectors have also
focused on the use of nanoproducts in medicine. Nanomedicine, an emerging area,
mainly emphasizes on the application of nanomaterial in medicine by exploiting its
unique properties for diagnosis and treatment of various disease. It is being used to
develop nanodevices and nanoproducts for the detection, monitoring, and treatment
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1103

of various lethal diseases. It also exhibits potential applications in the tissue engi-
neering, drug discovery and delivery, and surgical treatments.
Silver and gold nanoparticles are the most important and fascinating nano-
materials among several other magnetic nanomaterials that have been extensively
used in medicine, as targeted biomarkers, and in drug delivery for treatment of
cancer. The potential application of gold nanoparticles (AuNPs) in conjugation with
DNA and RNA as a molecular system for cellular delivery has been recently
reviewed [11]. DNA-gold nanoparticle conjugates have also been successfully
employed for the detection of pathogenic and genetic diseases. Similarly, silver
nanoparticles (AgNPs) have been shown to possess multifunctional bioapplications;
they are used as antifungal, antibacterial, antiviral, anti-inflammatory, and anticancer
agents [12]. Chitosan-based nanomaterials exhibit significant physical and chemical
properties, such as conductivity, porosity, high tensile strength and surface area, and
greater mechanical strength in comparison with natural chitosan. These properties
clearly make out that chitosan-based nanomaterial holds a greater potential for future
developments in various fields especially for the diagnosis and treatment of diseases
like cancer. Studies have shown that chitosan-based hybrid nanostructures can be
employed as bone, liver, and nerve tissue engineering material [13, 14].
The most important application of nanotechnology is the manufacturing of
nanoproducts and nanodevices, which are used for the early detection of ailments
like heart attack, tumor, or localized infections. Figure 2 displays the biomedical
applications of nanoproducts. Various nanomaterials possess biocidal properties, i.e.,
they have the ability to kill viruses, bacteria, and fungi, and these properties are being
exploited for the manufacturing/improvement of various disinfection and hygiene
products, hence benefitting human health and the environment. Advancements in
this field have also led to the development of numerous nanomaterial-based wound
therapy products and smart bandages. These bandages not only protect the wounds

Fig. 2 Biomedical applications of nanoproducts

1104 S. Kaushik

from further contamination but also exhibit natural antimicrobial properties which
help in combating bacterial infections. An enormous number of various biosensors
have also been developed in the recent years for detection as well as monitoring of
numerous mutagenic, carcinogenic, and toxic chemicals.
An online inventory, Nanotechnology Products Database (NPD), contains about
1016 nanoproducts of different types in the medicine sector. This category consisted
of various products: drugs for the treatment of cancer, ankylosing spondylitis,
hepatitis C, multiple myeloma, hypercholesterolemia, arthritis, tumors, severe
hypertriglyceridemia, and AIDS-related Kaposi’s sarcoma, to name but a few.
Antibodies, medical hydrogels, topical bioadhesives, antiangiogenesis, hyaluronan
fibers, protein membrane immobilizers, and occluders are some of the tissue
engineering-related nanoproducts. Dentistry category contains toothpastes, tooth-
brushes, contra-angles, polishers, mouthwashes, nanocoats, denture cleaners, fissure
sealants, bone substitute gels, toothbrush sterilizers, teeth whitening, multi-primer
pastes, and bone substitute powders. NPD shows that silver nanoparticles are the
most commonly used nanomaterials and have been used in about 75% of the
products in medicine industry [10].

Nanoproducts: Environmental Applications

(i) Waste Water treatment

Water is one of the most essential substances needed by all forms of life. In fact,
Earth is known as the “Blue Planet” because water covers 71% of the Earth’s surface
and oceans hold about 97.2% of total water present on it. In spite of the fact that
Earth has got copiousness amount of water, only a very small percentage is available
in usable form, and the rest is present in soil, ice caps and glaciers, oceans, and water
floating in the atmosphere. Apart from being essential for agriculture, it is required
for domestic, industrial, and commercial uses. With an increase in human population
across the world and rapid industrialization, the demand for water supply has also
been increased.
Water is defined by several physical, chemical, and biological characteristics like
color, taste, pH, total dissolved solids, etc. The different types of impurities present
in water can change its quality which can have adverse effect on all forms of life and
also make it unsuitable for various purposes. Water pollution is caused by the
discharge of domestic and industrial effluents, toxic metals, radioactive wastes,
and presence of certain microorganisms in the water bodies. Bacterial contamination
of drinking water is a major source of illness, and, in India, annually about 37.7
million people get affected by waterborne diseases, and 1.5 million children die of
diarrhea [15]. Therefore, various technologies have been employed for the treatment
of contaminated water. Water treatment is the removal of suspended impurities,
organic matter, inorganic materials, toxic metals, and various microorganisms from
water at lowest cost consumption with minimal impact on the environment. Water
from different sources like groundwater, drinking water, waste water, and industrial
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1105

process water have undergone treatment so as to make it suitable for drinking and
industrial or commercial use.
Different methods, like filtration, chemical oxidation, chemical disinfection, and UV
irradiation, have been employed over the years for the removal of impurities, patho-
genic organisms, and other contaminants from the water. At the same time, researchers
have also succeeded in developing various nanomaterials for cleaning up the radioac-
tive waste in water. Most notably, titanate nanotubes and nanofibers work as absorbents
for the removal of radioactive iodine and cesium ions from water [16]. Scientists have
also developed a molybdenum disulfide (MoS2) membrane (with nanopores) for
energy-efficient desalination, whose capacity to filter water is many times higher than
those of conventional filters [17, 18]. For the treatment of wastewater using nano-
products, three different methods have been adopted which utilized different nano-
materials [19]:

(i) Disinfection is a process, where nanomaterials are employed for the removal,
inactivation, or killing of disease-causing microorganisms present in water.
(ii) Adsorption/filtration: In this method, nanomaterials selectively target and take
up the pollutants from the water under treatment, and then, they are physically
removed from the bulk solution.
(iii) Chemical or photocatalytic reaction: Based on nanocatalysts, this is a very
promising approach used for the treatment of contaminated water. In this
method, nanomaterials are used to degrade various chemical and biological
pollutants present in water.

Literature is rich in demonstrating the role of nanosilver as a potential nano-

product exhibiting numerous applications in diverse sectors, and its antimicrobial
property has been extensively studied since the 1970s. It is used as an antimicrobial,
anticancer agent, disinfectant, and biosensor material, for medical device coating and
electronic component, in cosmetics, and for personal healthcare [20, 21]. In the
1960s, the US National Aeronautics and Space Administration (NASA) had devel-
oped a small lightweight device to release silver ions into the spacecraft’s water
supply, which eliminated bacteria from drinking water [22]. Based on this notion,
many companies then used this technology to discharge silver ions into swimming
pools to make them bacteria-free. This was the starting point which led to the
development of various silver-based nanoproducts, and, now, it has become the
most utilized nanomaterial exhibiting important applications in various fields.
Studies have shown that it is the positively charged silver ions (Ag+) that exhibit the
antimicrobial activity. The mechanism involves the binding of silver ions to
the membrane proteins responsible for transportation of substances in and out of the
bacterial cell. They are, then, transported into the bacterial cell and block the respira-
tory system and cell division, which ultimately led to the cell death [23]. Numerous
reports have shown the important role of silver nanoparticles as a disinfectant for
various pathogens present in wastewater and drinking water [24, 25]. It has also been
reported that silver nanoparticles can be easily incorporated into a plethora of other
materials, like dendrimers and zeolites, which can then be assimilated into disinfection
1106 S. Kaushik

treatment systems. Furthermore, the incorporation of silver nanoparticles into other

materials makes them considerably cheaper, optimizes the technology, and provides
one more practical approach for water treatment.
Carbon nanotubes (CNTs) exhibiting tunable physical, chemical, structural, and
electrical properties proved to be quite effective in circumventing the water pollution
problems. CNTs have profound water treatment applications in numerous fields, for
instance, they are used as catalysts, filters, membranes materials, and sorbents.
Studies have shown that CNTs are more effective in adsorption of organic pollutants
and heavy metals (Cd2+, Pb2+, and Cu2+) in comparison with activated carbon
[26, 27]. Also, they possess major advantage of adsorption of more complex
molecules like pharmaceuticals, polar aromatic compounds, dyes, and pesticides,
which are not readily adsorbed using traditional approaches. CNTs offer several
other advantages like strong antimicrobial activity, tunable pore size, large surface
area, and excellent electrical, mechanical, and optical properties, which make them
promising materials for adsorption, separation, and filtration processes. Studies on
CNT-based water technology boomed in the past decade; incorporating CNT mate-
rial into membranes used for water purification, portable water filters containing
CNT meshes or sheets to treat water polluted sources and CNTs also employed as an
anti-fouling membrane additives. The portable CNT water filter is quite significant
for remote area travelling, disaster relief, and military use and can also be attached at
the tap for residential use. Also, CNTs have been shown to be excellent catalyst
support system in wet-air oxidation for the treatment of organic pollutants (aniline
and phenol) and toxic wastewater [28].
The removal of heavy metal cations such as Zn, Cr, Cd, Pb, Cu, Mn, etc. from
wastewater using natural zeolites has been the subject of intense research and
employed, along with other conventional wastewater treatment methods such as
filtration, ion exchange, coagulation and flocculation, chemical precipitation, and
electrochemical methods. Zeolites are microporous, crystalline solid structures that
are composed of aluminum, silicon, and oxygen with unprecedented sorption and
ion-exchange properties. The size of natural and commercially synthesized zeolites
typically lies in the range of 1–10 (μm) micrometer; however, zeolites can also be
synthesized on the nanometer scale (5–100 nm) [29], and these nanoscale zeolites
possess higher surface area and smaller diffusion path in comparison with natural/
non-nanozeolites [30]. Nanozeolites have gained much attention in the recent past
because they possess great mechanical strength, high density of ion exchange sites,
and porosity. Studies have shown that nanozeolites have also been incorporated into
various types of membranes for desalination of seawater and brackish water
resources [31]. Nanozeolites also exhibit potential application in removing radioac-
tive metals from nuclear waste streams, heavy metals from acid mine drainage, and
electroplating wastewaters [32, 33].
Chitosan is a polysaccharide that is derived from chitin, the second most abundant
polysaccharide after cellulose. It can be obtained from the various sources in the
environment, for instance, from the outer shell of crustaceans, shellfish, insects, and
mushrooms. The advantage of using chitosan is that it can be operated at the low
costs since it is easily available from naturally occurring sources, which makes it one
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1107

of the polymers to be used for wastewater treatment and disinfection of drinking

water. Nanoscale chitosan has proven to be extremely advantageous for wastewater
treatment processes especially for coagulation and flocculation. It is a biocompatible,
nontoxic, and biodegradable material and thus exhibits versatile functionality. Addi-
tionally, nanoscale chitosan has also been shown to exhibit antimicrobial properties
and thus offers numerous use in biomedical applications [34]. Chitosan nano-
structures have been shown to be effective in the removal of various contaminants
such as heavy metals, dyes, and phenols from wastewater [35, 36].
Various other environment improvement technologies have also been employed
for wastewater treatment, and many of these used iron oxide nanomaterials in their
products. Iron oxide nanomaterials have gained much attention because of being
ubiquitous and its extremely small size, strong adsorbent properties, excellent
magnetic properties, high surface area, and most importantly, great biocompatibility.
The accumulation of heavy metals in water bodies is a great threat to human health,
aquatic life, and the ecosystem as a whole, as these metal ions are toxic and
carcinogenic in nature. Studies have shown that iron oxide nanoparticles (Fe3O4
NPs) can be used to treat wastewater systems as they absorb heavy metals from these
systems [37, 38].
Organic dyes are one among the major pollutants that are widely used in the
textile, medicine, plastic, and many other industries and contaminate the water
bodies. Similar to the heavy metals, they also pose a major menace to the environ-
ment. They are not readily degraded and cannot be removed from water using
conventional methods. Iron oxide nanoparticles have proven to be quite effective
in removing dyes from wastewater systems. A work by Singh et al. (2017) have
shown the synthesis and application of iron oxide nanoparticles (Fe3O4) coated with
green tea polyphenols (GTP). Results revealed that these GTP-coated Fe3O4 NPs
have proven their efficacy in removing methylene blue from wastewater [39]. Many
studies have demonstrated the efficiency of iron oxide nanoparticles in removing
various carcinogenic dyes for wastewater systems [40, 41]. Although iron oxide
nanoparticles are one of the best adsorbents for treating all sorts of pollutants, still,
researchers are looking for cheaper and more efficient way of purifying contami-
nated water to meet the total demand across the world.
As discussed earlier, different approaches and methods have been adopted by
researchers for water purification processes, and some techniques are still under
development. Advanced oxidation processes (AOPs) are one among the new
adopted technologies used for water purification. Photocatalysis by titanium dioxide
(TiO2) nanoparticles is one of the widely studied AOPs used for the treatment of
wastewater [42]. Of all the metal oxide nanomaterials (iron oxide, titanium dioxide,
tungsten oxide, zinc oxide, nickel oxide, and copper oxide), titanium dioxide (TiO2)
and zinc oxide (ZnO) are the highly versatile and most widely used oxides employed
for wastewater treatment processes. Metal oxide nanomaterials have effectively
contributed toward the cost-effective and robust water treatment processes [43].
TiO2 nanoparticles, using photocatalysis, have proven to be quite effective in
adsorbing toxic metals and organic/inorganic impurities, along with a wide range
of pathogens which contaminate water sources and are also capable of degrading
1108 S. Kaushik

Fig. 3 Applications of nanoproducts in wastewater treatment

certain pollutants. Pena et al. (2005) have demonstrated that nanocrystalline TiO2
has proven to be an effective adsorbent for arsenate [As(V)] and arsenite [As(III)] as
well as an efficient photocatalyst for As(III) [44]. A recent work on similar lines has
shown that doping of TiO2 nanoparticles with an appropriate amount of Gd (gado-
linium) induced a significant enhancement in photocatalytic as well as antibacterial
activity of titanium dioxide nanoparticles used for water treatment application [45].
TiO2 can be applied in the form of either thin film or nanorods, and it can also be
used in combination with other metal; when doped with iron or combined with silver
nanoparticles, it works effectively in all modes. Figure 3 shows nanoproduct used in
wastewater treatment.

(ii) Air Remediation

The presence of various contaminants in the air and poor air quality affect the
flora and fauna as well as the human health which can cause different types of
respiratory and cardiovascular diseases. So, it is very important to develop and
employ various strategies to reduce air pollution and get a cleaner environment. In
this section, we shall discuss the applications of nanoproducts and nanotechnologies
adopted to reduce indoor and outdoor air pollution. It is important to mention here
that there are certain materials which serve more than one purpose; for example,
nanocatalyst are used in engines to improve combustion, thus resulting in less energy
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1109

consumption as well as cleaner exhaust gases. Air pollution can be reduced using
nanotechnology by mainly two ways: one by using nanocatalysts and the other
through nanostructured membranes. Although nanocatalysts are being employed for
different purposes, nanostructure membranes are not much explored and are still at
development stage.
Catalysts made from nanomaterial have a greater surface area and interact quite
well with the chemicals and, hence, perform the reaction effectively. At the same
time, nanocatalyst exhibits wide applicability; they can transform the gases escaping
from vehicles and industrial plants into harmless gases, remove organic pollutants
from air, eradicate the hazardous chemicals, and hence reduce air pollution. A recent
work by Salehi et al. has reported that chromite spinel nanocatalysts proved to be
quite effective in removing maximum carbon monoxide (CO) from air and that too in
the shortest possible time [46]. Nanofiber catalysts made up of manganese oxide
have been shown to eradicate volatile organic compounds from smokestacks [47].
Another approach to combat air pollution employs nanostructured membranes
that have pores small enough to separate gases like carbon dioxide (CO2) and
methane (CH4) from the exhaust. Carbon nanotubes (CNT) can also be used for
trapping greenhouse gases emitted from coal mining and power generation that too
are hundred times faster than other methods and hence can be integrated into power
stations and large-scale manufacturing units. This advanced technology serves two
main purposes: It processes as well as separates large volumes of gas quite effec-
tively, whereas conventional membranes can only perform one or the other function,
effectively. The advantage of this technology is that substance that filtered out from
diesel fuel emission can be collected, reprocessed, and used for the synthesis of
single-walled carbon nanotubes (SWNTs). The produced SWNTs serve two main
functions: It provided economic benefits as well as a cleaner environment [48].
Different companies have developed various nano-based products to minimize air
pollution, for example, Nanostellar, Inc. has developed low-cost nanocomposite
catalyst which can be used in automotive catalytic converters. Similarly, American
Elements manufactured catalyst composed of manganese oxide nanoparticles for the
removal of volatile organic compounds from industrial emissions. Another com-
pany, Porifera, has developed nanotube-based membranes for the removal of carbon
dioxide from smokestacks, and this technology turned out to be potentially more
efficient and cost-effective in comparison with the methods which use chemical
solvents [49]. Various nanotechnological products employed for air remediation are
shown in Fig. 4.
Various approaches have also been employed to improve the indoor air quality,
and most of these systems are based on photocatalytic oxidation (PCO) that utilizes
nano-semiconductor catalyst and ultraviolet (UV) light that converts the pollutants
into water and carbon dioxide. Different nano-based photocatalytic air purification
devices are available in the market, and these nanoproducts function by simply
plugging into an electric receptacle which run the UV light source and fan circulating
the air through UV unit system in the device [19]. A study by Sharmin and Ray
demonstrated the effectiveness of UVLED (ultraviolet light emitting diode) photo-
catalysis in removing volatile organic compounds (toluene and xylene) from indoor
1110 S. Kaushik

Fig. 4 Nanoproducts used in air remediation

air [50]. A work on similar lines also showed that a PCO system based on nano-Ag/
TiO2 catalyst and UV light effectively removed indoor airborne bacteria [51]. These
studies show that PCO proved to be an effective technology in improving indoor air
quality due to its low cost, low maintenance, and potentially long life. Different
nanomaterials, e.g., nanosilver, graphene oxide, can also be incorporated or inserted
in ventilation filters to adsorb various harmful indoor air pollutants. Research is still
going on in this area, and the main focus is now to develop different strategies for the
removal of sulfur compounds and ammonia from air, hence minimizing air pollution.

Nanoproducts: Agricultural Applications

The Department of Economic and Social Affairs of the United Nations Secretariat
has mentioned in 2015 that the world’s population is increasing at a rate of 1.24
percent per year [52]. This study suggested that the world needs more crop output in
the coming years, and to fulfill our demands for food, we need to work on the
strategies to increase crop production and protection of agricultural crops. In the last
few years, there has been a considerable amount of research in this particular area.
Various methods and technologies have been developed by the researchers to get the
better and enormous crop in a short span of time. Among the various technologies
used, nanotechnology proved to be the one which showed the potential to accom-
plish the needs and demands of providing food to the growing population. The US
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1111

Department of Agriculture (USDA) was the first department to apply nanotechnol-

ogy to agriculture in 2002 [53]. In India, it was late Dr. A.P.J. Abdul Kalam who
emphasized on the application of nanotechnology in agriculture sector, as, “We have
to launch vertical missions under an umbrella organizations with the public-private
investment is atleast 10 nanotechnology products in water, energy, agriculture,
healthcare, space, defense sectors” [54]. The applications of advanced nano-
interventions in food and agriculture unit could provide low cost and highly efficient
solutions in terms of products, mainly for the developing nations.
The major challenging issues in agricultural production is how to accelerate
adaptation of plants to numerous weather changing factors such as water scarcity,
extreme temperatures, heavy rainfall, and presence of excessive salts, alkali, and
toxic metals without harming the ecosystem. The deficiencies of multi-micronutrient
in soils are also a common problem in many countries, and this affects the crop
productivity as field crops suffer from the deficiencies of one or more micronutrients.
Many conventional methods were employed in the past to get rid of this problem, but
they suffer from one or the other limitation. The development of nanofertilizers
(NFs) resolved the problem to a greater extent, and a controlled release of NFs
ominously proliferated the nutrient use efficiency of crops. Also, they worked well
with all types of crops they applied to, and most importantly, fertilizer runoff into
groundwater and surface water was reduced, which ultimately proved to be a boon
for society and aquatic organisms, as it also minimized the environmental pollution.
The other major concern in this field is the crop protection that requires the
intervention of nanotechnology, and this problem was solved with the development
of nanotechnology-based devices used for plant breeding and genetic transformation
and use of nano-biocomposites and nanoformulations of different insecticides or
biopesticides [55].
Studies have revealed that development and exploitation of various nanoproducts
to monitor plant growth, improve soil conditions, combat environmental stress, and
detect and protect from plant pathogens/diseases have substantially enhanced the
quality and production of various crops [56, 57]. A remarkable achievement in this
field is the engineered nanomaterial-based targeted delivery of CRISPR (clustered
regularly interspaced short palindromic repeats)/Cas (CRISPR-associated protein)
mRNA (messenger RNA) and sgRNA (single guide RNA) for genetic modification
(GM) of crops [58, 59]. A work on similar lines has shown that the encapsulation of
potassium nitrate pellets with graphene oxide (GO) films prolonged the fertilizer
release process and suggests that such formulations hold great promise for large-
scale crop production at relatively low cost [60]. Different nanoparticles, for
instance, silicon dioxide, zinc oxide, titanium dioxide, carbon nanotubes, iron
oxide, and hydroxyl fullerenes, have been incorporated into numerous agricultural
products and shown to enhance the overall growth, quality, and production of many
crops such as peanut, wheat, onion, tomato, potato, spinach, soybean, mung bean,
and mustard [61, 62]. All these studies have suggested that nanotechnology-based
products have provided excellent solutions for many environmental challenges by
improving the overall quality and quantity of crops (Fig. 5). Researchers have shown
that application of various nanoproducts has not only enhanced the various
1112 S. Kaushik

Fig. 5 Various nanoproducts used in agricultural sector

agronomic traits like quantity, quality, and size of fruits but also improved essential
oil contents of plants [63, 64]. Along with the development of effective agri-
nanoproducts, there come the major biosafety issues associated with them. At
present, the European Union along with Switzerland is the only part of the world
where particular provisions for safe application of agri-nanoproducts are available in
the legislation. Although, in some countries, no specific regulation for
agri-nanoproducts is available, these are regulated under existing legislative and
regulatory frameworks [65]. In India, nanoproducts in agriculture sector have been
regulated by different government bodies [66]. As, in most of the countries, no
separate standard protocols/guidelines are available for the application of agri-
nanoproducts and, this further unravel the opportunities to work in this area which
can be helpful for manufactures and importers of nano-agriproducts; also, securing
the human and environmental health.

Nanoproducts: Energy Applications

Recent development in the field of nanotechnology has shown that researchers are
also focusing on the alternative approaches and methods to produce energy to cater
the world’s increasing demands. A galaxy of scientists are looking into possible
ways to develop clean and affordable energy sources which can provide some
environmental benefits related to the energy consumption.
Various nanoproducts have been employed for the generation, conversion, stor-
age, and distribution/use of energy; at the same time, some refinements are also
being incorporated in the existing products to improve their functioning. Literature is
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1113

rich in illustrating the use of nanoproducts for energy production and consumption;
here, we will discuss only those nanotechnologies/nanoproducts which have maxi-
mally benefitted the environment as well as contributed toward the energy optimi-
zation mechanisms. Nanotechnology-based products such as batteries are in use, and
they are lighter in weight and more efficient, have a high power density and quicker
charging, and also hold electrical charge for a longer period. Similarly, epoxy-
containing CNTs are used to make the blades of windmills that are stronger, longer,
and lightweight and increase the amount of electricity generated by each windmill.
Also, numerous other energy-efficient and energy-saving products like stronger and
lighter vehicle materials for the transportation sector, high efficiency light bulbs, and
low energy consuming electronics have reduced the energy consumption and help in
meeting the consumer’s increasing demands. Still, many more nanoproducts and
methods for production and storage of energy are in the development stage, which
may bring new hopes and can also unravel the existing unsolved problems of the
environment in most possible ways. Table 1 summarizes various nanoproducts
employed in biomedical, environmental, agriculture, and energy sectors, along
with the nanomaterials used and their advantages.
Here are some of the examples of nanotechnological products (energy sector) that
have benefitted the environment.

1. Energy Source

(i) Solar cells: A solar cell or a photovoltaic (PV) cell epitomizes a renewable
source of energy. The photovoltaic device market is growing at a faster pace and
already represents a multi-dollar industry. However, conventional solar cells
suffer from two main drawbacks, i.e., they are less efficient and relatively high
cost of production. Nanotechnology is envisaged to play an important role
toward these limitations; besides lowering down the manufacturing cost, it
may also increase the efficiency of solar cells. Developments in the field of
solar cells have led to four different generations [67], and Table 2 summarizes
these four generations with their characteristics.

Numerous studies have efficaciously demonstrated the role of various nano-

materials in improving the light absorption of solar cells, hence enhancing its
efficiency. These nanomaterials can be used to construct different shapes such as
nanocombs, nanowires, nanobelts, nanosprings, and nanopagodas. A work by Gar-
nett and Yang has shown that silicon nanowires enhanced the path length of solar
radiation up to a factor of 73, using optical transmission and photocurrent measure-
ments [68]. Another study has revealed that the efficiency of graphene solar cells
was enhanced on chemical doping with bis(trifluoromethanesulfonyl) amide
[69]. Titanium dioxide (TiO2) has also been shown to be a promising candidate for
solar cells because of its low cost, high chemical and optical stability, and non-
toxicity. TiO2 works as a key material in excitonic solar cells and quantum
dot-sensitized solar cells (QDSSC), and TiO2 nanotubes have been used as
1114 S. Kaushik

Table 1 Nanoproducts used in biomedical, environmental, agriculture, and energy sectors, along
with the nanomaterial used and their advantages
Market
sector Nanoproducts Nanomaterials Advantages
Medicine Biosensors, Carbon nanoparticles, • Decrease in
and medical equipment, metals/metal oxide “biological pollution”
Healthcare high dissolution medicine, nanoparticles, of the environment
antibacterial agents, nanosilver, • Increased life
orthopedic and gold nanoparticles, expectancy
stomatologic products, dendrimers • Decrease in treatment
hormone therapy products, and surgery time
anticancer drugs, gene • Increased birth rate
therapy products, and decreased death rate
antibacterial bandages • Development of long-
term health control
systems
Wastewater Membranes, filters, CNTs, • High particle
treatment purifiers, nanofiltration chitosan nanoparticles, removing efficiency
plants, ionizers, portable nanosilver, • High dirt holding
water filters metal oxides, capacity than
mixed metal oxides, conventional filters
nanoparticles, • Better performance
titanium dioxide (TiO2) than conventional
filters
• Modular and compact
• Multifunctional
• Low cost
Air Filters, purifiers, sensors, CNTs, fullerene, • High dust-holding
remediation air conditioners, graphene oxide, silica capacity
scavengers, humidifiers, nanoparticles, zinc oxide • Detects ammonia and
catalysts, dust collector and zirconium hydroxide formaldehyde
cartridges, gas turbines, nanoparticles, titanium • Traps greenhouse
air quality monitor dioxide nanoparticles gases hundred times
faster than
conventional methods
• Highly efficient and
cost-effective
Agriculture Plant growth regulator, MWCNTs, • Enhanced
nanosensors, delivery quantum dots, germination and rapid
systems (pesticides, silicon dioxide growth
fertilizers, and nanoparticles, • Inhibits the bacterial
agrochemicals), zinc oxide nanoparticles, growth
agricultural diagnostics, silver nanoparticles, • Increased plant
DNA delivery agents, titanium dioxide growth by decreasing
agricultural waste nanoparticles bio-concentration and
management, translocation in plants
biofuel (catalyst) • Improved
photosynthesis and
biomass production
• Suppresses crop
diseases
(continued)
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1115

Table 1 (continued)
Market
sector Nanoproducts Nanomaterials Advantages
Energy Batteries, solar cells, Quantum dots, platinum, • Renewable energy
industry supercapacitors, solar titanium dioxide, CNTs, sources usage
water heaters, solar fullerene, silicon • Reduced energy (sun)
chargers, dioxide, metal/mixed- consumption
high brightness LEDs, metal oxide • Saves financial
space-saving fuel cells nanoparticles resources
• Decrease in
consumption of
resources
• Reduction in
semiconductor
material usage
• Reduced consumer
production cost
• Longer life of
batteries

Table 2 Generations of solar cells and their characteristics

Solar cell generations Type of materials Characteristics
First generation Bulk silicon High cost; high
(wafer-based cells) efficiency
Second generation Amorphous silicon, cadmium telluride (CdTe), Low cost;
(thin-film cells) copper indium gallium selenide (CIGS) moderate
efficiency
Third generation Quantum dots, gallium arsenide (GaAs)/germanium Low cost; high
(nanocrystalline (Ge)/gallium indium phosphide (GaInP2), efficiency
films) organic, perovskite, dye sensitized solar cells
(DSSC)
Fourth generation Hybrid: inorganic crystal with a polymer matrix Low cost; high
efficiency

transparent photoanodes for dye-sensitized solar cells [70]. Studies on similar lines
have also reported that the efficiency of solar cells can also be improved by
incorporating gold and green silver nanoparticles [71, 72].
The extensive research that has been carried out in the past decade has shown that
PV systems have been successfully employed for numerous industrial and domestic
purposes to cater energy needs. This technology is being used for various consumer-
based products such as watches, toys, radio, televisions, calculators, fans, etc. There
is an increased demand of PV devices across the world, ranging from large-scale
energy production to small portable chargers. These are used for numerous purposes,
for instance, in power plants, defense and space, agriculture sector, and military and
domestic, among others. Considering all these factors, it is expected that the PV
device market is likely to achieve a healthy growth rise in the years to come.
1116 S. Kaushik

(ii) Solar collectors: Solar collectors are a type of heat exchangers, which trans-
form solar radiations into heat and transfer this heat to a medium (the working
fluid). The working fluid (water, air, or solar fluid) then transmits this generated
heat for various applications. Solar thermal collectors are considered as one of
the promising tool used for heating purpose across the world due to abundant,
clean, and environmentally friendly (green) aspects of solar energy. Solar heat is
used mainly, where there is an excessive demand of hot water, and its main
commercial applications includes car washes, laundromats, military laundry,
and space heating in buildings and eating establishments. Several approaches
have been developed in the past few years to enhance the efficiency and thermal
working capacity of solar collectors for better energy conversions. One way to
achieve this is by replacing the working fluid (absorbing medium) with nano-
fluids (high thermal conductivity fluids) as nanofluids are considered as a
promising candidate for improving efficiency of solar collectors. Nanofluid
can be defined as a fluid engineered by dispersing nano-sized particles in base
fluid, which increases the rate of heat transfer.

A work by Mahbubul and group has shown that the thermal efficiency of
evacuated tube solar collectors was enhanced with carbon nanotube nanofluid
(0.2% vol) [73]. Yousefi et al. have also investigated the effect of Al2O3-water
nanofluid on the efficiency of flat plate solar collectors, and results revealed that
the efficiency of the solar collectors was enhanced with nanofluids [74]. A study on
similar lines has shown that efficiency of solar thermal collectors was enhanced up to
5% when nanofluids made up of different nanomaterials such as silver, graphite, and
CNT were employed as absorption medium [75]. This wide range of applicability of
solar energy and potential benefits associated with the use of solar energy systems
has made clear that it is the best source of renewable energy and should be used
wherever possible. The various nanoproducts used in energy sector are displayed in
Fig. 6.

2. Energy Storage

(i) Batteries: Batteries are required to store and deliver electrical energy, and
conventional batteries are not good at providing the needed combination of
fast recharge, high energy density, and high power. Also, many batteries may
be comprised of heavy metals such as cadmium, nickel, mercury, and lead, which
may pollute the environment and, at the same time, pose a threat to human health
if used batteries are not properly disposed of. Of the various types of batteries,
lithium-ion batteries have the greatest power density, and hence, they are used in
laptops, mobile phones, hybrid electric cars, as well as digital cameras. Research
has revealed that nanobatteries offer several benefits over conventional batteries,
like increasing available power and lesser time to recharge a battery, on coating
the electrode with nanoparticle. Also, the shelf life of a battery can be enhanced
using nanomaterials. Several types of nanomaterials have been shown to increase
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1117

Fig. 6 Nanoproducts in energy sector

the storage densities of lithium (Li) batteries, for example, lithium-ion batteries
with antimony electrode charge faster; the use of graphene oxide aerogel as an
electrode increases the lifetime of lithium-sulfur batteries; and the use of silicon-
coated CNTs in anodes can enhance the working ability of lithium-ion batteries
by up to ten times. Studies have also shown that addition of aluminum oxide
(Al2O3), silicon dioxide (SiO2), or zirconium dioxide (ZrO2) nanoparticles to
solid polymer gel increased the conductivity and storage capacity of the electro-
lyte, substantially [76]. Various metal oxide nanoparticles such as titanium
dioxide (TiO2), tin dioxide (SnO2), and lithium iron phosphate (LiFePO4) have
also been explored for their cathode and anode applications.

Different companies have developed and commercialized various nano-based

batteries with increased functionalities and remarkable features, for example,
Sony’s Nexelion hybrid lithium batteries with a tin-based amorphous anode offers
30 percent more capacity than conventional batteries and quicker recharge time. The
tin-based anode consists of multiple elements (e.g., carbon, cobalt, tin) mixed on
nanometer level, and it was the first time that a nanoalloy replaced the graphite
electrode [77]. One other company, A123Systems, has developed nano lithium-ion
battery with cathode made from nanophosphate. A123Systems claimed that their
battery exhibits several advantages such as higher power, quicker recharge, (i.e.,
they charge to high capacity in almost 5 min), and four times higher thermal
conductivity than conventional lithium-ion batteries. On the similar context,
AltairNano has developed a lithium-ion nanobattery with the anode composed of
nanostructured lithium titanate spinel oxide (LTO). These batteries are also equipped
with higher power and quicker recharge and are less combustible than conventional
lithium-ion batteries. Likewise, other companies like Valence Technology, Inc.,
Toshiba, Mphase Technologies, and ZPower have commercialized their batteries,
1118 S. Kaushik

which are known to possess desirable features like long shelf life, high power
density, and low combustibility [78]. The research on this field is in progress, and
many companies are in the process of developing nanobatteries utilizing “environ-
mentally friendly” nanomaterial for both the electrodes: anode and cathode.

(ii) Supercapacitors: Supercapacitors (SC), also known as electrochemical capac-

itor, are used to store electrical energy where high power and high energy
density are required. These are designed to endure high temperatures and
temperature fluctuations which conventional batteries cannot bear. Since the
surface area of each of the electrode is the key factor to attain maximum power
output and power density, this can be achieved by using nanostructured nano-
materials. Supercapacitors are used in numerous applications ranging from
consumer electronic goods to industrial electric utilities, and global market for
supercapacitors has been growing rapidly. Different strategies have been
employed to develop electrode material with high charge storage capacity and
long-term cyclic stability. Different nanostructure materials have been used for
different class of supercapacitors, for instance, mixed-metal oxide nano-
materials such as vanadium pentoxide (V2O5), manganese oxide (MnO2), iron
oxide (Fe3O4), and ruthenium dioxide (RuO2) are used for redox-based
SC. Numerous reports have demonstrated that carbon nanomaterials (graphene
and CNTs) and carbon aerogels have proven to be excellent candidates to
substitute activated carbons as electrode material in high-performance super-
capacitors [79, 80].

Conclusions

In recent years, nanotechnology has emerged as a potential tool that has provided
outstanding solution to various environmental problems. It has shown remarkable
achievement in providing clean water through rapid and affordable low-cost treat-
ment of contaminants in water. It helps in detecting and cleaning environmental
noxious wastes and at the same time offered energy-efficient products. Oil spills in
oceans are difficult to clean up, but nanotechnology has proven its efficacy even in
this task. Although its application in this field is still in infancy, it holds great promise
for the future. Scientists across the world have developed magnetic polymer nano-
composites, organoclays with magnetite Fe3O4 nanoparticles, and superwetting
nanowire membranes for cleaning oil spills. Nanosensors have been used in various
fields, most notably in medicine and healthcare, agriculture, and food and water for
the detection of chemical and biological agents. It has been seen that profuse use of
nanoproducts has brought potential benefits to farmers, energy sectors, medicine and
healthcare, food industry, and consumers too. According to the Nanodatabase, about
4000 nanoproducts have already reached the supermarkets, and the majority of these
products are used in electronics and electric goods, energy industry, medicine and
healthcare, food industry, cosmetics, and household products. However, after their
usage, these products (or residues) may find their way into the environment; our
48 Nanoproducts: Biomedical, Environmental, and Energy Applications 1119

main focus should be to find the numerous ways to combat this problem so that this
will not harm the ecosystem in any possible way. At the same time, we must also
consider both the negative and positive aspects of a product on the environment,
which can be achieved by examining the life cycle of a raw material from production
to disposal stage. As demand for these products increases, it would also accelerate
manufacturing of more and more nanoproducts, which also ascends concern for both
the environment and human health. To some extent, the problem can be resolved by
adopting green nanotechnology for environmentally safe and even more beneficial
nanoscale research and development.

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Composite Nanocoatings
for Environmental Remediation 49
A. Joseph Nathanael and Palaniswamy Suresh Kumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124
Nanocomposite Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1124
Nanocomposite Coating Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1125
Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD) . . . . . . . . . . . . . . 1127
Electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
Spray Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
Other Wet chemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
Applications of Nanocomposite Coating in Environmental Cleanup . . . . . . . . . . . . . . . . . . . . . . . . . 1130
Air Quality Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
Water Quality Monitoring and Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
Future Perspective and Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135

Abstract
Nanocomposites are a promising class of hybrid materials that exhibit combina-
tions of special property and possibilities of unique design. It may be of either
metal-polymer, metal-metal oxide, metal-ceramic, ceramic-polymer, or mixtures of
polymers with exceptional functional properties. Nanocomposite powders and
coatings are used in various fields such as hard coatings, biomedical coatings and
implants, sensors, aircraft manufacturing, and so on. In nanocomposite coatings,
different materials are homogenously embedded with each other in a nanometer
scale. This chapter deals about the nanocomposite coating, methods to produce
nanocomposite coatings, their possible application in environmental monitoring,
and remediation especially in air quality monitoring and water quality monitoring.
A. J. Nathanael (*)
Centre for Biomaterials, Cellular and Molecular Theranostics (CBCMT), Vellore Institute of
Technology (VIT), Vellore, TN, India
P. S. Kumar (*)
Environmental and Water Technology, Centre of Innovation (EWTCOI), Ngee Ann Polytechnic,
Singapore, Singapore

© Springer Nature Singapore Pte Ltd. 2022 1123

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_64
1124 A. J. Nathanael and P. S. Kumar

Keywords
Nanomaterials · Nanocoating · Physical and chemical techniques · Air quality
and water quality monitoring

Introduction

One of the most severe concerns that the society faces today is certainly environ-
mental pollution. Many new technologies are continually being tested for the
remediation of pollutants of the soil, air, and water [1]. Due to the continuous
urbanization and the industrial revolution, environmental pollution has recently
started to be an important concern in recent years. Few examples regarding the
contaminants are harmful materials, such as mercury, cadmium, lead, (toxic heavy
metal ions), residual pharmaceutical compounds (e.g., antibiotics, antipyretics drugs,
anticonvulsants), fertilizers, oil spills, toxic gases, and pathogens that are intimidat-
ing both human health and the environmental system even at low concentrations and
subsequently causing major global complications.
In order to improve the desired properties such as sensing, wear resistance,
corrosion resistance, friction, and hardness of the bulk materials, thin films and
coatings are applied to the surface. Coating of monolayer, multilayer, or gradient to
well-known materials provide new efficacy features. It is impossible to get all the
required features of the material in a single coating simultaneously. However, the
nanomaterials provide some solution to this issue. Various recent literatures are
reported about the applications of nanomaterials on environmental remediation
[1–4] . For environmental remediation, various types of materials can be used, and
thus, a wide variety of methods can be applied for this purpose. Since the environ-
mental pollutants are the mixture of different compounds with high volatility, and
low reactivity, it is very challenging to detect and remove the contaminants.
Recently, the use of nanomaterials-based pollution detection and removal systems
has gained great interest for the environmental remediation and removal of waste and
heavy metals [5–10]. Especially, nanocomposite coatings possess unique properties
due to their hybrid nature and nanometer scale length structure. Hence, they are
much advantageous for many industrial applications such as aerospace, biomedical
engineering, high-speed machining, magnetic storage devices, and automotive engi-
neering owing to their excellent mechanical, electronic, and magnetic properties due
to size effect as well as the mixture of different materials.

Nanocomposite Coatings

Nature and environment have mastered the advantages of nanocomposites with

incredible capacity. It provides perfect nanocomposites in the form of bones, abalone
shell, and wood using the mixture of proteins, carbohydrates, lipids, etc. Nano-
composites are materials that consist of a minimum of two elements combined on
49 Composite Nanocoatings for Environmental Remediation 1125

the molecular scale. If one of its structural elements is in 1–100 nm scale, then it is
termed as nanocomposite. Nanocomposite coatings have been used for many years for
numerous applications. It is a new class of hybrid materials with dissimilar inorganic
compounds with new and unique functional properties. The main aim behind the
development of nanocomposite coatings is to provide a high-performance coating at
relatively low cost to meet the demand of industrial requirements. There is also a great
concern about the environmental safety to reduce the hazardous compounds through
the nanocomposite coatings. Nanocomposites basically consists of at least two phases:
a nanocrystalline phase and amorphous phase or some time two different nanocrys-
talline phase. Usually nanocrystalline materials consist of components like crystallites,
grains, layers of a size of below 100 nm at least in one direction.
In nanocomposite coatings, different materials are homogenously embedded with
each other with a characteristic length scale of 1–100 nm. The size scale and the
mixing ability of the two components determine the property of the nanocomposite.
New characteristics and functional properties are elicited by the nanocomposite
material with a grain size of 10 nm or less. For example, there are some materials
with unique nanometric coatings which produce higher hardness, much higher than
the hardness of traditional coatings. The main reason behind this scenario is due to
the decrease in grain size which hamper the multiplication and mobility of the
dislocation and hence the hardness of the material amplified based on the Hall-
Petch relationship. Once the grain size is less than 10 nm, the dislocation movement
has less effect, and at this point, known as a critical value, the hardness of the
material reached a maximum value (Fig. 1). There are various kinds of nano-
composites such as polymer nanocomposite, metal nanocomposite, ceramic nano-
composite, and magnetic nanocomposite which finds application in different fields.

Nanocomposite Coating Methods

In the assessment of the performance of various coating methods, it must be accepted

that there is no single best coating method. Hence, in order to get most suitable
coating, extensive testing is always needed for a particular application. An effective
coating requires not only the essential properties of the nanocomposite but also
feasible technologies for coating the material on various kinds of substrates. “Fea-
sible” suggests compatible to numerous situations to warrant respectable coating
qualities such as uniformity of the coating surface, adhesion between the substrate
and the coating interphases, and the non-toxicity of the material. For large-scale
coating, manufacture capacity is added important consideration. There are numerous
methods employed for a coating process on a substrate, and a precise technique is
preferred based on the application of the coating, essential properties, thickness
requirement, temperature constraint of the substrate, etc., because the deposition
techniques and parameters strongly determine the structural properties and compos-
ites of the nanocomposite coatings. Nanocomposite thin film deposition remains a
challenge since it consists of materials with very dissimilar characters such as a
polymer with metals, metal with metal oxides, and mixed metal oxides. Coatings
1126 A. J. Nathanael and P. S. Kumar

Fig. 1 Change in hardness verses grain size of a material. (Reproduced with permission from [11].
Coryright 2012, Elsevier)

Table 1 Nanocomposite coating methods

Category Methods
Physical vapor deposition (PVD) Thermal evaporation [12, 13]
Sputtering deposition [14, 15]
Vapor arc deposition [16]
Ion implantation [17, 18]
Chemical vapor deposition (CVD) Plasma enhanced CVD [19, 20]
Plasma assisted CVD [21]
Electron cyclotron resonance CVD [22]
Electrodeposition Electrochemical deposition[23, 24]
Electroless chemical deposition [25, 26]
Spray coating Thermal spraying [27]
Plasma spraying [28]
High-velocity oxygen fuel spraying [29]
Cold spraying [30]
Warm spraying [31]
Other techniques Sol gel coatings [32]
Spin coatings [33]
Dip coating [34]

may be applied as liquids, gases, or solids. Table 1 summarizes some of the most
available techniques for the nanocomposite coatings. The most promising methods
for the nanocomposite coating are chemical vapor deposition (CVD) and physical
vapor deposition (PVD) such as magnetron sputtering, vacuum arc evaporation,
laser ablation, thermal evaporation, and ion beam deposition. Other methods, such as
spraying and ion implantation, electrodeposition, and sol-gel coatings, are also
employed.
49 Composite Nanocoatings for Environmental Remediation 1127

Chemical Vapor Deposition (CVD) and Physical Vapor Deposition

(PVD)

CVD is a chemical method that can be employed to produce nanocomposite

coatings. The main advantages of the CVD process are high deposition rate and
uniform coating for complex geometries. During CVD process, more than one
volatile precursor reacts and/or decomposes on the surface of the substrate to
produce the nanocomposite coating. Since the precursor gases are flammable and
corrosive, it may stance problems during deposition process. Dissociation of gaseous
species occur at high temperature thermally activated CVD. On the other hand, due
to its lower coating temperature, plasma-assisted CVD process displays a discrete
benefit over thermal CVD process.
A variety of vacuum deposition methods which comprises purely on physical
process such as electron beam evaporation, magnetron sputtering, pulsed laser depo-
sition, and ion implantation are referred to as PVD. Thin films are deposited by the
condensation of the vaporized form of material onto the substrate surface in a vacuum
atmosphere. In order to get a nanocomposite coating by PVD method, different source
materials for the composite should be vaporized at the same time by the same energy
sources like laser, electron beam, and plasma. In the same way, the vapors of the
different source materials should be condensed and deposited onto the substrate
surface under same processing conditions such as temperature, power, and vacuum
level. Hence it remains a challenging task to produce nanocomposite coatings with
expected outcome. Magnetron sputtering process uses an inert gas such as argon to
sputter the source (target) materials onto a substrate to form nanocomposite coatings.
A target may be of pre-mixed compounds of materials or use few targets of single
material simultaneously sputter using multitarget sputtering system (Fig. 2).
Pulsed laser deposition (PLD) is another type of PVD procedure for providing
nanocomposite coatings. In PLD, high-power pulsed laser beam with narrow fre-
quency bandwidth is focused onto a target material with desired composition. The
target material is then vaporized and deposited on a substrate material as a composite
coating, inside a vacuum chamber. For nanocomposite thin films, PLD is versatile,
since there are no restrictions on the target material. The target materials can be pre-
mixed powders of desired composition or simultaneously ablate different target
materials onto a substrate (Fig. 3). It is particularly preferable, where other methods
have been tricky or have unsuccessful to make any coatings. PLD uses a character-
istic laser wavelength of less than 250 nm. Almost all materials can be vaporized at
such a short wavelength which leads to the possibility of depositing nanocomposite
coating onto a substrate.

Electrodeposition

Electrodeposition is a simple, cost-effective, as well as a low-temperature, wet

chemical process for the deposition of various thin films and surface modification
including nanocomposite coatings in a single step without secondary treatment.
1128 A. J. Nathanael and P. S. Kumar

Fig. 2 Schematic illustration of nanocomposite coating by multitarget sputtering. (Reproduced

with permission from [15]. Coryright 2014, American Chemical Society)

Fig. 3 Schematic illustration of pulsed laser deposition (PLD)

It also provides several advantages to produce nanostructured multicomponent

deposition with high deposition rate with higher purity, easy control of thickness
and nanostructure, deposition on complex shapes and large sizes, and
low-temperature processing [35]. In order to form a metal oxide nanocomposite
deposition by electrodeposition, substrates (negatively charged cathode) are
49 Composite Nanocoatings for Environmental Remediation 1129

immersed in a metallic nanoparticle dispersion (electrolyte) and electrical potential is

applied. The positively charged anode completes the electric circuit. The metallic
nanoparticles are infused onto the substrate to form the nanocomposite deposition.

Spray Coatings

Spray coating is a broad term referring to a set of deposition procedures in which a

metal or non-metal substances is melted and sprayed with high-speed to a substrate to
produce a wide range of material coatings (thickness > 50 mm). Varieties of materials
such as metals, polymers, ceramics, or combination of these materials in any required
quantity can be sprayed in the processes. Powder particles or wires can be used as a
feedstock material. Heat source can be of combustion flame, plasma jet, or arc wires.
Based on the feedstock and heat source materials, thermal spray process can be
classified as (i) plasma spraying, in which inert gas is passed between two electrodes
to form a plasma flame, (ii) high-velocity oxygen fuel spraying (HVOF), in which heat
energy is produced by the combustion of fuel gas, and (iii) arc spraying, in which, the
heat energy is produced by an electric arc among the two electrically conductive wires.
Instead of heat source, high kinetic energy is used in cold spraying process. High-
pressure (~3.5  106 Nm 2) gas with critical velocity (500–1200 ms 1) propels the
powder particles to the substrate and develops a coating [35].

Other Wet chemical Synthesis

Comparing to PVD and CVD, other wet chemical processes such as sol-gel and spin
and dip coating methods have strong practical advantages due to their simplicity, low
cost, low-temperature processing, and suitable to deposit on complex and wide
varieties of substrates. Nanocomposite coatings using sol-gel precursor were formed
by spin coating or dip coating on a substrate. After that the organic residuals and
water are removed by pyrolysis and subsequently by nucleation and growth of the
nanocomposite film. Mostly the crystallinity, crystal size, and film porosity depend
on the pyrolysis treatment of the deposition. In addition to this, it is possible to
control numerous parameters such as precursor type, concentration, viscosity, pH,
temperature, addition of co-solvent, presence of doping elements, and thickness
control to develop simple but effective and uniform coating to attain the desired
properties of the final coatings [32]. Several kinds of nanocomposite coatings have
been developed by the sol-gel process for various applications.
Polymer nanocomposites are prepared by reinforcing small quantities (< 5 wt%)
of nanoparticles with various kinds of polymers (thermosets, thermoplastic, or
elastomers). For polymer nanocomposites, not all of the above are practically
possible. Vaporizing procedures such as PVD and CVD can easily damage the
polymer chains at very high temperatures or energies. Therefore, low deposition
temperature is typically a basic prerequisite for appropriate polymer nanocomposite
coatings.
1130 A. J. Nathanael and P. S. Kumar

Applications of Nanocomposite Coating in Environmental

Cleanup

Environmental pollution is a serious hazard to our planet. Pollutants such as pesti-

cides, heavy metals, various gases, and some microorganisms can generate terrible
harms to both human and the environment. Hence it is vital to monitor the various
pollution sources which affect air, water, and soils. The detection of these pollutions
is a demanding task, due to their complex nature, mixture of various compounds
with high volatility, and low reactivity. Metal oxide-based sensors generally work at
high temperature and are not stable in the long run. Nanocomposites with different
classes of materials such as metals, metal oxides, polymers, and ceramics can prevail
these issues and provide high performance in the sensing.
Some of the main attributes should be possessed by an ideal sensor such as the
following: (i) room temperature operation, (ii) high sensitivity and reproducibility,
(iii) quick response and recovery time, (iv) eco-friendly, (v) low cost, (vi) should not
need external source for response and recovery operation, and (vii) should work in
ambient surrounding without the supply of external air or oxygen. Many researches
are ongoing to develop new sensors which can satisfy many of the above require-
ments to satisfy the need of a good sensor for environmental monitoring. Following
are the most recent advancement of the nanocomposite coatings in the field of
environmental monitoring and pollution detection.

Air Quality Monitoring

Hydrogen sulfide (H2S) is extremely harmful to both the human beings and the
environment. Even at very low concentration, it can affect the nervous system and
can cause death. Its threshold limit is 10 ppm. Therefore, earlier detection even at
low or sub-ppm concentrations is crucial for the safety of the environment and the
population. H2S is usually released by biological products, natural gas, petroleum,
and mining fields. Polypyrrole and tungsten trioxide (PPy/WO3) nanocomposite thin
film was prepared by in situ photopolymerization on an alumina substrate using TiO2
nanoparticles as the co-photoinitiator by Su et al. [36]. Comparative studies revealed
that the H2S sensing response at room temperature of nanocomposite based on
PPy/WO3 film was strong even at low concentration than the sensor based on pure
WO3 or PPy film. It is claimed that the stretching of the depletion layers at the
interface of the PPy with the WO3 film resulted in the high response when the H2S
gases are adsorbed at room temperature [36].
Ammonia (NH3) gas is used in several fields such as petrochemical industries,
plastic production, textiles, explosives, and also as a fluid in refrigerator [37]. Nev-
ertheless, high concentration exposure to NH3 can cause serious health issues such as
respiratory damage, eyes and skin irritation [38]. The threshold limit for ammonia
exposure for 8 h is 25 ppm and for 15-min exposure is 35 ppm [37]. Thus, it is vital
to monitor NH3 gas to provide safe environment. Yan et al. [39] reported about
polyaniline/reduced graphene oxide (PANI/RGO) nanocomposite material filterer
49 Composite Nanocoatings for Environmental Remediation 1131

coated on 3D porous cellulose papers to produce paper-based flexible room-

temperature electronic sensor. It was prepared by in situ PANI polymerization in
RGO solution. Even after 1000 bending/extending cycles, this flexible sensor exposed
exceptional sensing ability for NH3 and consistent flexibility without noticeable
change in sensing performance at room temperature. Compared to pure PANI and
RGO, the nanocomposite film exhibits superior sensing ability. This was reported due
to the synergistic effects of RGO and PANI, higher specific surface area, higher carrier
mobility, and exposed active surfaces. Another NH3 sensor developed on surface
plasmon resonance-based fiber-optic gas sensor using poly(methyl methacrylate)
(PMMA)/RGO nanocomposite film has been reported by Mishra et al. [40]. Various
gases like NH3, H2S, and N2 were tested and found that the sensor probe was more
sensitive to NH3 gas. The result of their studies revealed that this sensor has high
sensitivity, wider operating range, reusability, and reproducibility. Additionally, the
optical fiber probe provides miniaturization, low cost, online monitoring and remote
sensing, and immunity to electromagnetic field interference.
Nitrogen dioxide (NO2) together with nitrogen oxide (NO) called NOx are
existing in the atmosphere due to various combustion processes from factories,
power plants, vehicles, and aircrafts. NO2 is a precursor to ozone by combining
with atmosphere and form ground-level ozone (O3). It also produces acid rain and a
fundamental element of smog. All of these impose massive threat to environment.
Layered surface acoustic wave (SAW) sensor using a ZnO guiding layer on LiTaO3
piezoelectric substrate was fabricated by Penza et al. [41]. The highly sensitive layer
was created using SWCNT-based nanocomposite coating prepared by the Langmuir-
Blodgett (LB) coating technique. To provide high sensitivity, the acoustic energy
near the surface was confined by a ZnO guiding layer on the SAW transducer. At
room temperature, the change in the SAW phase due to the interfering gases such as
H2, NH3, and NO2 was monitored in the range of 0.030–1%, 100–1000 ppm, and
1–10 ppm, respectively. The result revealed that high sensitivity, low detection limit,
good repeatability, reversibility, and fast response were achieved by this novel
layered SAW structures combined with nanocomposite layers.
Constant and on-site observation of sulfur dioxide (SO2) is very important due to
its poisonous nature to the living beings, plants, and environment. The major sources
of SO2 are vehicle exhaust, thermal power plants, and chemical factories. About
5 ppm of SO2 is enough to develop some serious problems, such as respiratory
issues, cardiovascular diseases and lung cancer. Room temperature, ultralow SO2
gas sensing was developed by layer-by-layer self-assembled titania (TiO2)/graphene
nanocomposite films (Fig. 4) by Zhang et al. [42]. This TiO2/RGO nanocomposite
hybrid gas sensor exhibited ppb-level sensing, quick response and recovery, good
reversibility, selectivity and repeatability for SO2 gas sensing at room temperature.
The excellent sensing was reported to be due to the synergistic effect of TiO2 and
RGO, as well as special interaction at TiO2/rGO interfaces [42].
Volatile organic compounds (VOCs) are liquids or solids under normal temper-
ature and pressure but stay as gases in the atmosphere. High level of VOCs is
harmful since it can yield new toxic products by reacting with oxygen-based free
radicals and can be potentially hazardous to living beings and environment. They are
1132 A. J. Nathanael and P. S. Kumar

Self-assembled
with (PDDA/PSS)2 1) TiO2 microspheres

2) Rinse and dry

3) Graphene Oxide
4) Rinse and dry
Substrate (PDDA/PSS)2 (PDDA/PSS)2

5) Alternative self-assembly

6) Thermal reduction

TiO2 /rGO (PDDA/PSS)2 (PDDA/PSS)2

PDDA PSS TiO2 Graphene

Fig. 4 Schematic illustration of TiO2/RGO multilayer hybrid film fabrication process.

(Reproduced with permission from [42]. Coryright 2017, Elsevier)

carcinogenic and can cause membrane irritation, dizziness, allergies and respiratory
issues. VOCs are usually highly reactive and have low boiling point. It also plays a
main role in the climate change and the destruction of the ozone layer. Zn-W-O
nanocomposite coatings were fabricated by the sol-gel method and coated on
alumina ceramic tube by dip coating method for the detection of VOCs. The proper
quantities of ZnWO4 in ZnO-rich samples and in WO3-rich samples provide
improve sensing activity towards VOCS. This sensor can detect VOCs like formal-
dehyde, benzene, and xylene. Due to the lower electronegativity of Zn, for example,
ZnO-rich sample shows higher sensitivity than that of WO3 rich sample for 100 ppm
formaldehyde [43]. Hierarchical SnO2/ZnO nanocomposite material for high-
performance ethanol sensor was developed by Khoang et. al [44] using combined
thermal evaporation and hydrothermal method. The result showed that this hierar-
chical nanocomposite possesses enhanced gas response and selectivity compared to
pristine SnO2 nanostructure and suggested that this method can be useful for various
other material for gas sensing application.
Swelling evaluation of polymer nanocomposite layers using simple thin film
optical interferometry method was reported for gas sensing application [45]. It is
based on the nanocomposite film expansion at a fixed wavelength to the various light
49 Composite Nanocoatings for Environmental Remediation 1133

intensities. This method was used for VOCs using poly(2-hydroxyethyl methacry-
late) (PHEMA) and carbon black/PHEMA nanocomposite layers. This process is
very sensitive and measurement of few nanometer swelling as achieved for measur-
ing ethanol. Compared to pristine polymer, nanocomposite film showed pronounced
swelling.

Water Quality Monitoring and Treatment

One of the other most serious environmental issue is water pollution. Water is a
valuable natural resource, and its quality is crucial for the survival of living beings.
Clean water access is one of the most basic humanitarian needs, but studies revealed
that safe drinking water is not available for more than 1.2 billion people and
staggering 2.6 billion people uses drinking water without or little hygienic condition.
Hence, the diseases due to water pollution kill millions of people every year. The
main source of water pollution is from the industries which release heavy metals
such as lead and mercury; synthetic dyes and pigments from textile industries;
organic pollutants from pesticides, pharmaceutical industries, and leather factories;
and various microbial infectious pollutants.
Nanocomposite materials provide promising candidate for monitoring the water
quality and also for removal of some kind of pollutants. Most of the nanocomposite
used for water purification and monitoring are in the form of nanopowders. Thin film
nanocomposite coatings are mainly used as permeable assisted material for filtering
heavy metals, salts, and organic contaminants and for desalination. Thin film
nanocomposite membranes use nanoparticles such as silica, TiO2, Ag, zeolites,
and CNTs. Membrane preparation has been carried out in various ways such as
interfacial polymerization, coatings, crosslinking, etc. [46]. Daraei et al.[47] pre-
pared a novel organoclay/chitosan nanocomposite coating on the commercial poly-
vinylidene fluoride (PVDF) microfiltration membrane. According to their studies,
addition of various organoclays with different fractions into the chitosan made it
more effective membranes with impressive dye elimination from effluents together
with higher permeate flux related to conventional nanofiltration membrane.
Nanofiltration (NF) thin film membranes using electrically conductive polyam-
ide-carbon nanotube nanocomposite shown to deliver biofilm-preventing capabili-
ties under extreme bacteria and organic material loadings [48] . The results showed
that this polymer nanocomposite thin film materials claim to have high electrical
conductivity (400 S/m), good NaCl rejection (>95%), and high-water permeabil-
ity. This nanocomposite thin film membrane provides a long-term effect and higher
reproducibility to prevent the formation of biofilm. Zwitterion functionalized carbon
nanotubes (CNTs)/polyamide nanocomposite was used to construct highly effective
desalination membranes by Chan et al. [49] (Fig. 5). The flux of water increased by
fourfold and the salt rejection ratio increased from 97.6% to 98.6% with the addition
of zwitterion functionalized CNTs in a polyamide membrane. Simulation studies
also provide conclusive evidence for the efficiency of this nanocomposite membrane
for water purification.
1134 A. J. Nathanael and P. S. Kumar

Fig. 5 Fabrication process for CNT/polyamide nanocomposite membrane. (A) Polyethersulfone

(PES) ultrafiltration membrane, sandwiched by two poly(tetrafluoroethylene) (PTFE) holders.
(B) Zwitterion functionalized CNTs, coated onto the PES membrane. (C) Interfacial polymerization
(trimesoyl chloride, (TMC), m-phenylenediamine, MPD)). (D) Photograph of the nanocomposite
membrane. (Reproduced with permission from [49]. Coryright 2013, American Chemical Society)

Aluminosilicate-incorporated single-walled nanotubes (SWNTs) within the poly

(vinyl alcohol) (PVA) offer a new type of thin film nanocomposite (TFN) mem-
branes for nanofiltration [50]. The surface hydrophilicity increased and the contact
angles decreased from 64.2 to 50.5. Due to the presence of nanotubes, the water flux
increased. Higher permeate water flux was attained due to the integration of the
aluminosilicate single-walled nanotubes. The divalent ion rejection was 97%,
whereas monovalent ion rejection was 59% for this thin film nanocomposite mem-
brane. Polystyrene and carbon black nanocomposite thin films were prepared as an
adsorbent material for the removal of heavy metals from industrial wastewater by
Alshabanat [51]. Thirty ppm of lead was separated in 120 min at pH 6. Freundlich
isotherm was used to describe the adsorption data and it followed the pseudo-
second-order kinetics.
Considering the microbial infections and pollution, very recently Chen et al. [52]
developed polyacrylate/Ag nanocomposite coating for antibacterial application. It
showed extreme hydrophilicity and wettability with excellent antibacterial and
antifouling properties. Biofouling is the unwanted progress of organisms on sub-
merged surfaces. Any unprotected material, which is submerged, will be colonized
by these microorganisms and affect the water body. Hence these types of coatings
will be of great interest for maintaining the water quality.
Chitosan nanocomposite coatings with various inorganic nanomaterials such as Ag,
Au, TiO2, ZnO, CdS, SnO2, etc. are used for waste water treatment and antifouling
49 Composite Nanocoatings for Environmental Remediation 1135

coatings. Detailed review about these nanocomposite coatings was given by Kumar
et al. [53]. Chitosan-zinc oxide (chitosan-ZnO) nanocomposite coatings were devel-
oped on a glass substrate for antifouling application. These nanocomposite coatings
displayed anti-diatom activity as well as antibacterial activity against the marine
bacterium [54]. Chitosan and halloysite clay nanotube coatings shown to provide
anticorrosive protective coating as well as provide improved passive barrier protection
and self-healing from the corrosion [55].

Future Perspective and Conclusion

The environmental pollution monitoring of nanocomposite coatings is interesting

and endless and provide promising perspectives. The advantages of using nano-
composite coatings for the pollution monitoring and remediation are efficient, cost-
effective, and multitasking. This chapter shows the effect of nanocomposite coating
in air and water quality monitoring. Various researchers in the literature reported
about their finding where the nanocomposite coatings have been successfully used in
the field of environmental pollution detection and remediation process. Numerous
advanced platforms that could be considered and exploited over recent years has
established the ability of nanocomposite materials to deliver cost-effective and
eco-friendly tactics for the removal, degradation, or the reduction of various pollut-
ants, including microorganisms, organic dyes, insecticides, and heavy metal ions.
Even though the nanocomposite coatings for environmental monitoring are very
promising, their real-world implementation is still challenging, as confirmed by the
limited number of reports. Currently the main challenge of nanocomposite coatings
is perhaps to translate these basic research discoveries from the laboratory to the
progress of commercially feasible environmental monitoring and remediation
technologies.
Links for further readings about this topic:

https://www.labmanager.com/insights/using-nanomaterials-for-environmental-reme
diation-750
https://frtr.gov/pdf/meetings/m%2D%2Dfryxell_1_09jun04.pdf
https://clu-in.org/techfocus/default.focus/sec/Nanotechnology%3A_Applications_
for_Environmental_Remediation/cat/Overview/

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Biomass-Based Carbon Materials for Heavy
Metal Removal 50
Sathya Moorthy Ponnuraj and Palaniswamy Suresh Kumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1140
Carbon and Its Allotropes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
Sources of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
Activated Carbon Production and Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1143
Classification of Activated Carbon Based on Pore Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1147
Adsorption Mechanism in Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1149
Evaluation of Property of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1149
Heavy Metal Classification, Properties, and Their Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1150
Effect of Heavy Metals in the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1151
Heavy Metal Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1153
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155

Abstract
Globally, in agriculture a part of plant products remains as an inedible portion
after harvest; such products are organically carbonaceous in nature. Agriculturist
used to combust the undesirable agricultural remains in to an amorphous carbon
to accelerate the decay and transform into manure for future farming agriculture
crops. After the official discovery of activated carbon in the eighteenth century, it
was reported to function as an antidote against poison and intestinal disorders.

S. M. Ponnuraj
Department of Nano Science and Technology, Tamil Nadu Agricultural University, Coimbatore,
Tamil Nadu, India
e-mail: [email protected]
P. S. Kumar (*)
Environmental and Water Technology, Centre of Innovation (EWTCOI), Ngee Ann Polytechnic,
Singapore, Singapore

© Springer Nature Singapore Pte Ltd. 2022 1139

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_65
1140 S. M. Ponnuraj and P. S. Kumar

The application of activated carbon is numerous in various fields; the search for
affordable carbon-rich raw materials for manufacturing activated carbon has
picked up the pace. Agricultural byproducts such as shells, cobs, seeds, stones,
husks, kernels, barks, and woods are available as a potentials source. In this
chapter, we discuss about brief history of carbonaceous materials and allotropes
of carbons, activated carbon, and various potential agricultural sources of acti-
vated carbon; production, activation, classification, and advantages of activated
carbon; adsorption and evaluation properties of activated carbon; and its appli-
cation as heavy metal remediation.

Keywords
Agricultural · Activated carbon · Pore size · Heavy metal ions · Adsorption

Introduction

Charcoal was reported to possess a ascertain role to carve in the stone of history due
to its adsorptive and medical property. Use of charcoal was first reported by Native
American around 8000 B.C. for treating stomach ailment using water along with
charcoal. Egyptians reported the use of charcoal for purification of bronze metal
from its ore by smelting on 3700 B.C. [12]. Later after 2200 years, in 1500 B.C., they
used charcoal (a) for the treatment of stomach ailments, (b) to absorb the unpleasant
odors from the infected wounds, and (c) for writing on papyrus. Romans around
27 B.C. used charcoal along with crushed bones, oyster, and bark and as a tooth
powder to brush the teeth. Accounting the anti-septic property of the charcoal,
Indians and Phoenicians around 400 B.C. used it for the purification of water
(University of Kentucky, 2012). Voyager used the technique of preserving the
water for month together throughout their journey using charcoal. Around 50 A.
D., Hippocrates, a great Greek physician considered to be as a father of medicine,
was first to report the use of charcoal for the treatment of neural disorder like
epilepsy, chlorosis, and vertigo [9]. Later in 2 A.D., famous and pioneering person
in the field of physician named as Claudius Galen has regularly referred the use of
charcoal in various treatments. Throughout many centuries, charcoal has been
widely used in many countries as an excellent antibacterial and antiseptic material.
Later in the seventeenth century, a Russian chemist Johann Lowitz initially
discovered the discoloration property of charcoal in liquids particularly used in
sugar refineries production of white sugar and made it as a visually exciting material
to the customers around the world [12]. This iconic discovery had accelerated the
scientist to work on the carbonaceous materials and later led to development of
official discovery of activated carbon (AC) in the early 1800. Soon after the
discovery AC, it was referred in many medical journals to use as an antidote against
poison and intestinal disorders around 1820. Frederick Lipscombe was the first
person to use AC in commercial applications to purify potable water in 1862.
50 Biomass-Based Carbon Materials for Heavy Metal Removal 1141

A German physicist, Heinrich Kayser, was the first person to coin the word “adsorp-
tion” and explained the mechanism of gas uptake by charcoal in the year 1881.
Where as in 1883, a French chemist, Gabriel Bertrand, has proved the antidote
potential of charcoal in treatment against poison intake; he himself swallowed
arsenic mixed with charcoal and demonstrated that he can save himself against the
lethal dose of arsenic along with charcoal. Later many such studies were demon-
strated by various scientists with different poison with lethal dose.
Industrial production of AC was started in early 1909, and soon after the
production, it was used in sugar refineries, chemical industries, and food industry
as discoloration agents. During World War I (1914–1918), AC was used in the mask
worn as personal protective equipment (PPE) by American soldiers to de-toxify the
inhaled poisonous gases, in spite it accelerated the production of granular carbons in
large scale. From 1979 onwards, AC was widely applied industrially in water
purification, industrial waste, offset of gases, cleaning of bottles and wine tanks,
etc., Currently, AC was greatly adopted in pharmaceuticals, cosmetic, and food
industries. AC was not only used in removing odor and disease causing germs to
make water potable but also used in heavy metal remediation. AC was also used in
clinical fields in liver, kidney dialysis machines, markers for breast cancer surgery,
and many more.

Carbon and Its Allotropes

Carbon has been known from ancient times. It is the sixth most abundant element in
the earth. Carbon adopts different allotropic forms, i.e., different structural arrange-
ment of the same carbon. Carbon appears naturally in two different forms: amorphous
forms (i.e., the application of high pressure and temperature without oxygen turning
wood into coal is known as carbonization, e.g., coal, etc.) and crystalline forms
(i.e., regular arrangement of carbon atoms in hexagonal and tetragonal arrangement
as graphite and diamond, respectively). Fullerene is an artificial crystalline allotrope of
carbon, whereas all other forms of carbon, namely coke, wood charcoal, animal
charcoal, plant charcoal, sugar charcoal, lamp black, fullerenes, graphene, and CNT
are artificial allotropes of carbons. Schematic representation of classification of
carbonaceous material based on its allotropic nature is shown in the Fig. 1.

Activated Carbon

Activated carbon may be defined as an amorphous form of carbonaceous materials

with rich inherent multidimensional property like high degree of porosity with an
extended interparticular surface area [5], long shelf life, low density, great surface
reactive, high performance in electrical conductivity, and thermal conductivity and
good thermal stability characteristics in nature. Properties of an activated carbon are
schematically represented in Fig. 2.
1142 S. M. Ponnuraj and P. S. Kumar

Carbon

Crystalline Amorphous

Diamond Graphite Coal Charcoal Lamp

Black
Coke Gas
Carbon

Plant Animal
Charcoal Charcoal

Bone Blood
Wood Sugar
Charcoal Charcoal
Charcoal Charcoal

Fig. 1 Different allotropes of carbon

Sources of Activated Carbon

Activated carbon can be prepared from wide variety of renewable and non-renewable
materials of organic origin. Variety of plant, animal, and fossil fuels can be used as an
excellent raw material for activated carbon [30]. Materials used in production of
activated carbon must satisfy two critical prerequisite, namely, (a) extremely carbon
rich and (b) contains low ash content and trace elements, (c) less expensive, (d) less
degradation during storage, (e) potent extent of activation, and (f) uninterrupted supply
[7]. Sources of the activated carbon can be broadly classified into two major catego-
ries: non-renewable (i.e., the source of energy that eventually runs out, namely, fossil
fuels like coal, crude oil, natural gas, etc.) is mainly used as raw material for
commercial production activated carbon [6] and renewable energy source is a naturally
inexhaustible energy source continuously replenished by nature, namely, various
agricultural byproducts like nut shells, stones, seeds, huls, seed kernels, bark wood,
corn cob, husks, straws, peels, piths, woods, saw dusts, coir dust, bagasse, etc. [18].
Agricultural byproducts have been documented as excellent sources of activated
carbon [13]. Agricultural byproducts are easily available and affordable, reduce
great distance of transportation and soil waste management, and improve the value
addition of crops by increasing the revenue of farmers. Potential agricultural source of
carbon-rich materials is categorized in Fig. 3.
Moisture, ash, volatile, carbon, hydrogen, nitrogen, sulfur, oxygen, cellulose, hemi-
celluloses, and lignin contents of an activated carbon produced from agricultural
byproducts like nut shells, stones, seeds, seed kernels, bark wood, corn cobs, husks,
straws, peels, piths, woods, saw dusts, coir dust, bagasse, etc., were characterized and
shown in Fig. 4 [32].
50 Biomass-Based Carbon Materials for Heavy Metal Removal 1143

Fig. 2 Properties of an activated carbon

Activated Carbon Production and Activation

A variety of activated carbon production methods are found elsewhere with appro-
priate change in raw materials and production process. The AC production involves
two important processes, namely, (i) carbonization (i.e., conversion of carbon-rich
material into pure carbon material devoid of non-carbon and volatile organic com-
pounds). During the processes of carbonization, the non-carbon materials like
nitrogen oxygen and hydrogen are released with increase in temperature of the
material. Carbonization was carried out by pyrolysis (i.e., thermal disintegration of
material at very high temperature (below 800
C) in inert atmosphere) and
(ii) activation (i.e., process of introducing countless pores and capillary like arrange-
ments inside the carbonaceous materials). Carbonized material can be activated
either by gas or chemical process (Fig. 5).
 1144

Fig. 3 Potential agricultural source of carbon-rich materials

S. M. Ponnuraj and P. S. Kumar
 50
Biomass-Based Carbon Materials for Heavy Metal Removal

Fig. 4 Analytical characteristic and composition of agricultural biomasses

1145
1146 S. M. Ponnuraj and P. S. Kumar

In carbonization of agricultural byproducts such as nut shells, stones, seeds, seed

kernels, bark wood, corn cobs, husks, straws, peels, piths, woods, saw dusts, coir
dust, bagasse, etc., material takes place at different phases with the removal of
non-carbonaceous materials at different temperatures as shown in Fig. 6.
The initial process of heating the agro byproducts below 200
C causes loss in
weight due to the decrease in moisture content of the material. Further heating of the
material at the temperature range of 170–200
C initiates the precarbonization phase
which results in production of non-pyroligneous liquids and non-condensable gas-
ses. Rise of temperature of the materials (around 250–300
C) causes elimination of
non-pyroligneous liquids and tars and results in production of charcoal. Further
continuing the rise in temperature above 300
C enriches the carbon content of the
charcoal by the release of residual volatile organic compounds. Activation of
charcoal was carried out by any one of two different ways, namely, (i) physical

Fig. 5 Process involved in activated carbon production

Fig. 6 Different phases of charcoal carbonization

50 Biomass-Based Carbon Materials for Heavy Metal Removal 1147

Fig. 7 Schematic diagram of physical and chemical activation of charcoal

activation or (ii) chemical activation [30] as shown in figure (7). Physical activation
of charcoal is preceded by the carbonization of material. Physical activation of
charcoal was carried at the temperature range of 700–1100
C. The charcoal is
oxidized by the stream of gases, namely, steam, oxygen, air, and CO2 or a mixture
constituting of all the above. Carbon becomes porous, partially gasified and highly
activated skeleton was produced due to physical activation. The chemical reaction
occurring during the activation is as follows:

C þ H2 O➝CO þ H2

C þ 2 H2 O➝CO2 þ 2 H2

During the chemical activation, the carbonization and activation of charcoal takes
place simultaneously. Initially, agricultural waste products were submerged with
oxidizing and reducing agents such as KOH, K2CO3, H3PO4, and ZnCl2. Chemical
activation of charcoal takes place at the temperature of about 450–900
C. After
activation of charcoal, the surplus activating agents are leached out and recovered.
The process of chemical reaction was quicker than the physical activation. Trace
amount of activating agents absorbed by the activated carbon may affect the
performance.

Classification of Activated Carbon Based on Pore Size

The formation of countless pores and capillaries inside charcoal is known as

activation. Size of the capillaries and pore formation increases the internal surface
area of the activated carbon which may be used in variety of application such gas, air,
1148 S. M. Ponnuraj and P. S. Kumar

and water treatments by the process of adsorption. Based on the pore size, activated
carbon can be generally classified into three types, namely, microporous (<2 nm),
mesoporous (2–50 nm), and macroporous (>50 nm). Kinetic property of the acti-
vated carbon inherently depends upon the pore size and capillarity. Each activated
carbon has different functions such as gas absorption, recovery of solvent with mild
and high boiling point, and absorption of liquid phase, respectively. The classifica-
tion of activated carbon and schematic representation of activated carbon is as shown
in Figs. 8 and 9. Pore distribution inside the activated carbon depends on the inherent
nature of the chosen material. Quantity of accumulation depends upon the significant
degree of increase of internal surface area of the activated carbon. Internal surface
area of the activated carbon is evaluated using BET (Brunauer, Emmett, and Teller)
and nitrogen isotherm at 196
C (www.donau-carbon.com). Internal surface area
of activated carbon evaluated as 800–1500 m2/g and 500–1500 m2/g is well suited
for gas and air treatment and water purification, respectively.

Fig. 8 Classification of activated carbon

Fig. 9 Activated carbon representing micro-, meso-, and macropore

50 Biomass-Based Carbon Materials for Heavy Metal Removal 1149

Adsorption Mechanism in Activated Carbon

The process of accumulation of atom or molecule or ion of gas, solutes of liquid, and
thin layer of dissolved solid on the micro-, meso-, and macroporous surface of
activated carbon was referred as adsorption. Adsorption is an exothermic process
that occurs with the release of heat to the environment. Adsorbent capacity of the
activated carbon depends on the (i) nature of the material, (ii) manufacturing process
of activated carbon, and (iii) mode of activation. Van der Waals force is understood
as the intermolecular force of attraction or repulsion between atoms or molecules or
surfaces. Capillary condensation is defined as confinement of condensed gas into
liquid at a chemical potential below the corresponding liquid vapor coexist in bulk
state. Van der Waals force and capillary condensation play a major role during the
adsorption. Adsorption process may be classified into two types, namely,
physisorption and chemisorption. During the process of physisorption, no chemical
reactions are activated between the activated carbon surfaces and accumulating
substances. Accumulation on the activated carbon surface was stabilized by Van
der Waals forces or London dispersion forces. Whereas in the process of chemisorp-
tion, a chemical reaction is triggered inbetween activated carbon and accumulating
substance causing chemical alteration. Physisorption and chemisorptions are sche-
matically represented in Figs. 10 and 11, respectively.

Evaluation of Property of Activated Carbon

Activated carbon possesses three significant properties, namely, surface area, pore
radius, and total pore volume. The above said properties of the activated carbon highly
depend on the intrinsic nature of the source material, manufacturing process, and mode
of activation. During the activation process, innumerable pores are created. The
surface area of the activated carbon was enhanced about 500–1500 m2/g or even
more than that. A spoonful of activated carbon is equivalent to the surface area of the
soccer field. Pore radius refers to the average size of the pore formed during activation
of carbon. Pore size is usually measured in angstroms (Å). Each carbon has their
unique distribution of pore size. Based on the pore size, activated carbon can be
classified in to micro-, meso-, and macroporous materials. Summation of volume of
each pore on the activated carbon refers to the total pore volume. Total pore volume is
usually measured in milliliter per gram (ml/g). In general, higher pore volume is
correlated with effectiveness of the activated carbon. The quality of the activated
carbon can be evaluated by following any of the international standard protocols
enacted by the American Society for Testing and Materials (ASTM), or American
Water Work Association (AWWA), or Council of European Federation for Industrial
Chemicals (CEFIC) based on the region and application of the product. All other
properties like (i) ash content, (ii) water content, (iii) pH, (iv) bulk and vibration
density, (v) iodine absorption, (vi) molasses decoloration behavior, (vii) methylene
blue absorption, (viii) tetrachloride carbon and butane absorption, (ix) absorption
isotherms of various solvents, (x) particle distribution, (xi) hardness, (xii) BET
1150 S. M. Ponnuraj and P. S. Kumar

Fig. 10 Classification of adsorption in activated carbon

Fig. 11 Schematic representation of physisorption and chemisorptions process. (Source: Adam

Hugmanic berger and Abhoyjit S. Bhown 2001)

analysis, (xiii) pore radius, (xiv) phenol concentration, (xv) chlorine half vale length,
(xvi) water- and acid-soluble components, and (xvii) estimation of halogen hydrocar-
bons and other purity test protocols are followed as referred in ASTM, AWWA, and
CEFIC (Source: CEFIC, test method for activated carbon).

Heavy Metal Classification, Properties, and Their Sources

Metals are natural components of the earth’s crust. Metals having an atomic weight
greater than 63, an atomic number >20, and a specific gravity greater than 5 gm/cm3
such as lead (Pb), cadmium (Cd), zinc (Zn), mercury (Hg), arsenic (As), silver (Ag),
chromium (Cr), copper (Cu), iron (Fe), and platinum (Pt) are generally referred as
heavy metals. Heavy metals can be classified in (a) macronutrient elements,
(b) micronutrient elements, (c) highly toxic elements, and (d) precious elements
(Fig. 12).
50 Biomass-Based Carbon Materials for Heavy Metal Removal 1151

Fig. 12 Classification of heavy metals

Fig. 13 Properties of heavy metals

Most common heavy metal contaminants are Cd, Cr, Cu, Hg, Pb, and Zn. Living
organisms require an optimum concentration of some metal such as Fe, Co, Cu, Mn,
Mo, and Zn for proper functioning and coordination of living system [14]. Any metal
at higher concentration causes acute toxicity to the living system. Uncontrolled
population explosion, rapid industrialization, unplanned urbanization, unskilled
use of natural resources, and negligence over production, usage, and discard of
remnant products may lead to the progressive release of a quantum of heavy metals
into land, water, and air leading to perturbation in biotic environment. Heavy metals
are (i) readily soluble in water to form ions [1], (ii) toxic, carcinogenic, and
teratogenic insusceptible to biological degradation to transform into harmless prod-
ucts (iii) owing to their long half-life and soil residence >1000 years. (iv) prolonged
exposure of food crops and livestock animals in the polluted land and water
resources may lead to bio-accumulation and bio-magnification (i.e.) gradually infil-
tration of heavy metals inside various parts of crops and animals and finally to
humans by food chain causing deleterious health effects [29] (Fig. 13).

Effect of Heavy Metals in the Environment

Heavy metals have different route source to the environment; their effect on human
health on exposure and their critical concentration are enumerated in Fig. 14
[4, 24]. Metabolism of heavy metal remains complex on exceeding its critical
 1152

Fig. 14 Heavy metals and their effect on human health with their permissible limits. (Source: Singh et al. [29])
S. M. Ponnuraj and P. S. Kumar
50 Biomass-Based Carbon Materials for Heavy Metal Removal 1153

concentration. Heavy metal accumulation above the critical limit disturbs the metabolic
function by two different ways: (i) they disturb the function of the organ by accumu-
lation and (ii) they replace the essential nutrient minerals from their appropriate binding
place and by hampering the biological system. Toxic effects due to heavy metals in
humans are exhibited in the form such as gastrointestinal disorders, diarrhea, stomatitis,
tremor, hemoglobinuria, ataxia, paralysis, and vomiting, and convulsion, depression,
and pneumonia either due to ingestion or inhalation of fumes or vapors. These heavy
metals are not biodegradable; as a consequence, their presence in water causes serious
health problems in human, plants, and animals. Wastewater commonly contains copper,
nickel, and lead [22, 35]. Excessive intake of copper can cause capillary damage, hepatic
toxicity, and renal damage [3]. Exposure to nickel results in skin irritation and damage to
lungs and mucous membrane [23]. The presence of lead in drinking water causes
various health disorders and enzyme inhibition. Importantly, the inorganic form of
lead is reported to exert drastic effects as compared with organic isoforms [15, 33].
Some heavy metals cause cancer; therefore, it is necessary to remove toxic heavy metal
ions from wastewater in order to protect human. In the current year, persistence of
numerous chemicals and their derivatives reported to be above the tolerable limit is the
prime reason for causing deleterious effect on environment. Children are highly sus-
ceptible to ingestion and inhalation of heavy metals causing hampering of multiple
organs like the brain, kidney, lungs, bone marrow, and others. Heavy metals contaminate
the natural resources and remains as a socioenvironmental threat [2].

Heavy Metal Remediation

The removal of toxic heavy metal ions from industrial effluents in recent years gains
much attention [19, 25]. The removal of heavy metals from the environment can be
classified into biotic and abiotic methods. Biotic methods mean the removal of heavy
metals by plants or microorganisms, while abiotic methods consist of physiochemical
processes such as precipitation, co-precipitation, electrochemical treatment, ion
exchange, liquid–liquid extraction, resins, cementation, electrodialysis, and sorption
[16, 21, 27]. Among these methods, sorption is one of the most effective, economic,
and simplest methods for the removal of pollutants from wastewaters [11]. Among the
different sorbents that have been conventionally used for the removal of heavy metals
from solution are zeolite [36], clay [28], and activated charcoal [8]. Activated carbon is
widely applied as sorbent due to its high sorption capacity, the sorption capacity is
related to the surface characteristics (surface area, pore size and pore volume) of the
activated carbon, while surface characteristics of the activated carbon depend on
preparation conditions [10, 17].
Activated carbon prepared from Salvadora persica was applied to the sorption
study of divalent cations from diluted aqueous solution of lead copper, and nickel was
evaluated using Langmuir model. Studies revealed the Activated Carbon prepared at
30 min heating time showed a greater sorption capacity for Cu2+, Pb2+, and Ni2+, and
its order of cation sorption is Cu2+ > Pb2+ > Ni2+. An increase in time for the
preparation of activated carbon gives a smaller surface area and hence causes decrease
1154 S. M. Ponnuraj and P. S. Kumar

in the sorption capacity of cations [34]. Similarly, the activated biochar produced from
Pinus taeda and the absorption studies were carried out using an aromatic model
compound, phenanthrene. The increasing aromaticity and non-protonated carbon
fraction of the activated biochar treated at 300
C amounted to 14.7% and 24.0%,
respectively, compared to 7.4% and 4.4% for biochar treated at 700
C. The surface
area and pore volume were reduced with the increase in pyrolysis temperature, but
increased after activation [26].
Activated carbons obtained from corncobs by corncobs were carbonized at 500
C
and steam activated (in one- or two-step schemes), or activated with H3PO4. The
products were characterized by N2 adsorption at 77 K, using the BET and DR methods.
Adsorption capacity was demonstrated by the iodine and phenol numbers, and the
isotherms of methylene blue and Pb_2 ions, from aqueous solutions. These activated
carbons proved highly porous and rich in mesopores and showed high adsorption
capacity for methylene blue and Pb2_ ions. The adsorption capacity of Pb2_, from an
unbuffered solution of Pb(NO3)2, was carried out by mixing 50 mg of the powdered
carbon with 100 ml of Pb2_ solution of varying concentrations and shaking for 24 h. The
residual lead was estimated in the filtered solution using a Perkin-Elmer model 2380
atomic absorption spectrometer. Analysis of the adsorption isotherms of MB and Pb2_
was carried out by applying the linear Langmuir equation [20].
Palm shell AC has been reported to remove heavy metals such as lead, chromium,
and copper ions in wastewater due to presence of some functional groups on Palm
shell AC that have chemical attraction toward metal ions, such as hydroxyl, lactone,
and carboxylic [31]. Lead is often found in wastewater from printed circuit board
factories, electronics assembly plants, battery recycling plants, and landfill leachate.
If exposed to human body, they can cause central nervous system damage. Apart
from that, lead can also damage the kidney, liver, and reproductive system, basic
cellular processes, and brain functions. The toxic symptoms of lead are anemia,
insomnia, headache, dizziness, and irritability, weakness of muscles, hallucination,
and renal damages. Other than lead, copper is also widely used in electronics
industry. The copper in animal body is essential in their metabolism. However,
excessive ingestion of copper brings about serious toxicological concerns, such as
vomiting, cramps, convulsions, or even death.

Conclusion

Agriculture-based byproducts like nutshells, stones, seeds, hulls, seed kernels, bark
wood, corn cob, husks, straws, peels, piths, woods, saw dust, coir dust, bagasse, etc.
remain as a primary resource of carbonaceous materials. Carbonization of raw
materials is achieved using pyrolysis, whereas activation was accomplished either
using physical or chemical activation. Based on the pore radius, pore surface area,
and total pore volume, activated carbons are classified functionally. Classification,
properties, and their intervention in environment and human health are portrayed.
Heavy metal remediation from various possible sources using the activated carbon is
discussed in this chapter.
50 Biomass-Based Carbon Materials for Heavy Metal Removal 1155

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Environmental and Occupational Health
Hazards of Nanomaterials in Construction 51
Sites

S. Ajith and V. Arumugaprabu

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1158
Human Health Risk Assessment Using Hazard Identification and Risk Assessment
Technique (HIRA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1160
Basic Mitigation Measures for the Workers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1161
Control Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1163
Green Alternatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
Environmental Hazards of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
Assessment of Nanoparticles in Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
Assessment of Nanoparticles in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
Assessment of Nanoparticles in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
Life Cycle Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1165
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166

Abstract
The use of nanomaterials has become increasing in the field of construction to
enhance the structural strength of the building and to conserve energy. Besides the
foreseeable advantages of nanoproducts, many of the nanotoxicology studies
have revealed that the impacts on both health and environment are severe. As
large amount of nanomaterials are used in construction sites, its adverse effects on
workers’ health and environment have to be addressed. Risk assessment (RA) and
life cycle assessment (LCA) are the effective tools which are used to quantify the

S. Ajith
Department of Civil Engineering, Kalasalingam Academy of Research and Education,
Krishnankoil, Tamil Nadu, India
V. Arumugaprabu (*)
Department of Mechanical Engineering, School of Automotive and Mechanical Engineering,
Kalasalingam Academy of Research and Education, Krishnankovil, Tamil Nadu, India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1157

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_66
1158 S. Ajith and V. Arumugaprabu

risk of both workers and environment. The quantified risk value gives a clear
picture about the hazards which made the environment to get depleted as well as
the occupational risk of workers. The most promising technical recommendations
are suggested in order to overcome the risk of nanoproducts which are used in
construction sites.

Keywords
Nanoproducts · Hazard · Risk assessment · Health

Introduction

Nanotechnology is defined as the study of extremely small things whose size ranges
between 1 and 100 nm. It has the ability to acquire new materials or improve the
existing materials with enriched properties. Nowadays it has application in all fields of
science and engineering, as it has the ability to see and control each and every atom in
the material. The application of nanotechnology in construction materials has several
features such as low-weight and high-strength materials and fire retardant, and main-
tenance is low in coatings. As size is one of the key factors in construction, nanotech-
nology plays a major role [1]. The role of construction industries in India is significant
due to the development of smart cities, transportation, and industrial expansion.
Construction industries hold lots of workers all over the country and fulfill peoples
demand such as employment and the country’s growth. The construction industries
use materials like coarse aggregate (CA), fine aggregate (FA), sand, steel, cement,
glass, insulation materials for buildings, etc., but in order to have sustainable buildings,
nanomaterials are more emphasized. The evolution of nanoproducts in concrete with
its mix ingredients is as shown in Table 1.
Nanotechnology has important role in building materials as it has high perfor-
mance and durability. The mandatory material for any construction is concrete. The
advanced characterization techniques and the superior understanding of the cemen-
titious materials at the micro/nano level have the ability to produce large-scale
materials [3]. The usage of nanomaterials in building materials and its improvement
with the existing materials are listed in Table 2.
A report from the United Nations says that almost 50% of the world’s population
lives in urban area and it is predicted to increase by 16% at 2050. This will increase
the usage of construction materials and demolition of existing buildings. The waste
generation due to urbanization reached three billion till 2012. Hence waste manage-
ment practices with low technology are essential to save the environment in the
future [21, 22]. It is known that nanoparticles have a vital role in the building
materials, and the need for such materials still exists, but it is seen that the usage
of these particles in building materials seems to be very much low. Nevertheless, the
most important material in construction such as concrete and asphalt doesn’t reach
large-scale manufacturing due to some drawbacks such as increase in price,
51 Environmental and Occupational Health Hazards of Nanomaterials in. . . 1159

Table 1 Evolution of nanomaterials in concrete [2]

S. No Type of Concrete Ingredients Size
1. Ordinary concrete FA, CA, cement, and water mm
2. High-performance concrete FA, CA, cement, micro-silica, and water μm
3. Ultrahigh-performance concrete FA, CA, cement, nano-silica, and water nm

Table 2 Usage and improvements of nanomaterials in building materials

Existing
Type of materials/
S. no nanomaterials process Necessity Reference
1. Nano-SiO2 Mixed with Increase in flexural and compressive [4, 5]
cement mortar strength
2. Nano-SiO2 Mixed with Increase in consistency and reduced [6, 7]
hardened setting time and permeability
cement paste
3. Nano-SiO2 Mixed with Increases the compressive strength, [8]
high-volume fly reduced porosity
ash concrete
4. Nano-TiO2 Added in Increase in flexural and compressive [9, 10]
concrete strength, accelerate the early age
hydration
5. Nano-Al2O3 Mixed with Increase in modulus of elasticity [11]
cement mortar
6. Nano-ZrO2 Added in Increase in compressive strength, [12]
cement reduction in permeability and
porosity
7. Nano-CaCO3 Added in Increase in flexural strength, impact [13, 14]
concrete resistance, sound absorption, and
low specific weight
8. Nano-silica Added in Improved workability, high [15, 16]
concrete performance, and strength
9. Nano-cement Added in Increase in hardening of concrete as [17, 18]
cement well as higher compressive and
tensile strength
10. Nanotubes/ Added in Increase ductility, durability, and [19, 20]
nanofibers cement tensile strength

uncertain performance, and health issues [23, 24]. In addition to this, the workers in
the site should have basic knowledge to handle the nanoproducts, hazards, and its
consequences. Only then the usage of nanomaterials in construction sites will
become effective in practice.
This chapter is organized as follows. The next section discusses about the
environmental effects of nanoparticles. This is followed by the human health effects
of nanoparticles, and finally conclusions are drawn.
1160 S. Ajith and V. Arumugaprabu

Human Health Risk Assessment Using Hazard Identification

and Risk Assessment Technique (HIRA)

HIRA is a general tool for identifying risk in the workplace which can be used both for
the workers and for the environment. This has two main steps such as likelihood rating
and severity rating. These scores can be given based on frequency of the hazard and its
consequences, and it differs based on the nature of the workplace. There are also some
other techniques to assess the risk in the workplace such as job safety analysis (JSA), job
hazard analysis (JHA), and chemical health risk assessment (CHRA). JSA and JHA
determine the risk qualitatively by separating each task into sub-activities, whereas
CHRA determines the risk using various factors such as duration of the exposure,
degree of chemical release and absorbed, and magnitude rating. The risk value is
calculated using hazard rating and exposure rating [25], but HIRA is different from
those techniques as this can calculate the risk likelihood and severity of the hazards. The
likelihood rating as shown in Table 3 is defined as the number of frequency for the
particular risk in which it can occur until the completion of an activity. Severity rating as
shown in Table 4 is defined as the consequences of the hazards, and risk value is the
product of both the likelihood and the severity ratings. Then the risk range as shown in
Table 5 is given according to the risk matrix (i.e., as the likelihood level is 5 and the
severity level is 5, then the risk matrix will be 5 x 5), and it is categorized accordingly.

Table 3 Likelihood rating [26]

S. no Likelihood Description Level
1. Almost certain Repeating occurrence 5
2. Frequent Common occurrence 4
3. Conceivable Possible to occur 3
4. Remote Isn’t expected to happen under normal circumstances 2
5. Inconceivable Not likely to happen 1

Table 4 Severity rating [27]

S. No Severity Description Level
1. Serious Fatality 5
2. Major Multiple injuries, occupational cancer 4
3. Moderate Burns, lacerations, dermatitis 3
4. Minor Temporary uneasiness, irritation 2
5. Negligible Unlikely to cause harm 1

Table 5 Risk category S. No Risk Range Risk Category

[28]
1. 1–5 Low (L)
2. 5–10 Medium (M)
3. 10–15 High (H)
4. 15–25 Extreme (E)
51 Environmental and Occupational Health Hazards of Nanomaterials in. . . 1161

The activities in the construction site are chosen based on the usage of nano-
materials to quantify the risk as mentioned in Table 5. The hazards and its conse-
quences for each activity are then listed correspondingly. As per the likelihood and
severity ratings, the risk value is calculated.
As per the risk assessment from Table 6, it can be known that there is now low
risk of any of the construction activities. It indicates that handling and working with
nanoproducts has higher risk both in terms of acute and chronic diseases. The use of
nanoproducts in construction site cannot be restricted, but if safe handling pro-
cedures are followed, then the exposure of nanoproducts and its severity can be
reduced.
Some of the other methods which are used to assess the risk of nanomaterials are
as follows. The impacts of nanoproducts in construction sites were analyzed with
respect to children in Thailand. It is identified that respiratory problem and skin
irritation were the two major consequences of the nanoproducts. Multinomial and
binary logistic regression is used for data analysis in both the cases [30]. The multi-
criteria decision analyses (MCDA) which are used in risk assessment are multi-
attribute utility theory (MAUT), analytical hierarchy process (AHP), and
outranking. These are the optimization methods in which the identified risk can
be ranked according to the expert score and are also known as the decision-making
tools. MCDA techniques incorporate stakeholders and decision-makers in policy
decision and superior management [31]. The process involved in environmental
risk assessment is problem definition, identifying the criteria to compare the
alternatives, relative importance, and determining the performance of the alterna-
tives. Furthermore the cyclic steps involved in management are to develop the
management plan, implement the strategy, and periodic monitoring and data
analysis [32].

Basic Mitigation Measures for the Workers

There are different safety measures that have to be followed by the workers by
considering the place and type of nanomaterials they are working with. Ingestion,
injection, inhalation, dermal, and ocular are some of the types of exposure of
nanomaterials. To mitigate the exposure rate, the following points should be
considered. In order to avoid dermal exposure, the workers should wear proper
hand gloves and coverall while handling nanoparticles in the site. To avoid
ingestion of nanoparticles, the workers should not eat or drink in the workplace
or after the sudden completion of work, i.e., they are advised to eat after properly
washing their hands and face with suitable solutions. To avoid inhaling the
nanoparticles, workers should wear respiratory air filters of size N 100 or N95 to
avoid lung diseases. To avoid injection personal protective equipments must be
used by the workers. To avoid ocular exposure, safety goggles and respirators are
mandatory [33].
 1162

Table 6 Human health risk assessment [29]

Risk Risk
S. no Activity Hazards Consequence Likelihood Severity value category
1. Excavation Particulate matter such as dust, smoke, and Respiratory problems 4 4 20 E
liquid droplets
2. Cement sack Crystalline silica Rashes, eye irritation 4 2 8 M
handling
3. Cement paste Nano-SiO2 Fibrotic lung disease 3 3 9 M
mixing
4. Mixing of Particulate matter such as dust and liquid Chemical burns, silicosis 4 4 16 E
concrete droplets
5. Concreting Nano-TiO2, nano-CaCO3, liquid droplets Chemical burns, lung 4 4 16 E
cancer
6. Drilling Fine, ultrafine nanoparticles, airborne Asthma, deafness 3 3 9 M
nanoparticles
7. Steel cutting Fine, ultrafine nanoparticles, airborne First- or second-degree 3 3 9 M
nanoparticles burns
8. Wood cutting Fine, airborne nanoparticles Lacerations, respiratory 3 3 9 M
problems
9. Polishing Agglomerate particles Silicosis 4 3 12 H
10. Painting Fine pure matrix materials, liquid aerosol Neurological problems 4 4 16 E
droplets
11. Spraying Liquid aerosol droplets Nausea, damages to the 3 4 12 H
liver
S. Ajith and V. Arumugaprabu
51 Environmental and Occupational Health Hazards of Nanomaterials in. . . 1163

Control Strategies

A plan of controls that is designed to achieve the overall objective is known as

strategic controls. The different categories of controls in chronological order are as
shown in Fig.1.
Engineering controls are those which include how to eliminate the hazard from the
nanomaterials or how to use an alternative for the same materials. The hierarchy of
control indicates that engineering controls must be given top priority and PPE must be
given least priority. Substitution is a tough process which requires a lot of experimen-
tation and research for identifying a new material. For instance, local exhaust venti-
lation system (LEVS) is a suitable engineering control for the workers working in
airborne nanomaterials. Furthermore if the hazards cannot be mitigated with the
engineering controls then the engineers/managers will prefer for the second hierarchy
of control. Administrative controls are preferred when the suggested engineering
controls are not much effective. Housekeeping, personal hygiene, reduction in work
period, and job rotation are some of the examples of administrative controls. Personal
protective equipments (PPE) are those in which the worker is asked to use it every time

Fig. 1 Control strategies

1164 S. Ajith and V. Arumugaprabu

while handling the nanomaterials to reduce its penetration or exposure. There are
different types of PPE’s that can be used which are goggles, respirators, coverall, and
hand gloves. PPEs are made of high-density polyethylene textile which is suggested as
the most effective material to resist in nanoparticles in human body. Waste must be
disposed away from the work site on daily basis, and while handling the waste, several
safety precautions has to be taken as same as handling the raw materials [34].

Green Alternatives

There are several alternatives to mitigate the severity of nanomaterials for the
workers and environment. Green alternatives are those which focus to control the
impacts from the manufacturing, usage, and disposal of nanomaterials. The key
concepts which are considered in green alternatives are design, usage, and minimi-
zation/maximization. For instance, in designing the overall process, there must be
significant contribution for safer chemicals, process involved in chemical synthesis,
and type of degradation system after use. The materials which are used must be safer
solvents and renewable. Also it should minimize the waste and potential health
hazards in the workplace [35].

Environmental Hazards of Nanomaterials

Environmental risk assessment (ERA) has become a key role in assessing the
environmental hazards due to increase in engineered nanoparticles in construction
materials. The increased usage of nanoparticles releases sufficient potential risk to
the environment in various forms. Due to scarce data and hazard identification
techniques, it is difficult to quantify the risk of nanomaterials in construction sites.
ERA consists of assessment of hazard, exposure, and risk characterization in which
each of these assessment techniques adopts different tools. In order to assess the
exposure of nanomaterials, SimpleBox4nano (SB4N) model, for hazard assessment
probabilistic species sensitivity distribution (pSSD) model, is used [36]. Due to the
unique properties of nanoparticles such as tiny in size, high surface volume, the
severity and the toxicity to the environment is relatively high. The demand of
nanoparticles in construction materials is increasing for several purposes along
with the impacts to the environment. The toxicity effects of the nanoparticles are
high, but it is difficult to access as their reactivity is high along with uniqueness in
chemical properties and insolubility [37].

Assessment of Nanoparticles in Air

The impact of nanoparticles in air is determined by three major factors such as the
time taken by the particles to remain airborne, the contact with other particles in the
atmosphere, and distance for which the particles can able to travel. There are five
51 Environmental and Occupational Health Hazards of Nanomaterials in. . . 1165

different process which helps to identify the aspects of nanoparticles in atmosphere

such as gravitational settling, agglomeration, diffusion, and wet and dry deposition.
In general, it is known that the particles of less than 100 nm have reduced residence
time when compared to particles which are greater than 100 nm [38].

Assessment of Nanoparticles in Water

The risk of nanoparticles in water can be determined by several factors such as

reactivity, solubility, and interaction of the particles with the biological process. As
the particles have low mass, the settling time is too high when compared with other
particles. These can be removed when the water sample undergoes biotic and abiotic
degradation. In order to remove or change the chemical properties of the nano-
particles, the surface area is exposed to the sunlight. Due to the exposure to sunlight,
photoreactions may take place which help in changing the properties of the
materials [39].

Assessment of Nanoparticles in Soil

The performance of nanomaterials in soil generally varies due to the physical and
chemical properties of the materials. Nanomaterials which sorb to the soil become
immobile, whereas the other material which doesn’t sorb to the soil has higher
mobility. The sorption strength of the nanomaterials is subjective to surface charac-
teristics, composition, and size of the particles. The mobility of the soil depends on
the properties of the soil such as grain size and porosity [40].

Life Cycle Risk Assessment

Life cycle risk assessment (LCRA) is one of the screening techniques in which the
risk of nanomaterials throughout its life cycle can be quantified. The following are
the steps which is used for LCRA:

(a) The life cycle of the product or material has to be described. It includes how the
material has replaced the existing materials and its advantages. The life cycle of
any product has four different stages such as introduction, growth, maturity, and
decline. Each stage has its own importance about the product.
(b) The type of material used for the product and its hazards must be identified in
each cycle of the product.
(c) Qualitative exposure assessment of the material should be done by estimating the
duration and frequency of the particular hazard.
(d) The possible stages in which exposure may occur have to be identified.
(e) With the exposure assessment, the impacts to human and environment have to be
evaluated.
1166 S. Ajith and V. Arumugaprabu

(f) High-risk zones in each life cycle have to be analyzed.

(g) Engineering controls/mitigation measures should be implemented to make the
risk zones as low as reasonably practical.
(h) Assessing the implemented mitigation measures and its efficiency.

These steps are repeated until the risk level in each stage becomes low. If the
process becomes new and some additional materials are added for the product, then
LCRA has to be done. In some cases, if the control strategies are modified or changed,
then its efficiency can be checked with respect to the category of risk [41, 42].

Conclusion

(a) This chapter discusses about the environmental and occupational health hazards
of nanomaterials in construction sites.
(b) As infrastructure development in India is high due to smart cities and extension
of highways and airports, the need for nanomaterials in construction is also high,
but the workers have to follow certain safety steps to avoid its exposure.
(c) Health risk assessment of nanomaterials used in construction site is tabulated
with the likelihood and severity ratings of the hazards in the site.
(d) Suitable mitigation measures, green alternatives, and control strategies have
been suggested to reduce the risk level to as low as reasonably practical.
(e) Environmental hazards of nanomaterials and its assessment of various environ-
mental factors are briefed to get insight of impacts of nanomaterials.
(f) In addition to this, regular safety meetings and toolbox talk must be conducted to
create awareness among the workers.

Important Websites

1. www.ckmnt.com
2. https://theconstructor.org/building/nanomaterials-in-construction-applications/
5638/
3. https://www.nano.gov/you/nanotechnology-benefits

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Consumer Nanoproducts for Environment
52
Anika Tasnim Chowdhury, Nazifa Rafa, Ahmedul Kabir, and
Paulraj Mosae Selvakumar

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
Environmental Benefits from Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173
Application of Green Nanotechnology in Energy Generation and Conservation . . . . . . . . . 1174
Application of Green Nanotechnology in Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1178
Application of Green Nanotechnology in Environmental Remediation:
Nano-remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1179
Application of Nanotechnology in Sensing and Monitoring: Nanocontact Sensors . . . . . . 1181
Application of Green Nanotechnology in Manufacturing, Waste Reduction, and
Pollution Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1182
Application of Green Nanotechnology: An Unexplored Horizon . . . . . . . . . . . . . . . . . . . . . . . . . 1184
Environmental Harms Caused by Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1184
Nanotoxicology: The Emerging Challenges and Call for Safer Nanomaterial Design . . . 1185
Threats Posed by Nanoproducts to the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1187
Nano Waste Management: Challenges Posed by Nanoparticles and Recommended
Waste Disposal Practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1190
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
Useful Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1196

Abstract
Nanotechnology is the study and application of nanoparticles in all fields of
science, engineering, and technology, and is one of the fastest-growing branches
of technology that takes advantage of the physicochemical benefits that arise from
the manipulation of matter at the atomic scale. Consumer nanoproducts have the
potential to revolutionize the lifestyles leading in the contemporary world. How-
ever, the relation between nanotechnology and the environment has proved to be
interesting, yet controversial. This chapter presents the numerous benefits that
nanoproducts offer to the environment, as well as the risks that they pose. Green
A. T. Chowdhury · N. Rafa · A. Kabir · P. M. Selvakumar (*)
Science and Math Program, Asian University for Women, Chittagong, Bangladesh
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1169

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_67
1170 A. T. Chowdhury et al.

nanotechnology is a subset of green chemistry that mandates the use of safer

solvents and reaction conditions and avoids dependence on processes that may
produce pollutants. Through green nanotechnology, several far-reaching applica-
tions are possible in the sectors of energy generation and conservation, water
treatment, environmental sensing, monitoring, and remediation, and waste man-
agement. As the field is currently still in the nascent phase, many applications still
remain unexplored and the full potential of nanoproducts remains untapped.
However, nanoproducts also have the potential to cause great damages to
human health and the environment, if not managed well. Therefore, proper safety
measures and disposal procedures after appropriate risk assessments are neces-
sary for handling nano waste and need to be urgently incorporated in nations’
policies and legislations. Moreover, awareness and knowledge sharing regarding
the benefits and challenges of nanoproducts need to be encouraged between all
relevant stakeholders, including the end-users.

Keywords
Consumer nanoproducts · Green nanotechnology · Nano-remediation ·
Nanotoxicology · Nano waste

Introduction

Throughout history, scientific discoveries and technological advancements have

significantly changed the world by improving our living standards and making our
lives easier. However, most inventions are double-edged swords – several of the
negative consequences of such technologies are unprecedented and/or evade the
attention of the scientific community. For example, with the creation of steam
engines, while the world reached a milestone called the industrial revolution,
human activities have contributed to the total atmospheric concentration of the
greenhouse gas carbon dioxide. Other such examples include chlorofluorocarbons
(CFCs), polychlorinated biphenyls, asbestos, and DDTs. Because of human inven-
tions and interventions, the world has been constantly changing; notably, the envi-
ronment has been deteriorating due to pollution; depletion of resources like air,
water, and soil; extinction of wildlife; and destruction of ecosystems. Therefore,
significant adjustments need to bring in the behavior of human production and
consumption to ensure environmental sustainability. One promising approach to
making changes in our lifestyles can be via the use of nanoproducts.
The era of nanotechnology, often dubbed as the second industrial revolution, is a
fast-emerging branch of technology that exploits the physicochemical benefits that
arise from the manipulation of matter at the atomic scale. Nanotechnology is the
study and application of nanoparticles in all fields of science, engineering, and
technology. More often, nanotechnology is identified as the field of study where
phenomena and materials are manipulated at a scale of under 10 nanometers. The
European Commission adopted the definition of a nanomaterial in 2011 to be a
52 Consumer Nanoproducts for Environment 1171

natural, incidental, or manufactured material containing particles, in an unbound

state or as an aggregate or as an agglomerate and where, for 50% or more of the
particles in the number size distribution, one or more external dimensions is in the
size range 1 nm–100 nm [1]. The size of nanomaterial is usually smaller than
bacterial cells but bigger than most molecules. Elements such as metals, groups of
compounds such as metal oxides, form groups to build the nanomaterial that takes
various shapes and structures like a soccer ball, branching, and interminable com-
binations of these structures. Besides, nanoparticles also are known to be in the
regular and geometric crystal structures, or sometimes irregular. Nanoparticles can
be classified into three major groups: natural, incidental, and engineered. The nano-
particles existing in our environments such as ocean spray, volcanic ash, magnetotactic
bacteria, mineral composites, and other naturally occurring nanomaterials fall into the
first class of nanoparticles. The second group of nanoparticles is known as incidental
nanoparticles or waste particles, which are produced through some industrial processes.
Engineered nanoparticles – the third category of nanoparticles – are the ones associated
with nanotechnology. This group of nanoparticles is further subclassified by the type of
basic material and its use, such as metals, semiconductors, metal oxides, nano clays,
nanotubules, and quantum dots. The shapes, sizes, and surface coatings of each category
are responsible to determine the structure and function of these molecules, giving rise to
a specialized function [2]. Such specialized features of nanoparticles have allowed them
to demonstrate industrial applications such as increased sensitivity, magnifying precision
and improving production limits [3]. Functionalized nanoparticles, commonly known as
a type of engineered nanoparticles, have also been discovered to have useful chemical,
physical, and mechanical properties that could possibly outperform their regular coun-
terparts. These particles are more likely to produce cheaper and effective consumer
products and are mainly used in the development and innovation of various industrial
processes. However, functionalized nanoparticles are still in their early stage in most
industrial settings, and their adverse effects on human health and environment are yet to
be explored if used inappropriately [4]. Thus, engineered nanoparticles have led nano-
technology to successfully penetrate the various sectors of the world economy due to its
structural and functional diversity. This implies that due to the rapid evolution of
nanoscience and nanotechnology in the past 20 years, the key to many technological
innovations is dominated by this branch of science and technology in the twenty-first
century. Currently, nanotechnology’s endeavors range from producing unique or
upgraded materials, optimizing the fabrication processes, and removing hindrances
from the agenda of sustainable development. Its application in the real world is diverse,
ranging from its use in drug delivery, as antimicrobials, carbon-based nanomaterials for
technology, electrical and electrical components, nanoparticle-reinforced high-perfor-
mance composite materials, self-cleaning surfaces, and so on. Nanomaterials and
polymer nanocomposites have shown significant potential in enhancing some current
manufacturing techniques that give rise to the production of more sustainable products.
However, the common challenges such as the lack of information, the probable adverse
impacts on the environment, human health, safety and sustainability, and economical
and legal aspects need to be addressed accordingly [5, 6]. Besides, the application of
nanomaterials is also thought to have a promising aspect in environmental protection,
1172 A. T. Chowdhury et al.

especially in environmental sustainability. Global water challenges related to clean

drinking water are an issue presenting immense distress in this era of scientific vision.
One of them is the scientific challenge associated with groundwater remediation,
requiring immediate attention. To address this challenge, nanoparticle with their huge
potential is opening the way for a broader vision and newer realm in the field of
environmental engineering [7]. There are many other applications and market trends
in nanotechnologies than those already mentioned, particularly in addressing environ-
mental and climate protection goals. Consumer nanoproducts have the potential to act as
tools to mediate the environment. As movements for the environment become popular,
nanoproducts can allow consumers to bypass lifestyles that further pollute the environ-
ment. However, the future implications of nanotechnology are controversial among
scientists. Some groups highlight the fact that applications of nanotechnology are
widespread in areas like nanomedicine, nanoelectronics, biomaterials energy produc-
tion, and consumer products. Others express their concerns on nanotechnology-related
toxicity and environmental impact of the nanomaterials, followed by their potential
effects on global economics [8]. These concerns have led to disputes in the scientific
community as well as among advocacy groups and governments on whether regulation
of nanotechnology should be considered as authorized.
The relation between nanotechnology and the environment has proved to be
interesting, yet controversial. In the energy sector, nanomaterials intervene at a
number of stages of the energy flow starting from the primary energy sources and
finishing at the end user [9]. Nanotechnology is visioned to transform the way
society develops, uses, and disperses materials by recovering and recycling valuable
resources in the process of transportation of people and goods, the supply of food,
availability of clean water, etc. For the past 30 years, technology responsible for the
sustainability of materials has become of great interest as it is an integral subject that
addresses environmental quality. Scientists and engineers have shown significant
attention toward the generation of cleaner energy by using catalysts in chemical
processes that prevent the production of unwanted by-products or by upgrading the
quality of effluent and exhaust fumes from vehicles. But, engineers or designers of
such technology do not always consider the material functionality of the product. For
example, to design a battery-powered vehicle which is considered as a “greener”
vehicle, a large amount of toxic and hazardous materials are required, considering it
as a cleaner choice in comparison with other gasoline-powered vehicles. However,
the use of all the toxic materials in supporting this technology needs to be considered
when the assessment of environmental benefit is done.
This calls for a joint collaboration of scientists from different disciplines to
communicate and take part in balanced basic research. The basic research supporting
the development and sustainability of nanotechnology should include some funda-
mental conditions such as knowledge development related to structure and function
at nanoscale; developing a new material that can be modified to experience multi-
functioning; method of optimizing the stability control at all possible scales and
conditions during use, synthesis, assembly, and processing at all scale; and finally
designing research tools that facilitate its operation across multiple length
scales [10].
52 Consumer Nanoproducts for Environment 1173

This chapter provides insights into how nanoproducts can be used for the benefit
of the environment. It primarily looks into eco-friendly and sustainable methods of
generating electricity, increasing the efficiency of devices, remediation of the envi-
ronment, and pollution and waste management through the employment of nano-
products. It also later presents the rebuttal against the proponents of using
nanotechnology for the environment by highlighting the potential risks and harms
of nanoparticles to the environment. Attempts have also been made to draw up
recommendations from existing sources as a way to ensure that the advantages of
nanotechnology can be exploited for the environment by minimizing the potential
environmental degradation brought about by nanoproducts.

Environmental Benefits from Nanoproducts

As mentioned above, the utilization of nanoproducts for the environment can lead to
several unprecedented harms. Many of these will be discussed in the next section.
Primarily, concerns may arise in the processes of production of nanoparticles as
procedures may involve the use of a large number of toxic chemicals and extreme
environments, as well as the emission of a huge amount of toxic by-products. In fact,
most nanoproducts are made from chemical processes that may generate pollutants,
waste energy, or waste materials that are harmful or toxic and therefore require well-
planned and expensive disposal methods. However, this risk can be avoided through
the integration of the principles of green chemistry and green engineering to make
nanoparticles using what is known as green nanotechnology [11]. Green chemistry
mandates the use of safer solvents and reaction conditions and avoidance of depen-
dence on processes that may produce pollutants. For example, instead of using
synthetic inorganic chemicals to synthesize nanoproducts, biological sources such
as phytochemicals can be used to create safe and eco-friendly metal nanoparticles
[12]. On the other hand, green engineering dictates a more sustainable form of
design, commercialization, and the use of products that minimize pollution as
much as possible to reduce the potential risks to human health and the environment,
in a way that does not entail trade-offs with economic viability and efficiency. As a
result, the environmentally detrimental origin of nanoparticles can be avoided if the
production of nanoparticles involved an environmental sustainability agenda. Green
nanotechnology, therefore, arises from marrying these two disciplines.
This recently emerged subdiscipline of green nanotechnology, which refers to the use
of nanotechnology to manage the potential environmental, health, and safety costs of
human activities that can arise from both the production and consumption of goods or
services, can be employed to ensure not only an eco-friendly source for these nano-
products but also to promote eco-friendly uses and ends for the nanoproducts. Green
nanotechnology, particularly focused on phytoformulation methods of creation, signif-
icantly contributes to environmental sustainability due to their abundances and posses-
sion of a broad variability of metabolites, such as vitamins, antioxidants, and
nucleotides. Many commonly used nanoparticles, such as gold, copper, copper oxide,
titanium dioxide, and zinc oxide, have already been synthesized from plant extracts [13].
1174 A. T. Chowdhury et al.

It is worth noting that most of the nanomaterials are made from abundant elements like
carbon in diamond or diamondoid form. Products made of such materials will be strong
and will require smaller amounts of materials. Other than plants, many microorganisms
have also been reported to biosynthesize gold and silver nanoparticles by reducing metal
salts to nanoparticles using their NADPH-dependent reductase enzymes through elec-
tron shuttle enzymatic metal reduction processes [14]. These nanoparticles are sensitive
to pollutants and are thus often used in environmental monitoring systems. Such
biophysical abilities of microbes allow the manufacture of nanoparticles cost-effectively
and at larger scales.
Green nanotechnology has two goals: (i) The first involves the creation of nano-
products to address environmental problems through the prevention of harm from
known pollutant or through the addition of nanoproducts into environmental technol-
ogies to clean up polluted environments, and (ii) the second requires for the production
of nanoproducts and materials that can minimize the harms of anthropogenic activities
to the human health or the environment [11]. As the subdiscipline of green technology
specifically aims for environmental protection and conservation and steers the whole
discipline of nanotechnology away from causing, sometimes unanticipated, damages
to the environment by completely focusing on benefiting the environment, this chapter
henceforth dubs the application of nanotechnology for the improvement of the envi-
ronment as green nanotechnology. To name some benefits, green nanotechnology can
considerably contribute to renewable energy generation, thermal insulation, and
energy storage and act as sustainable raw materials for manufacturing processes of
inorganic products, building materials, and other industrial production processes.
Many of these uses of nanoparticles are important for environmental conservation
and are thus explored in detail in the coming subsections.

Application of Green Nanotechnology in Energy Generation

and Conservation

Climate change is slowly occupying an integral part of the concerns of policymakers.

Scientists and leaders alike are looking to curb its perpetrator, anthropogenic green-
house gas emissions. However, reducing greenhouse gas emissions is much more
complex, and it needs to be accompanied by reduced demand for high carbon energy
sources and increased efficiency of low carbon ones. Nevertheless, as the energy
demand continues to expand in the world with the growing population, particularly in
developing nations, so does the need for efficient and sustainable technologies for
generating and storing energy. Nanotechnology is the field of science that has been and
can be used to meet the growing need for energy. Many scientists and engineers today
are exploring the prospects of using nanoparticles to increase energy efficiency and
renewable energy generation at competitive costs because of the inherent properties of
the nanoparticles such as shape, size, crystallinity, and surface which provides advan-
tages like high surface area, well-defined structure, high dispersibility, and high
reactivity. In fact, the employment of nanotechnology in fuel cells, solar cells,
thermoelectric devices, and improved batteries has become notable in recent years.
52 Consumer Nanoproducts for Environment 1175

As an optimistic view expects that nanotechnology will gradually occupy a significant

role in energy production, the world’s average carbon footprint would reduce, thereby
halting and decelerating climate change and its disastrous impacts.
The process of designing and creating devices on the nanoscale, also known as
nanofabrication, is creating opportunities for new and greener ways to capture, store,
and transfer energy. Development and precision in nanofabrication are crucial in
solving the world’s current energy crisis [15]. The kinds of nanomaterials used in
regards to innovation in the energy sector are often either one dimensional or two
dimensional. One-dimensional nanomaterials increase energy density, safety, charge
storage (through double layering), and the cycling life of energy storage systems
[16, 17]. The use of one-dimensional nanoparticles can mainly be observed in
battery electrodes and supercapacitors. On the other hand, two-dimensional nano-
materials draw their strengths from being able to ensure great precision in control
and can be engineered into porous structures by applying facile charge and mass
transport, which can be used for energy storage and catalytic applications [18]. How-
ever, there is still not much applicability of two-dimensional nanomaterials on the
industrial scale, where their large-scale use is still being investigated.
The most widely used particle in nanofabrication technology is graphene, an
allotrope of carbon. It exists as a thin sheet of carbon atoms organized in a hexagonal
lattice, and it is extolled for its advantages like low weight, chemical inertness, and
low price. Graphene has caused a great stir due to the improvements it has brought in
the efficiency of batteries, apart from its other uses that draw advantages from its
structure. For example, it can be used to modify sulfur in sulfur-carbon composites to
encourage a better electrochemical performance – better than pure sulfur itself,
which is important for battery design. As a result, graphene’s scope in improving
the performance of lithium-sulfur (Li-S) batteries has been the subject of a growing
research body in recent years [19–21]. A nanostructure-based Li-S battery composed
of graphene/sulfur/carbon nanocomposite with a multilayer structure (G/S/C), in
which nanosized sulfur is layered on both sides of chemically reduced graphene
sheets and covered with amorphous carbon layers, has been developed that achieves
high conductivity and surface protection of sulfur simultaneously [22]. This simple
alteration to composites gives rise to excellent charge/discharge performance,
thereby revealing promising characteristics as a high-performance cathode material
for Li-S batteries. Li-S batteries have been attracting worldwide attention in recent
years because it addresses the limitation of lithium-ion batteries, particularly their
reduced gravimetric energy density [23]. Lithium-ion batteries are seen as a green
replacement to the usual batteries because of their rechargeability and as a result of
producing less toxic waste. It also has a higher energy density and voltage capacity
and lower self-discharge rate than other rechargeable batteries, which makes for
better power efficiency as a single cell has longer charge retention than other battery
types. However, currently, it is a less attractive option for manufacturers because it is
a far more expensive and low-yielding option to fossil fuels. With the development
of efficient Li-S batteries, the predicament of prioritizing environment versus econ-
omy can thus be resolved. Placing nanoparticles onto electrodes of batteries can
significantly improve the performance of batteries. Another rechargeable battery that
1176 A. T. Chowdhury et al.

suffers from low efficiency is the vanadium redox flow battery. However, with the
deposition of carbon nanoparticles onto the graphite electrodes of vanadium redox
flow batteries, the energy efficiency rose to up to 84.8% at a current density of as
high as 100 milliamperes per square centimeters, and the peak power density reached
a value of 508 milliwatts per square centimeters [24]. However, depositing nano-
particles onto electrodes can be energy-expensive. An eco-friendly and energy-
efficient way of depositing metal nanoparticles onto graphite electrodes to make
supercapacitors, electrocatalytic materials, and electrochemical energy storage
devices was recently found [25]. The major principle that dictates this advantage
of energy efficiency, in this case, was graphite’s inherent reducing potential. Apart
from graphene, the prospects of cellulose-based nanomaterials in photovoltaic
(PV) devices, energy-storing systems, mechanical energy harvesters, and catalyst
components are also being studied [26]. Cellulose is the most abundant plant
polymer, making it easily available and applicable on a large scale and at low
costs. It, therefore, also serves as an eco-friendly alternative and addresses several
environmental challenges. A comprehensive list of nanoparticles and their uses is
being looked into to revolutionize the energy sector. It is beyond the scope of this
chapter to delve into discussions for them.
Nanomaterials are one of the major components of solar cells. As mentioned,
nanotechnology can be used to significantly improve the efficiency of PV technolo-
gies, and it can do so by plasmonic enhancement in dye-sensitized solar cells [27],
increasing the amount of light trapped in crystalline silicon [28], improving the current
collection in amorphous silicon devices [29], increasing the efficiency of light con-
version by utilizing the flexible bandgaps of nanomaterials [30], and controlling the
directivity and photon escape probability of photovoltaic devices [31]. For example,
designing titanium dioxide in the form of core-shell structured nanomaterial greatly
improves the performances of PV cells by capturing light rays beyond the ultraviolet
range [32, 33], as these initially used to capture only the ultraviolet light from the solar
spectrum due to its wide bandgap [34]. In fact, core-shell structured titanium oxide
nanoparticles derive additional advantages from their structures, such as beneficial
tunable optical and electrical properties [34]. The thin-film copper-indium-gallium
diselenide (CIGS) technology is considered as the most promising PV nanotechnol-
ogy, as the cells made from this technology exhibit very high conversion efficiency at
relatively lower costs, compared to the rest of the nano-PV technologies [14]. Research
is also underway to produce nanowires and other nanostructured materials so that solar
cells can be made more efficient than conventional planar silicon solar cells [29].
Nanotechnology also has the potential to increase the energy efficiency of
thermoelectric structures as it enables for the optimization of optical, optoelectrical,
and thermal responses and therefore provides refrigerant free cooling [35]. Nano-
photonics, or nano-optics, is the branch of nanotechnology that studies the behavior
of light on the nanometer scale and of the interaction of nanometer-scale objects with
light. This subdiscipline is greatly enhancing the optical devices. Nanoparticles are
also increasingly being used in coatings, composites, and polymeric structures used
in windows, roof, and wall coatings, energy storage, insulation, and other compo-
nents in buildings that are cautious about their energy consumption. The advantages
52 Consumer Nanoproducts for Environment 1177

of energy-efficient buildings span far beyond the energy savings and the environ-
mental benefits of cool roofs.
The discovery of fuel cells, particularly hydrogen fuel cells, had been a great
eureka moment for environmentalists because the only by-product they release is
water vapor, which means they could significantly reduce pollution and man-made
greenhouse gases. However, their use is still met with wariness. One of the biggest
challenges for hydrogen fuel cells is that they require catalysts made of noble metals,
such as platinum, which tend to be sensitive to corrosion by carbon monoxide and
are also expensive to acquire. Methods of storing hydrogen fuel at a feasible cost are
still actively being researched, and thus, the fuel cells are yet not feasible enough for
commercial scale. However, nanotechnology can be used to design catalysts in a
way that the incomplete combustion that produces carbon monoxide is reduced,
therefore increasing efficiency [36]. Carbon nanotubes (CNTs) can also serve as tiny,
lightweight cylinders to provide solutions to the storage problems pertaining to
hydrogen fuel cells [14]. In fact, CNTs can be used for constructing safe, efficient,
and high-density adsorbents for hydrogen storage applications for other kinds of fuel
cells and batteries in electronic and automobile applications. Several green nano-
particles are being looked into to bring down the cost of photo splitting of water
[37]. Lower cost, more efficient fuel cells, and lower cost of production, distribution,
and storage of hydrogen fuel can also be established via nanotechnology [38]. Fur-
thermore, nanotechnology has the capacity to shift the world’s energy need to be
met almost fully by nuclear energy, natural gas, and biomass with the transition to a
new class of renewable energy composed of solar, wind, and wave [38]. For
example, windmills with blades made of epoxy-containing CNTs generate greater
amounts of electricity. Solar cells, as discussed, can be made cheaper and more
efficient when an array of silicon nanowires is embedded in a polymer in its
components. Energy is also conserved by nanoelectronics, as they consume less
power to operate and have longer lifespans. Thus, nanotechnology can be used as a
vehicle that helps the world enter the post-fossil energy age.
Nanomaterials can also be used to increase the efficiency of the combustion of fuels
and thus reduce energy consumption. The inclusion of carbon nanoparticles has
considerably increased the burning rate and ignition delay in jet fuel [39]. In a study,
the addition of iron nanoparticles to biodiesel and diesel fuels has also shown to reduce
fuel consumption and volumetric emissions of nitrogen oxides by 4–11%, carbon
monoxide by 6–12%, and hydrocarbons by 3–6% [40], many of which are toxic and
can cause physical ailments or contribute to the increase in the world’s average
temperature. However, this area still warrants further research as the utilization of
nanomaterial additives can also have toxic by-products. Cerium oxide nanoparticles
have proven to increase engine efficiency and decrease emissions of oxides of nitrogen
but can also be emitted as toxic exhausts, which can cause lung inflammation and
increased bronchial alveolar lavage fluid, according to a study done on rats [41].
Because of the great prospects of nanotechnology in energy generation and
conservation, nanotechnology can further direct a future with green transportations.
For example, cerium oxide integrated diesel can help reduce consumers’ carbon
footprint by producing lower amounts of carbon dioxide [42]. Nanoparticles are
1178 A. T. Chowdhury et al.

already being used to increase the fuel efficiency of buses in the UK, which could
reduce the emission of up to two to three billion tons of carbon dioxide per year
[43]. The manufacture of propylene oxide (used to make brake fluid, as well as
detergents, paint, and plastics) can produce polluting by-products, which can be
reduced by the use of silver nanoclusters as catalysts [42]. In addition, electric cars, a
vehicle that has been increasingly occupying the automotive market, are made of
lithium-ion batteries that use nanoparticle-based electrodes [42].
To sum up, nanotechnology can make a difference to five specific areas relating to
the energy sector: 1. fuel additives to increase the efficiency of diesel engines, 2. PV
technology for solar cells, 3. the hydrogen economy and fuel cells, 4. batteries and
supercapacitors for energy storage, and 5. improved insulation for houses and offices
[44]. They reduce the overall energy consumption, provide a cheaper and environ-
mentally friendly way of energy generation, create independent power sources sepa-
rate from national grids, and facilitate the transition from nonrenewable to clean,
renewable energy sources [14]. The implications of nanotechnology in the energy
sector are therefore incredibly large, and scientists are yet to explore its full prospects.

Application of Green Nanotechnology in Water Treatment

Water is an important natural resource, and safe drinking water is vital for human
existence and good quality of life. The rise in demand for water for food production,
industries, and the growing population has led to a growing scarcity of freshwater in
many parts of the world, exacerbated by the impacts of climate change. When the
Sustainable Development Goals were established by the United Nations General
Assembly in 2015, ensuring clean water and sanitation (Goal 6) became an impor-
tant goal for many nations that are severely lacking in the two. Surface water and
groundwater are being depleted at a rate faster than they can be replenished,
exhausting aquifers and the base flows of rivers [45]. As of 2017, about 30% of
the world’s people still lack access to safe drinking water [46]. Seven hundred
eighty-five million people lack even a basic drinking water source, and at least
two billion people use a drinking water source contaminated with feces [46]. Con-
taminated water can give rise to waterborne diseases in the population, such as
diarrhea, cholera, dysentery, typhoid, and polio. In fact, contaminated drinking water
is estimated to cause 485,000 diarrheal deaths each year [46]. Consequently, gov-
ernments, corporations, and communities are occupied with ensuring the future
availability and sustainability of water supplies [47].
Green nanotechnology offers a solution to meet the need of the thirsty population
by availing safe water from previously unusable resources. It can be used to purify
water through desalination as well as membrane technologies or nano-based pro-
cedures that kill pathogens and remove toxic chemicals [11]. Currently, a form of
nanotechnology that utilizes nanomaterials like nanofiber filters, CNTs, and other
nanoparticles is already making up water treatment systems such as reverse osmosis
(RO) plants, nano-filtration, and ultrafiltration membranes. For water treatment spe-
cifically, dendrimers, zeolites, carbonaceous nanomaterials, and metals composed of
52 Consumer Nanoproducts for Environment 1179

nanoparticles [48, 49] are being used because their small size provides advantages in
contact efficiency and better elution properties due to their greater surface area
[50]. Such nanoparticles possess special antimicrobial properties displayed via various
mechanisms, like photocatalytic production of reactive oxygen species that react with
the cell wall and cell components of microorganisms, or like oligodynamic disinfec-
tion, thereby killing or inactivating those [50, 51]. For example, titanium oxide induces
photocatalysis to completely inactivate fecal coliforms within 15 min, which are
employed in some commercial purification systems [50]. For areas in developing
countries which are struggling with arsenic contamination, magnetic nanoparticles can
successfully remove arsenic from drinking water for point of use treatment. Iron oxide
nanoparticles, notably of size 12 nm, can bind strongly and specifically to arsenic, over
99% of which can be pulled out by magnets [14].
Nano-filtration (NF), a recently discovered membrane filtration process which
utilizes nanometer-sized pores that pass through thin filtration membranes primarily
created from polymers, is being widely used to remove polyvalent cations and disin-
fection by-product precursors such as natural and synthetic organic matters from the
surface and fresh groundwater and waters that have low total dissolved solids [52]. Ini-
tially, NF had been used in water treatment for a procedure known as “water softening,”
where nanofilters basically retain scale-forming hydrated divalent ions while passing
smaller hydrated monovalent ions to “soften” water [53, 54]. However, NF is now
increasingly being used in pharmaceuticals, fine chemicals, and flavor and fragrance
industries [53]. Some water treatment systems drawing principles of nanotechnology are
already in use and being developed to cover large-scale commercial use.
Nanotechnology also offers remediation opportunities for surface water, ground-
water, and wastewater that have contaminated with toxic metal ions, microorgan-
isms, and organic and inorganic solutes. It is expected to be far more efficient in
treating water containing heavy metals, bacteria, and viruses, attributed to the
nanoparticles’ high dissolution, reactivity, and sorption capacities due to their high
specific surface area. Many nanomaterials are actively being investigated to be
developed into water treatment systems or remediation of contaminated sites
because of their unique activity toward recalcitrant [55, 56]. Examples include
iron nanomaterial, ferritin, and polymer nanoparticles [49]. The application of
nanotechnology to remediate the environment is another subdiscipline called nano-
remediation, described below.
Currently, water treatment plants are incredibly resource and capital-draining.
However, the ability of nanoparticles to effectively remove toxic and harmful patho-
gens, metals, and other pollutants could mean cheaper water treatment facilities.

Application of Green Nanotechnology in Environmental

Remediation: Nano-remediation

Human activities are constantly degrading the environment, leading to a loss of

sensitive ecosystems and a diverse pool of genes. Pollutants released from industries
and households to air and water alter the natural habitats of many wildlife species,
1180 A. T. Chowdhury et al.

and like a circular pathway, the negative impacts ricochet back to the human
population. Natural systems can self-regulate to some extent, but if the pollutants’
concentrations are above nature’s capacities to withstand and decontaminate by
itself, remediation strategies need to be undertaken by humans. Nano-remediation,
the use of nanoparticles to remediate the environment, is a growing industry that is
increasingly being developed and used in the treatment of groundwater and waste-
water, soil, and other contaminated environments [55, 57]. During nano-
remediation, which is often conducted in situ, the target contaminants are brought
in contact with nanomaterials under conditions where the nanoparticles can under-
take detoxification or immobilization.
At the moment, the most frequent and widespread commercial application of
nano-remediation is in the cleaning up of groundwater. This is done primarily by
using zerovalent metals (ZVMs) because ZVMs are widely available and are able to
degrade or sequester contaminants, where contaminants are typically converted to
harmless products via redox reactions [58]. The fact that nano-remediation allows
for in situ treatment saves a lot of resources, time, and money that may have been
spent on excavation or pumping groundwater up. As mentioned above, nano-
materials like CNTs and titanium oxide can clean surface water by purifying,
disinfecting, and desalinating [49, 59]. Heavy metals and organic solvents can be
degraded by combining zerovalent nanoparticles of iron and magnesium with
emulsion liquid membranes, where the membranes are used to increase the contact
between these catalytic nanoparticles and the targeted pollutants [14]. This allows
for areas to tap into their groundwater sources to meet their water needs, without fear
of the negative implications of using contaminated water. In the oil industries,
molybdenum disulfide nanocrystals are being used to remove harmful sulfur com-
pounds from crude oil [60]. Both single-walled and multi-walled CNTs and gold
particles have shown to adsorb pollutants onto their surfaces. CNTs can effectively
rid both air and water streams of organic and inorganic pollutants, thanks to their pore
structures and the broad spectrum of functional groups that CNTs can possess due to
the manipulation of heat or chemicals [49]. Significant improvements have been
shown in capturing toxic or harmful pollutants like dioxins, oxides of nitrogen,
volatile organic compounds (VOCs), isopropyl alcohol, and even the greenhouse
gas, carbon dioxide, using nanotechnology [49].
The use of nanomaterials to remove toxic gases is also being further inquired into
[49, 61]. Although catalysts have been used before to clean exhaust fumes released
from industries, the use of nanotechnology provides a better method of removing air
pollutants because nanoparticles are far more likely to react with harmful pollutants
in the air because of their relatively higher surface area. The use of nanotechnology
to clean air is crucial in the bustling urban and industrialized cities, where air
pollution is significant. Cities in every part of the world have dangerously high
levels of air pollution, thus exposing their inhabitants to risks related to pollutants in
the air. This is why the reduction of air pollution is an indirect focus of SDG
3, “Ensure healthy lives and promote wellbeing for all at all ages” and SDG
11, “Make cities and human settlements inclusive, safe, resilient, and sustainable.”
52 Consumer Nanoproducts for Environment 1181

Application of Nanotechnology in Sensing and Monitoring:

Nanocontact Sensors

Continuous and long-term exposure to such particulate matter can lead to the
development of physical problems, such as lung cancer and heart conditions. In
urban areas especially, risks associated with exposure to particulate matter
are high. Different particulate and pollutant monitoring and sensing devices can
significantly reduce the risks to human health and restrain the amount of
unsustainable economic activities. Nanoproducts make for sophisticated rapid
and precise sensing and monitoring devices that can detect hazardous pollutants,
plant pathogens, and related toxins [11], allowing for higher protection of human
health and environment. Several nanocontact sensors are able to detect some
metal ions or radioactive elements without a required preconcentration. These are
incredibly cost-effective and energy-efficient as they are made of conventional
microelectronics manufacturing equipment using simple electrochemical tech-
niques [49]. They are also easy to use onsite, making assessment and monitoring
of the environment convenient, with continuous information generation [49].
Nanowires or nanotubes can serve as adequate chemical and biological sensors,
while cantilever sensors, or devices made of silicon cantilever array coated with
nano-coating, display sensitivity to specific pollutants like volatile organic
compounds, heavy metals, pesticides, and harmful bacteria such as salmonella
[49]. Pollution can be monitored for both air and water. For air, for example,
nanocrystalline metal oxide thin films, called solid-state gas sensors (SGSs),
can provide information regarding pollutants in the air using very simplified
operation at a faster rate with real-time analysis capability, at a higher resolution,
and at lower running costs compared to conventional methods [62]. There
have been many other advances in nano-based monitoring and detecting
technologies [49]:

• Carcinogenic substances, such as chromium (VI) and argon (V), can be

detected at very low concentrations by functionalized tetraphenylsilole
nanoparticles.
• Peptide nano-electrodes produce electric current unique to different metal ions,
making identification easy.
• Some nanotube and copper composite electrodes are able to detect substances
such as organophosphorus pesticides, carbohydrates, and other wood pathogenic
substances in low concentrations.
• Polymer nanospheres can measure organic contaminants that are present in the
environment at very low concentrations.

Rapid sensing and monitoring of the environment make for rapid and relevant
initiatives to reduce the extent of pollution by allowing for the decision to either
reduce pollutants released in the environment or take steps to remediate the
environment.
1182 A. T. Chowdhury et al.

Application of Green Nanotechnology in Manufacturing, Waste

Reduction, and Pollution Prevention

Manufacturing is critical to a sustainable world economy and is the primary driver of

innovation and high-value job creation in both developed and developing countries [63].
However, current practices of manufacturing are incredibly resource-draining and
environmentally degrading. Nanotechnology can bridge the grab between today’s
methods of manufacturing and sustainability by what is known as green manufacturing.
Green manufacturing is a method of conducting manufacturing processes in a way that
uses fewer natural resources, recycles and reuses raw and other materials, and reduces
pollution, waste generation, and emission. By promoting green manufacturing, advance-
ments have already been made by nanotechnology in the semiconductor, chemical,
petrochemical, materials processing, pharmaceutical, and many other industries [64].
In fact, products miniaturized via nanotechnology require less material and are
easy to transport because of their lightness, thus saving both energy and time, but
also possess better mechanical and other properties. Nanotechnology thus increases
resilience and reduces system cost and replacement tendencies and the overall
environmental impact. For instance, plastic pollution, one of the most notable and
detested kinds of pollution ravaging aquatic lives due to its non-biodegradability, is
being tackled by nanotechnology. Biodegradable plastics are being made from
polymers with a molecular structure that is easy to decompose by using the tools
and techniques of nanotechnology.
Manufacturing processes of goods are often accompanied by a wide range of waste
products as well. Many countries are unable to exercise proper disposal methods of
these waste products, most of which are harmful or toxic, due to their lack of resources,
capital, or even awareness. Another issue of the progressing world is leaving heaps of
waste in its wake. Countries without proper disposal technology or resources like land
are grappling with the issues pertaining to waste disposal. With the advancement of
technology and the elevations of peoples’ living standards, there has been a rapid
creation of electronic waste every minute. Electronic waste or e-waste is the discarded
electrical or electronic devices which are destined for refurbishment, reuse, resale, and
recycle through metal recovery or direct disposal. Many informal sectors in develop-
ing nations undertake processing of e-waste, which can cause adverse health effects
and environmental pollution. One way to reduce waste generated per capita is by
increasing the useful life of consumer products. Nanotechnology can be used to
minimize raw material usage, waste production, and energy consumption. Because
nanotechnology involves atom by atom construction, it is a clean form of technology
that is able to create substances without the production of harmful or toxic
by-products; any by-products produced can be fed back into the manufacturing
processes [14]. One great innovation is the liquid crystalline display (LCD) screens,
which are quickly replacing the screen cathode ray tubes (CRTs) in people’s houses.
CNTs being used in the liquid crystalline display (LCD) decreases the impact of the
e-waste created from such screens due to the elimination of toxic heavy metals and by
increasing energy efficiency and performance. Toxic waste generation and energy
consumption are also being decreased.
52 Consumer Nanoproducts for Environment 1183

Nanotechnology can be used to increase the sustainability of products by making

them more efficient, reducing e-waste. Since the 2D organic semiconductors created
from nanotechnology were found, it caused a huge uproar due to its optical,
electronic, optoelectronic, and mechatronic properties. Such nanostructures can be
used as highly efficient biosensors due to their high sensitivity to bioanalytes [65].
Most importantly, the structures being biodegradable and nontoxic due to their
natural origin allow them to be a better alternative to inorganic materials that give
rise to electronic waste. However, the structures require further research and devel-
opment for the long-term and large-scale application. Nanoproducts have also been
investigated for their ability to salvage usable materials from e-waste. A mixture of
epoxy resin, phenolic resin, silica, and additives was able to recover valuable
elements and materials from e-waste after the e-waste had been mesoporous mate-
rials [66]. Thus, nanotechnology advances the sustainability of products, as well as
the environment.
Green nanotechnology also led to the development of aqueous microemulsions as
an alternative to VOCs in cleaning industries [49]. This means that nanoparticles are
replacing toxic and carcinogenic VOCs and other chemicals like chloroform,
hexane, and perchloroethylene, which are commonly used in the cleaning, textile,
and oil extraction industry. Nanosized aggregates on microemulsions increase spec-
ificity for molecules. A microemulsion has recently been synthesized that acts as a
connector between water-attractive and water-repellent substances, inserted between
the head and tail of the surfactant molecules [49]. The resultant surfactant was able to
clean oil from textiles and was very competitive with the conventional cleaning
compounds. Nanoscientists are also currently working intensively to create
eco-friendly coatings for products like electronics and medicine to bypass pollution.
For example, alternatives to chrome VI coatings are being studied to prevent the use
of toxic or carcinogenic by-products [14]. Nanoengineered thermites, or nano
thermites, with tailored properties, are also being developed using the principles of
green nanotechnology for use as primers, reactive materials, and propellant initiators
in micro thrusters, power generators, micro-shock generators for drug delivery, and
microinitiators [14].
Indiscriminate and improper waste disposal can enter the environment in several
ways. A concerning category of waste that often experiences underfunding in
disposal, particularly in developing countries, is hospital waste, which can cause
environmental hazards because of unsafe disposal in open landfills, groundwater
contamination by leachate, and the direct release of untreated hospital wastewater to
common drainage, public sewerage systems, or rivers and lakes. Improper healthcare
waste management might lead to the pollution and contamination of soil, air, and
surface water and groundwater [67]. Pharmaceutical drugs, such as antibiotics, can
easily enter the environment because of a lack of proper disposal of antibiotics and
can lead to the proliferation of multidrug-resistant (MDR) microbes that can cause
infections that may not be treatable using existing antibiotics, thereby increasing
mortality and morbidity. Nanoparticles provide one of the most promising strategies
in overcoming microbial drug resistance. While packaging nanoparticles with anti-
microbial agents itself prevent the development of drug resistance, nitric oxide-
1184 A. T. Chowdhury et al.

releasing nanoparticles (NO NPs), chitosan-containing nanoparticles (chitosan NPs),

and metal-containing nanoparticles all use multiple mechanisms simultaneously to
combat microbes, thereby making the development of resistance to these nano-
particles unlikely [68]. Nanoparticles inhibit resistance development by decreasing
uptake and increasing the efflux of drugs from the microbial cell, biofilm formation,
and intracellular bacteria. In addition, nanoparticles themselves have shown effective
antimicrobial activity against MDR pathogens, such as Acinetobacter baumannii,
Pseudomonas aeruginosa, Klebsiella pneumoniae, Mycobacterium tuberculosis,
vancomycin-resistant enterococci, methicillin-resistant Staphylococcus aureus, and
others [69], which is an important advancement in the medical sector as more and
more individuals are developing resistance to antibiotics and are thus may become
untreatable using existing medicines.
As observed from the discussion above, the scope of nanotechnology in
manufacturing and waste and pollution reduction is so wide and diverse that it is
beyond the scope of this chapter to note down every innovative solution that
nanotechnology has brought to these issues.

Application of Green Nanotechnology: An Unexplored Horizon

The application of nanotechnology to protect, conserve, and remediate the environ-

ment is vast and mostly unexplored. Despite such an exhaustive discussion, the
prospects of nanotechnology in the water and energy generation, two of the most
important sectors for the human civilization, and in pollution reduction, monitoring,
and attenuation have barely been broached. As scientists discover many more
nanoparticles, more applications will come up, some as groundbreaking solutions
to many of the world’s alarming issues. However, the area of green nanotechnology
is not without debates or controversies. Many still view this area with scrutiny and its
advantages over conventional methods with skepticism and caution. The impact of
freely released nanoparticles on human health and the environment is an actively
researched area, so much so that a whole subdiscipline called nanotoxicology
emerged from it. The following sections deal with the kinds of harms inflicted
upon the environment by nanotechnology and its creations.

Environmental Harms Caused by Nanoproducts

The principles of green nanotechnology are yet to be accepted and applied on a scale
that spans the whole area of nanotechnology. This means that unsustainable practices of
nanoparticle synthesis are still taking place, and thus the environmental harm pertaining
to nanoparticle manufacturing processes is still occurring widely worldwide.
The most common and special property of all nanoparticles is their miniature size,
giving rise to applications for which they are deliberately designed to be unique.
Nanoparticles own unique physical and chemical properties due to their high surface
area and nanoscale size. Their optical properties are also accounted to be reliant on
52 Consumer Nanoproducts for Environment 1185

the size, transmitting different colors due to absorption in the visible spectrum. The
unique size, shape, and structure bring about properties such as reactivity, toughness,
and some additional properties [70]. It cannot be denied that the area of nanotech-
nology has come up with significant developments and far-reaching discoveries
during the past decade. Years back, it was foreseen by researchers that by 2020,
the widespread application of nanotechnology would conventionally be applied in
all aspects of our daily lives. Despite all the optimism and useful application
portrayed by nanotechnology, recently it has been also understood that there is
limited knowledge of the potential negative effect imposed by nanoproducts on
human health and the environment. Although the future of nanotechnology is
supported by a bright outlook, there is also the existence of an increasing concern
that some types of nanoparticles might lead to serious health consequences and
environmental pollution, both intentionally and unintentionally.
Environmental protection and safety have not been the primary goal for most
commercially available consumer nanoproducts. Neither textiles with nanosilver to
remove perspiration odor nor stable golf clubs with carbon nanotubes were designed
to reserve the environmental safety. It is often promised by manufacturers about the
benefits of a product, typically without providing the relevant evidence and its
negative impacts. At times, the reason behind this is manufacturers themselves are
not aware of what adverse effects the nanoproducts can undergo. To determine this,
examining the entire life cycle of the raw material from production to disposal at the
end of the life cycle is highly recommended and should be strictly maintained. The
life cycle assessment (LCA) is recommended as a suitable approach in analyzing and
evaluating the ecological advantages or sustainable benefits and the environmental
impact of a nanoproduct. Environmental impacts enclose all the environmentally
relevant factors, such as extracting resources from the environment as well as the
emission of waste gases like carbon dioxide [71].

Nanotoxicology: The Emerging Challenges and Call for Safer

Nanomaterial Design

A new field, known as nanotoxicology, has emerged nationally and internationally to

deal with the impacts and potential harms of nanoparticles. It is a subfield of
toxicology, concerning the study of the adverse effects of nanomaterials on ecosys-
tems and organisms. Nanotoxicology gives an understanding of the toxic and
biological effects of the nanomaterials and deals with completing the existing
knowledge on how they interact with the biological systems. In comparison with
the bulk matters, the toxicity of some nanosized chemicals has generally emerged
from the fact that nanoparticles have a high surface-to-volume ratio which makes
them increasingly reactive. Thus, the smaller size of the nanoparticles serves them an
advantage, and they are assumed to perforate efficiently through the cellular mem-
branes and tissues. However, numerous biokinetic studies have also demonstrated
that biodistribution does not have a major influence on particle size [72, 73]. The fact
that the application of engineered nanomaterials is very widespread in recent days,
1186 A. T. Chowdhury et al.

being increasingly manufactured and utilized by a wide variety of products, with

uncertainties regarding their potential adverse health effects, makes the risk assess-
ment process challenging. Some in vitro, in vivo, and epidemiological studies have
demonstrated evidence of adverse effects due to nanotoxicology. However, in many
cases, the interpretation of available data was perplexed by the use of very high doses
of nanoparticles to understand its adverse effects [74].
Nanoparticles of heavy metals such as lead, mercury, and tin are viewed to be very
stable with a slow degradation rate, leading to many environmental toxicities. To
predict the toxicity of a particular type of nanoparticle, the most necessary step is to
understand which of its property is significantly responsible for promoting its toxicity.
Therefore, even before their use, it is important to recognize how nanoparticles interact
with the environment and the human body, to understand the cost of the resulting
damage. The undetermined structure and chemical compositions of some nano-
materials could be the reason for increased environmental toxicological pollution.
For instance, the size, type, charge, etc. are some of the properties of nanomaterials
which turn on the toxicity of nanoparticles in the aqueous environment. Among the
environmental damage caused by various nanoparticles, the threat to aquatic life and
the movement of nanoparticles through the food chain are some of the serious issues.
There is a strong interaction between nanoparticles and the soil, and this results in toxic
products which are due to the matrix conditions and the nanoparticle properties.
Environmental factors such as temperature, humidity, rate of airflow, etc. contribute
to the way how nanoparticles influence the environment. The dispersion rate of
nanoparticles increases with high temperature, whereas wind speed facilitates the
invasion of nanoparticles through human and plant tissues [75]. Yet, the nano-
toxicology community has been trying for almost a decade now to address more
technical questions through their research since all of what is thought regarding
the nanotoxicity of the particles is mostly based on some mere assumptions. More
than thousands of research have been published to explore the impact of nanomaterials
on the biological system, but reaching a mutual conclusion is what they lack [76].
Meanwhile, some studies have also come up with potential predictions and guide-
lines in developing sustainable nanoparticles with safer applications. They have
predicted how properties like particle size, charge, composition, and anisotropic
morphology are associated with the toxicity of the nanoparticle. It has been well
hypothesized from the beginning that reduction in particle size is correlated with
increased toxicity of the particle. Correlation between ionic dissolution and toxicity
index has also been marked to be definite. Anisotropic morphology or nanoparticles
with the rod-shaped structure are assumed to be taken up less efficiently by the tissues
and other cellular barriers [77]. To conclude, it could be stated that the current research
in the field of nanotoxicology is still in the process of understanding the complexity of
the nanoparticles and is struggling to keep up with the fundamental processes of how
these materials come in contact with the biological systems. Due to very subtle
differences in the properties such as slight changes in the size, the function of the
nanoparticle shows immense variation. As a result, expanding the use of nanoproducts
makes nanotoxicology research extremely important for society to develop safer
nanomaterials for the future [78].
52 Consumer Nanoproducts for Environment 1187

Threats Posed by Nanoproducts to the Environment

It is rare to find documented proof stating every “nanoproduct” is environmentally

friendly or sustainable by definition. It is often emphasized by environmental
organizations that in many cases the advantages promoted by industries are often
overestimated and untested. To date, often the production of nanomaterials requires
large amounts of energy, water, and not very environmentally friendly chemicals or
solvents. CNTs are one of the most energy-intensive materials known to mankind
because, at present, 1 kilogram of it is capable of holding 0.1–1 terajoule (TJ) of
energy. This is almost equivalent to the energy content of nearly 167 barrels, i.e.,
26,550 liters of crude oil [79]. The carbon-based high-tech production of fullerenes,
carbon nanotubes, and carbon nanofibers negates any potential benefits served to the
environment, like saving fuel using lighter car bodies due to its energy intensiveness,
as high energy demand contributes to the mass production of such products, utilizing
large amounts of a nanomaterial. Contrarily, for instance, if only small amounts of
CNTs are used to produce specialized plastic films, then environmental advantages
can be considered [80]. Thus, benefits such as any potential energy savings in using a
nanoproduct must be determined by comparing with the energy consumed during its
production. However, this should be considered to be done on a case by case basis.

Properties of Nanoparticles and Related Issues

Particle size and surface area are the key to the interaction of materials with
biological systems. Evidently, it has been understood reducing the size of the
materials leads to an exponential increase in surface area relative to volume. There-
fore, the reduced size of the nanomaterials makes the nanomaterial surface more
reactive on itself and to its contiguous surrounding. So, particle size and surface area
control how the system counters, distributes, and eliminates the surrounding mate-
rials. Research has established that various biological processes like endocytosis,
cellular uptakes, and the particle efficiency in these processes depend on the size of
the material [81]. Some researchers have also explored in vitro cytotoxicity of
nanoparticles of distinctive size and varying the other possible factors such as
various cell types, conditions in the culture media, and exposure times. The
in vivo evaluation is far more difficult as it requires a more comprehensive under-
standing of the complex nature of the biological systems with different in vivo
models [82]. In summary, the size-dependent toxicity of nanoparticles is thought to
be credited for its ability to invade the biological systems, interacting with the
chemical structure of the organic compounds in living cells and finally modifying
the structure. This is thought to cause potential hazards to the system where it
interferes with critical biological functions. Some other studies have also demon-
strated that the miniature size of nanoparticles also dominates its pharmacological
behaviors. Nanoparticles with a size less than 50 nm were seen to rapidly pass across
the tissues and possibly impart toxic manifestations. Conversely, nanoparticles with
a size greater than 50 nm are positively charged in nature and are taken up by the
reticuloendothelial system (RES), which interrupts its path to enter the biological
cells. Toxicological studies have revealed the smaller size of nanoparticles leads to
1188 A. T. Chowdhury et al.

some potential hazards such as causing respiratory health effects. As per some study
observation, nanoparticles with size less than 10 nm deposit in the tracheobronchial
region of the respiratory tract leading to toxic effects. The oral toxicity of nano-
particles is also influenced by its size. Generally, oral toxicity and size are inversely
proportional. The toxicity of the nanoparticle is also reliant on its shape, such as
spherical-shaped nanoparticles undergo endocytosis in a quicker and easier manner
in contrast to fiber or rod-shaped particles. Most importantly, the spherical nano-
particles were observed to be relatively less toxic in comparison with their counter-
parts. Nonspherical nanomaterials are more prone to flow through capillaries leading
to biological consequences. The surface charge of nanoparticles significantly influ-
ences their interactions with biological systems. This property of the nanoparticle
strongly dictates how a neighboring cell responds when exposed to it. Research has
found that surface charge of nanoparticles is responsible to change blood-brain
barrier integrity and transmembrane permeability. Since surface charge greatly
influences the interactions of nanoparticles with the biological systems, the
researchers have applied various amendments to regulate their surface characteristics
to cause less toxicity [81].

Interaction of Nanoproducts with Humans and the Environment:

Potential Hazards
New technological developments do not always benefit a society; usually, it involves
hazards as well. A hazardous material imposes a threat when exposed to humans
and/or the environment, and the level of risk served can be minimized by controlling
its exposure through understanding the mechanism of the harm. So far there is no
convincing epidemiological evidence that nanometer-sized component serves as the
toxic component of particulate air; however, a recent study reported to the Govern-
ment’s Committee on Medical Effects of Air Pollution has proposed that particle
count, reflecting the sub-100 nm component, was discovered to be finely related to
the risk of a heart attack. An additional approach was also been taken to investigate
the correlation between particulate pollution and cardiac consequences, and these
studies have indicated interconnection, leading to inflammation and occasional
reduction in red blood cell counts [83, 84]. Moreover, an association between
exposure to combustion-driven nanoparticles from diesel soot and atherothrombosis
was also recognized by a series of studies.
The most vulnerable situation to come in contact with the health hazards due to
nanoparticles is an unsafe occupational setting. It is possible to get exposed to the
nanoparticle at all phases of the material’s life cycle. Therefore, an inflated risk
remains due to the undesirable changes in the surrounding atmosphere, meaning
both to the environment and indoor and outdoor workers. Construction workers,
petroleum and gas transmission pipeline workers, traffic police officers, farmers, and
other workers in many other jobs spend their entire work time or a significant amount
of the time in outdoor environments. Yet, barely studies have been conducted to
assess the potential health impact due to the exposure of such workers to nano-
particles. However, the existing limited research indicates that people with such
occupations are highly exposed to nanoparticles and are put at a high risk of adverse
52 Consumer Nanoproducts for Environment 1189

health effects. The nanoparticles are also likely to invade from an indoor environ-
ment into the outdoors in some cases; as an example, the nanoparticles moving
through a filtration system can get into the outdoor spaces through ventilation ducts,
affecting the people working outside. The unique physical and chemical properties
of nanoparticles enable them to enter and get distributed into indoor and outdoor
workplaces rapidly. This ultimately ends up causing biochemical damage to the
human cells by initiating chemical reactions. The effects of nanoparticles in leading
to environmental and occupational health-related issues are often neglected and not
as much prioritized as they should be. In recent days, this issue seems to have
received little more attention, and many researchers have now shed some light on the
significance of how to determine the workers’ levels of exposure by measuring
concentrations of various nanoparticles at indoor and outdoor workplaces [85]. Still,
large-scale research should be designed to understand the reaction mechanism of
these nanoparticles with the biological system, their biodistribution, and the excre-
tion pathway from the body.
The growth and survival of plants and animals in both terrestrial and aquatic
environments are greatly influenced when exposed to nanoparticles. A study has
claimed to observe a slight reduction in the growth of plant roots in the presence of
uncoated aluminum oxide nanoparticles, although using alumina with a phenan-
threne coat demonstrated no reduction in root growth. This implies that the
surface properties of aluminum oxide play a crucial role in giving rise to the
entire toxicity [86]. For the nanoparticles to interact with plants’ roots, it needs to
get absorbed from the surface of the roots first and then end up entering the cell
wall and finally being absorbed into the roots’ cells. Absorption by the cellular
membrane is also possible when the nanoparticles enter the intercellular space.
The negative charge on the surface of plants’ cells facilitates the entry of other
negatively charged nanoparticles into the intercellular space of the roots’ bark.
These nanoparticles then land onto the woody tissue of the plant by entering this
space [87]. Sometimes, the nanoparticles are observed to interact with other toxic
materials or compounds surrounding them, and this results in both an increase and
a decrease in their toxic functionality. This phenomenon of nanoparticles is
sometimes speculated to be beneficial to plants, animals, and the environment
because the toxic effect of the contaminants gets neutralized by its own toxicity. In
contrast, if the nanoparticle seems to interact with a pollutant that is not neces-
sarily harmful, it does not show any toxic effects. The presence of nanoparticles
could possibly interfere and alter some other environmental processes like the
formation of dust clouds and the stratospheric temperature. The particulate matter
and carbon nanosized components, generally released from the burning of plas-
tics, fossil fuels, and industrial fumes, make up the brown clouds. These brown
clouds may end up depositing on glaciers, enhancing the absorption of sunlight
and resulting in melted glaciers. The nanoparticles and hydrogen present in the
atmosphere have a tendency of moving up the stratosphere, resulting in excessive
water vapor. Thus, the accumulation of excess water vapor in the stratosphere
cools the stratosphere, reducing the stratospheric temperature and also depleting
the ozone layer [88].
1190 A. T. Chowdhury et al.

Finally, to study the environmental impacts of nanoparticles, it is important to

understand how they are used in the workplace, which means to what extent they
were exposed to environmental factors. Their interaction and how they are separated
into different media like water and air, their feasibility to move in each of these
media, and stability should be extensively studied. Therefore, to evaluate their risk,
general information about the behavior and toxicity is essential. Yet, this does not
serve the absolute information to conduct a realistic evaluation of the potential
harms. Rather more specific data such as the expected concentration of nanoparticles
in environmental systems would be necessary, to justify an actual risk assessment,
which has not been claimed to date. To start the environmental risk assessment of
nanoparticles, factors such as the resources, environmental pathways, daily applica-
tions of nanoparticles, and which of these nanoparticles are sensitive to plants and
animals must be identified [89].

Nano Waste Management: Challenges Posed by Nanoparticles

and Recommended Waste Disposal Practices

Nano wastes are collectively referred to as the new forms of waste streams. These are
the stream of wastes containing nanomaterials or any manufactured nanoscale
by-product synthesized during its production, storage, and distribution. It could be
any product contaminated by nanomaterials such as pipes, personal protection
equipment, etc. Over the last two decades, the number of nanoparticles and nano-
products had massive escalation from a few kilograms to thousands of tons, resulting
in the uncontrollable release into the environment. This is only expected to dramat-
ically increase, considering the flourishment of nanotechnology as a new era of
miniaturization at industrial-scale production. Although this was proposed by
numerous research publications, the research contains limited scientific information
on the feasibility of dealing with the waste streams generated by the nanotechnol-
ogy-based products at various stages of their lifecycle. The nanomaterials are
introduced into the environmental systems mostly through nano waste. When the
release of these wastes is not controlled effectively, the nanomaterials continue to
interact with the abiotic factors (air, water, soil) and result in contamination of soils,
as well as surface and underground water resources. Eventually, this threatens the
security of water resources, and the contaminated areas could also possibly be
difficult to remediate due to issues like high cleanup costs and lack of appropriate
technology for the remediation procedure [90]. To look at some of the examples, fuel
additives, lubricants, and cosmetics are some consumer nanoproducts impacting the
environment. The nanotechnologically synthesized fuel additives and lubricants are
expected to be discharged into the air, soil, and water system through different waste
streams. In the due course, entering the aquatic and terrestrial lives through spillages
during use or leakages from vehicles, sewage drainage systems become the ultimate
fate of the nanomaterials. Similarly, the increased production and use of cosmetics
give rise to the waste streams containing nanomaterials directly to the aquatic
environment through bathing and swimming, sometimes indirectly through the
52 Consumer Nanoproducts for Environment 1191

sewage systems as a result of showering and washing processes [91]. So, dealing
with nano waste is not very safe due to its small size. Nanoparticles are not
decomposed by the traditional methods of waste treatment processes like filtering
or incineration, giving them the direct license to release into the environment. Since
this ultimately leads to some adverse outcomes, numerous methods have been
recently proposed to eliminate or reuse nanoparticles from waste, before the accu-
mulated amount poses a threat to the environment and becomes a serious issue
[92]. To address this issue and prevent potential environmental risks, some research
findings have suggested establishing a unique waste management approach for nano
wastes. Marking such an approach would not be surprising as each nanoparticle has
a distinctive way of functioning in the fabrication method, with varying crystal
morphologies, toxicity testing procedures, and interaction with abiotic factors at
the point where it enters the environment [93–97].

Disposal Procedures for Nano Wastes

Due to the fact that a broad range of nanomaterials exists in the nanoproducts, a
single procedure for disposal will not serve all classes of nanomaterials. Hence,
understanding the properties of specific nano wastes before developing effective
discharging practices would be a suitable approach to implement environmentally
friendly disposal. It is recommended that the safety measures and disposal pro-
cedures necessary for handling nano waste must be based on current knowledge and
existing legislation should be taken into account. It should be well ensured before
disposal that the hazardous properties of the waste are inactivated. The industrial
nano waste that is thought to be concentrated should undergo dilution and deacti-
vation mechanism before disposal. Most importantly, industries responsible for the
production of such waste as a by-product of their company operations must go
through the EPA approval to prove that the nano waste produced is non-hazardous to
the environment. The latest nanoproducts must not be released to the market without
suitable disposal procedures. Also, the nano waste disposal procedures developed
recently must be assessed and approved by government agencies grounded on
reliable evidence provided by the claim-lodging organization. To back up the
authenticity of their waste disposal procedures, industries should provide adequate
evidence by self-testing their products if possible, concerning current scientific
procedures [98]. Thus, initiating sound waste management practices and protocols
to limit the spread of nanomaterials into the environment would be a fundamental
approach to minimize the long-term accountability by consumer nanoproducts [90].

Importance of Raising Public Awareness Regarding Nano Waste

Management
It is highly recommended to bring the consumer’s attention toward the understand-
ing of the risks posed by nanoproducts. The consumers and the broader community
should be educated with comprehensive knowledge of the potential fate of these
nanoproducts. They must be well acquainted with the current scenario that does not
deny the fact that nanotechnology can decode many latest challenges; however, it
can also possibly pose a serious threat to the environment if used irresponsibly
1192 A. T. Chowdhury et al.

[99]. Hence, awareness-raising campaigns, well communication, and proper educa-

tion are the keys to strengthening the correct understanding and preventing hazard-
ous situations. To understand more about the consequences led by nano wastes
containing nanoparticles, increased government and industry funding should be
allocated to research institutes to evaluate the existing protocols and evolve the
latest disposal and recycling processes as per the situation. It is often argued that a
substantial amount of funding is being granted for developing the contemporary
nanoproducts but the least attention is offered in designing nano waste disposal
techniques. At present, several organizations have taken the initiatives and are
currently investigating this emerging concern in an attempt to begin suitable and
efficient regulations and policies. However, this initiative would be a finer approach
if a unified collaboration at all levels is being addressed for this rising and potentially
very hazardous issue. Collaborative approaches such as knowledge and experience
sharing, coordinated research, and developing proper guidelines for the producers,
users, and waste disposal procedures are some of the addressed ways to move this
agenda forward [98].

Application of Nanoproducts and Related Consumer Awareness

The striking improvements of nanotechnology were followed by a wide range of
industrial and academic applications. The field has advanced and resulted in innu-
merable options for consumer product applications, out of which many have
succeeded in the initial laboratory procedures and are already available in the market
for purchase. Nanoparticles are undoubtedly integrated within consumer products,
and to know their potential effects on human health and environment, much research
has been carried out, and a good number of them are still ongoing [100]. The
products based on nanotechnology and nanomaterials have created a booming
consumer market industry over the last 10 years. The supermarkets have gained
over 1827 consumer products and millions of customers. A minimum of about
39 different nanomaterials had reached the market, mostly made from silver, tita-
nium, zinc, gold, titanium oxide, iron (III) oxide, zinc oxide, metals, and metal
oxides, respectively, alongside some other compounds like carbonaceous (carbon,
fullerenes, CNTs, graphene) and silica. Most nanotechnology items are typically
utilized in healthcare and wellness services, home and nursery, automotive appli-
ances, electronic gadgets, and food and drink purposes [101]. Biotechnology, drug
delivery, cosmetics, and biosensors are some other territories where the application
of nanotechnology has branched out, showcasing extraordinary potential in the
generation of new market products. There is no doubt that the rapid growth of
consumer nanoproducts has facilitated the market industry with a huge profit;
however, concern toward human health due to the exposure of the nanoproducts
has also increased in recent days. Various organizations including research institutes,
universities, and government bodies are trying to address the potential adverse
impacts of nanoproducts. However, it is claimed that even though widespread
research has been conducted, consumers, one of the significant stakeholders, seem
to lack the knowledge and attention on the severe consequences of nanoproducts.
When several studies reviewed the public perception of nanotechnology, very few
52 Consumer Nanoproducts for Environment 1193

respondents demonstrated finite knowledge on nanotechnology, and most of them

were likely to think that it offered more benefits than risks [102].
Numerous studies have examined public opinion on nanotechnology in the USA
and Europe, to understand what attitudes they demonstrate toward nanotechnology.
The majority of them reported that the public perception about nanotechnology was
expressed to be less pessimistic and they seemed to have little knowledge about the
field [103, 104]. In many European studies, it was found that less than half of
Europeans have ever heard about nanotechnology and only one of four of them
claimed to have spoken to someone on this topic; not very surprisingly, men and the
people with higher education seemed to have increased awareness. Also, Northern
Europeans had a better understanding than the Southerns [105]. When the public
opinion among them was evaluated, they were more leaned toward the benefits of
nanotechnology, having slightly satisfying opinions in comparison with risks,
whereas a large proportion of the population was indecisive regarding which one
to choose [106]. A study in Cardiff, Wales, investigated public knowledge and
perception of unfamiliar technologies and products. The majority of participants
responded with a relatively positive yet inconclusive opinion about nanotechnology
and nanoproducts. A good number of respondents expressed ignorance or claimed
that nanoproducts were mostly related to areas making use of advanced technology
like electronics, medicine, research, etc. and hardly with everyday products [107].
Another study conducted in South Korea assessed consumer awareness, concerns,
expectations for various nanoproducts, and the need for assessment in educating
them regarding nanotechnology and nanomaterials. The research revealed that
consumers have manifested an unambiguous image of nanotechnology and nano-
products but do not comprehensively understand what they are. Therefore, they
depict a vague picture of nanotechnology in their understanding. Additionally, they
discovered that disseminating information on nanoproducts to consumers is highly
needed to provide the actual knowledge to the public [108]. The consumers signif-
icantly lack the understanding of the technological principles, which is followed by
limited awareness regarding the possible harmful effects of nanoproducts on the
environment.

Conclusion

The major expansion in medicine, agriculture, industry, and other related science
fields has experienced rapid progress due to the introduction of nanotechnology.
Nanoparticles are the basis of nanotechnology and the key contributors to the
advancement of this branch of technology. Among scientists, engineers, and all
other people related to this field, the usefulness and threat of nanotechnology have
always been a topic of dispute. The particle size has been the major and unique
property of nanoparticles that have put this entire field of science into prolonged
controversy. Despite the fact that the major effect of particle size on materials’
toxicities has been specified earlier, it is still not very clear what has been the
exact mechanism behind particle size, its behavior, and reactivity giving rise to the
1194 A. T. Chowdhury et al.

toxicity of nanoparticles. The current situation demands extensive research with

appropriate laboratory methods to keep up with the latest issues and ideas of
nanoparticles. Nanotechnology takes part in building an environmentally friendly
atmosphere by removing contaminants from the air, water, and sewage, besides all
other benefits. From being applied in environmental sensors to creating green nano-
technology through the minimization of greenhouse gases, the list of benefits
surrounded by this field of technology continues. However, other research findings
claiming nanoparticles posing threats to the environment during the disposal of nano
waste product are an irony to the entire situation. Also, confusions arise among
scientists as yet it has not been successfully established how nanotechnology could
be responsible for risking environmental health. At the same time, the fact that a good
number of the research findings have stated the toxicity of nanoparticles and their
adverse effects on humans and the environment cannot be abandoned without showing
concern. To address this concern, scientists, nanotech experts, and all the other
important stakeholders are now making an effort to jointly take steps to resolve this
dilemma in the scientific community. The main key ideas of the discussion in section
“Environmental Harms Caused by Nanoproducts” have been shown in Fig. 1.
Some common approaches and guidelines are also proposed to gain a better under-
standing of the current issue. The risk assessment approach is one of the significant
procedures where risk should be assessed at every stage in the life cycle of the

Impact of Consumer
Nanoproducts on the
environment

Benefits Problems

Energy Nanowaste Threatens

Water Pollution Disrupts Food
Conservation Disposal Aquatic and
Treatment Prevention Chain
& Generation Issues Terrestrial
Lives

Surface/Ground Ozone
Sensors for Nano- Water
pollutants remediation depletion
Contamination

Environ-
Reduced mental
Reduced
Waste Green MDR Stratospheric Toxicological
Plant Growth
Reduction Manufacture prevention Temperature Pollution

Brown Cloud Glacier

Formation Melting

Fig. 1 The effects of consumer nanoproducts on the environment

52 Consumer Nanoproducts for Environment 1195

nanomaterial. It should be kept into consideration that most “conventional” manufactur-

ing methods also have sources that are very much likely to generate contaminants and
the process of determining whether nano-based methods are more or less sustainable is
by assessing the life cycle. However, it has also been pointed out that investigating the
implications of these technologies should be done at the critical period which is in the
early development phase, as new methods come in and previous ones are intervened in
favor of nano-based approaches [108]. It is also recommended to create a database
gathering the properties of different nanoparticles mainly with their toxicological data
containing all relevant information related to the nanoparticles to make it readily
available for researchers. Occupational exposure is another concern toward human
health, and to keep it minimum, safety measures should be well considered while
dealing with plants with engineered nanoparticles. The safe handling and application
of nanoparticles for research purposes should also be maintained by forming appropriate
guidelines. Also, while promoting the benefits of the use of nanoparticles in various
fields, we should ensure that no adverse effects result from their use [85].
Finally, apart from the experts, consumers should also own the right to have basic
knowledge regarding nanotechnology as their daily lives are surrounded by nano-
products. Multiple studies conducted so far did not gain satisfactory results on
assessing the knowledge and attitude of consumers toward nanoproducts. The major-
ity of the consumers could hardly believe the severity of the consequences it might
lead due to unsafe handling and disposal. The need for consumers to understand that
they lack the proper understanding of nanoparticles and it is strongly recommended for
them to seek this knowledge for their own benefit is something that is still difficult to
establish among customers. However, there were also a good number of them who
realized the need for awareness and education. Therefore, a risk communication
system targeted to the nanoproduct consumers should get initiated to recognize the
multiple values and to get them incorporated into the decision-making process.
Simultaneously, mass media or other communications channels should be organized
and at the same time be executed to ensure an ongoing process of learning the latest
developing nanotechnologies and products. Some studies have recommended educa-
tion and promotional programs for consumers which should focus on receiving
reliable and relevant information and make the consumers familiar with different
concepts and definitions of nanotechnologies. Besides, the government should start
exercising tighter control over nanomaterials, and conducting further social surveil-
lance should be encouraged to examine the levels of public understanding of both the
risks and benefits of nanotechnology and nanoproducts [102].

Useful Websites

• https://www.youris.com/nano/toxicology/dr_ndeke_musee_to_protect_our_envi
ronment_we_need_to_understand_nanotechnology_risks_because_todays_nano
products_will_be_tomorrows_waste_streams.kl
• https://www.g20-insights.org/policy_briefs/nanowaste-need-disposal-recycling-
standards/
1196 A. T. Chowdhury et al.

• https://www.safenano.org/knowledgebase/resources/faqs/what-happens-to-nano
materials-in-the-environment/
• https://natureecoevocommunity.nature.com/posts/16310-nano-and-the-
environment
• https://www.mistra.org/en/research/mistra-environmental-nanosafety/
• https://www.nanowerk.com/spotlight/spotid¼25937.php
• https://www.understandingnano.com/

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Bio-nanocomposites for Modern
Agricultural Applications 53
Matias Menossi , Claudia Casalongué, and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1202
Bio-nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1208
Bio-nanocomposite Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1208
Bio-nanocomposites as Controlled-Release Systems for Agrochemicals . . . . . . . . . . . . . . . . . 1215
Nanotechnology-Based Agroproducts Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1219
Commercial and Emerging Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1220
Nanotoxicity and Environmental Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1228
Regulation and Legislation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1229
Public Awareness and Acceptance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1233

Abstract
Agriculture represents one of the most important human activities in the world.
Currently, the agricultural system deals with multiple challenges, including
population growth, dietary choices, technological progress, climate change, and
sustainability.

M. Menossi (*)
Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones en Ciencia y
Tecnología de Materiales (INTEMA), Facultad de Ingeniería, Universidad Nacional de Mar del
Plata (UNMdP) y Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Buenos
Aires, Argentina
e-mail: [email protected]
C. Casalongué
Grupo de Fisiología del Estrés en Plantas, Instituto de Investigaciones Biológicas (IIB), Facultad de
Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata (UNMdP) y Consejo Nacional
de Investigaciones Científicas y Técnicas (CONICET), Buenos Aires, Argentina
V. A. Alvarez
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina

© Springer Nature Singapore Pte Ltd. 2022 1201

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_68
1202 M. Menossi et al.

In order to overcome these challenges, many agricultural applications have

emerged to enhance productivity and yield of crops: greenhouses, tunnels, mulch,
and silage. All of them consist of polymeric films that are placed to increase
moisture and temperature and prevent weed growth, and, consequently, they
allow less dependence on agrochemicals. The polymer used for these agricultural
practices is polyethylene (PE), a nonbiodegradable and nonrenewable material
derived from petroleum. Despite their appropriate mechanical and radiometric
properties, PE has several environmental disadvantages.
The combination of nanotechnology and biopolymers could represent a potential
solution to ensure environmental safety, replacing PE with bio-nanocomposites.
When bio-based polymers are combined with nanofillers, the resulting bio-nano-
composites exhibit improvements in mechanical, thermal, and barrier properties.
Bio-nanocomposites can provide controlled release (CR) of agrochemicals, while
efficiently improving permeability, stability, and solubility. The use of biodegradable
nanomaterials in agricultural practices can promote sustainable and eco-friendly
cultivation reducing soil, water, and air pollution and the indiscriminate use of
agrochemicals.
Until now, the commercialization of nanotechnology-based agroformulations
has been limited and related to several issues: nanotoxicity, government regula-
tion, public knowledge, and production costs.
This work highlights the promising application of bio-nanocomposites from
organic origin for sustainable development in agriculture applications, in partic-
ular chitosan-based nanocomposites, and analyzes their commercial insertion as
CR systems for agrochemicals and the limits of their commercialization.

Keywords
Agriculture · Biopolymers · Controlled release · Nanocomposites ·
Nanotechnology

Introduction

Since the 1930s/1940s, the incorporation of plastic films with different applications
such as greenhouse coating, tunnel covering, and mulching has been increased in
agriculture [1]. All these practices can be employed for a wide variety of purposes to
protect plants from atmospheric agents, to increase air temperature, to control soil
temperature, to reduce water consumption, to limit soil erosion, and to reduce the
growth of weeds, as well as for controlled-release (CR) systems of fertilizers, pesti-
cides, and herbicides, among others [2]. Historically, the polymers conventionally used
for all these agricultural applications are from petroleum-based nondegradable/non-
renewable materials, particularly polyethylene (PE). This universal polymer has been
well-accepted for its mechanical and thermo-optical properties, resistance to all forms
of degradation, easy processing, and low cost [2]. However, at the end of their lifetime,
every one or two cultivation periods, these nondegradable/nonrenewable polymers
have exerted negative consequences, such as:
53 Bio-nanocomposites for Modern Agricultural Applications 1203

1-. Economical disadvantages. The removal of the plastic wastes is time-

consuming with economic costs for farmers. According to Brodhagen et al.
[3], US growers spend between $358 and $584 per hectare for removal and
disposal of PE mulch films. These films are covered by a wide variety of
agrochemicals, rests of soil, and organic matter. For these reasons, PE films
need a correct collection and final disposal or recycling with expensive costs for
the growers.
2-. Environmental-social disadvantages. As a consequence of economical disad-
vantages, plastic materials are usually accumulated, stockpiled, or abandoned in
landfills or rivers, incorporated into the soil, or burned causing the continual
emission of contaminating gases/substances in the atmosphere, water, and soil.
Additionally, when the film wastes are incorporated into the soil, their structure
can be damaged which can affect the absorption of water and nutrients by plants
impacting in their crop yields [1].

In order to overcome these problems associated with the petroleum-based agri-

cultural plastic products and to increase the sustainability of agricultural applica-
tions, the use of biodegradable and renewable raw materials becomes to be highly
desirable. Contrary to PE films, biodegradable films can be incorporated directly into
the soil and be biodegraded by soil moisture and microorganisms at the end of the
crop season. The mulching, for example, is an agricultural practice where the
biodegradable material is in direct contact with the soil. In this context, the mulching
materials should not affect the performance of agricultural soil, i.e., there should be
no accumulation of harmful substances [2].
Bio-based polymers or biopolymers are polymers directly extracted/removed
from natural resources or produced by the synthesis of monomers obtained from
renewable resources or by microorganisms. A number of naturally occurring pro-
teins, lipids, polysaccharides, polyesters, and synthetic biodegradable polymers are
considered as bio-based materials for agricultural applications [1]. Averous and
Boquillon [4] categorized bio-based polymers in four families according to the
method of production (Fig. 1).
In contrast to PE films, biodegradable polyesters contain ester bonds that make
them susceptible to chemical degradation, including hydrolysis. The hydrolysis
breaks up the chemical structure into smaller molecules causing more susceptibility
to enzymatic reactions [1].
To replace petroleum-based agricultural plastic, biopolymers-based materials face
multiple challenges to improve:

• Mechanical behavior, spectra-radiometric characteristics, and barrier prop-

erties. The correct combination of mechanical, radiometric, and barrier properties
of bio-based materials to agricultural applications is essential. According to
Briassoulis [5], the mechanical properties of biodegradable materials mainly
depend on their chemical structure, processing and storage variables, application,
and degradation. The development of biodegradable agricultural films must
achieve the appropriate mechanical properties to assure an easy handling and
installation, i.e., adequate strength and elongation at break. Additionally, the
1204 M. Menossi et al.

Fig. 1 Classification of bio-based polymers according to the method of production [4]

radiometric properties must be adjusted with special additives depending on crop

type, the season, and the geographical area, for the purpose of inhibiting
the growth of weed or providing an increase in the soil temperature
[5]. Agro-films require different optical properties depending on their application:
53 Bio-nanocomposites for Modern Agricultural Applications 1205

lower opacity is necessary for greenhouse materials and low tunnels, and higher
opacity for mulching films. Concerning barrier properties, biopolymers-based
agro-materials should have low enough water vapor permeability (WVP). Low
values of WVP will allow to store the soil moisture, reducing the water consump-
tion and preventing the risk of water stress [5].
• Hydrophilic/hydrophobic nature and biodegradability. Biodegradable agri-
cultural films should meet an optimal point regarding their biopolymer hydro-
philic/hydrophobic nature since they should degrade 100% at the end of the crop
season. Biomass-based polymers are polymers formed in nature, and their
hydrophilic character (tendency for brittle) is associated with problems when
they are exposed to moisture [3]. On the other hand, the biodegradability of
synthesized biopolymers largely depends on their hydrophilic/hydrophobic
character. Biodegradability is higher to those biopolymers with hydrophilic/
hydrophobic chains than those with only hydrophilic/hydrophobic segment.
The biodegradation rate of hydrophobic biopolymers (which do not allow
enzymes, water, and aqueous solutes into their surface) is lower since enzyme
reaction rates depend upon the presence of substrate at the active site of an
enzyme [3].
• Availability and cost. Compared with PE materials, the major limitation of the
biodegradable plastics for agricultural practices is their high cost. This fact
applies to biopolyesters, particularly polylactic acid (PLA) and polyhydro-
xyalkanoate (PHA) [1]. Instead, natural polymers continue to remain a viable
alternative to nonrenewable petroleum-based plastics basically due to its low cost
and wide availability.

Because of all these issues, the performance of biopolymers could be increased

considerably, with respect to petroleum-based materials, to represent a potential
alternative to agricultural practices.
Hence, nanoscience and nanotechnology have the potential to overcome and to
make a beneficial impact on these challenges where unique physic-chemical char-
acteristics make novel applications possible. The nanotechnology term involves the
understanding, synthesis or preparation, characterization, and manipulation of mate-
rial at nanoscale. The mechanical, physical, chemical, and functional properties can
be significantly improved by reducing from macro-dimension to nano-dimensions a
specific dimension of the material [6]. Until now, in the agricultural sector, unlike
other fields like pharmaceutical, cosmetic, electronic, and medical, nanotechnology
and its benefits have received little attention, and it has not been possible to achieve
its massiveness in the market. But, in the last decade, this trend has reversed, and the
number of patents and original science publications about agro-nanotechnology has
substantially increased [7]. Increasing the efficiency and the productivity, crop
protection, and production, through the optimized management of different
resources such as water and nutrients, are some of the benefits of working with
nanoscale materials for agricultural applications.
Pesticides, fertilizers, herbicides, and other agrochemicals have been traditionally
applied by spraying or soaking, and because of this, factors such as rain, wind, or
1206 M. Menossi et al.

sunlight can remove, degrade, or decompose them. Consequently, only a small

portion of the added agrochemicals reach their target species and functions
[8]. Then, the indiscriminate application of agrochemicals potentially has caused
water contamination, increase of pathogen and pest resistance, and loss of soil
biodiversity, among others worldwide [9]. In addition to the economic disadvantage,
agrochemicals have had a direct negative effect on human health and environment.
In addition to the costs related to the environment and health, the economic disad-
vantage is added.
In this sense, nanotechnology can provide nano-solutions mainly due to the
possibility of reducing the doses of applied agrochemicals. This fact is mainly due
to that nanotools-based agrochemical formulations offer advantages such as larger
surface structure, higher surface charge, larger mass transfer, higher solubility, larger
durability, and lower toxicity, allowing them to improve their properties interactions
with target tissues [9].
Nanomaterials manage to minimize the loss of nutrients and decrease the number
of chemical products, reducing environmental impact as compared with conven-
tional approaches [8]. Iavicoli et al. [8] summarized the potential applications of
nanotechnology in agriculture. They recognized nanopesticides employed to pro-
mote plant protection against pests and weeds and prevention of crop diseases,
nanosensors which have been utilized as devices to provide smart monitoring of
pollutants, and nanofertilizers used to stimulate plant growth and to supply precise
nutrient management and obtain high levels of agricultural yield. All these nanotools
try to mitigate crop losses caused by biotic and/or abiotic stress. Figure 2 shows
benefits of nanotechnology applied to sustainable agriculture to improve plant
productivity, increase food and human health, and avoid environmental impacts.
Nanomaterials from inorganic and organic origins have been assayed in plant
protection and nutritional applications. Among inorganic nanomaterials, metal nano-
particles (NPs) such as silver (Ag), aluminum (Al), copper (Cu), and zinc (Zn) and
metal oxides NPs such as zinc oxide (ZnO), silver oxide (Ag2O), and titanium oxide

Productivity
Environment • Reduce agrochemicals losses and their
• Reduce soil biodiversity costs
losses and enhance the • Slow and sustained release of water
quality of the soil • Sensing and monitoring soil conditions
• Protection and remediation
of water
• Reduce emission of
contaminating gases into the
atmosphere
Plants
•Improve agrochemicals availability
• Cellular delivery of genes and drugs
Food & human health molecules to specific sites
• Reduce farmers exposition to • Stimulate plant growth and fight
agrochemicals against diseases
• Improve food quality, decreasing
agrochemicals levels

Fig. 2 Benefits of nanotechnology in sustainable agriculture

53 Bio-nanocomposites for Modern Agricultural Applications 1207

Compatibility with Thermal stability

biologically active Thermal plasticity
molecules Melting point

Environmental impact Simple formulation

Control release
Biodegradability rate
behavior

Fig. 3 Advantages of biopolymers into agro-nanotechnology

(TiO2) are proper due to their particular characteristics. Unfortunately, these metal
and metal oxides NPs might cause negative effects on the environment, humans, and
plants [7]. Particularly, some examples of adverse effects on plants are inhibition in
cell growth and nitrogen fixation, reduced germination, decreased root length, and
reduced biomass growth, among others.
Alternatively, nanomaterials from organic origin like lipids and polymers repre-
sent powerful alternatives. Biopolymers have been investigated as CR systems of
insecticides, pesticides, fungicides, germicides, and growth stimulants [7]. The
advantages of applying biopolymers into agro-nanotechnological materials are sum-
marized in Fig. 3.
Between polymers from organic origin, starch has been one of the most com-
monly used raw materials because it is widely available and relatively easy to handle
to prepare biodegradable nanomaterials. However starch films have often resulted
brittle and sensitive to environmental humidity and difficult to process [6]. Thus, to
innovate in biodegradable nanomaterials, many other different natural polysaccha-
rides including alginate, hyaluronic acid, cellulose, hemicelluloses, as well as the
cationic chitin/chitosan have been considered. Moreover, blends of them have
resulted in a superlative bio-based composite with beneficial properties for the
desired application [6].
In particular, chitosan is a polycationic polymer composed of N-acetyl-D-glucos-
amine and D-glucosamine units with one amino (NH2) group and two hydroxyl
(OH) groups in each repeating glycosidic unit (Fig. 4). In addition to its biodegrad-
ability and biocompatibility, the low insolubility and thermal stability confer on
chitosan beneficial properties for its nanocomposites as film or agrochemical delivery.
This chapter highlights studies on bio-nanocomposites from organic origin and
their potentiality as eco-friendly nanomaterials for modern agricultural applications.
Chitosan-based nanocomposites as agricultural films as well as carrier for agrochem-
ical delivery will be revised. Finally, it will summarize commercial and emerging
nanoformulations as CR systems for agrochemicals, as well as analyze their multiple
challenges for their commercialization.
1208 M. Menossi et al.

Fig. 4 Chemical structure of chitosan

Bio-nanocomposites

Bio-based and biodegradable polymers from renewable resources appear as potential

alternative to traditional nonrenewable/nonbiodegradable synthetic polymers. Nev-
ertheless, as mentioned above, some properties must be improved to obtain a
competitive product and to expand their applicability. In this sense, the common
way to overcome these limits is through the formulation of multiphase materials such
as blends or composites. Bio-nanocomposites are materials obtained by the incor-
poration of inorganic or organic reinforcement, with at least one dimension in the
range of the nanometer (10 9 m), into a bio-based matrix. The nano-reinforcement
can be incorporated into biopolymer matrix by three different methods: in situ
polymerization, solution exfoliation, and melt intercalation process [10].

Bio-nanocomposite Properties

The main reason for incorporating small amounts of nano-sized reinforcements into
the biopolymer matrix is due to the improvement of certain properties with respect to
neat bio-based polymers (Fig. 5). The behavior of these novel eco-nanomaterials
depends on the type and content of reinforcement, the structure polymer/nanofiller,
the conditions of the process, and the final dispersion.
In general, drastic enhancements in Young’s modulus of bio-nanocomposites are
exhibited with the addition of organic nanofillers. In the case of tensile strength and
elongation at break (%), the improvements are occasional. For example, Lu et al. [11]
studied chitin whiskers as nano-reinforcements into soy protein isolate (SPI) matrix.
They prepared bio-nanocomposite films based on glycerol-plasticized SPI with 0, 5,
10, 15, 20, and 30 wt % of chitin whiskers. These authors concluded that Young’s
modulus of the 20 wt% chitin whiskers increased approximately six times with respect
to neat glycerol-plasticized SPI. In the same work, the elongation at break was in all
cases less than 135% with chitin whisker content. The tensile properties of the
bio-nanocomposites containing different amounts of nanofillers are shown in Table 1.
53 Bio-nanocomposites for Modern Agricultural Applications 1209

Properties improved with nano-fillers introduction

1 2 3 4 5
Mechanical Thermal Barrier Optical Bio-
properties properties properties properties degradability

Fig. 5 Properties improved with nanofillers introduction

In contrast, Arrieta et al. [12] obtained bio-nanocomposite films based on PLA as

bio-based matrix and used yerba mate NPs (mate NPs) as nanofillers in two pro-
portions: 0 and 5 wt%. They concluded that the incorporation of mate NPs consider-
ably increased the Young’s modulus in comparison with neat PLA, from 2 to 2.65 GPa
approximately. The tensile strength value is two times higher compared with neat
PLA, while no considerable modifications were observed on the elongation at break.
Other case of bio-nanocomposite with bio-based nanofillers is the work of Cao
et al. [13]. They synthesized green nanocomposites with hemp nanocrystals (HNCs)
in thermoplastic starch (PS) by casting method and prepared HCNs-PS nano-
composites with 0, 5, 10, 15, 20, 25, and 30 wt% HNCs. Young’s modulus was
significantly improved from 0.032 GPa to 0.824 GPa, when increasing the HNCs
content from 0 to 30 wt%, while the elongation at break values decreased from 68%
to 7.5% with 0 and 30 wt% HNCs content, respectively. In addition, the tensile
strength increased 200% in relation to neat PS.
Other studies with similar results are the works of Chang et al. that investigated
glycerol-plasticized potato starch (GPPS) using chitosan NPs [16] and chitin NPs
[14] as nano-reinforcements. Hosseini et al. [15] evaluated the incorporation of
chitosan NPs into fish gelatin (FG) matrix films. Young’s modulus, tensile strength,
and elongation at break of each mentioned work are indicated in Table 1.
In summary, the improvement on Young’s modulus and tensile strength by adding
small amounts of nano-reinforcements can be explained by high interaction between
the nanofiller and the bio-based matrix [11]. This interaction is increased when both
chemical structures are quite similar and the nanomaterial exhibits a homogeneous
dispersion [14]. Meanwhile, the opposite happened with elongation at break: the
incorporation of nanofillers reduced the motion of the bio-based matrix due to
increased intermolecular attractive forces [13].
The mechanical properties for agricultural materials must meet several requirements
and standards that have been summarized in the review of Briassoulis [5]: thickness
30–40μm, tensile strength 27 Mpa, and elongation at break 300%. To obtain these
standards mechanical properties, many alternatives can be employed: reactive modifi-
cation, surface functionalization, blending with other biopolymer, changing the plasti-
cizer, varying nanofiller contents, etc. In this sense, Arrieta et al. [12] demonstrated that
higher values of elongation at break are achieved when acetyl (tributyl citrate) is
incorporated, as a plasticizer, into PLA-mate NPs bio-nanocomposite films.
1210 M. Menossi et al.

Table 1 Tensile properties of bio-nanocomposites with different nanofiller contents

Tensile
Bio- Nanofiller Young’s strength Elongation at
nanocomposite content (%) modulus (GPa) (MPa) break (%) Ref.
SPI-chitin 0 ≈ 0.026 ≈ 3.3 ≈ 205.0 [11]
whiskers 5 ≈ 0.032 ≈ 3.8 ≈ 134.2
10 ≈ 0.036 ≈ 5.0 ≈ 106.7
15 ≈ 0.042 ≈ 5.7 ≈ 102.6
20 ≈ 0.158 ≈ 8.4 ≈ 34.8
25 ≈ 0.138 ≈ 8.3 ≈ 32.3
30 ≈ 0.105 ≈ 6.3 ≈ 28.6
PLA-mate NPs 0 ≈ 2.00 ≈ 27.11 ≈ 4.00 [12]
5 ≈ 2.65 ≈ 48.60 ≈ 2.65
HCNs-PS 0 0.032 3.9 68.2 [13]
5 0.035 4.5 57.3
10 0.112 6.1 50.4
15 0.169 6.9 31.2
20 0.243 7.4 20.3
25 0.395 8.7 16.4
30 0.824 11.5 7.5
GPPS-chitosan 0 – ≈ 2.84 ≈ 59.3 [14]
NPs 1 – ≈ 4.40 ≈ 45.5
2 – ≈ 6.93 ≈ 37.6
4 – ≈ 8.50 ≈ 28.1
6 – ≈ 10.80 ≈ 22.6
8 – ≈ 8.90 ≈ 18.2
FG-chitosan 0 0.287 7.44 102.04 [15]
NPs 2 0.371 7.99 70.09
4 0.392 8.77 64.72
6 0.453 10.57 44.71
8 0.467 11.28 32.73
GPPS-chitin 0 – ≈ 2.80 ≈ 59.3 [16]
NPs 1 – ≈ 3.45 ≈ 43.5
2 – ≈ 5.15 ≈ 30.7
3 – ≈ 6.29 ≈ 26.3
4 – ≈ 7.52 ≈ 21.7
5 – ≈ 7.80 ≈ 19.4

Several researchers [12, 14, 17, 18] investigated bio-nanocomposites and their
thermal stability by thermogravimetric analysis (TGA). In particular, Han et al. [17]
synthesized eco-friendly bio-nanocomposites based on glycerol-plasticized PSI with
nanocellulose fibers. These films were prepared by the addition of 0, 2, 4, 6, and 8 wt%
of nanocellulose, and these bio-nanocomposites presented slightly enhanced thermal
stability in comparison with glycerol-plasticized SPI film without nanofiller. Films with
53 Bio-nanocomposites for Modern Agricultural Applications 1211

low values of nanocellulose content registered lower mass loss with respect to SPI film
with 0 wt% nanocellulose fibers; nevertheless, the opposite happened with high nano-
reinforcement contents.
Sahraee et al. [18] prepared gelatin-based nanocomposite films containing chitin
NPs with 0, 3, 5, and 10 wt% content. The thermographs showed major thermal
stability for 5 wt% chitin NPs than 10 wt%, due to agglomeration of NPs. They
concluded that films thermal stability enhanced when the chitin NPs are homoge-
neously dispersed within gelatin matrix. Arrieta et al. [12] studied the incorporation
of mate NPs as nanofillers into PLA matrix, besides measuring tensile properties of
mate NPs – PLA films. They also investigated thermal stability of these
bio-nanocomposites. Their results led to the conclusion that mate NPs protect PLA
from thermal degradation and can be associated with the presence of antioxidant
agents. Chang et al. [14] studied the influence of chitosan NPs into GPPS matrix
films applying TGA analysis and compared to neat GPPS film. The introduction of
chitosan NPs decreased mass loss through temperature range, and the improvement
of bio-nanocomposites thermal stability was attributed better interactions between
the nanofiller and GPPS matrix.
Furthermore, works of Abdulkhani et al. [19], Lu et al. [20], and Siqueira et al. [21]
prepared bio-nanocomposites and analyzed thermal properties by differential scanning
calorimetry (DSC). Abdulkhani et al. [19] investigated bio-nanocomposites of modified
cellulose nanofibers as filler into PLA matrix. Bio-nanocomposite films were developed
at low contents of NPs, 0, 1, 3, and 5 wt%, and studied the effects of modified cellulose
nanofibers with DSC analysis. Nanocomposite films thermal behavior showed quite
similar pattern with respect to neat PLA film, and the glass transition temperature (Tg)
showed a slight improvement by the addition of nanofibers. The incorporation of
cellulose crystallites as filler into PS matrix was studied by Lu et al. [20]. The contents
of cellulose nanocrystallites into PS matrix were 0, 2.5, 5, 10, 15, 20, and 30 wt%. By
DSC analysis, they concluded that Tg increased with the content of nano-reinforcement.
This behavior may be attributed to stronger interactions between starch and cellulose
crystallites, making bio-nanocomposite films less flexible. On the other hand, Siqueira
et al. [21] used cellulose nanocrystals as reinforcements for preparing bio-nano-
composites using poly(ε-caprolactone) (PCL) as matrix. Bio-nanocomposite films
with different amounts of cellulose nano-crystals, 0, 3, 6, 9, and 12 wt%, were
processed. DSC analysis reported that Tg values increased when cellulose nanocrystals
content was added but no drastic modification was exhibited when varying the filler
content. It can be explained as the nanofillers restrict the motion of PCL polymer chains
by making hydrogen bonding forces. These works with their experimental Tg data are
condensed in Table 2.
In general, polysaccharides like cellulose, chitin, chitosan, and starch as nano-
reinforcements of bio-based polymer matrix increase Tg through the restriction of
polymer chains mobility or making hydrogen bonding forces and, consequently,
enhance thermal stability and crystallinity. Eco-nanomaterials with uniform distri-
bution of NPs showed better thermal properties.
As previously mentioned, barrier to vapor water is desirable in agriculture field
since it allows storing the soil moisture, decreasing water consumption, and
1212 M. Menossi et al.

Table 2 Thermal properties of bio-nanocomposites with different nanofiller contents

Bio-nanocomposite Nanofiller contents (%) Tg ( C) Ref.
PLA-cellulose nanofibers 0 57.5 [19]
1 58.3
3 58.5
5 58.9
PS-cellulose crystallites 0 ≈ 22.3 [20]
2.5 ≈ 22.6
5 ≈ 26.9
10 ≈ 30.6
15 ≈ 36.6
20 ≈ 38.4
30 ≈ 48.7
PCL-cellulose nanocrystals 0 62 [21]
3 59.2
6 57.7
9 57.4
12 58.8

preventing the risk associated with water stress. Significant reductions in diffusivity
were reported in several investigations [15–17] [22]. Hosseini et al. [15] analyzed the
effect on WVP when chitosan NPs content increased into FG bio-nanocomposite
films. WVP of FG with 0% content of chitosan NPs was around 4 x 10 9 g/m.s.Pa.
WVP was reduced, approximately, 38% when 8% of chitosan NPs content was
introduced. The development of bio-nanocomposite films based on starch matrix and
the use of chitin NPs as reinforcements were studied by Chang et al. [16]. WVP of
neat GPPS film was, approximately, 5.60 x 10 10 g/m.s.Pa, which decreased
between 19 and 25% when 1–2 wt% of chitin NPs are added, respectively. From
2 wt% to higher chitin NPs contents, WVP values reported were slightly lower.
Other case that evaluated WVP and compared it with neat biopolymer matrix is the
work of Han et al. [17]. They studied the introduction of nanocellulose into glycerol-
plasticized PSI and the effect of the nanofiller content on barrier property. They
reported 1.91 x 10 10 g/m.s.Pa as WVP value to glycerol-plasticized PSI without
nanocellulose, and it immediately decreases when nano-reinforcements are added. In
comparison with this value, WVP was reduced to 16% when 8% of nanocellulose
content was incorporated into bio-nanocomposite film.
Besides varying the nano-reinforcement content, film dispersion, and type of
nanofiller, Follain et al. [22] prepared bio-nanocomposites based on PCL matrix with
cellulose nanocrystals surface-chemical modification by grafting of long-chain iso-
cyanate as nanofiller. In their work they compared the WVP values of these
eco-nanomaterials with and without chemical modification and obtained better
barrier properties when reactive modification of cellulose nanocrystals was incorpo-
rated into PCL matrix.
53 Bio-nanocomposites for Modern Agricultural Applications 1213

In summary, the barrier properties are enhanced when impermeable nano-

reinforcements are added and have a good dispersion in the polymer matrix as
well as a high aspect ratio. This dramatic improvement can be explained by the
increasing of tortuosity in bio-nanocomposite films, and the diffusion processes are
slower and, thus, present lower permeability values.
Many studies reported that incorporation of nano-reinforcements into biopolymer
matrix generates a decrease in spectra-radiometric characteristics in the visible range
and the UV region [15, 18, 23]. This behavior is desirable for agricultural
applications, such as mulching films, since one of their purposes is to inhibit the
light-dependent growth of weeds [2]. FG-based bio-nanocomposite films with the
incorporation of different chitosan NPs contents were prepared and optically eval-
uated by Hosseini et al. [15]. Light barrier properties of bio-nanocomposite films
containing high level of chitosan NPs showed a reduction of transparency with
respect to neat FG films. Multiple issues are related to this performance; for instance,
researchers explain that the increase of opacity could be attributed to the obstruction
of light passage by NPs or to the formation of fewer agglomerates [18]. Specifically,
according to Chen and Liu [23] when NPs content level is high, the transmitted light
could pass through several interfaces between the nano-reinforcement and the
bio-based matrix. In consequence, light loss becomes inevitable and is ascribed to
the strong reflections and refractions at those interfaces.
Particularly, the work of Nasri-Nasrabadi et al. [24] and Han et al. [17] developed
eco-friendly nanomaterials that showed increases in transparency levels or did not
produce changes in their opacity. Nasri-Nasrabadi et al. [24] explain that their results
may be related to the narrow-diameter dispersity of the nanofibers, homogeneous
dispersion into polymer matrix, and a strong interaction between nanofiller and
matrix. Bio-nanocomposites that increase the transparency levels could be used as
greenhouse or low tunnels in agricultural practices [5].
Agro-nanomaterials should disintegrate completely at the end of the crop season.
For this reason, disintegrability in composting and enzymatic, in vitro, and soil
degradation of green and eco-friendly nanocomposites have been investigated by
several authors [25–28]. For the case of Deepa et al. [25] described that the
disintegrability in compost conditions exhibited that the rate of degradation of
alginate and cellulose nanofibrils bio-nanocomposite films changes with different
amounts of reinforcement added into alginate matrix. Due to homogeneous disper-
sion and strong interaction between the alginate matrix and cellulose nanofibrils,
nanocomposites are harder to degrade when the nanofiller contents increase. Nev-
ertheless, at high contents of nanofillers, nanofibrils agglomeration was observed
and, in consequence, disintegration is higher.
The in vitro degradation of electrospun bio-nanocomposite mats from PLA and
cellulose nanocrystals in phosphate buffer solution tests were investigated by Shi
et al. [28]. These authors concluded that cellulose nanocrystals incorporation into
PLA matrix degraded easier than neat PLA. The enzymatic degradation, using
proteinase K as enzyme, of neat PLA and PLA nanocomposites reinforced with
cellulose nanocrystals unmodified and modified using a commercial surfactant was
1214 M. Menossi et al.

studied by Luzi et al. [26]. Approximately, 100% weight loss for neat PLA and PLA
reinforced with cellulose nanocrystals unmodified composite was reached in 3 days
of enzymatic degradation. However, nanocomposites composed of PLA with the
presence of surfactant showed slower degradation than neat PLA and PLA with
cellulose nanocrystals unmodified. Similar evidence was demonstrated by Pinheiro
et al. [27]. The authors compared soil biodegradation of neat cellulose, neat poly-
butylene adipate terephthalate (PBAT), and PBAT bio-nanocomposites with cellu-
lose nanocrystals and cellulose-functionalized nanocrystals. The addition of
cellulose nanocrystals unmodified into PBAT matrix generated a less hydrophobic
system and, therefore, had greater trend of biodegradation than the neat PBAT and
nanocomposite films reinforced with cellulose nanocrystals modified. Neat PBAT
and bio-nanocomposites of PBAT-based cellulose-functionalized nanocrystals
showed similar biodegradation rate. For both, their biodegradation rate was lower
than 5% after 120 days.
In short, bio-nanocomposites can be adapted to meet the biodegradability
requirements imposed by agricultural practice. These traits will depend on the
crop type, polymer matrix, and nano-reinforcements including their chemical
modifications.

Chitosan-Based Nanocomposites
In this section, we will carefully review some representative studies focused on
bio-based nanocomposites which offered benefits to be used as mulch films. In
particular, chitosan-based nanocomposites incorporating organic nanofillers will be
prioritized to interpret the advantages and disadvantages of these innovative and
promising materials in agriculture.
Chitosan-based nanocomposites refer to the chitosan polymer acting as a matrix or
chitosan NPs acting as nanofiller with an average particle size less than 100 nm. This
nanocomposite could retain exceptionally improved properties from both polymer and
NPs [7]. In agriculture, the potential of chitosan-based nanocomposites has an increas-
ing relevance in enhancing plant protection against stress and improving crop yield
and management [29]. In this same field, other essential trait is low water solubility of
mulch films due to their intimate contact with the irrigation water. Thus, a chitosan and
starch blend used as matrix has been designed to contribute to the solution of this
problem [30]. The same authors demonstrated that the addition of a specific amount of
chitosan caused a twofold reduction in solubility of starch films. However, the
maximum tensile strength at rupture did not vary with the addition of chitosan and
citric acid, this latter added as cross-linker. In addition to starch, chitosan can also be
modified by blending with cellulose because it has modifiable chemical groups
[31]. Thus, the stability of chitosan and cellulose blends improves physical properties
of different bio-based composites [31]. Innovative bio-based pesticide mulch obtained
by blending chitosan and hydroxypropyl methylcellulose (Me-CS50/HPMC50) with a
controlled-release ability of the pesticide metalaxyl (Me) proved to be effective in
reducing the incidence of Phytophthora-mediated disease in soybean plants
[32]. Other cellulose and chitosan-based composite film with an associated anti-
bacterial activity has been proposed as a biomedical material [33]; however, since
53 Bio-nanocomposites for Modern Agricultural Applications 1215

chitosan antimicrobial properties were also very well demonstrated on a wide range of
pathogens, we cannot discard that this bio-based blend could be adaptable for its use in
agriculture [34]. Focusing on reducing the hazardous environmental impacts of
nonbiodegradable films, several chitosan and cellulose blends were successfully
characterized [31]. However, one important problem on chitosan-cellulose blend has
been the use of solvents to dissolve them. Most of chemical approaches have resulted
inappropriate for the production of that blend at industrial scale. Accordingly, to
optimize and contribute with a more environmentally friendly procedure, a novel
alternative of preparing pH-responsive cellulose-chitosan nanocomposites has been
performed [35]. These pH-responsive cellulose-chitosan nanocomposite films also
exert slow release of chitosan besides to be nontoxic, biocompatible, and biodegrad-
able, representing a promissory eco-material in the field. Therefore, although several
studies exemplify the wide aspects that must be taken into account for the development
of a bio-based composite, it is interpreted that the knowledge about its design and
characterization to final application consequences, including biodegradability and life
cycle, is very limited.

Bio-nanocomposites as Controlled-Release Systems

for Agrochemicals

CR is defined as the regulated transfer of biologically active ingredients that are

available to a targeted site, with the aim to provide certain content level over a longer
period [7]. CR technology presents advantages in agriculture field such as reduction
of agrochemical doses, minimized losses for evaporation, decreased phytotoxicity,
and reduction of harmful chemicals. In this way, nanotechnology could take an
important place into the crop productivity due to its potential for efficient delivery of
agrochemicals and genetic material using nanocomposites [36].
In order to apply the use of agrochemical nanoformulations, a promising option
results from the combination of nanotechnology and renewable/biodegradable poly-
mers due to their biodegradability, biocompatibility, thermal stability, and nontoxic
and simple preparation. In this direction, natural biopolymers, more specifically
polysaccharides – alginate, starch, cellulose, cyclodextrin, pectin, chitosan, and
others – are used as vehicles to encapsulate or absorb active ingredients to elaborate
CR systems for agrochemicals [7]. Some strategies such as incorporating pendant
groups, cross-linking, and grafting with other polymers are required to enhance the
natural polymer properties as CR nanocarriers [7]. Other natural polymers less used
as CR systems for agrochemicals are proteins. Casein, collagen, gelatin, soy protein,
zein protein, and others are low-cost and high-availability heteropolymers
conformed by different amino acids and can play a fundamental role like N source
after its disintegration [10]. Among biopolyesters, PLA and PCL are the most used
for CR delivery system.
According to Ghormade et al. [9], polymer-based nanomaterials as CR systems
for agrochemicals can be classified in relation to their nanostructure, as the
following:
1216 M. Menossi et al.

• Nanocapsules. Heterogeneous reservoir-type structures. The active ingredient is

located and concentrated in an inner central cavity, lined and surrounded by
polymer matrix.
• Nanospheres. Uniform monolithic structures. The active molecule is homoge-
neously distributed throughout the polymer matrix.
• Nanogels. Water-swollen polymeric networks. Hydrophilic or amphiphilic poly-
mers, physically or chemically cross-linked, which can swell and absorb high
quantity of water. The active ingredient is trapped between the nanomaterial
networks.
• Nanofibers. Homogeneous spinning structures. The spinning solution contained
the active ingredient in various concentrations along with the polymer matrix.
• Nanomicelles. Core-shell-type structures. Block copolymers with amphiphilic
behavior self-assemble in water to form colloidal particles. The process of self-
assembly is developed by the hydrophobic interactions on the formation of the
hydrophobic micellar core which is coated by a hydrophilic shell. The active
ingredient is concentrated inside hydrophobic micellar core.

Briefly, investigations on polysaccharides, proteins, and biopolyesters used as

vehicles to encapsulate or absorb active ingredients to elaborate CR fertilizer and
pesticide are summarized in Table 3 with their nanostructures and benefits.
In relation to nanoencapsulation, Kumar et al. [37] developed and evaluated
nanocapsules based on alginate and chitosan for CR of acetamiprid as pesticide.
This nanoformulation was prepared by polyelectrolyte complexation, characterized
by different studies, and analyzed as carriers for CR in vitro at different pH. The same
authors concluded that nanocomposites made of alginate and chitosan were better in
terms of CR than the commercial agrochemicals. This novel nanoformulation can be
employed in different types of soil due to the stability of pesticide at all the pH ranges.
Alginate and chitosan matrix used in nanocapsules loading paraquat dichloride as
herbicide were also investigated and characterized by Silvia et al. [38]. Size distribu-
tion, polydispersion, zeta potential, pH, and chemical stability measurements were
used in order to characterize chitosan and alginate nanocapsules. The authors con-
cluded that the formulation of paraquat with chitosan/alginate NPs showed an
improvement of herbicidal action than paraquat-free. Finally, chitosan/alginate NP
as a carrier system for gibberellic acid as plant growth hormone was studied by Pereira
et al. [39]. These authors developed nanocarriers with high encapsulation efficiency.
The release of plant growth hormone was modified depending on changes in temper-
ature and pH. With respect to biological activity assays, alginate-chitosan with
gibberellic acid showed stronger effects in comparison to the free hormone. Kumar
et al. [40] synthesized imidacloprid-loaded sodium alginate NPs as CR for pesticide.
NPs were obtained by emulsion cross-linking technology and varying polysaccharide
and emulsifier content in the preparation. Nanoformulation was characterized by
different methods to confirm NPs belong to nano-size with high encapsulation effi-
ciency. Imidacloprid encapsulation resulted in lower toxicity than plane pesticide.
Neem oil/alginate nanoemulsion coated by starch showed a drastic effect on slowing
down the release of Azadirachta indica. Imidacloprid was assayed with the purpose of
53 Bio-nanocomposites for Modern Agricultural Applications 1217

Table 3 Bio-nanocomposites as CR systems

Active
Nanostructure Biopolymer ingredient(s) Advantage(s) Ref.
Nanocapsule Alginate- Acetamiprid Reduction of pesticides application [37]
chitosan Major stability and CR profile for
different pH and types of soil
Alginate- Paraquat Improve the herbicidal action [38]
chitosan dichloride Herbicide and biopolymers showed
good association
Alginate- Gibberellic acid High encapsulation efficiency [39]
chitosan Showed high effect on biological
activity assays
Alginate Imidacloprid High-efficiency encapsulation [40]
Lower toxicity
Chitosan- Imidacloprid Improve CR for herbicide behavior [41]
PLA
Alginate- Imazapic Encapsulation showed lower [42]
chitosan Imazapyr toxicity
Improve herbicide action
PCL Rosmarinus Reduce the concentration of the [43]
officinalis applied doses and number of
essential oil applications
Zein Geraniol High-efficiency encapsulation [44]
protein R-citronellal Encapsulation showed decrease in
their toxicity
Nanosphere PCL Azadirachta Enhance photostability and [45]
indica thermostability
Improve insecticide performance
Nanogel Chitosan- Lippia sidoides Prolong insecticide action [46]
cashew essential oil
gum
Nanofiber Cellulose- Dimethyl Reduce initial release rate and [47]
starch phthalate higher overall CR of herbicide

preparing nanocapsules of chitosan-PLA graft copolymer as CR for pesticide [41].

Imidacloprid-loaded chitosan-PLA nanoformulations were developed by two tech-
niques: nanoprecipitation technique and emulsion/solvent evaporation method at three
different copolymer/active ingredient weight ratios. These biodegradable amphiphilic
copolymer nanocapsules loaded with imidacloprid could prolong pesticide release
behavior and presented great influence on the particle size and their distribution.
Alginate-chitosan NPs loaded with two different herbicides, imazapic and imazapyr,
were studied by Maruyama et al. [42]. Nanoformulation was manufactured using
ionotropic gelification method and tested by material characterization techniques. In
this work, alginate-chitosan NPs were able to encapsulate imazapic and imazapyr with
efficiencies between 50 and 70% and presented more improvements as CR for
herbicide than the free forms. Also, these authors demonstrated that alginate-chitosan
nanoformulation led to a reduction in toxicity. Khoobdel et al. [43] investigated PCL
1218 M. Menossi et al.

biopolyester as nanocarrier to encapsulate Rosmarinus officinalis essential oil as CR

system for pesticides. Nanoprecipitation technique was applied in the development of
pesticide-loaded nanocapsules. Rosmarinus officinalis nanocapsules showed an
important reduction in the concentration and number of the applied doses. Oliveira
et al. [44] manufactured zein protein NPs loaded with two pesticides, geraniol and
R-citronellal, using antisolvent precipitation technique and analyzed by different
material characterization methods. The zein NPs containing the botanical repellents
showed high encapsulation efficiency (>90%), good physicochemical stability, and
protection against UV degradation. The nanoencapsulation of this protein with gera-
niol and R-citronellal decreased the toxicity of these both active ingredients.
Regarding nanosphere as nanostructured formulation, Costa et al. [45] used
Azadirachta indica as pesticide against Zabrotes subfasciatus to prepare spherical
nanocomposite employing PCL as matrix. Nanospheres were developed by using
nanoemulsion/solvent displacement and interfacial deposition nanoencapsulation
process. PCL and Azadirachta indica nanospheres presented higher stability than
conventional agrochemicals and enhanced biological performance to control of
pests.
An example of nanogel as nanoformulation was demonstrated by Abreu et al. [46].
These authors elaborated this nanostructure based on chitosan-cashew gum and loaded
Lippia sidoides as active ingredient. Nanocomposite hydrogel was produced varying
cashew gum/chitosan ratios, cashew gum weight percent, and matrix/oil ratio. The
results obtained led to the conclusion that chitosan-cashew gum nanogel using relative
ratios matrix/oil 10:2 and gum/chitosan 1:1 and 5% cashew gum concentration
showed encapsulation levels over 70%. Nanoformulation with relative ratio
gum/chitosan 1:10 presented the lowest percentage of oil released after 30 h, compared
with ratios of 1:1 and 10:1.
Regarding nanofiber as nanostructure, bio-based matrix composed of nano-
fibrillated cellulose and starch granules was used to develop and evaluate nanofibers
as CR system for dimethyl phthalate as herbicide. Patil et al. [47] investigated and
morphologically characterized nanofibers with three cellulose-nanofiller contents
(0, 2, and 4 wt%) and morphologically analyzed. The authors concluded that
reinforcing starch with 2–4 wt% cellulose nanofibers caused significant influence
on morphology and release performance of starch granules, decreasing initial release
rate and higher overall release of dimethyl phthalate than starch without nanofibers.

Chitosan-Based Nanocomposites as Controlled-Release Systems

for Agrochemicals
In addition to the agricultural applications mentioned in the previous section, several
nanoparticulated systems are being currently incorporated to the chitosan-based
nanocomposite in order to minimize environmental pollution caused by over-
application and nonspecific delivery of agrochemicals. Depending on nanofillers,
new properties including physical barriers and smart delivery of active compounds
could be obtained in the nanocomposite. Besides, results of research indicated that
supplying bulk chitosan promotes plant growth and development including innate
defense [48]; chitosan NPs were also reported to improve biophysical characteristics
53 Bio-nanocomposites for Modern Agricultural Applications 1219

and antimicrobial activity on several types of plant pathogens [48]. Bioactivity of

chitosan-based NPs in plants is directly influenced by physicochemical properties
like particle size, size distribution/polydispersity index, and surface charge [48].
On the other hand, application of chitosan-based NPs and nanocomposites
containing essential micro- and macronutrients exerts positive effects on several
crop yields including horticultural, nonwoody herbaceous fruits and fruit trees
[49]. Nanoparticulated nutrients are often applied to formulations since they improve
the incorporation in plant cells and, in consequence, minimize nutrient loss.
Although these nanofertilizers were sprayed at very low concentrations on plants,
they showed very high efficiency in increasing plant growth and quality of seeds and
fruits [48].
Some interesting works were studied on preparation and property characterization
of chitosan-coated fertilizer with CR. Hence, to improve the utilization of nitrogen
(N), phosphorus (P), and potassium (K) compounds as well as water resource at the
same time, a new type of chitosan-coated fertilizer of three-layer structure was
prepared [50]. The core of this particle was water-soluble nitrogen, while phospho-
rus and potassium were granular; the inner and the outer coatings were chitosan and
poly(acrylic acid-co-acrylamide) polymers, respectively. Both the controlled-
nutritional release and its high water-retention capacity confer to it significant
advantages over the current slow-release fertilizers. Although the same authors
described that the chitosan in the first layer of the coating material is a biodegradable
material and the copolymer poly(acrylic acid-co-acrylamide) in the outer coating
material can also be degraded, no experiments on the degradation properties of this
material in the soil were included. In this same sense, chitosan NPs were obtained by
polymerizing methacrylic acid (MAA) for the entrapment of NPK [51]. Interestingly,
when this chitosan-PMAA-NPK nanofertilizer was applied via roots of garden pea
(Pisum sativum var. Master B) plants, a significant reduction in root length was
detected in a dose-dependent manner. However, CS-PMAA-NPK nanofertilizer had
positive effects on growth and productivity upon foliar applications on wheat plant
growth in well-drained sand [52]. These apparently contradictory pieces of evi-
dences could be justified on the bases of multiple facts, but they clearly give insights
about the putative effect that nanofertilizer delivery system might have in case of
being accumulated in soil and how it could impact on different crops cultivated in the
same field.

Nanotechnology-Based Agroproducts Challenges

According to recent statistics about growing global population, with the current
agricultural production levels and their systems, it would be impossible to achieve
food security [7]. Conventional agrochemicals and their indiscriminate and exten-
sive use to maximize crop yield and to protect fields from pests and weeds, among
others, caused disadvantages regarding environmental impacts and multiple dis-
eases, including animals and human beings. In addition, drastic loss of biodiversity,
1220 M. Menossi et al.

soil fertility, and erosion are other consequences of modern agriculture and tradi-
tional agrochemicals [9].
In the context of green nanotechnology and sustainable agriculture, this innova-
tive technology and their applications as smart agroformulations aim to provide
solutions in order to minimize nutrient losses, decrease the amount of agrochemical
doses, prolong their action, detect environmental pollutants, optimize cost produc-
tion, increase agronomic yields through enhanced nutrient management, and protect
human security. Moreover, it is also necessary to provide knowledge in relation to
nanomaterials and their properties, particularly about toxicity issues [7]. Figure 6
illustrates multiple challenges facing nanotechnology-based products to enter the
market.

Commercial and Emerging Nanoproducts

As mentioned, in contrast to other industrial fields, applications of nanotechnology-

based agroproducts continue to be substantially lower. In the last years, this trend has
reversed with the rising number of patents from agrochemical companies and
original research publications regarding the development of nano-based
agroproducts [7]. Unfortunately, in agriculture field, the commercialization of
nanotechnology-based formulations is drastically limited and is related to the exis-
tence of multiple issues surrounding their usage. Some nanoproducts-wide chal-
lenges are high cost associated with their industrial production/processing as well as
the difficulty in the scalability of research, the shortcomings in the necessary

Commercial challenges Nanotixicity and

• Difficulties in the scaling Environmental safety
• Lack of infrastructure • Studies of nanotoxicity
• High economic costs over time are required
• Inherent limits on • Apply controls in all
agriculture sector stages of life-cycle
Nanotechnology-based
agroproducts
Legislation and regulation challenges Public awareness and
• Divergence on acceptance
nanomaterials regulatory • Deficiency in
• Evaluate “case-by-case”
nanotechnology
• Lack of international information and advantages
collaboration

Fig. 6 Multiple challenges faced by commercialization of nanoproducts in agriculture

53 Bio-nanocomposites for Modern Agricultural Applications 1221

infrastructure, economic feasibility of traditional agrochemicals, and limits associ-

ated with agriculture field and the implementation of technology [53]. Additionally,
the commercialization of nanoformulations must face social perception of the
products; in other words, these products may exhibit risks to agriculture and food
supply chain and, consequently, impact/damage on environmental safety and human
health [36]. Despite increasing agrochemical company patent trend, only a limited
number of nanotechnology-based products have reached the market. From the
economic perspective, electronic, cosmetic, medical, and pharmaceutical nano-
materials also present high economic costs, but this financial expense is, generally,
compensated by high returns [7]. In this direction, one way to decrease costs and
expenses is employing NPs derived from renewable natural resources like biopoly-
mers (proteins, polysaccharides) as delivery systems for agrochemicals with low
human health and environment impact [36]. Despite the advancements and signif-
icant efforts of biopolymers into agro-nanotechnology, the commercialization of
nanoproducts from organic origin is still low. It is necessary to put the bio-based
polymers with their wide advantages, challenges, and properties in a fundamental
role to the implementation, development, and commercialization of this novel
technology in the agriculture field. Therefore, it is also essential to carry out studies
that focus on the understanding of the fate, transport, behavior, and degradation of
NPs in the environment in order to promote safe nanotechnology applications into
agricultural sector [53].
Merino et al. [7] have already summarized some breakthroughs in nanotechnol-
ogy from huge agrochemical companies and institutions. Some examples of these
companies that lead nanoformulation production are as follows: BASF German
company developed pesticides encapsulated in NPs as controlled-release system;
Syngenta American company manufactured nanoemulsions for greater crop effi-
ciency; Bayer German company produced silicate NPs for food production; and
Nestlé American company generated nanosensors for pathogen detection and pol-
lutants into food packaging. On the other hand, the University of Kyoto, Clemson,
VIT, and Cornell applied nanotechnology to develop nanofertilizers, nanoproducts
from agroindustry wastes, and nanoemulsions as herbicide, among others. Fertilizers
and pesticides based on nanotechnology are the most commercialized among
agroformulations. These nanoproducts oriented for agriculture field have been
developed and put on the market by small companies [7]. Table 4 shows the list of
some commercial nanoproducts, from organic and inorganic origin, already avail-
able in the market with their application and brief description of the nanomaterials
that compose them.
Details of some nanoproducts with compositions and their advantages, exposed
in Table 4, are explained below.
Particularly, about commercial nanofertilizers, an Egyptian company produces
fertilizers, fungicides, and growth stimulants through normal methods and introduces
nanotechnology to promote improvements into agriculture field. More specifically,
Saula ® and Vitro NPK are two nanomaterials aimed to improve the utilization of N, P,
and K compound as well as supplemented with other metal NPs, such as iron (Fe), Zn,
manganese (Mn), Cu, and boron (B), amino acids, and organic acids. On the other
1222 M. Menossi et al.

Table 4 Commercial nanoproducts available in the market

Nanoproduct Commercial
type nanoproduct Company* Composition
®
Nanofertilizer Nano-Ag Answer Urth Agriculture, Unknown nanomaterials
USA
Nanopro ® Aqua-Yield® Unknown nanomaterials
NanoRise ® Operations, LLC,
NanoGro ® USA
NanoN+™
NanoPhos ®
Nanok ®
NanoPack ™
NanoCalSi ™
NanoStress ®
NanoZn ™
pH5® Bio-Nano Unknown nanomaterials
Saula Drip Technology, NPK formulas supplemented
Saula Solo Egypt with NPs (Fe, Zn, Mn, Cu, and
Saula Motawazen B)
Vitro NPK NPK formulas supplemented
with nanomaterials (Calcium,
Sulfur, Mn, Fe, B, Cu, among
other NPs)
AgriHit ™ Green Earth Unknown nanomaterials
Nano Science,
Inc., Canada
NovaLand-Nano Land Green & Mn, Cu, Fe, Zn, molybdenum
Technology (Mo), and N NPs
Co., Ltd., Taiwan
Biozar Nano-Fertilizer Fanavar Nano- Fe, Zn, and Mn NPs
Pazhoohesh
Markazi
Company, Iran
NanoMax NPK JU Agri Sciences Unknown nanomaterials
NanoMax Cal Pvt. Ltd., India
NanoMax Zinc
NanoMax Potash
NeuCytokin ® Neu Farm Unknown nanomaterials
NeuCombi ® GmbH, Germany Zn, Fe, Mn, B, Cu, and Mo
NPs
®
Nubiotek Ultra HBK Bioteksa, Unknown nanomaterials
Nubiotek ®
Ultra K México
®
Nubiotek Ultra Mg
®
Nubiotek Ultra N
®
Nubiotek Ultra NPK
®
Nubiotek Ultra P
®
Nubiotek Ultra SN
(continued)
53 Bio-nanocomposites for Modern Agricultural Applications 1223

Table 4 (continued)
Nanoproduct Commercial
type nanoproduct Company* Composition
Nubiotek ® Hyper
Bmo
Nubiotek ® Hyper CaB
Nubiotek ® Hyper
FBK
Nubiotek ® Hyper Fe
+Mg
Nubiotek ® Hyper K
Nubiotek ® Hyper
OXY
Nubiotek ® Hyper RFZ
Nubiotek ® Hyper Zn
VitaSoil Vitasoil Nano Unknown nanomaterials
Science, Brazil
Nano Zinc Alert Biotech, Unknown nanomaterials
India
Nano Organic Lazuriton Nano Unknown nanomaterials
Compound Biotechnology,
Nano High Nitrogen Co., Ltd. Taiwan
Compound
Nano Low Nitrogen,
High Phosphorus, High
Potassium Compound
Nano High
Phosphorus, High
Potassium Compound
Nano Organic
Tag Nano NPK Tropical Unknown nanomaterials
Tag Nano Cal Agrosystem
Tag Nano Phos India Pvt. Ltd.,
India
Tag Nano Potash
Tag Nano Zinc
Argentum PlantoSys, Ag NPs
Netherlands
Nano-5 ® Uno Fortune Unknown nanomaterials
N-3 ® Inc., Taiwan
Nanopesticide Nanocu ® Bio-Nano Copper NPs
Technology,
Egypt
®
NanoGreen Nano Silver Bio-ceramics and mixture of
Manufacturing metallic oxides
Sdn. Bhd.,
Malaysia
(continued)
1224 M. Menossi et al.

Table 4 (continued)
Nanoproduct Commercial
type nanoproduct Company* Composition
NSPW-L30SS Nanosilva, LLC., Ag NPs and silica
USA
HTSi Nanjing Haitai Silica oxide NPs
Nanomaterials
Co., Ltd., China
Agro 2400 Silvertech Kimya Formula with Ag NPs
Agro 2475 San. Tic. Ltd. Formula with Ag and Cu NPs
Agro 2490 Şti., Turkey Formula with Ag, Cu, and
chitosan NPs
*Information is available through company’s website

hand, pH5 ® is a nano-size material used to increase the permeability and adjust pH
number. Conversely, a hi-tech Taiwanese company focuses its work on nanotechnol-
ogy applicability in organic farming. NovaLand-Nano was manufactured as liquid
miscellaneous substances trace element fertilizer and contains Mn, Cu, Fe, Zn,
molybdenum (Mo), and N NPs. Some advantages are to accelerate nutrient penetration
into the plants and speed up plant growth, to increase plant resistance to soil saliniza-
tion and drought, to improve crop productivity, to contribute seeds germination, and to
enhance plant disease resistance. Biozar Nano-Fertilizer ® is a type of biological
fertilizer manufactured in Iran to enhance soil fertility and promote growth plant.
Biozar Nano-Fertilizer® decreases the application of chemical fertilizers and improves
crop yield. Metal NPs of Fe, Zn, and Mn compose the biological fertilizer. On the other
hand, NeuCombi ® was developed by a German company. This nanofertilizer is
composed of chelated nano-elements (Zn, Fe, Mn, B, Cu, and Mo NPs) and natural
phytohormones with nanotechnology. A Brazilian company has developed and
manufactured VitaSoil as nanopesticide. This product is a nutrient complex with
organic substances that stimulate and promote microorganism’s growth with multiple
soil benefits. Another Latin-American company, with business/scientific approach that
used nanotechnology in their products, has elaborated two lines of products to enhance
yield vegetable crops and fruit trees: Nubiotek ® Ultra and Nubiotek ® Hyper. The first
line of products is oriented to restore soil characteristics, and the second line to
improve nutrients and their availability. Argentum is another example of nanopesticide
that was elaborated by an innovative Netherlander company. This nanoproduct is a
bio-based stimulant containing silver (Ag) NPs. They reported benefits to used Ag
NPs as biostimulant, such as increase in crop growth and improvement of the
absorption of magnesium (Mg), N, Fe, and other elements.
Regarding commercial nanopesticides, Nanocu ® was developed by hi-tech
Egyptian company and used as fungicide and bactericide. This nanoproduct
manufactured with nanotechnology contains Cu NPs in their formula. A Malaysian
company developed NanoGreen ® as bactericide product. This nanopesticide is a
mixture of bio-ceramics and metallic oxides and presents advantages such as free
from harmful ceramics, also can replace chemical fertilizer, improve soil fertility,
53 Bio-nanocomposites for Modern Agricultural Applications 1225

and decrease content of heavy metal elements. Finally, a high-technology Chinese

Company manufactured HTSi line nanoproducts, with pesticidal function. These
nanopesticides are based on inorganic, nontoxic, and silica oxide NPs.
Although commercial nanoproducts available in the market from inorganic origin
are quantitatively greater than eco-friendly, biodegradable, and biocompatibility
nanoformulations, this trend seems to be balanced with agro-inventions that emerged
recently. With respect to nano-enabled patents and publications in agriculture, plant
protection, fertilizer, and UV protection inventions/formulas lead in numbers. In this
section, some representative nanotechnology-based agro-inventions and their bene-
fits will be revised. Table 5 summarizes the newest emerging nano-inventions,
nanoproduct types, and their nano-ingredients.
Among nanofertilizer recent patent trends, novel eco-friendly and organic agro-
based invention was developed using nanochitin crystal particles in aqueous suspen-
sion and mixed with fertilizer to promote plant growth, reduce the dosage of chemical
fertilizer, and protect environmental safety [54]. In addition, this invention is produced
by utilizing agricultural waste resources and can improve the utilization rate of the
fertilizer by 25–50%. Another novel agro-based patent was developed, as aqueous
formulation for plant nutrition and fortification, containing two or more metal NPs
[55]. Cu, Ag, and Fe NPs were used to manufacture these nanoformulations that, with
small proportions, promoted plant growth, decreased the dosage of fertilizer, and, at
the same time, reduced environmental impact. A novel nanocomposite fertilizer was
prepared using rice as nano-matrix and metal NPs [56]. Mo dioxide or trioxide, Zn
oxide, Mn monoxide, dioxide or sesquioxide, zirconium (Zr) dioxide, lanthanum
(Ln) sesquioxide, and Mg metal NPs were used to prepare smart nanomaterial with
the following benefits: it promotes root and seed system; it protects crop; and it solves
all kinds of nutritional deficiency symptoms of rice shoot. To improve the bioavail-
ability of macro- and micronutrients, NPs comprising a nano-matrix core, a release
coating layer, and single or plurality of bioactive agent(s) were manufactured as CR
system for pesticide, plant growth, fungicide, and insecticide, among others. This
novel invention can improve crop efficiency, decrease plant pathogens, and reduce
abiotic stress. In relation to biopolyesters and patents, PCL and polyethylene glycol
(PEG) were used as release control coating and coronatine as nano-matrix core
comprises at least one polymeric material [57]. Other nanofertilizer-based invention
was prepared by adding ZnO, TiO2, and other NPs to the NPK nanocomposite for
plant nutrition [58]. This aerosol nanoproduct based on foliar application was
manufactured to deliver NPK and oxide metal NPs to the plants and exhibits advan-
tages, such as stability of the nanocomposite over time; the dosage can be optimized
based on the composition; nanoformulation can increase light absorption; and
improvement of fresh weight biomass, root length, area, and diameter. Lastly, a
nanofertilizer invention utilizes polymer-based stabilized NPs for the production of
self-sanitizing photocatalyst coating for wide agricultural applications: growth stimu-
lation, pre- and postharvest protection, and reduction in water and pesticide dosage
[59]. This invention is based on biopolymer chitosan and their derivates as stabilizer
and fixator of metal NPs, derivates and others with stabilizers, surfactants, oils, flavors,
and amino acids, among others.
1226 M. Menossi et al.

Table 5 Recent agro-inventions based on nanotechnology

Nanoproduct
type Patent invention Nano-ingredients Patent number Ref.
Nanofertilizer Application of nanochitin in Chitin CN 111116263 [54]
improving fertilizer nanocrystals A
utilization rate
Aqueous fertilizer with metal Two or more metal ES 2726996 T3 [55]
nanoparticles NPs
A kind of rice composite Nanocomposite CN 110511094 [56]
nano-matrix fertilizer and based on starch as A
preparation method thereof nano-matrix and
metal NPs
Nanoformulations for plants PCL – PEG NPs US 2018/ [57]
0343854 A1
Synthesis of nanocomposites NPK and metal WO [58]
and their use in enhancing oxides NPs 2018005930
plant nutrition A1
Photocatalyst polymeric Metal NPs BR [59]
coatings and their uses in 102017007914-
sustainable agriculture 7 A2
Nanopesticide Light/pH double Sodium alginate CN 110183549 [60]
responsiveness sodium nanocapsules A
alginate derivative and the
preparation method and
application thereof
Double-loading PLA nanocapsules CN 110786324 [61]
nanopesticide sustained- A
release capsule for
preventing and treating rice
sheath blight disease and
preparation method thereof
Nano-photolysis-resistant Lignin CN 110946133 [62]
controlled-release pesticide nanocapsules A
with lignin as coating matrix
and preparation method
thereof
Nano-pesticide composite Nanocomposite CN 110881462 [63]
preparation based on based on A
phosphate and metal ions and phosphate as
preparation method thereof matrix and metal
NPs
Nanoparticles of titanium TiO-TiO2 NPs BR [64]
salts obtained from 102018013348
Trichoderma harzianum for A2
the control of agricultural
pests
Nanosensor Cationic carbon dot, Cationic carbon CN 110724527 [65]
preparation method thereof, quantum dot A
and application thereof in
nano-silver detection
(continued)
53 Bio-nanocomposites for Modern Agricultural Applications 1227

Table 5 (continued)
Nanoproduct
type Patent invention Nano-ingredients Patent number Ref.
A kind of Gold nanograins CN 109387503 [66]
chemiluminescence A
nanosensor and its
application for detecting
remains of pesticide thiram
Field-effect nanosensor for Graphene WO [67]
detecting simple metabolites nanoribbons 2020039377
in living organisms A1

Inventions have been developed in relation to nanopesticides as CR systems of

agrochemicals; among the newest nanopesticides patents, novel pH/light double
responsiveness sodium alginate for CR of nanometer 2,4-dichloro benzene
ethoxyacetic acid pesticide was manufactured [60]. This novel eco-friendly nano-
material provided the following advantages: good water solubility, degradability,
and biocompatibility. Other bio-based nanoformulation was developed with nano-
capsules of PLA containing double-loading pesticide for sustained release for
pesticide [61]. Many nanoformulations could be prepared following the steps of
this invention, and their benefits are high performance of slow release, good effective
utilization rate, crop protection, easy preparation process, and contribution to indus-
trialization. Another eco-friendly nanopesticide, used as CR system, was developed
utilizing lignin as coating matrix [62]. In addition to presenting good photolysis and
oxidation resistance, this nanotechnology-based invention showed good slow-
release effect and has high and controllable drug loading. Novel nanopesticide
composite was manufactured based on phosphate and Zn, Cu, Fe, cobalt (Co),
calcium (Ca), Mg, Mn, and Ag ions NPs [63]. This hybrid nanocomposite can be
synthesized through one-step, present pH stability, low-cost production and can be
loaded with different pesticides. Finally, NPs of titanium oxide and dioxide (TiO,
TiO2), obtained from microorganisms, were manufactured to control agricultural
fungicide, particularly, control of Sclerotinia sclerotiorum [64].
In recent years, nanosensors in agriculture have gained attention, increasing
patent numbers and origin scientific publications. In this sense, nanosensors with
the ability to detect metal or pesticide have been developed to ensure environmental
safety [68]. A nanosensor was prepared using cationic carbon quantum dot to detect
Ag NPs [65]. Through electrostatic action, this cationic carbon quantum dot can
monitor and detect Ag NPs quantitatively or semiquantitatively by changing their
fluorescence characteristics. Cationic carbon quantum dots can combine with nano-
Ag colloids and produce a fluorescence response, depending on the concentration
and the size of nano-Ag. Gold nanograins were used to develop nanosensors with
chemiluminescence property and detect the application of remains of thiram pesti-
cide [66]. By gold chemiluminescence, their nanograins generate optical signaling at
thiram pesticide presence. This invention presents advantages such as high sensibil-
ity and selectivity to monitor pesticide at real time and cheap and simple device.
1228 M. Menossi et al.

Carbon-based nanostructured materials were used to detect and measure metabolites

in living organisms [67]. Due to their electrical properties, graphene is susceptible to
donor analytes and electron receptors, allowing different molecules to be absorbed
on their surface. Graphene-based nanostructured sensors can change their electronic
properties when linked with biomolecules.

Nanotoxicity and Environmental Safety

Nanotechnology-based products and their applicability into agriculture as CR

systems for agrochemicals may represent a pollution source into environment,
food chain, and human health, i.e., produce nanotoxicity [8]. Due to the wide
variety of chemicals used into agriculture field, differences in geographic/meteo-
rological characteristics, and dosage quantity of chemicals employed, analyzing
nanoproducts impact on human health and the environment is a hard work. As a
result, researchers have focused their studies on NPs and their toxicity to protect
the environment and human health from the detrimental impacts of nano-sized
agro-composites. The ecotoxicology studies of nanomaterials are important to
study NPs and their delayed effects of environmental exposure. Unfortunately,
most of the work associated with agrochemicals over time was developed as
laboratory tests over relatively short periods of time. Current data suggests that
the efficacy of agrochemicals in the field may be quite different to that suggested in
laboratory trials, and, therefore, studies considering performances across a range of
scales are considered very valuable [8].
In general, larger particles are less toxic than NPs with identical chemical
composition. A wide variety of physicochemical and surface properties such as
size, area, and reactivity give complexity to nanotoxicity [7]. According to several
authors [68, 69], toxicity of nanoformulations can be affected by different factors,
such as duration of exposure, particle size and aggregation, particle size and shape,
surface area, types of plant species, environmental conditions, and coating.
• Duration of exposure. Major quantity of NPs can penetrate the cell and produce
negative effects depending on the molar concentration and the exposition time.
• Particle size, concentration, and aggregation. There are divergent reports about
concentration of NPs and their toxicity. Aggregation may occur when high
concentrations of NPs are added. For this reason, this cumulative of NPs pro-
motes an increased size, nano-size to micro-size, hindering cell penetration and
losing their toxicity.
• Particle size and shape. Different NPs aspect ratios can produce dissimilar
toxicity levels, i.e., NPs present shape-dependent toxicity.
• Surface area. The toxicity level and surface area are totally related. An increase
of surface area of NPs causes the same effect on toxicity level.
• Types of plant species. Differences in the toxicity of NPs could be attributed to
variability in the size of seeds and the single-leaf and xylem structure of double-
leaf plants.
53 Bio-nanocomposites for Modern Agricultural Applications 1229

• Environmental conditions. Environmental factors such as light irradiation, soil

organic matter, pH, salinity, temperature, coexisting pollutants, and NPs ionic
strength modify nanotoxicity behavior.
• Coating. The surface of any material is another factor which contributes to NPs
toxicity. In general, coatings have benefits since they reduce toxicity, enhance
NPs stabilization, and prevent NPs agglomeration.

In order to analyze the toxicity and to develop environmental risk assessment

studies, nanoformulations must be compared with conventional agrochemicals in
relation to freely dissolved ions [70]. Nanotoxicity can be associated with the
electrostatic interactions with active ingredients nanomaterials and their concentra-
tion in the cytoplasm [54]. Particularly, nanotoxicity and ecotoxicity can be related to
some metal oxides NPs, such as TiO2, ZnO, and SiO2. These molecules are photo-
chemically active, i.e., they produce superoxide radicals when they are exposed to
light and oxygen and cause plant oxidative stress. In this direction, several works
reported that encapsulation of active ingredients decreases their cyto-, gen-, and
ecotoxicity in comparison with conventional agrochemicals [54]. Particularly, in the
study of Guan et al. [71], a novel photodegradable nanoformulation was prepared
based on encapsulation of nano-imidacloprid, as pesticide, with chitosan and sodium
alginate as bio-based coating. They investigated the residues of imidacloprid and
nano-imidacloprid in a soybean field and concluded that the use of biopolymer-
coated nano-imidacloprid formulations reduces deposit in soil during the experi-
ence, in comparison with the suspension concentrate of imidacloprid.
In the review of Iavicoli et al. [8], they exposed that a potential strategy to address
agricultural nanotechnology risk study could be a suitable management plan that
includes hierarchy of controls. In this direction, this control plan should promote
actions in order to eliminate or substitute exposures and, at the same time, apply
administrative controls in all stages of life cycle of nano-based formulations. Under-
standing and knowing the relationships between nanocomposite properties and
biological impacts continues to be a priority to modify some nanomaterial features
and, thus, minimize and/or mitigate their nanotoxicity and harmful environmental
effects [8].
Summarizing, the development and production of nano-agroformulations is hin-
dered by, in first place, high costs and, secondly, lack of nanotoxicity and environ-
mental safety studies. In relation to the last point, environmental risk assessment
study is mandatory before these can be placed in market [36].

Regulation and Legislation

It is imperative to balance the growth of social acceptance of nanotechnology with

regulatory changes, in order to apply nanomaterials in agriculture field and, at same
time, protect the environment and human health from potential risks [8]. In this way,
regulation and legislation not only play a key role for the application of nanotechnology
1230 M. Menossi et al.

but also in the marketing of their products, in addition to serve as source of public
knowledge and awareness [72].
Currently, the major part of nanomaterial regulatory framework is based on size
criteria (<100 nm at one dimension). In general, traditional agrochemical products
include a high quantity of particles with a wide range of size; therefore, they contain
a fraction of nanoscale particles. For this reason, formulators of nanotechnology-
based agrochemicals should question current regulatory framework and their defi-
nitions solely based on size criteria [73].
Unlike conventional materials, nanomaterials deal with different protocols,
including comprehension and control of NPs and their interactions, properties,
functions, and toxicities in order to establish negative consequences, advantages in
their application, and environmental effects. In addition to this, regulation and
legislation should evaluate “case-by-case” or “product-by-product” since each type
of nano-based products has particular properties, hindering this type of products
from reaching the market [72]. Mitter and Hussey [73] focused their work on
different actions that could be taken from national legislations and regulatory
agencies to move forward for nanotechnology applications in agriculture and cate-
gorized them in the following points:

• Build capacity in regulatory agencies. Specific analytical tools and equipment,

qualified staff, and certified methodologies are needed by regulators to identify and
characterize nanomaterials in an accurate way, to implement regulatory arrange-
ments successfully. Additionally, regulators must have financial resources, and
good coordination/communication with other areas in the supply chain is required.
• Use other new or emerging technologies in the design and delivery of regu-
lation. Regulatory agencies could enhance the design and delivery of regulation,
working from opportunities offered by new and emerging technologies. Tools
such as advanced toxicology, novel government surveys and data collection, real-
time monitoring and reporting, etc. are particularly useful for nanotechnology
regulators to address public concerns.
• Intensify efforts toward transnational cooperation. The introduction of nano-
technology into agriculture and food fields, intricately connected, requires com-
munication and cooperation at international level. In this sense, this global
cooperation faces the following challenges: first, to provide clear information
related to nanotechnology and their direct, indirect, and medium-/long-term
impacts in agriculture and food and, second, to homogenize regulatory criteria
to promote nanoproducts commercialization.
• Use all tools in the regulatory toolbox. There exist three different broad
approaches to manage and mitigate nanotechnology risks: “command and con-
trol” laws and regulatory, economic regulatory instruments, and “light-handed”
approaches. These approaches can be potentially applied together in order to
adapt and implement the nanotechnology products.

In general, only few countries do have concrete polices in relation to the promo-
tion of nanotechnology in agriculture, the use of agro-based nanoproducts, and their
53 Bio-nanocomposites for Modern Agricultural Applications 1231

Table 6 Agro-based nanomaterials legislation in different countries

Country Governing body Regulator agency/legislation*
Australia and Australia New Zealand Food Australia New Zealand Food Standards Code
New Zealand Standards (FSANZ)
Brazil Ministry of Agriculture, National Agency of Sanitary Surveillance
Livestock, and Food Supply (ANVISA)
(MAPA)
Canada Department of Agriculture Pest Control Products Act
and Agri-Food Canada Fertilizers Act
(AAFC)
Public Health Agency of
Canada (PHAC)
China Ministry of Agriculture of the Food Safety Law of the People’s Republic of
People’s Republic of China China
EU European Parliament and The making available on the market and use
Council of biocidal products
India Ministry of Health and Insecticides Act
Family Welfare Food Safety and Standards Act 2006
Food Safety and Standards
Authority of India (FSSAI)
Iran Iran Nanotechnology European Food Safety Authority (EFSA)
Initiative Council (INIC) Guidance on risk assessment of the
application of nanoscience and
nanotechnologies in the food and feed chain
Japan Ministry of Agriculture, Agricultural Chemicals Control Act
Forestry and Fisheries
(MAFF)
Malaysia Ministry of Science, The Nanotechnology Industry Development
Technology and Innovation Act
(MOSTI) The Nanotechnology Safety-Related Act
Switzerland Swiss Federal Council Action plan for synthetic nanomaterials
South Korea Ministry of Environment Toxic Chemicals Control Act
Wastes Control Act
Occupational Safety and Health Act
United States United States Environmental Federal Insecticide, Fungicide, and
of America Protection Safety (EPA) Rodenticide Act (FIFRA)
(USA)
*Information is available through Ministry’s website

regulation. Table 6 details some countries and their regulatory frameworks regarding
the use of nanomaterials directly or indirectly in agriculture and associated fields
with the aim of ensuring human and environmental safety [74].
In contrast to other countries, the European Union (EU) and their policy tried to
establish a specific regulation about nanomaterials, in relation to their usage and
applicability into agriculture and food field [7]. Among nano-specific regulations,
the EU incorporated “nanomaterial” as a legal definition, developed specific infor-
mation requirements for nanomaterials risk assessments, and made it mandatory to
inform about the existence of nanomaterials in products [72, 74]. Unlike EU
1232 M. Menossi et al.

nanomaterials legislation, the United States of America (USA) has a less strict
nanoproducts policy that can be summarized in three points: (1) to avoid food
contamination, monitoring of nanomaterials focuses only on the manufacturing
and processing; (2) only science assessments are able to analyze nanomaterials
risks in order to take regulatory actions; and (3) from all nanoproducts registered,
only in particular cases, the submission of safety data is required.

Public Awareness and Acceptance

Another challenge for agro-nanoformulations commercialization is the public awareness

and acceptance. In particular, the combination of nanotechnology, food, and agrochem-
icals can generate a huge concern among public opinions. In spite of the efforts by agro-
companies with based on nanotechnology to generate innovative nano-solutions, the
public acceptance levels about NPs and nanoformulations continue to be low. According
to several authors [8, 73], this could be associated with the following factors:

• Possibility of incorporating NPs from agriculture field to food, whether in the

food itself or taking part in food packing (metal oxides NPs and metal NPs).
In this way, NPs will be direct or indirectly in contact with animals or humans.
Nanomaterials can infiltrate or migrate into human body and cause harmful health
consequences.
• Concerns associated with agrochemicals and their indiscriminate use. Agro-
chemicals in general, pesticides, herbicides, and fertilizers, are a topic of concern,
regardless of whether they are non-nano- or nanoproducts.
• Nanotechnology continues to be a relatively new concept for society. Their
applications to agriculture field are still at the research stage and present difficul-
ties to be commercialized.

Overall, the greatest impediment to adopt nanotechnology by society is the lack

of information and knowledge. Great efforts should be focused to improve commu-
nication, information, and understanding from industrial companies, research cen-
ters, and government entities with the aim of educating all individuals connected
with agriculture and food industry. This information should be addressed to teach
what this innovate technology is, different ways to apply it, and the advantages and
cost associated with it. Thus, it is extraordinarily important to guarantee appropriate
information about nanotechnology, its benefits and risks, in order to protect public
and occupational opinion from general stigmatization of this novel technology [8].

Conclusion

Due to multiple known benefits, nonbiodegradable-based films for agricultural

applications have been used since long time ago. However, the accumulation of
these films has led to negative impact for productivity and environment. For these
53 Bio-nanocomposites for Modern Agricultural Applications 1233

reasons, one of the challenges has been to replace them by those manufactured with
biodegradable materials but also providing the same benefits as conventional plastic
films. The dependence of polymer properties, soil characteristics, and prevailing
environmental conditions are some of the major parameters that must be taken into
account to infer about the functionality and biodegradability of films in the field.
Notably, despite the large number of nonconventional films made from biodegrad-
able material, our knowledge about the real properties of its biodegradability on the
productivity scale is still scarce. Several innovative bio-based nanocomposite films
have been improved and highly modified to fulfill extensive capabilities on the
ground. In turn, the incorporation of nano-reinforcements into bio-based films has
succeeded in modifying the biodegradation times. This could be one of the reasons
why complete and integrated studies on nonconventional bio-based nanocomposite
mulches should be very welcomed.
The indiscriminate use of conventional agrochemicals and their harmful environ-
mental impacts place nanotechnology in a key role to provide efficient and
eco-friendly solutions. In this sense, novel bio-based nanomaterials with a wide
variety of properties and advantages have emerged as vehicle carriers for slow,
controlled, and targeted release of active substances. Unfortunately, despite that
biopolymers have evidenced highly successful results as smart delivery systems,
their potential application as bio-nanocomposite of organic origin is still marginal
from the commercial perspective. Bio-based nanocomposites could revolutionize
modern agriculture and their practices, but to achieve this, research efforts should be
addressed to focus on the understanding of fate, transport, behavior, and degradation
of nanoformulations; the study of NPs and plant-NP interactions; the environmental
exposure; and their short- and long-term effects as well as the scalability of produc-
tion to facilitate the laboratory to field transition. The public acceptance and aware-
ness of these novel nanoproducts must be facilitated with information and
knowledge. Criteria and protocols for their evaluation and regulation need to be
homogenized. Lastly, collaboration among countries must be fostered since it would
allow bringing rapid advances in the commercialization of biocompatible
nanoproducts.
Although chitosan-based nanocomposites are currently at laboratory stage, the
low cost and wide availability of this polysaccharide confer it high potential to
implement it into modern agricultural practices. They can be used as possible
replacement of PE films and as CR systems for pesticides and fertilizers. In order
to successfully apply chitosan into agriculture fields, studies related to life cycle
assessments, different biodegradability assays, as well as its interaction with other
compounds in soil, plants, and environment are still required.

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Consumer Nanoproducts
and Environmental Engineering Science: 54
Critical Overview

Sukanchan Palit and Chaudhery Mustansar Hussain

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1240
The Vision of the Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
Environmental and Energy Sustainability and the Visionary Future . . . . . . . . . . . . . . . . . . . . . . . . . . 1242
What Do You Mean by Consumer Nanoproducts? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1242
The Scientific Doctrine of Nanoscience and Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1243
Recent Scientific Advancements in the Field of Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . 1243
Recent Scientific Advancements in the Field of Environmental Pollution Control . . . . . . . . . . . 1245
The Scientific Sagacity and the Scientific Innovations in the Field of Heavy Metal
Groundwater Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1247
Arsenic Groundwater Contamination, Scientific Vision, and the March of Science . . . . . . . . . 1248
Application of Consumer Nanoproducts in Environmental Pollution Control . . . . . . . . . . . . . . . . 1248
Future Recommendations of This Study and the Future of Nanotechnology . . . . . . . . . . . . . . . . . 1249
Conclusion, Summary, and Scientific Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1249
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1250

Abstract
The world of chemical process engineering, environmental engineering, nano-
technology, and material science is today in the path of newer reinventing and
new scientific ingenuity. Human civilization, science, and technology are in the
similar vein and are in the avenues of newer scientific regeneration. Consumer
nanoproducts are today aligned to the science and engineering of nanotechnol-
ogy. Rapid mass industrialization, burgeoning global population, and degradation

S. Palit
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Post-Office-Bidholi via Premnagar, Dehradun, Uttarakhand, India
e-mail: [email protected]
C. M. Hussain (*)
Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, USA
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1239

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_69
1240 S. Palit and C. M. Hussain

of environment are urging and reiterating science and technology to move

towards newer innovation and newer scientific instinct. In this chapter, the
authors deeply elucidate on the application of consumer nanoproducts in the
field of environmental pollution control. Application of nanotechnology, nano-
materials, and engineered nanomaterials in the vast field of water remediation are
the other hallmarks of the chapter. Heavy metal contamination of groundwater is
an immense environmental engineering and public health engineering globally.
There is an immense need of groundwater and drinking water remediation in the
global scientific landscape. Billions of people around the world are without pure
drinking water and proper sanitation. The United Nations Sustainable Develop-
ment goals thus comes into the picture. There should be a strong envisioning and
reinventing of conventional and nonconventional environmental engineering
tools if civilization wants to move forward. The authors deeply elucidate on
these scientific and engineering techniques. Application of graphenes and other
nanomaterials in the advancement of science and engineering of environmental
protection will eventually widen man and mankind’s vision in the field of
nanotechnology and nanoengineering. Scientific truth and deep scientific perse-
verance in the domain of nanomaterials and its environmental and ecological
health effects will be the other areas of introspection in future. Drinking water
treatment and industrial wastewater treatment in the similar premise and vision
are in the middle of deep scientific comprehension. Provision of basic human
needs such as water, food, habitat, sustainability, education, and energy will go a
long and visionary way in the true realization of United Nations Sustainable
Development Goals. The authors deeply target all these areas with scientific and
engineering vision.

Keywords
Sustainability · Nanotechnology · Environment · Water · Nanoproducts · Vision

Introduction

Human race, science, engineering, and technology are today drastically moving
forward surpassing one visionary boundary over another. Degradation of environ-
ment, loss of agricultural and ecological biodiversity are challenging the human
society today. Thus the need of both conventional and nonconventional environ-
mental engineering tools for the highly betterment of society. Consumer nano-
products in environmental engineering science are marvels of science and
technology today. Consumer nanoproducts involves graphenes, fullerenes, carbon
nanoproducts, etc. A new field of scientific and engineering introspection is the field
of environmental protection and environmental integrity. Thus here nanotechnology
comes into play. This is a scientifically rich and promising area of science and
engineering. In this entire treatise, the authors deeply stress on application of
54 Consumer Nanoproducts and Environmental Engineering Science: Critical. . . 1241

consumer nanoproducts in environmental engineering and water and wastewater

treatment. Desalination and membrane science are today interlinked with each other.
In water scarce regions around the world, desalination is a marvel of science and
engineering. The authors deeply reiterate the need of both membrane science,
desalination, and other nanotechnology-based water treatment tools. A really new
dawn in the field of environmental engineering science will usher in as concerted
efforts by scientific, engineers, researchers, postgraduate students, policy-makers,
and governments around the world are taken with immense scientific will and
determination. The authors also elucidate on the field of nonconventional environ-
mental engineering techniques such as advanced oxidation processes and ozone
oxidation. Human society’s vast and varied scientific and engineering endeavor
will surely be emboldened if research directions in the field of both nanotechnology
and environmental engineering surpasses one visionary frontier over another.
The main crux of this chapter is to elucidate on the greater emancipation of
nanomaterials and engineered nanomaterials applications in diverse areas of science
and technology.

The Vision of the Study

Human scientific vision, deep scientific imagination, and scientific destiny will
utterly propel humankind towards a new scientific order in the field of environ-
mental engineering and nanotechnology. Mankind’s scientific destiny and the
vision of engineering science are the utmost needs of the hour. The main vision of
the study is to elucidate on the interfaces of nanotechnology on environmental
engineering science. Global climate change, rapid loss of ecological biodiversity,
and the convoluted vision of rapid industrialization of human society are chal-
lenging human scientific progress and the paths of human civilization. The aim
and objective of this chapter will widen a scientist’s imagination and profundity if
global research and development initiatives are targeted towards application of
nanotechnology and nanomaterials towards deep scientific understanding in
environmental protection. Here comes the veritable need of application of con-
sumer nanoproducts in environmental engineering science. The fundamentals of
engineering and science of both environmental engineering and chemical process
engineering will surely be enhanced and bolstered if nanomaterials play an
important role in environmental protection, drinking water and industrial
wastewater treatment. Today, membrane science is integrated with the science
of nanotechnology. Nanofiltration is playing a major role in the true realization
of water and wastewater treatment. The other areas of deep scientific and
engineering comprehension are advanced oxidation processes, membrane
separation processes, and desalination. A new scientific era will surely emerge
if science and technology of both environmental engineering and chemical
process engineering marches forward with deep scientific insight and scientific
forbearance.
1242 S. Palit and C. M. Hussain

Environmental and Energy Sustainability and the Visionary

Future

The science and engineering vision of environmental and energy sustainability are today
vast and varied. United Nations Sustainable Development Goals are the needs of
civilization and science today. Today in developing and disadvantaged nations around
the world, human suffering and human hardships are immense due to socioeconomic
conditions. Provision of basic human needs have plunged developing countries around
the world into untold agony and suffering. Unsafe drinking water, no proper sanitation
system, and absolute lack of public health engineering are veritably challenging many
developing nations around the world and thus the need of environmental and energy
sustainability in many developing nations and emerging nations around the world. The
visionary future needs to be reinvented and re-envisaged as regards water and waste-
water treatment around the global. Water sustainability and green sustainability are the
coinwords of tomorrow’s vision and will power. The 17 United Nations Sustainable
Development Goals should be implemented in every nations around the globe in the true
emancipation of global efforts in science and technology. Poverty and hunger will never
be solved in the global scenario if United Nations Sustainable Development Goals are
not implemented in a positive manner and in a war footing. Provision of pure drinking
water is one of the most important goal of United Nations Sustainable Development
Goals. Thus the need of both environmental and energy sustainability with a greater
emancipation of scientific might and scientific determination. The visionary future of
sustainability lies in the hands of scientists, engineers, policy-makers, and governments
around the world. The success of the science of environmental engineering, chemical
process engineering, and nanotechnology will surely be enhanced if there are mergers of
the science of sustainability with these areas of engineering endeavor. In this entire
chapter, the authors stress on the necessities of environmental and energy sustainability
in solving global climate change, global warming, and environmental protection
science. A new dawn in the field of chemical engineering, nanotechnology, and material
science will surely evolve as civilization surpasses one difficult barrier over another.

What Do You Mean by Consumer Nanoproducts?

Nanotechnology essentially means controlling matter on a tiny scale, at the atomic or

molecular level. This truly sounds like a science fiction, but it can be put to some
very ordinary uses in surprisingly everyday products. The scientific vision of
consumer nanoproducts and its application are the needs of the hour. Nanoparticles
are now being used in the manufacture of scratchproof eyeglasses, crack-resistant
paints, anti-graffiti coatings for walls, transparent sunscreens, stain-repellent fabrics,
self-cleaning windows, and ceramic coatings for solar uses. Current consumer
products using nanotechnology are:

1. Sunglasses produced using nanotechnology

2. Nanotechnology in textiles
54 Consumer Nanoproducts and Environmental Engineering Science: Critical. . . 1243

3. Sensors to monitor body functions

4. Wrinkle-resistant nanotechnology fabrics
5. Nanotechnology in sports equipment
6. Nanotechnology involvement in sunscreens

Nanomaterials can be defined as materials possessing, at minimum, one external

dimension measuring 1–100 nm. The definition given by European Commission states
that the particle size of at least half of the particles in the number size distribution must
measure 100 nm or below. In this entire treatise, the authors deeply elucidate on the
application of nanoproducts and nanomaterials in environmental pollution control.
This is a novel area of science, and a deep introspection is the need of the hour.

The Scientific Doctrine of Nanoscience and Nanotechnology

Nanoscience and nanotechnology today stand in the middle of vision, purpose, and
ingenuity. Human society and environmental engineering science are today linked with
each other. The scientific doctrine in the field of nanotechnology will veritably change
the notion and scientific prudence of human scientific progress globally. Application of
nanotechnology in environmental pollution control will surely widen mankind’s scien-
tific thoughts and also futuristic recommendations in years to come. Nanotechnology
should be integrated with diverse areas of water and wastewater treatment and integrated
water resource management. Mankind’s scientific intellect, urge towards research,
scientific perceptions and vision will all lead a long and effective way in overcoming
scientific frontiers and scientific truth. Nanotechnology due to its physical and chemical
properties are needed for application in diverse areas of research endeavor. Drinking
water and industrial wastewater treatment are the scientific vision of tomorrow. The
scientific and knowledge prowess needs to be reorganized as regards environmental
ethics of application of nanotechnology in human society. In the similar premise,
groundwater remediation, environmental sustainability, and environmental management
should be integrated with the vast domain of nanoscience and nanotechnology. Rapid
industrialization is a bane to human scientific progress. In this chapter, the authors
deeply enunciate the today’s needs of nanotechnology, chemical engineering, and
environmental engineering research. Surely a new era in the field of green nanotech-
nology and green chemistry will evolve if global research and development initiatives
opens up new windows of innovation and scientific might.

Recent Scientific Advancements in the Field of Consumer

Nanoproducts

Nanomaterials and engineered nanomaterials have diverse applications in every area

of scientific research pursuit. Environmental pollution control is one such visionary
area. In the similar vein, consumer nanoproducts have immense application in water
1244 S. Palit and C. M. Hussain

and wastewater treatment. The author in this treatise deeply elucidates these scien-
tific and engineering issues.
Kanchi (2014) [1] deeply dealt with cogent insight nanotechnology for water
treatment. Nanotechnology is among the most revolutionary technologies in this
century. The scientific truth and the scientific divination in the field of nanotechnol-
ogy applications need to be discussed with engineering introspection. Human
scientific success and travails in the field of nanotechnology applications in water
treatment need to be explored in minute details. The term nanotechnology describes
a wide range of technologies performed on a nanometer scale with varied and
widespread applications as an enabling technology in various industries [1]. Thus
human vision and human academic rigor are in the process of newer regeneration.
Nanotechnology encompasses the production and application of physical, chemical,
and biological systems at scales ranging from individual atoms or molecules to
around 100 nm as well as the vast integration of the resulting nanostructures into
larger systems. Civilization’s scientific upbringing, upbraiding, and vision in the
field of nanotechnology need to be reformed with the passage of time. The principle
way nanotechnologies might help water scarcity issues is by solving the technical
challenges that removing water contaminants including bacteria, viruses, toxic
metals, pesticides, and salt pose. The author discussed in details the significance of
nanotechnology in wastewater treatment and instrument-based wastewater analysis
with nanomaterials [1]. Nanomaterials may be classified into various groups based
on physical and chemical properties. Nanomaterials include carbon nanoadsorbents,
metal nanoadsorbents, metallic nanoparticles, mixed oxide nanoparticles, polymer
nanoadsorbents, nanofibers, and nanoclays. Chemical engineering, material science,
and nanotechnology are thus integrated with each other. Also instrumentation and
process control are integrated with the science of nanotechnology. Wastewater
treatment techniques are designed to achieve improvements in the quality of indus-
trial wastewater and drinking water [1]. The various treatment processes may reduce
and degrade: (1) suspended solids, (2) biodegradable organics, (3) pathogenic bac-
teria, (4) nitrates and phosphates. Wastewater treatment are classified into
(a) primary, (b) secondary, and (c) tertiary treatment tools. Based on the type of
treatment and stage of purification, nanomaterials are selected for the effective
removal of contaminants from water and industrial wastewater system. The author
deeply discusses these intricate engineering issues. Recently, several advancements
came into light on applications of nanomaterials in analytical chemistry, and these
areas are discussed with scientific insight and precision. Nanotechnology principles
and concepts are economical, reliable, rapid, and extremely durable to treat waste-
waters by eliminating specific types of pollutants from industrial wastewater. A
newer emerging field in the field of process integration and process intensification
applications in water and wastewater treatment will extremely a boon of human
scientific progress [1].
Werkneh et al. (2019) [2] deeply discussed with foresight and scientific vision
applications of nanotechnology and biotechnology for sustainable water and waste-
water treatment. Deep scientific imagination and true scientific profundity are the
pillars of scientific research pursuit globally. In recent times, water pollution and
54 Consumer Nanoproducts and Environmental Engineering Science: Critical. . . 1245

freshwater scarcity have become a serious problem worldwide and need to be

mitigated at the utmost. To reduce these challenges, various treatment techniques
have been seriously adopted. Among these technologies, nanotechnology- and
biotechnology-based techniques are usually applied separately for water in domestic
purposes and wastewater treatment for reuse [2]. Circular economy is a coinword of
environmental management and sustainable resource management today. This chap-
ter focuses on new and emerging nano-and biotechnologies for the effective and
sustainable removal of recalcitrant pollutants during water and industrial wastewater
treatment. Environmental pollution together with global warming are the primary
challenges of twenty-first century. The conventional water treatment technologies
used for the remediation of water pollutants are activated carbon-based adsorption,
membrane filtration, ion-exchange, coagulation and flocculation, reverse osmosis,
flotation and extraction, electrochemical treatment, advanced oxidation processes,
and biosorption [2]. But these techniques have serious drawbacks. For a sustainabil-
ity point of view, the use of microbes and nanomaterials for the removal of
dangerous pollutants has received tremendous attention from the scientific and
engineering community [2]. Nanomaterials are very small in size; approximately
1–100 nm and shows unique characteristics that enables them to be used for a wide
variety of industrial applications. The authors discussed in details nanomaterials for
the disinfection of pathogenic microbes, photocatalytic applications of nano-
materials, applications of nanomaterials as adsorbents, and environmental biotech-
nology perspectives. Bioremediation and biotransformation tools are the other pillars
of this article. Bioreactor configurations in water and wastewater treatment and
toxicological perspectives of nano/biotechnology are also discussed in details.
Nanotechnologies have demonstrated higher removal efficiency of the pollutants
from water and wastewater but their immense toxicity is highly questionable. The
application of chemical agents (nanomaterials) and biocatalysts in an integrated
approach are discussed in details in this chapter [2].
Human civilization’s immense scientific stance and positivity are the extreme needs
of the hour. In this entire article, the author deeply elucidates the scientific intricacies of
conventional and nonconventional environmental engineering techniques. The bar-
riers and difficulties in nanotechnology applications are discussed in details.

Recent Scientific Advancements in the Field of Environmental

Pollution Control

Environmental protection science and industrial pollution control are the needs of
the hour for human scientific progress today. In this section, the authors with deep
scientific and engineering conscience and far-sightedness details some of the recent
advances in pollution control techniques. Advanced oxidation processes and ozone
oxidation of industrial wastewater are changing the vast scientific scenario.
Mishra et al. (2017) [3] deeply discussed with lucidity and insight in the paper
“A Review on Advanced Oxidation Processes for Effective Water Treatment.”
Advanced oxidation processes such as Fenton, ozonation, sonolysis, photocatalysis,
1246 S. Palit and C. M. Hussain

UV photolysis, and wet air oxidation are among the most suitable techniques for
water and wastewater treatment. Science and engineering of advanced oxidation
processes are today crossing vast and versatile scientific frontiers. This article
provides a vivid view of the mechanistic features of various AOPs and its possible
synergization for process enhancement to achieve better efficiency. Today, the
future of environmental protection science depends on both conventional and
nonconventional environmental treatment techniques [3]. The availability of
earth’s freshwater resources has definitely depleted or contaminated due to
improper water management and improper integrated wastewater management.
On the other hand, the demand for safe potable water is increasing day by day due
to the burgeoning population growth. Human civilization and human scientific
and engineering progress today depend on grit, girth, and determination. In this
review paper, the authors deeply elucidate sonolysis, ozonation, aquatic phase
reaction with ozone, ozone/hydrogen peroxide, ozone/catalyst, ultraviolet-based
advanced oxidation processes, and ultraviolet/ozone processes. Fenton’s pro-
cesses are other areas of deep scientific introspection. A new avenue in the field
of pollution control techniques will surely usher in newer scientific imagination
and ingenuity [3].
Gogate et al. (2004) [4] reviewed imperative technologies for wastewater
treatment and oxidation technologies at ambient conditions. In recent years, due
to the presence of recalcitrant molecules, refractory to microorganisms in the
wastewater stream, the conventional biological methods cannot be used for com-
plete treatment of the effluents and thus introduction of newer technologies is of
immense importance [4]. The present work highlights five different oxidation
processes operating at ambient conditions which are cavitation, photocatalytic
oxidation, Fenton’s chemistry, ozonation, use of hydrogen peroxide, and other
chemical oxidation technologies. This work also highlights the basics of the
individual processes including the optimum operating parameters and the reactor
design part. Hybrid technologies are also discussed in minute details. The authors
deeply discussed the areas of cavitation, acoustic cavitation, overview of the work
done in recent years, hydrodynamic cavitation, the area of photocatalysis, and the
vast area of Fenton chemistry. In each of the areas, overview of the earlier work is
enumerated in details [4]. Oxidation systems with direct attack of oxidants are also
a huge pillar of this research endeavor. Use of hydrogen peroxide is another vast
area of scientific introspection. Advanced oxidation processes such as cavitation,
photocatalytic oxidation, and Fenton chemistry work on the principle of generation
of free radicals, whereas ozonation and hydrogen peroxide work on the direct
attack of oxidants on recalcitrant substances. This research is a watershed text in
the field of chemical oxidation technologies and will veritably open new windows
of futuristic innovation [4].
Abdullah et al. (2019) [5] discussed and enumerated with insight recent trends of
heavy metal removal from water and wastewater by membrane technologies. An
extensive literature search revealed the lack of up-to-date and detailed review article
on the use of membrane technologies for heavy metal removal. This review paper
54 Consumer Nanoproducts and Environmental Engineering Science: Critical. . . 1247

elucidates these areas. This article gives a comprehensive review of the performance
and capability of different membrane processes and the advantages and disadvantages
of each techniques [5]. The authors discussed in details the membrane theory of water
pollutant separation, size exclusion, steric hindrance, adsorption, the concept of
Donnan exclusion, microporous membranes, complexation-enhanced ultrafiltration,
micellar-enhanced ultrafiltration, and mixed matrix membranes. The very difficult
concept of separation phenomenon in membranes still needs to be investigated. The
authors deeply elucidate these engineering issues [5]. Nanofiltration membranes,
forward osmosis, and supported liquid membranes are the other areas of deep scientific
comprehension. Over the past few years, extensive efforts have been made to remove
heavy metals in water and wastewater streams. A deep scientific insight will surely
open new areas of innovation and scientific insight in membrane science will usher in
with deep scientific perseverance. The authors widen these scientific and technological
issues [5].
Conventional and nonconventional environmental engineering techniques are
today in the path of scientific glory and immense greatness. Human society immense
water scarcity issues are confronting the path of science and civilization. The authors
deeply reiterate these problems with cogent insight.

The Scientific Sagacity and the Scientific Innovations in the Field

of Heavy Metal Groundwater Remediation

The scientific sagacity and the visionary world of scientific innovations are today in
the path of glory and scientific greatness. The needs of human society and engineer-
ing science are today targeted towards proper implementation of United Nations
Sustainable Development Goals. Physicochemical and biological treatments will
surely usher in a newer era in heavy metal groundwater remediation. Developed
nations around the globe are today far ahead in heavy metal groundwater remedia-
tion, but developing nations are still in deep crisis. The scientific and engineering
status of human civilization are in the midst of immense catastrophe. Human
sufferings, hunger, and elimination of poverty are the prime needs of civilization
and need to be deeply understood with introspection. In the other side of the
visionary coin, environmental engineering and chemical engineering curriculum
needs to be revamped and reorganized as science and engineering move forward.
The scientific destiny and the learning outcomes of research endeavor in environ-
mental engineering science need to be deeply understood with vision, girth, and
perseverance as mankind moves forward. A new global scientific and engineering
order will reform the entire civilization and human scientific progress. Desalination
and membrane science are today the wonders of science and are huge colossus of its
own. Mankind’s perseverance and strong determination will one day open newer
doors of scientific innovation and engineering vision and instinct in decades to come.
The author repeatedly stresses on these water scarcity issues and the role of sustain-
ability [6–8].
1248 S. Palit and C. M. Hussain

Arsenic Groundwater Contamination, Scientific Vision,

and the March of Science

Arsenic and heavy metal groundwater and drinking water contamination are today
plundering the human society mainly developing countries in South Asia.
Bangladesh and the neighboring state of West Bengal, India, today stands in the
middle of deep vision and vast scientific barriers. Environmental ethics and public
health engineering are in the midst of a scientific disaster. Scientific vision and the
march of science are today leading human civilization to a greater glory, might, and
vast scientific understanding. The vision and the march of science need to be
rethought and reinvented as regards application of sustainable development and
environmental management to human progress [9–12]. Diverse areas of science
and engineering such as environmental engineering, chemical engineering, biotech-
nology, medical science, biological engineering, and geological sciences are the
domains which are equally involved with groundwater remediation. Technical
chemistry and technical physics in the vast scientific arena are the immediate
needs of the hour in order to mitigate climate change, water treatment, and applica-
tion of sustainability. Human suffering and human struggle are today immense due to
pure water scarcity in many disadvantaged nations around the world. Billions of
people around the world are without drinking water and proper habitat. A new
scientific and environmental engineering genre will surely usher in newer develop-
ments and new economic growth in countries around the world if environmental
engineering science and water remediation are assumed to be of immense scientific
importance. Due to arsenic poisoning, health effects are tremendous and highly
thought-provoking. The futuristic vision of water and wastewater management will
be targeted towards integration with the science of nanotechnology. Man’s immense
scientific discerning and mankind’s scientific verve in heavy metal remediation will
pave the path towards vision, scientific validation, and purpose.

Application of Consumer Nanoproducts in Environmental

Pollution Control

Application of consumer nanoproducts and the wide domain of nanotechnology in

environmental pollution control are the newer epoch and path-breaking areas of
science and technology. Application of graphene, carbon nanotubes, and fullerenes
along with the application of nanoadsorbents in water and wastewater treatment are
changing the face of vast scientific landscape. The redeeming of environmental
engineering science and its immense scientific profundity will veritably be an immense
need and necessity of the hour. In this entire treatise, the authors deeply pronounce the
veritable need of nanotechnology, nanoadsorbents, nanomaterials, and engineered
nanomaterials in the true advancement of global science and engineering. Scientific
ingenuity, scientific fortitude, and deep scientific progeny will be the pallbearers
towards a newer realm in the field of environmental protection, drinking water and
industrial wastewater treatment. Drinking water issues are destroying the vast domain
of science and engineering globally. Here comes the need of the definition of
54 Consumer Nanoproducts and Environmental Engineering Science: Critical. . . 1249

“sustainability” and the application of United Nations Sustainable Development

Goals. Hunger, poverty, and deprivation are today the main pillars of United Nations
Sustainable Development Goals. Thus in the similar vein, water scarcity and energy
security and integrity will today be aligned with Sustainable Development Goals.
Energy sustainability, green engineering, and green chemistry should be linked with
the science of environmental engineering. In this entire treatise, the authors deeply
reiterate the needs of nanotechnology, conventional and nonconventional environmen-
tal engineering techniques in solving global climate change and global environmental
issues. The author deeply deals with these scientific and engineering issues in the
proper realization of water science and technology [13–19].

Future Recommendations of This Study and the Future

of Nanotechnology

Future of the science of nanotechnology as well as visionary. Application of consumer

nanoproducts in diverse areas of science and technology are the torchbearers and
eye-openers of tomorrow’s scientific research pursuit. Water science and technology
today stands in the visionary path of vision and scientific forbearance. Human
civilization’s immense suffering due to lack of provision of basic needs such as
water, food, habitat, housing, education, and sustainability are endless and needs to
be furbished and rethought as science and engineering move forward. Future recom-
mendations of this well researched treatise are the targets towards waste minimization,
circular economy, sustainable resource management, and environmental management.
The pillars of the science of sustainability are people, planet, and profit. In the similar
vision, sustainable resource management envisions reuse, reduce, and recycle con-
cepts. Application of consumer nanoproducts in environmental protection as well as
other diverse areas of applied sciences will truly reopen human concepts and human
successful endeavor in sustainability and sustainable resource management. Circular
economy is the keyword of today’s scientific vision. Many developed and developing
nations around the world are positively implementing the concept of circular economy.
Integrated waste management and urban air quality management will ultimately open
up newer views in the field of industrial pollution control and water remediation. The
application of United Nations Sustainable Development Goals in poor, disadvantaged,
and developing nations around the world will immensely improve the economic
growth and human scientific advancement of the nation. Thus the immediate need
of water economy, water sustainability, and economic growth will surely open up
newer dimensions in the field of integrated wastewater management and sustainable
resource management.

Conclusion, Summary, and Scientific Perspectives

Human civilization’s immense suffering, hardship, difficulties, and travails are due
to intense environmental pollution which includes industrial pollution. The status of
global environmental engineering research along with chemical engineering
1250 S. Palit and C. M. Hussain

research are highly visionary and bright and at the same time needs to be
reenvisioned with the progress of scientific and academic rigor in the field of
environmental protection integrity. Today, scientific perspectives in environmental
engineering are in a state of immense disaster. The challenges and the barriers are
immense as environmental degradation, depletion of fossil fuel resources, and total
loss of biodiversity are in the process of seriously damaging the scientific truth of
humankind. Scientific and engineering destiny and vision as regards drinking water
heavy metal contamination are in a state of total scientific distress. In such a
situation, a deep introspection and vast comprehension in the field of application
of consumer nanoproducts in environmental protection stand tall among different
environmental engineering techniques. The authors deeply stress on the vast scien-
tific success in application of nanomaterials and engineered nanomaterials in envi-
ronmental pollution control. Man’s vision and mankind’s immense suffering are both
in immense peril and total turmoil. In such a situation, a deep scientific and
engineering introspection will surely lead a long way in opening up the scientific
truth and scientific intricacies of industrial pollution control. A new era in the field of
environmental engineering science will emerge if science and engineering crosses
distant frontiers. Disadvantaged nations around the world are confronting with
unending social and economic crisis and thus the need of United Nations Sustainable
Development Goals and the path towards water sustainability. Mankind’s deep
scientific discernment and scientific and engineering stance will surely be
emboldened if sustainability is implemented at diverse areas of human progress.
The objective of this chapter is to widen man and mankind’s true vision in the field of
nanotechnology and environmental protection science.

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Toxicological Perspectives
and Environmental Risks of Consumer 55
Nanoproducts

Shikha Gulati, Sanjay Kumar, Shradha Jain, Radhika,

Nandini Sharma, and Kanchan Batra

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1254
Consumer Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1255
Classes of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1256
Modes of Entry of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1256
Modes of Entry of Nanoparticles in Soil and Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1256
Modes of Entry of Nanoparticles in Animals and Humans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1257
Effects of NPs on Terrestrial Ecosystem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
Effects of NPs on Crops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
Effects of NPs on Humans and Other Animals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1260
Toxic Effects of NPs on Aquatic Ecosystem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1261
Toxic Effects of NPs on Aquatic Plants and Algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1263
Toxic Effects of NPs on Aquatic Microbes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1263
Toxic Effects of NPs on Aquatic Animals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1264
Toxicity of Some Widely Used Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1264
Toxicological Effects of Gold Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1264
Toxicological Effects of Titanium Dioxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1266
Toxicological Effects of Carbon-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1267
Toxicological Effects of Silver Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1267
Management Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1269
Methods for Risk Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1269
Traditional Risk Assessment (RA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1270
Hazard Assessment for Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1271
Dose Metric . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1271
Target Tissue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1272
Physical Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1272

S. Gulati (*) · S. Kumar

Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, Delhi, India
S. Jain · Radhika · N. Sharma
Department of Biological Sciences, Sri Venkateswara College, University of Delhi, New Delhi,
Delhi, India
K. Batra
Department of Zoology, Kalindi College, University of Delhi, New Delhi, Delhi, India

© Springer Nature Singapore Pte Ltd. 2022 1253

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_102
1254 S. Gulati et al.

Challenges for Nanospecific Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1272

Methods to Decrease Toxicity in Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1273
Conclusion and Future Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1273
Important Websites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1274
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1274

Abstract
Nanoparticles have gained a great deal of public attention due to their diverse
properties and applications in almost all aspects of human life. Their applications
are extremely diverse, ranging from therapeutics and medicine to agriculture. But
the environmental risks of consumer nanoproducts need to be pondered upon
before these applications are put to use.
Because of their smaller dimensions (1 to 100 nm), these nanoparticles have
the property to agglomerate or aggregate and eventually add to particulate matter
in the environment which further causes pollution. The nanoparticles may accu-
mulate within cells and lead to intracellular changes such as disruption of
organelle integrity or gene alternations. The nanoparticles are particularly useful
because of their unique dimensions, but with the decrease in size, there is an
increase in the inherent toxicity of nanoparticles.
The metals silver, gold, aluminium, and copper are inert in their bulk form, but
as the particle size decreases, these metal-based nanoparticles exhibit increased
toxicity. Prolonged exposure to nanoparticles can harm both human health and the
environment. Nanoparticles can cause oxidative stress, DNA damage, and cytokine
inductions among organisms. On waste disposal, due to the degradation of these
particles, heavy metals are released into the soil which contaminates the soil and
water and even gets accumulated in the food chain. This chapter highlights the
various toxicological and environmental risks related to consumer nanoproducts.

Keywords
Toxicity · Consumer nanoproducts · Environment · Pollution · Nanotoxicology ·
Nanoparticles · Risk assessment

Introduction

“Nano” is an umbrella term encompassing several technical and scientific fields,

processes, and properties at the nanoscale or microscale. The International Organi-
zation for Standardization (ISO) defines a nanoparticle as a nano-object with all
three external dimensions in the nanoscale, which is approximately 1 to 100 nm.
Engineered nanoparticles are finding applications in a wide range of areas including
cosmetics, medicine, food and food packaging, bioremediation, paints, coatings,
electronics and fuel catalysts, and water treatment. Although nanosized particles
have always occurred in nature, the recent development and production of consumer
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1255

nanoparticles have raised various environmental concerns due to their toxic and
harmful effects on the environment and living organisms.
We come across a variety of nanotech products in our everyday life such as
hand washes, bandages, drugs, and socks in which nanoparticles of silver are
used. Even in our sunscreen, zinc and titanium nanoparticles are being used as
UV protective elements. Hence, there is a need to check for their toxicity and
other risks. For considering occupational safety and the various health concerns
associated with engineered nanomaterials, the National Institute for Occupational
Safety and Health (NIOSH) established the Nanotechnology Research Centre
(NTRC) in 2004. Once in the environment, these nanoparticles interact with
cellular constituents, and their accumulation leads to severe harmful effects
and risks. Nanoparticles released by industries are not easy to degrade which
leads to contamination of soil and water, and further they enter into different
trophic levels of aquatic and terrestrial ecosystems through biological magnifi-
cation. They also affect human health, and their inhalation leads to lung inflam-
mation, heart problems, and cancer. Nanoparticles being about a billionth of a
meter in size could damage the DNA and lead to mutations, which might result in
cancer.
In this chapter, the most frequently encountered nanomaterials in our daily life,
their numerous entry routes in our body, and their toxicities and environmental risks
are discussed. Environmental impacts, risk assessments, and control and manage-
ment techniques are also discussed. This chapter also gives a brief account of careful
handling and manipulation techniques of engineered nanoparticles and steps that can
be taken towards increasing the validation and standardization of nanoparticle
toxicity tests.

Consumer Nanoproducts

As the name suggests, the nanoproducts which are available to consumers are
simply known as consumer nanoproducts. These are present in hair products, lip
balms, and various other skincare products. Nanoparticles are far more toxic than
larger particles. These can enter the body through inhalation, ingestion, injections,
or dermally. If inhaled, these can be accumulated into the respiratory tract and lead
to lung inflammation. They can move from lungs to other body parts as well
including the brain, which it affects through the olfactory nerve, and the heart.
The toxicity of many nanoparticles (AuNPs, AgNPs, CuONPs, etc.) is discussed in
detail in this chapter. Still, scarce attention is paid to the toxic effects of these
nanoparticles, and their use is continuously increasing. This increasing usage
makes them more toxic as it ensures a high exposure period and hence can show
maximized damage to body organs. Not only humans but plants, other animals, and
even microbes are affected by nanoparticles as discussed further in the chapter.
Hence there is a need for extensive research in this field to minimize the toxico-
logical effects of nanoproducts.
1256 S. Gulati et al.

Classes of Nanoparticles

The NPs can be divided into the following four categories:

1. Carbon-based nanomaterials (single-walled carbon nanotubes)

2. Metal-based nanoparticles (quantum dots, nanogold, nanosilver, etc.)
3. Dendrites (nanosized polymers composed of branched units synthesized for
specific chemical function)
4. Composites (made of two or more substances) [1]

Based on the purpose of production, NPs can be further divided into two groups:

1. Ultrafine nanosized particles – not intentionally produced

2. Engineered nanoparticles – these include the NPs produced in a controlled and
engineered way [2]

There are a variety of classifications of NPs, based on a number of differences and

that is why based on the dimensions which are present in nanoscale, nanoparticles
are broadly classified into three types:

1. One-dimensional nanoparticles: One-dimensional system (thin film or

manufactured surfaces) has been used for decades. Thin films (sizes 1–100 nm)
or monolayer is now commonly used in solar cells offering different technolog-
ical applications, such as chemical and biological sensors, information storage
systems, magneto-optic and optical devices, fibre optic systems, etc.
2. Two-dimensional nanoparticles: They include carbon nanotubes.
3. Three-dimensional nanoparticles: They include dendrimers, quantum dots, and
fullerenes (Carbon 60).

Modes of Entry of Nanoparticles

Nanoparticles can enter the environment as well as the human body through
medicines, cosmetics, fabrics, semiconductors, electronics, paints, etc. [Fig.1].

Modes of Entry of Nanoparticles in Soil and Plants

In soil, nanoparticles can enter via wastewater discharge, nanofertilizers, and nano-
pesticides, as suspended particles and through various other means. No matter by
what means they enter the soil, NPs can concentrate more as compared to air or water
because they are relatively immobile in soil.
The soil has indeed become a reservoir of nanoparticles which have detrimental
effects on the quality of soil and the physiology and growth and metabolism of plants,
animals, insects, and microbes that thrive in the soil. The increasing concentration of
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1257

FABRICS COSMETICS

AUTO- PACKAGING
INDUSTRIES

SEMI-
MEDICINES
CONDUCTORS

PAINTS ENVIRONMENT ELECTRONICS

Fig. 1 Various modes of entry of nanoparticles in the environment

NPs into the soil will eventually have adverse effects on humans as well through
bio-magnification.
NPs can enter the soil by various modes which include the following:

1. Precipitation
2. Sedimentation in the form of dust
3. Aerosols
4. By abscission of leaves
5. Absorption of gaseous compounds by soil
6. Through human activities which include disposal of toxic waste like drugs
7. Use of nanofertilizers and nanopesticides
8. Seepage of industrial wastewater, etc.

Modes of Entry of Nanoparticles in Animals and Humans

Nanoparticles affect the overall functioning of various parts of humans and other
animals which includes the skin, brain, reproduction, sexual and psychological
behaviour, etc.
NPs can enter the body of animals and humans by various routes which include:

1. Ingestion – NPs are used in various food products to enhance taste or texture.
They are also widely used as drug delivery agents and in certain kinds of drugs
itself. After ingestion, there are two pathways by which NPs can be absorbed. The
first is paracellular absorption, which occurs when the nanoparticles are small
enough and can pass through the spaces between the cells. The second is the
1258 S. Gulati et al.

transcellular uptake through enterocytes in the intestine, either passively or by

binding to specific receptors. Hence, depending on the size, dispersibility, and
charge of the nanoparticles, they can diffuse through the gastrointestinal tract and
can reach various organs via the circulatory system. As the size reduces, the
chances of nanoparticles crossing the blood-brain barrier and accumulation in the
brain increase.
2. Absorption through the skin – The skin can absorb both lipophilic and hydro-
philic molecules through different routes. Depending on their physicochemical
properties, nanoparticles can permeate the skin through various pathways from
where they can be transported through the systemic circulation. Mainly NPs can
enter intracellularly through corneocytes, around corneocytes (intracellular
entry), or via dermal structures like hair follicles and sweat glands.
3. Inhalation – In case of accidental inhalation, the nanoparticles in form of
powders, suspensions, or sprays, which are ubiquitously used in textiles, paints,
cosmetics, water disinfectants, and food packaging, pose a high risk.
Depending on the size, different NPs have various uptake possibilities:
– Larger particles, which have a diameter range of 5–30μm, may remain in the
nasopharyngeal region.
– Particles with size of 1–5μm can accumulate in the tracheobronchial region.
– Smaller particles, with a diameter between 0.1 and 1μm, can reach the alveolar
region.
– Alternatively, nanoparticles with dimensions less than 0.5μm have the poten-
tial to cross the thin epithelium and reach the blood capillaries.
In addition to this, nanoparticles found in the nasal cavity can either cross the
respiratory epithelium to reach the underlying blood vessels or they can be
absorbed through the olfactory epithelium and reach the brain.
4. Injection – The exposure to nanoparticles can also be through intravenous or
intramuscular injections which may occur intentionally or almost exclusively in
nanomedicine. The main purposes of their application are for the diagnosis and
therapeutics of various diseases. Some of these NPs used for medical purposes are
capable of crossing even the blood-brain barrier [3].

Effects of NPs on Terrestrial Ecosystem

Effects of NPs on Crops

Nanoparticles can enter the plants via symplastic or apoplastic; movement. These
nanoparticles accumulate in various tissues and organs of the plants, some in the
edible plant parts like grains and fruits, while others in the non-edible parts like
leaves and flowers.
When nanoparticles are in excess, they may harm the plant either by themselves
or by releasing toxic ions during their degradation. In either of the ways, these may
affect the plant by hindering the growth, germination, and root and shoot develop-
ment or by decreasing the biomass. Due to their smaller size, nanoparticles have a
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1259

relatively higher surface area as compared to bulk and, thus, release more reactive
oxygen species (ROS). These ROS increase the oxidative stress in the plants which
further affects physiological functions like water uptake and transport as well as
metabolic activities like photosynthesis.
These nanoparticles can also induce genotoxic effects like a chromosomal aber-
ration, DNA fragmentation, and micronuclei formation in plants. Such effects have
been reported in plant species like Nicotiana tabacum and Allium cepa in response to
TiO2 nanoparticles. It has also been reported that the uptake of CeO2 nanoparticles
can induce enzymatic profile changes in Cucumis sativus and can also lead to
destruction of chloroplast and vascular bundle and affect the absorption of nutrients
like zinc, magnesium, iron, and phosphorus in cotton plants.
The silver nanoparticles which are present in socks and other consumer products
are released into the soil and have bacteriostatic properties. They simply destroy the
useful bacteria that breakdown the organic matter present in the soil and further
diminish the fertility of the soil in the farms.
CuO nanoparticles can also have many adverse effects on plants as shown in
Fig. 2. CuONPs can potentially reduce the uptake of nutrients such as B, Mo, Mn,
Mg, Zn, and Fe in plants. The CuONPs can accumulate and disturb the ultrastructure
of leaves especially in the photosynthetic apparatus by lowering the number of
thylakoids per granum, plastoglobules, and starch content as well as stomatal
aperture.
Copper nanoparticles can have an array of adverse effects on plants. CuNPs
reduced 90% biomass of zucchini (Cucurbita pepo), retarded seedling growth of
mung bean (Phaseolus radiatus), and wheat (Triticum aestivum). Copper NPs have
the potential to change the root morphology of wheat grown in sandy soil. It can also
have adverse effects on the tuber biomass of sweet potato (Ipomoea batatas) [4].
Some other toxic effects of NPs in plants have been listed in Table 1.

DEGRADES PLANT
CHANGES ROOT GROWTH BY LOWERING
MORPHOLOGY OF PLANTS GERMINATION RATE,
DECREASING BIOMASS

EFFECTS OF CuO NPs

ON PLANTS

CHANGES RATE OF REDUCES CHLOROPHYLL

TRANSPIRATION AND AND CAROTENOID
PHOTOSYNTESIS CONTENTS

Fig. 2 Effects of CuO nanoparticles on plants

1260 S. Gulati et al.

Effects of NPs on Humans and Other Animals

Effects of NPs on the Skin

The skin is the largest organ of the body which accounts for more than 10% of body
mass. It plays the vital role of a barrier against the external environment. In addition
to this, it also plays the function of protection and maintaining homeostasis and
metabolism, synthesis, and deposition. There are four pathways of penetration across
the skin that have been identified depending on physicochemical properties of the
compound: intercellular, transcellular, transappendageal, and through hair follicles
and sweat glands.
Polystyrene nanoparticles are experimentally found to preferentially accumulate
in the follicular openings and increase in a time-dependent manner. This follicular
localization is favoured by the smaller-sized particle. Nanoparticles administered in
the dermis tend to migrate to regional lymph nodes, potentially via skin macro-
phages and Langerhans cells, thus, raising potential concern for immunomodulation.
The nanoparticles which are absorbed through the skin can accumulate within the
body and escalate the oxidative stress by increasing the free radicals, which in turn
decreases the antioxidants and leads to the loss of cell viability. Table 2 incorporates
the various toxic effects of nanoparticles on the skin.

Table 1 Physiological and biochemical changes in plants under nanoparticle stress

Size
Plants Nanoparticles (nm) Biochemical activity References
Romaine Nano-CeO2 16.5 Increased oxidative stress, increased [5]
lettuce nitrate-N level in shoots, inhibited
biomass production
Arabidopsis CuONPs 30–50 Root damage, ROS generation in root [6]
tips, and upregulation of oxidative
stress-related genes
Cucumis nCeO2 and >50 Reduced fruit firmness [7]
sativus nCuONPs
Allium cepa ZnONPs <100 Mitotic index decreased with increase [8]
in pycnotic cell TBARS increase
Phaseolus CeO2NPs 10–30 NP application-induced membrane [9]
vulgaris damage

Table 2 Nanoparticle skin absorption studies

Compounds Effects References
Silver Some evidence of penetration through [10]
damaged skin
Four different formulations containing NPs penetrated stratum granulosum via [11]
titanium dioxide intercellular space
Fullerenes Skin flexion increased NPs dermal [12]
Polystyrene NPs accumulated in follicular openings [13]
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1261

Effects of NPs on the Brain

The dimensions of engineered NPs are close to the dimension of cells because of
which their action might interfere with vital cellular processes. Unfortunately, the
physicochemical characteristics that are responsible for the unique properties of
nanoparticles can also lead to their toxicity, resulting in various health concerns.
Thus, understanding the toxicological perspective of engineered NPs is quite impor-
tant before implementing their various applications. After crossing the blood-brain
barrier, nanoparticles tend to accumulate in specific brain regions, where they can
access the neural cells, including neurons, astrocytes, and microglia.
The neurotoxic effect can either cause the direct alteration of the structure and activity
of the neural system, or it can lead to subsequent effects due to glial activations and glial-
neuronal interactions. The manifestation of neurotoxicity can be through various mech-
anisms, including oxidative stress, resulting in cell apoptosis and autophagy, immune
responses, and neuroinflammation, which will affect the functions of blood-brain barrier.
The field that includes the study of the functional and structural changes of the
nervous system that are caused by exposure to foreign substances is neurotoxicology.
It involves observing various adverse effects on the structure, function, or chemistry of
the central nervous system due to foreign substances.
As shown in Fig. 3, nanoparticles have adverse effects on the brain such as
oxidative stress, neuroinflammation, cognitive dysfunction, etc.
Nanoparticles lead to extensive production of reactive oxygen species which
further induce the release of cytokines, thus causing neuroinflammation. This finally,
through the apoptotic mechanism, causes neural death. Many of the commonly used
nanoparticles, including titanium dioxide nanoparticles, iron oxide nanoparticles,
silver nanoparticles, gold nanoparticles, silica nanoparticles, and carbon-based nano-
particles, have been reported as potential neurotoxic materials. The administration of
titanium oxide nanoparticles by any of the means can lead to their absorption and
translocation to the brain where they may interfere with the functioning of the brain.
Further, they may cross the placental barrier and can accumulate in the foetal brain
leading to impaired brain development.
Exposure to silica nanoparticles can result in neurotoxic effects, whereas very low
levels increase the oxidative stress leading to an alteration in the microglial function,
with a highly negative impact on the striatum and dopaminergic neurons. The
intranasal administration of silica nanoparticles can further cause cognitive dysfunc-
tion and impairment.
The neurotoxic effects of some common NPs have been given in Table 3.

Toxic Effects of NPs on Aquatic Ecosystem

The aquatic ecosystem has become a major sufferer of environmental pollution due to
the extensive use and disposal of engineered nanoparticles in daily life. These nano-
particles reach the aquatic ecosystem through the release of industrial waste, sewage
sludge, and from surface run-off of soil as well. These pathways are of great importance
1262 S. Gulati et al.

OXIDATIVE STRESS

NEUROINFLAMMATION

SYNAPTIC PLASTICITY

NEUROTOXICITY OF
NANOPARTICLES ASTROGLIOSIS

COGNITIVE
DYSFUNCTION

MICROGLIAL
FUNCTION
ALTERATIONS

DISRUPTED SIGNALING
PATHWAYS

Fig. 3 Neurotoxic effects of nanoparticles

Table 3 Neurotoxic effects of different nanoparticles

Nanoparticle Neurotoxic effects References
Titanium oxide Impairments in foetal brain development, dysregulated [2]
nanoparticles neurotransmitters, and disturbed distribution of trace,
(TiO2NPs) synthetic plasticity and disrupted signalling pathway
Silver nanoparticles Oxidative stress, mitochondrial damage, and increase in [2]
(AgNPs) the calcium levels related to transporter/receptor
mechanism
Gold nanoparticles Astrogliosis, increased seizure activity and cognition [2]
(AuNPs) defects such as attention, memory, and judgment
impairments
Carbon-based Inflammatory response by activating microglial cells [2]
nanoparticles
Iron oxide Affected synaptic transmissions and nerve conduction, [2]
nanoparticle neural inflammation, apoptosis, induced neural
antioxidant responses, and immune cell infiltration

and need to be addressed for sustainable implications of nanoparticles (NPs) without

environmental liabilities. Their dissolution in water may release potentially toxic com-
ponents into the environment. This may be taken up by the aquatic plants, vertebrates,
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1263

and microbes through paths like gills, olfactory organs, and body wall or even through
direct ingestion and may lead to significant damage. The toxicity of NPs to algae
involves adsorption to cell surface and disruption of membrane transport. Higher
organisms can directly ingest these toxic NPs and lead to their accumulation in food
chains. In fishes, the liver is a probable target of NPs and can be significantly damaged.
The transformation of engineered nanoparticles (ENPs) from their original state has
greatly controlled their toxicity in the environment, thus making it critical to understand
their toxicity. The examples of some widely used ENPs are silver nanoparticles
(AgNPs), graphene oxide nanoparticles (GONPs), zinc oxide nanoparticles (ZnONPs),
titanium dioxide nanoparticles (TiO2NPs), and single-walled or multiwalled carbon
nanotubes (CNTs). In water, these nanoparticles can aggregate with other nanoparticles,
called homo-aggregation or with natural minerals and organic colloids known as hetero-
aggregation, which change their fate and toxicity to the environment. Even during the
wastewater treatment process, NPs from urban, medical, and industrial sources may
undergo significant transformations. For example, sulphidation of silver nanoparticles in
water treatment system converts most of NPs to silver sulphide (Ag2S).
In addition to metallic ENPs, carbon-based materials including carbon nanotubes,
graphene oxides are found to be very toxic to the aquatic ecosystem as they can lead
to damage at the cellular level. Hence there is an urgent need to research and
investigate further on the toxicity of nanoparticles to tackle their effects.

Toxic Effects of NPs on Aquatic Plants and Algae

Plants are a very essential component of any ecosystem but are always at the receiving
end of environmental pollution and toxicity created by humans. The lower plants like
algae are much more susceptible to the harmful effects of NPs due to their simple
configuration and low defences. For example, according to research, in Spirodela
polyrhiza, TiO2NPs enter the tissues and significantly reduce the growth parameters,
photosynthetic pigment, and activity of certain oxidative stress-controlling enzymes.
Also after exposure for 72 hours, algal growth due to ROS (reactive oxygen species)
production resulted in antioxidant enzyme imbalance and growth retardation. Some
studies show that GONPs, owing to physical penetration by algal cells, induce
oxidative stress that leads to membrane damage and nutrient depletion in freshwater
algae. These findings are laboratory-based investigations and may differ under a
natural environment, and it recapitulates the fact that higher research and dedication
are needed in this field due its wide ranging and critical impact.

Toxic Effects of NPs on Aquatic Microbes

Engineered nanoproducts also have toxic effects on aquatic microbes. According to

some studies, the toxic effect of ENPs is significantly reduced by doping. TiO2NPs
cause much toxicity to the microbes, but when doped (sulphur-doped S-TiO2NPs
and also nitrogen-fluorine co-doped N-F-TiO2NPs), the toxicity is reduced. The
toxicity of TiO2NPs is mainly dependent on the generation of ROS.
1264 S. Gulati et al.

The TiO2NPs also affect E. coli and cause depolarization and membrane loss
integrity leading to the release of K+ and Mg2+, when exposed to dark conditions.
The increased permeability induces osmotic pressure and hence nanoproducts enter
the cell. This increases oxidative stress which plays a role in induced toxicity and the
regulation of certain genes or proteins. Similarly engineered silver nanoparticles also
have toxic effect on E. coli. This is due to the pH-dependent dissolution of Ag+ ions.
These ions bind with the cell cytoplasm and further, because of oxidative stress, lead
to cell death (apoptosis). Similarly, according to a research, ZnONPs also have toxic
effect on aquatic microbes as they exert a form of dose-dependent impairment on the
bacterial cells.

Toxic Effects of NPs on Aquatic Animals

Nanoproducts have harmful effects on aquatic animals as well, such as fishes,

crustaceans, and some other animals. Recent works are focused on bony fishes,
especially the zebrafish Danio rerio, or the trout Oncorhynchus mykiss, Daphnia,
and other crustaceans like sea urchin, molluscs, etc.
According to research, when salmons were exposed to AgNPs, disruption of
osmoregulation was seen at medium concentrations, and necrosis of gill lamellae
and consequently death was observed in higher concentrations. The effect of AgNPs
was also studied on common carp (Cyprinus carpio). But interestingly, the observed
silver accumulation was not in the form of nanoparticles but as an ionic form in all
tissues. Similarly, a study showed that AgNPs were more toxic than their equivalent
AgNO3 when exposed to sea urchin Paracentrotus lividus and caused development
defects, asymmetrical body, and changes in swimming patterns.
A research investigated the toxicity of ZnONPs on zebrafish embryos and found
that nano-ZnO at a concentration of 50 and 100 mg/L killed the zebrafish embryos
and at a concentration of 1–25 mg/L retarded the embryo hatching and caused body
malformation.
Crustaceans such as Daphnia magna or Thamnocephalus platyurus have been
also used to test the harmful effects of NPs. In Daphnia magna, AgNO3 affects
reproduction and growth. Moreover, AgNPs linked to proteins were at least ten times
stronger in effect for Daphnia magna and Thamnocephalus platyurus, as compared
to AgNO3. But the techniques are not that efficient and advanced yet; hence there is a
need for further research in this field [14].

Toxicity of Some Widely Used Nanoparticles

Toxicological Effects of Gold Nanoparticles

Gold nanoparticles are extensively used in biomedicines, but their safety is an

equally important concern. Though in low concentrations, gold nanoparticles do
not show significant toxicity but in higher concentrations, the gold nanoparticles can
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1265

SIZE

IN VIVO HAZARD
MODIFICATIO POTENTIAL SURFACE
NS IN OF GOLD COATING
BIOLOGICAL NANOPARTIC
SYSTEM LES

SURFACE
VOLUME
RATIO

Fig. 4 Toxic effects of gold nanoparticles

lead to a decrease in body weight, red blood cells, and haematocrit (the haematocrit
is the proportion, by volume, of the blood that consists of red blood cells).
As shown in Fig. 4, depending upon size, surface coating, surface-volume ratio,
and modification in biological systems, gold nanoparticles can show toxic effects on
an organism’s body.

Gold Nanoparticles Inside the Cells

Once ingested or absorbed through the skin, AuNPs usually end up in the liver and
spleen where they are internalized by macrophages and sequestered inside lyso-
somes. Gold is a noble metal, i.e. it is chemically inert. Hence there would be
negligible physiological interactions. This suggests the fact that gold nanoparticles
would remain unharmed within these cellular structures for indefinite periods.

Mode of Exposure to Gold Nanoparticles

Exposure to gold nanoparticles can be from AuNP composite bound to consumer
products in markets and homes. From here, they can also be accumulated in the soil,
water bodies, and environment. Absorption through skin contact and inhalation can
also act as potential entry routes. Also, their bioaccumulation in the environment can
fix them into the food chain which further will affect both biotic and abiotic
components of the environment.
1266 S. Gulati et al.

Factors Affecting Toxicity of Gold Nanoparticles

Studies have shown that toxicity is highly dependent on the physicochemical
properties of nanoparticles. These are:

1. Size
2. Shape
3. Aggregation state
4. Dose
5. Route of administration
6. Surface charge
7. Surface chemistry
8. Interaction with physiological media and biological fluids

Reducing Toxicity of Gold Nanoparticles

It is very important to maintain the stability of AuNPs by preventing their aggre-
gation. Studies show that phosphotyrosine significantly stabilizes AuNPs, and the
resulting modified AuNPs show a high level of stability in various solutions.
Similarly, modifying the gold surface with polyethylene glycol modified with
thiol groups confirmed high efficiency in the protection of AuNPs, in particular
against the release of gold. Since blood is a strongly ionic medium, it can reduce
the quality of nanosystems, and aggregation can take place within a few minutes of
exposure. Therefore, modified nanoparticles must be used to reduce their harmful
effects [15].

Toxicological Effects of Titanium Dioxide Nanoparticles

Titanium dioxide in bulk (aggregated) form is not classified as a harmful/lethal

substance; however, nanoparticles may cause adverse health effects. For instance,
exposure by inhalation can cause pulmonary inflammation leading to fibrosis and
proliferative changes in the lungs.
Titanium nanoparticles can enter the human body through inhalation, ingestion,
skin uptake (through skin lesions), and medical injections and are distributed to
different body organs through the circulatory system. Moreover, TiO2 in water is
sometimes taken up by fishes, and it makes its way through the food chain by
bioaccumulation, ultimately being consumed by humans. After entering the body,
TiO2NPs interact with cytoplasmic proteome and induce oxidative stress. These also
enter the cells and damage the DNA.
Toxicity can be summarized as follows.

Neurotoxicity
TiO2NPs enter the brain through the olfactory bulb and reside in the hippocampus
region. Brain tissues are the most harmed due to oxidative stress-induced damage.
Due to TiO2 exposure, the integrity of the blood-brain barrier (BBB) is affected
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1267

because of the persistence of NPs in endothelial cells, resulting in breakdown of

BBB. According to a study, the TiO2NPs cause injury to neurons via ROS genera-
tion. They also sometimes are known to damage the organelle, mitochondria.

Aquatic Nanotoxicity
There is very limited data on toxicity of TiO2NPs in aquatic organisms. There is a
higher concentration of these NPs in sewage due to their excessive use in industries.
The nanoparticles intermingle with various toxins and make agglomerates and
further cause damage to aquatic organisms. According to a study, the exposure of
adult zebra fish to 1.0 mg/L TiO2 for 21 days has been shown to decrease the number
of viable embryos and inhibit the growth of goldfish (Carassius auratus). TiO2 also
has adverse impacts on the survival, growth, and reproduction of D. magna. There-
fore, the study of harmful effects of various NPs on aquatic species is necessary to
assess their potential environmentally hazardous effects.

Respiratory Toxicity
The exposures of these nanoparticles through inhalation affect the respiratory tract,
leading to risk of lung cancer, fibrosis, etc. These particles enter the lungs through
inhalation and then reach every part of body by circulatory system. They may also be
accumulated in the lungs and cause bleeding and inflammation. The ultrafine TiO2
also leads to pulmonary fibrosis, lung tumour, and genotoxicity. They may also
cause damage to liver cells and induce hepatotoxicity [16, 17].

Toxicological Effects of Carbon-Based Nanoparticles

Carbon nanomaterials are one of the most important and novel class of multi-
functional nanoparticles because of their array of applications. The carbon NPs
have been divided into a variety of classes: single-walled carbon nanohorn, fuller-
ene, carbon black nanoparticle, multiwalled carbon nanotubes, and nanographite
(Fig. 5) [18, 19].
The various toxicity effects of carbon nanoparticles on the animals are listed in
the Table 4.

Toxicological Effects of Silver Nanoparticles

Silver nanoparticles (AgNPs) are one of the most available and commercially
distributed nanomaterials around the world. To understand how human health can
be affected by AgNPs, quantification and detection of AgNPs in biological systems
have to be conducted in different models. It seems that respiratory and gastrointes-
tinal systems, as well as the skin, are the major routes of AgNP penetration into the
body. Research on AgNP toxicity is mostly conducted in vitro, and the availability of
human and animal data is relatively limited.
1268 S. Gulati et al.

Nanographite

Multiwalled Single-walled
Carbon Carbon
Nanotube Nanotube

CARBON
NANOMATERIAL

Single-
Carbon
walled
Black
Carbon
Nanoparticle
Nanohorn
Fullerene

Fig. 5 Classification of carbon nanoparticles

Table 4 Toxic effects of carbon nanoparticles on animals

Mode of toxicity Type of CNTs Effects References
Pulmonary Fullerene soot Changes in pulmonary function [20]
toxicity MWCNTs Multifocal granulomas; mild [21]
SWCNTs fibrosis in alveolar septa, [20]
Ultrafine carbon black inflammatory reactions of
terminal/respiratory bronchioles
Transient inflammation, cell
injury effects, multifocal
granulomas
Granulomas in centrilobular
location
Hispopathologic MWCNTs with varying Increased inflammation [22]
analysis lengths (825 nm)
Pulmonary SWCNTs suspended in Oxidative stress, disturbed [23]
cytotoxicity. pulmonic F108 intracellular equilibrium
(a non-ionic surfactant)

Silver nanoparticles are absorbed through lungs by inhalation and reach every
organ (liver, brain, spleen, kidney, etc.) with the help of circulatory system. They can
also cause skin irritation and mild eye irritation. Studies show that silver nano-
particles can induce genotoxicity to mammalian cells and also effect on reproduction
of animals. They may also cause impairment of short-term and working memory on
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1269

accumulation. They can also reach plant cell through sludge and surface water and
can break the cell wall causing damage to vacuoles of root cells.
Researchers have found that silver nanoparticles have a toxic effect on cells, and
they suppress cellular growth and multiplication and also cause cell death in higher
concentration levels. They also cause damage to the DNA [24, 25].

Antimicrobial Uses and Antimicrobial Resistances of Silver

Nanoparticles
AgNPs are widely used as potent antimicrobial agents in cosmetic and hygienic
products. Alternatively, silver-containing nanomaterials can be employed to elimi-
nate microorganisms. Even though the NPs are used in high frequency, the mecha-
nism of action of nanoparticles (NPs) as bactericides in aqueous solutions and solid
media is not very well known and applicable. The antibacterial activity shown by
silver is caused by the release of silver cations from the nanostructured surface of
AgNPs. The high reactivity of NPs is considered to be due to the large surface
compared to the low volume ratio.

Management Strategies

While the technologies for developing nanomaterials and incorporating them into
products are advancing rapidly worldwide, understanding of the harmful effects of
nanomaterials has proceeded at a much slower pace. Hence there is a need to
evaluate safety and risk management associated with nano-synthesized foods,
drugs, medical devices, and cosmetics. Therefore, the criteria and methods to assess
the harmful effects of nanomaterials have been taken into consideration by many
international organizations such as the World Health Organization, the Organization
for Economic and Commercial Development, and the European Commission, with
the objective of developing risk assessment principles for safety management of
nanoproducts and also identifying areas of research to strengthen risk assessment
(Fig. 6).

Methods for Risk Management

1. Collecting Information to Estimate Exposure

Knowing about the exposure is crucial for assessing the risks of nanoproducts. This
study in the initial phase focuses on collecting information from available resources
and can be obtained more easily and quickly on the Internet than from traditional
sources. This data can be used to determine the consumer’s exposure of nano-
products because there is no evidence that can tell whether a targeted product is
actually a nanoproduct or whether there is an inventory of nanoproducts at the
governmental level as of now.
1270 S. Gulati et al.

RISK
PRE-
ASSESSMENT

RISK RISK
MANAGEMENT MONITORING CONCERN
AND DECISION SAFETY
MAKING ASSESSMENT

RISK
EVALUATION

Fig. 6 Monitoring strategies for risk management of nanoparticles

2. Developing Nano Risk Assessment Principles

The data or information obtained must be accurate to develop principles for

assessment of risks posed by nanoproducts.

Traditional Risk Assessment (RA)

It is a well-established and formalized process to estimate the risk of nanoproducts to

an organism or a system. The process consists of four steps:

1. Hazard identification
2. Hazard characterization including dose-response assessment
3. Exposure assessment
4. Risk characterization

RA process primarily deals with the effects of noxious agents to human health
and the probability of a harmful effect to individuals or populations. In general, this
traditional approach is a chemical-by-chemical approach which focuses on a single
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1271

substance, a single media and a single toxic endpoint. When, for instance, the risk of
adverse effects at exposures below a safe level is expected to be practically zero, the
margin of exposure can be calculated to describe the quotient between expected
exposure and the no adverse effect level. Thus, the output of RA is based on quotient
produced on an absolute basis.
The quantities of a chemical, the properties like bioaccumulation, and the
effects like chronic toxicity, sensitization, reproductive toxicity, etc. activate
the chemical RA process. This process has been the standard approach for esti-
mating the potential health and environmental risks of nanomaterials in recent
years.
RA process uses weight of evidence approach, i.e. based on the totality of data
in a holistic manner. The data provided by toxicology is ranked and scored by
considering the varying quality, relevance, and consistency. RA of nanoproducts
falls under the specific regulations for foods, cosmetics, or biocidal products.
For example, the nanospecific RA for foods follows a relative approach using
the data of a relevant comparator. With the aid of attributes like solubility,
persistence, and translocation, it is decided whether a specific toxicological assess-
ment is required.

Hazard Assessment for Nanoproducts

Hazard assessment is the same for nanomaterials as for other substances. Though
current toxicology tests are considered applicable to hazard evaluation of nano-
materials, there is a need to consider substance-specific factors in evaluating toxicity.
Some factors that may influence the toxicity of nanomaterials include the following:

1. Dose metric
2. Target tissue
3. Physical-chemical properties

These interrelated factors can affect the uptake as well as interaction of these
nanomaterials with biological systems and thus may influence the internal dose
and response. Hence there is a need for enhancement in current assessment
processes.

Dose Metric

The mass dose metric is the exposure concentration in air or lung dose. It has been
shown as a poor predictor of toxicity for nanoparticles which are not readily soluble
as compared to larger particles. Since the airborne particle size determines the
deposition efficiency in the respiratory tract, agglomeration can also influence
the dose.
1272 S. Gulati et al.

Target Tissue

Knowing about the target organ or tissue is crucial for efficiency of assessment. For
respirable nanoparticles, the respiratory tract, and specifically the alveolar region, is
the main target. The deposition efficiency of these inhaled particles generally
increases with decrease in particle size into the nanoscale range. Some types of
nanoparticles have been shown to enter the lung’s interstitial space as well. Nano-
particles may also translocate from the lungs to other organs and may gain access to
cells and their organelles that are not readily accessible to larger particles and may
even interact with DNA. Hence the effects of nanoparticles on other organs also need
to be evaluated.

Physical Chemical Properties

Particle size, shape, surface area, surface reactivity, solubility, etc. can all influence
the particle toxicity. These properties may also influence the internal dose and
toxicity at the initial target tissue and distal organs. Because of the greater surface
area per unit mass, nanoparticles can be more soluble than larger particles. Dissolu-
tion rate may also be affected by agglomeration.

Challenges for Nanospecific Risk Assessment

There are serious concerns that traditional risk assessment methods may not be sufficient
to evaluate all the dimensions of risk which may arise not only from its material toxicity
but also from its interactions with biological and environmental systems. The main
limitations of that procedure for the RA of nanomaterials are as follows:

1. The identification and definition of nanomaterials poses a challenge for framing a

“substance class” with a high diversity.
2. Equipment and methods for classification detection are often not appropriate and
need further enhancement. It is also a challenge to detect nanomaterials in
biological matrices.
3. There is still no agreement about a concept for the dose or concentration of
nanomaterials in assessment methods.
4. High-quality exposure data is also largely missing.
5. There is a need of standardized toxicological methods along with controls.
Factors such as surface functionalization, dispersing behaviour in biological
media, or the use of solvents in case of non-dispersing nanoparticles in aqueous
media are not addressed sufficiently in many studies.
6. In eco-toxicological studies, it is difficult to simulate real environmental
scenarios.
7. The most important challenge is the fact that nanomaterials share no common
characteristics with anything other than the nanoscale size.
55 Toxicological Perspectives and Environmental Risks of Consumer Nanoproducts 1273

Hence, RA requires the full dataset for each and every kind of nanomaterial which
makes this process highly tedious, and consequently its progress is extremely slow.
Therefore, a complete RA is only possible for a small selection of high-abundance
nanomaterials.

Methods to Decrease Toxicity in Plants

Studies have shown that toxicity of NPs such as silver and sulphide in water can be
lowered by the presence of organic compounds such as perfluorocarboxylic acid,
fulvic acid, and humic acid. These organic compounds decrease the toxicity of NPs
by diminishing the dissolution and aggregation of NPs and generation of reactive
oxygen species (ROS).
The cytotoxicity of carbon nanotubes to microbes can also be diminished by the
presence of natural suspended solids in aquatic systems due to hetero-aggregation
between suspended solids and carbon nanotubes. This limits the accessibility of the
carbon nanotubes to microbes. The microbes also show physiological responses,
such as alteration of fatty acid composition of membranes, in the presence of carbon
nanotubes to enhance the adaptability towards NPs.

Conclusion and Future Outlook

We encounter nanoparticles in our day-to-day life as they have vast applications in

biomedicines and prove to be very useful for cancer treatment as well. Their
increasing use however leads us to check for their toxicological effects to humans,
plants, animals, and even environment. Recent studies have shown that these
nanoparticles are more harmful than larger particles. Inhalation of these nano-
particles can cause lung inflammation and an aggregation can cause lung cancer.
From lungs, these can also travel to other body parts via circulatory system. They
also have adverse effects on plants as well, and they spread around to contaminate
the soil and affect microbes. Their presence in the soil can lead to accumulation in
various levels of food chain (bio-magnification) and ultimately affect the humans in
a negative way.
Hence there is a need of proper research into the field of toxicity of nano-
particles so that it can be reduced to a value which is as small as possible. Also
governmental authorities should encourage active research and experimentation in
this field. Some future steps should be taken such as providing information about
monitoring of ENPs and dose-response parameters reflecting environmental expo-
sure conditions. These can help to tackle down their negative effects, and the same
can then be reduced or eliminated. Also, we lack proper technologies for the
purpose, and hence there is an increasing need for development of efficient
technologies so as to study the toxicology of NPs of all kinds in a systematic and
efficient manner, which can consequently prove to be the solution to this imperti-
nent problem.
1274 S. Gulati et al.

Important Websites

1. https://www.google.com/url?sa¼t&source¼web&rct¼j&url¼https://www.
hindawi.com/journals/jnt/2015/861092/&ved¼2ahUKEwjFk-bLmMbvAh
XaxzgGHW3cB5UQFjADegQIChAC&usg¼AOvVaw1si4aNNf1gAT0Wsh6
E7S4w
2. https://ec.europa.eu/health/scientific_committees/opinions_layman/en/nanotechnol
ogies/l-2/6-health-effects-nanoparticles.htm#:~:text¼Materials%20which%20by%
20themselves%20are,lung%20inflammation%20and%20heart%20problems.
3. https://www.azonano.com/article.aspx?ArticleID¼5113
4. https://www.imedpub.com/scholarly/nanoparticle-toxicity-journals-articles-
ppts-list.php
5. https://www.journals.elsevier.com/nano-today/news/safe-by-design-nano
particles-show-reduced-toxicity
6. https://www.horiba.com/en_en/science-in-action/should-you-be-worried-about-
nanotoxicity/#:~:text¼Nanotoxicity%2C%20or%20nanotoxicology%20refers
%20to,Environmental%20Science%20at%20Baylor%20University.
7. http://www.bionanoteam.com/environmental-nanotoxicology/
8. https://www.alliedacademies.org/articles/environmental-nanotoxicology-
where-are-we-now-8881.html
9. https://www.ohsrep.org.au/nanotechnology_-_a_new_hazard
10. https://www.news-medical.net/life-sciences/Safety-of-Nanoparticles.aspx

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Consumer Nanoproducts Based on Polymer
Nanocomposites for Food Packaging 56
Caren Rosales, Magdalena L. Iglesias-Montes, and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1278
Polymers Matrices for Packaging Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1279
Conventional Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1279
Biodegradable Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1281
Nanotechnology in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1284
Nanoclay or Nano-Layered Silicate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1285
Cellulose Nanocrystals or Nanofibrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1286
Chitin Nanowhiskers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1287
Lignin Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1287
Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1288
Inorganic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1288
Applications of Nano-Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
Improved Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1289
Active Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1292
Intelligent/Smart Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1293
Safety Issues of Nanoparticles in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1294
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1295
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1295

C. Rosales
Grupo de Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones de Ciencia y
Tecnología de Materiales (INTEMA), CONICET-UNMdP, Mar del Plata, Argentina
M. L. Iglesias-Montes
Grupo de Ecomateriales, Instituto de Investigaciones de Ciencia y Tecnología de Materiales
(INTEMA), CONICET-UNMdP, Mar del Plata, Argentina
V. A. Alvarez (*)
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina
e-mail: alvarezvera@fi.mdp.edu.ar

© Springer Nature Singapore Pte Ltd. 2022 1277

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_103
1278 C. Rosales et al.

Abstract
Polymers are one of the main materials of choice in food packaging applications
because of their performance, cost effectiveness, and durability. Recently,
changes in consumer concerns about sustainability and environmental impact
have led to the development of new bio-based polymer materials as alternatives to
the traditional plastics derived from non-renewable sources. A food container has
to be lightweight to reduce the cost of production, but at the same time must be
resistant to withstand handling, transport and storage. It also must protect the food
from external agents such as microorganisms, and should avoid the migration of
small particles for maintaining quality foodstuff. In this sense, biodegradable
polymers are very promising for food packaging applications but present lower
mechanical and barrier properties. Scientific community applied innovative strat-
egies in order to enhance the performance of biobased polymers for food pack-
aging applications. Several reports have demonstrated that nanotechnology could
improve physical properties of biopolymers, including mechanical strength,
thermal stability, and high barrier properties against the permeability of oxygen,
carbon dioxide, flavor compounds, and water vapor. Additionally, several nano-
structures present antimicrobial and antibacterial properties useful to provide
active nanotechnology-based consumer products for food packaging systems.
This chapter focuses on how the use of nanotechnology can improve the
performance of environmentally friendly packaging materials and promote the
use of biopolymers in food packaging applications.

Keywords
Nanocomposite · biopolymer · food · packaging · nanoproducts

Introduction

Food packaging is crucial for current life because it guards food products. It is
important for transportation for long distances maintaining the quality but also
providing information to the consumers [1]. Processed food production would be
unthinkable without packaging, and thus packaging has become one of the largest
industries in the world, representing around 2% of gross national product (GNP) in
developed countries. Plastics used in packaging represents more than 40% and they
are mainly used for food packaging in the form of films, sheets, bottles, cups, tubs,
and trays. It is mainly because they are flexible and compatible with foodstuffs [2].
The use of plastic materials has been continuously made for packaging because
their versatility, processing properties and suitable cost/performance ratio. Tradition-
ally, non-degradable petroleum based polymers have used for food packaging
[3]. Those synthetic polymers are non-degradable and produce waste accumulation.
On the other hand, biopolymers are capable to be decomposed into natural chemical
compounds [3]. Nevertheless, these polymers generally displayed lower properties
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1279

than those required for packaging applications and, so that, some strategies have to
be implemented in order to improve their performances.
Nanotechnology is an innovative and emerging technique of the twenty-first
century that has driven to radical changes and rapid advances in many fields,
including the food and packaging industry. This enabling technology involves the
creation, characterization, and manipulation of material structures or devices that
have at least one characteristic dimension measured in the nanometer scale [4].
In this chapter the use of nanotechnology on the improvement of the performance
of environmentally friendly packaging materials are explored trying to promote the
use of biopolymers in food packaging applications.

Polymers Matrices for Packaging Applications

Conventional Plastics

Since the mid-twentieth century, petrochemical polymers have been widely used.
Over the past few decades, there has been a dramatic increase in polymers
consumption as a consequence of the constant growth in world population.
These materials are deeply ingrained in our consumer society, where it would be
difficult to imagine a life without them. Plastics have found applications as diverse
as household appliances, construction, medicine, electronics and components
automotive and aerospace. But the wide use is in packaging, especially packaging
food. More than 40% of the plastics are used for packaging and are used in
different forms (Fig. 1) [2].
The continuous growth in the use of plastic materials for containers and packag-
ing compared to paper and cardboard, glass, metal, are motivated by their versatility
and good processing property for several applications and their convenient cost/
performance ratio. In particular, the versatility in use of these materials is that very
suitable packaging can be achieved to the specific needs of each product to be
preserved. This advantage comes from the characteristics such as the diversity of
materials and compositions, molding ability and shaped in an unlimited variety of
shapes and sizes. They are not only light with low density, but also can be adapted to
specific optical properties in terms of transparency and brightness according to the
product requirements. Petrochemical based plastics are used in food packaging due
to their valuable property to not allow moisture to penetrate the plastic films and
provide favorable atmosphere to microorganisms growth [2].
The most commonly petroleum polymers used in the field of food packaging are
polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polysty-
rene (PS), polyvinyl chloride (PVC), and nylon. Polyolefins are the polymers of
major industrial importance, because PE and PP are two of the most widely used
plastics. PE is defined by the degree and regularity of branching. There are three
main classes of PE, low-density polyethylene (LDPE), linear low-density polyeth-
ylene (LLDPE) and high-density polyethylene (HDPE) [5].
1280 C. Rosales et al.

Fig. 1 Different uses of plastics in packaging

HDPE is characterized by low branching and therefore high densities. On the other
hand, LDPE exhibits a high level of branches, both long and short at irregular
intervals, whereas LLDPE is a linear polymer, with a large number of short branches.
Their properties, and therefore, the uses of PE depend significantly on variables such
as the length and type of branching, crystal structure, molecular weight and melting
point [6]. HDPE can be used in numerous applications, both indoor and outdoor due to
its notable properties, such as impact strength and elevated toughness, low thermal
conductivity, effective barrier to humidity, resistance to abrasion, inertness to several
chemicals [7]. LDPE is the most used plastic for food packaging application because
of its chemical inertness, despite the fact that it shows a moderate humidity barrier, low
gas barrier against oxygen and carbon dioxide and exhibits low tensile strength [8].
Although it can be produced such as bottles, glasses, tubes and trays, the most used
format for LDPE is in the form of sheets or films. Polyolefins are significantly sensitive
to UV irradiation in presence of oxygen as a consequence of impurities in their
structure due to polymerization mechanism. Polyolefins degrades via a free radical
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1281

mechanism initiated by UV light, occurring both chain scission and cross-linking of

the polymer matrix that causes reorientation of the macromolecular chains, this makes
a decrease in mechanical properties and the global behavior of the material and
eventually leads to significant failures [7].
PET is the most favorable packaging material for water and soft drink bottles. The
reason for this application is the favorable material properties of PET, especially its
toughness and its very low weight of the bottles compared to glass bottles of the
same volume. PET also has high transparency and excellent barrier properties
against oxygen and moisture, as well as very good barrier properties against flavors
and contaminants. The remarkable oxygen barrier properties of PET are considerably
higher than those of LDPE, which as was already commented, is widely used in the
manufacture of films. Oxygen permeability is an extremely important property
necessary to control the food environment under controlled conditions [5].
Though the traditional polymers derived from non-renewable resources are
widely used for packaging food today, they generate complex environmental prob-
lems after being used. The worldwide plastic waste generation is overwhelming.
Over the last decades is raising a strong environmental concern due to consequences
caused by the persistent plastic packaging and the final disposal of waste. The
current inefficient management (open burning, disposal in garbage dumps) are
generating problems such as the contamination of groundwater tables due to the
leakage of leached liquids, risky situations such as fires or accumulations of gases,
and proliferation of infectious vectors transmitting diseases, producing health prob-
lems and damage to the environment [9]. In addition, there is an increasing concern
about exhausting natural resources and the need for biodegradable packaging mate-
rials from renewable sources (biopolymers) as an alternative to non-renewable
plastic packaging materials, especially for use in single use and short-term packaging
and disposable applications such as disposable cutlery, disposable plate, cups and
utensils, diapers, trash bags, beverage containers, agricultural mulching films, fast
food containers, medical devices, etc.
In order to recover traditional plastics, recycling them is a common practice [5].
Plastic recycling consists of basic stages of collecting, cleaning, sorting, and reduc-
ing size. However, this activity shows two negative eco-balances due to the need to
separate the broad variety of polymers and to wash them because they coming from
food packaging sector [5].

Biodegradable Polymers

The above-mentioned synthetic polymers extensively used for packaging applica-

tions are non-degradable and hence not friendly to the environment. Biopolymers,
on the other hand, are polymers that have the capability to be decomposed into
natural chemical compounds – such as carbon dioxide, methane, water, inorganic
compounds, or biomass – by the enzymatic action of microorganisms [3, 10, 11].
Under suitable conditions of temperature, humidity, and oxygen availability, bio-
degradation leads to the fragmentation and/or disintegration of the biopolymers
1282 C. Rosales et al.

Fig. 2 Classification of biodegradable polymers

without toxic or environmentally harmful residues and they turn into humus or
compost [11, 12].
Depending on their origins, biodegradable polymers may be classified as being
bio-based or petrochemical-based [13]. The former can be roughly divided into three
main categories according to the origin of the bio-based raw materials and their
manufacturing processes: natural biopolymers extracted directly from nature (such
as polysaccharides like starches, ligno-cellulosic products, chitosan, chitin, etc., and
animal or plant origin proteins and lipids like casein, whey, soy protein, corn zein,
wheat gluten, etc.); synthetic biopolymers from bio-derived monomers (for example
poly(lactic acid) (PLA)); and biopolymers produced by microbial fermentation like
microbial polyesters (such as poly(hydroxyalkanoates) (PHAs) including poly
(3-hydroxybutyrate) (PHB), poly(3- hydroxybutyrate-co-3-hydroxyvalerate)
(PHBV), etc.) [11, 14, 15]. (Fig. 2).
The biodegradability of polymers is directly related to their chemical structure,
and not to the origin of their raw materials. That is why there are biodegradable
polymers obtained from fossil resources, such as poly(ε-caprolactone) (PCL), poly-
butylene adipate-co-terephthalate (PBAT), polyvinyl alcohol (PVA), polyvinyl acid
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1283

(PVOH), or polyglycolic acid (PGA) [12, 16, 17]. Nevertheless, comparatively, they
constitute a small group within the classification of bioplastics.
The bio-based polymers most commonly exploited for the production of food
packaging are PLA, PHB, chitosan, and thermoplastic starch (TPS) [11, 15].
PLA has become a growing alternative to PS and PET polymers in food packag-
ing. PLA is a highly transparent semi-crystalline polyester which has high mechan-
ical performance and easy processability, and is accepted by US Food and Drug
Administration (FDA) as a food contact matter, non-toxic or carcinogenetic
[18, 19]. It is mainly commercialized as rigid single-use packages in the form of
trays, cups, plates and bottles [20]. However, although presenting successful prop-
erties like being biodegradable, it presents also the drawbacks of being highly
fragile, having limited thermal stability and insufficient gas barrier properties,
besides being relatively expensive when compared to its durable competitors (e.g.,
polyolefins) [18].
PHB is a highly crystalline thermoplastic polyester with similar properties to
those of synthetic PP and presents a very low water vapor permeability similar to that
of synthetic LDPE [10, 18]. Despite presenting some drawbacks like a narrow
processing window or its inherent brittleness [18, 21], PHB polymers are already
being used in small disposable products and in packaging materials [20].
Chitosan is a natural biological polymer formed by deacetylation of chitin, which
is the second most abundant polysaccharide in nature after cellulose. Because of its
numerous important advantages, including nontoxicity, biodegradability, and bio-
compatibility, and antibacterial properties, chitosan presents potential application in
diverse fields like biomedical applications, wastewater purification and food preser-
vation, among others. Its well-known good film-forming ability turns it into a fine
alternative as biodegradable food packaging material, especially as edible film and
coating. However, chitosan membrane exhibits poor mechanical properties and high
hydrophilic character which limit its further development, especially for applications
in the presence of water and humid environments [22].
Starch, a polymeric carbohydrate, is one of the most widely studied biodegrad-
able polymer as a choice material for food packaging applications due to its
environmental compatibility, wide availability, edibility, suitability for food contact,
and low cost [14]. The gelatinization of starch with plasticizers such as glycerol,
water, citric acid, sorbitol and other sugars, give rise to thermoplastic starch (TPS)
which enhance the starch processability. However, TPS has low mechanical prop-
erties and a high water-transfer rate, which act as limitations for its use in commercial
food packaging applications [21].
Petrochemical-based biopolymers are also extensively investigated, and are
mainly used in combination with starch [23] or other biopolymers to increase their
mechanical resistance and reduce their cost [16]. PCL is one of the earliest, com-
mercially available, synthetic polymers characterized by high elongation at break
and low modulus, and is easily processed using conventional melt blending tech-
nologies [20]. Because of its low melting point and viscosity, in conventional
applications it must be blended with other polymers, like chitosan or PLA [10].
1284 C. Rosales et al.

Despite the fact that the research and development of biopolymeric materials has
had a remarkable growth in the packaging sector, the general use of biopolymers has
been limited compared to the conventional non-biodegradable materials due to their
several disadvantages such as poor mechanical and barrier properties. Biopolymers
are generally brittle and have low heat distortion temperature and low resistance to
prolonged process operations. Moreover, plasticizers are frequently incorporated
into biopolymeric packaging materials intended for flexible film applications to
overcome brittleness and to improve their processability, consequently increasing
the polymer chains mobility and the gas and vapor permeability through the material.
Therefore, many investigations have been directed towards improving the perfor-
mance of biopolymers for food packaging applications. In this sense, the usage of
nanotechnology to produce nanocomposites has been recognized to be a promising
route to enhance those properties; this is by adding reinforcing nano-sized com-
pounds or fillers to the polymer matrices and form nanocomposites [21].

Nanotechnology in Food Packaging

Nano-science provides the means to develop novel nanocomposite materials with

increase performance and capabilities, aiming to improve not only the principal
features of traditional polymers and biopolymers packaging systems, but also the
cost-price efficiency. In the food packaging sector, nanotechnology applications may
include enhancement and extension of shelf-life of food due to packaging with
higher barrier, mechanical and thermal properties, improvement of food safety, the
release of preservatives to extend the life of the food in the package, and even the
pathogen detection in food systems to alert consumers that food is contaminated or
spoiled [4].
A polymeric nanocomposite is a multiphase material characterized by a contin-
uous phase called matrix and the homogeneous dispersion of a discontinuous nano-
dimensional phase with at least one of the dimensions in the range from 1 to 100 nm.
Usually, the content of nanoparticles may not exceed the 10% of the final weight of
the material [4].
Nanoparticles can be classified according to their aspect ratio and geometry, into
spherical or isodimensional nanoparticles with 3 nanometric dimensions (e.g., sil-
ica), acicular nanoparticles with 2 nanometric dimensions like whiskers or nanotubes
(e.g., carbon nanotubes or cellulose nanocrystals), and, finally, layered nanoparticles
with 1 nanometric dimension (e.g., nanoclays). Nanofillers can also be classified
according to their origin (natural, semi-synthetic or synthetic). In this sense, for the
production of nanocomposites of biopolymeric matrices, natural nanoparticles are
preferred, thus obtaining a bio-nanocomposite and preserving the biobased and
biodegradable characteristics in the final material. The development of
bio-nanocomposite materials for food packaging can not only protect efficiently
shelf-life of foodstuff, but also reduce environmental problems associated with the
use of plastic [4]. Several nanomaterilas are being used as nanofillers of biodegrad-
able polymers (Fig. 3).
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1285

Fig. 3 Materials used as nanofiller of biodegradable polymers

Nanoclay or Nano-Layered Silicate

Nanoclay and silicates are the most commonly studied nanoparticles. They exist in a
wide range of sizes and structures, but the layered silicates are the most frequently
employed for the production of nanocomposites, i.e., in the form of sheets with a
thickness of 1 nm and several microns long. Their low cost respect to most other
nanoparticles, simple processability, full-scale production and availability from
natural sources make them potential nanofillers for several applications in the
nanotechnology field [5, 24, 25]. The nano-clay most often used is montmorillonite
(i.e., bentonite), a natural clay commonly obtained from volcanic ashes [26].
Different types of composites can be obtained when layered nanoclays and
polymer chains are combined, namely, a typical phase separate microcomposite
and two kinds of nanocomposites (intercalated or exfoliated). On the one hand, the
intercalated nanocomposite is an alternating structure made up of polymer/clay
layers separated by a few nanometers. On the other hand, the exfoliated nano-
composite consists of individual nm-thick silicate layers randomly dispersed in a
polymer matrix, which is obtained by an extensive polymer penetration and layer
delamination [27].
1286 C. Rosales et al.

The preparation of polymer/clay nanocomposites are usually intended to enhance

both mechanical and barrier properties with respect to their pure polymer counter-
parts [5, 24]. Nanoclay layers represent impermeable barriers against gases and
vapors, due to the fact that the pathway that these molecules must take through the
material becomes longer and more tortuous Moreover, the integration of nano-clays
in biopolymers may enhance their mechanical strength properties [28].

Cellulose Nanocrystals or Nanofibrils

Cellulose is the most abundant biomolecule that exists on the planet and the most
important among the structural polysaccharides. It is the main component of the
cell wall of plants. Cellulose is a polymer made with repeated glucose units bonded
together by beta-linkages and is assembled into long microfilaments a few nano-
meters in diameter. Moreover, each single microfilament is built of nanofibrils with
a high length-diameter aspect ratio. The common magnitude of its diameter is 10 to
20 nanometers and its length is 10 times its diameter. Nanocellulose is composed
mostly by ordered crystallites linked together by amorphous regions. The crystal-
line zone is constituted by a packed cellulose chain connected by hydrogen
bonds [5].
Two types of nanostructure can be obtained from nanocellulose, cellulose nano-
fibrils (CNFs) and cellulose nanocrystals (CNCs) [29]. CNCs are nanostructures
development from monocrystalline domains together with some amorphous parts
with diameter about 4–25 nm and 100–1000 nm in length, obtained by acid
hydrolysis which removes amorphous cellulose regions leaving the crystalline
regions [29, 30]. CNFs are built from crystalline and amorphous parts and have
10–100 m in diameter. The isolation methods are by high-pressure homogenization,
grinding and refining [5, 29].
However, the interfacial adhesion between cellulose and hydrophobic polymer
matrices is weak, making it difficult to favor a good dispersion of nanoparticles as a
consequence of the high polarity of cellulose surface [30]. Despite this problem,
homogeneous dispersion can be reached modifying the nanocrystal surfaces.
Among the different strategies that can be applied, there is a reaction on the
hydroxyl groups (─OH) on the CNCs to change superficial cellulose crystals
[31]. Also, to improve interaction, it is possible to modify CNC surfaces by
grafting polymer chains onto CNCs’ surfaces. In order to achieve this task, the
OH group of the CNC is used as the initiator to the grafting process, to increase
polymer-nanofiller interaction [32].
Finally, nanocellulose has certain characteristics that make it a useful reinforce-
ment, low density, cost-effective, availability in nature, biodegradable under certain
conditions and low toxicity. Although in this case attention must be paid to the
decontamination during the extraction process if fibers will be used for food appli-
cations [5]. As a reinforcement material, nanocellulose provides really good char-
acteristics because it improves strength and modulus of pure polymers, but also
improves thermal stability and barrier properties [24].
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1287

Chitin Nanowhiskers

Chitin is the second most abundant polysaccharide in nature after cellulose, with
global reserves of 100 billion tons. It is widely distributed in the animal and plant
kingdom, constituting an important renewable resource. It is part of the skeletal
structure of many invertebrates such as arthropods, mollusks, and annelids. It is also
found in the structural tissue of some species of fungi and algae [33].
Chitin is a linear and semi-crystalline polymer composed of N-acetylglucosamine
via a β (1–4) linkage. Chitin chains are organized in a parallel structure, linked
together through hydrogen bonds. There is a great structural similarity between
chitin and cellulose; the difference between them is that the hydroxyl group of the
C2 carbon in cellulose is replaced by an acetamide group in chitin. Both biopolymers
play similar roles, since both acts as structural support and defense materials in living
organisms [33]. However, contrary to cellulose, chitin presents antimicrobial activity
thanks to its chemical structure [34].
Commercial chitin is extracted from crustacean waste from the fishing industry
and extraction techniques are mainly based on chemical hydrolysis processes of the
protein and the elimination of inorganic material [33]. Despite its great abundance,
chitin was for a long time an underutilized resource and treated as waste, compared
to other polysaccharides (including chitosan which is a derivative of chitin), due to
its insoluble character. It is a fairly recent trend that chitin has gained importance as a
promising source of new materials, especially as a nanostructured material in the
form of chitin nanocrystals (CHNC) and/or nanowhiskers (CHW) [34]. Paillet and
Dusfrene [35] published in 2001 one of the first scientific papers in which it was
registered the use of chitin whiskers as new ecological nano-reinforcements in
thermoplastic nanocomposites.
Different techniques have been reported to prepare nano-sized chitin particles
with different morphologies [36], although the most widely used is acid hydrolysis,
generally with hydrochloric acid. The important advantages of nanochitin such as
non-toxicity, low density, insolubility in water, biodegradability, biocompatibility,
easy surface modification, and especially its antimicrobial activity, favor its use in
wide areas such as nanocomposites, food packaging, cosmetics, drug administration,
and tissue engineering. However, the exploitation of chitin nanoparticles as a route to
manufacture nanocomposites with high performance and specific functionalities, in
particular because of their attractive antifungal and barrier properties, remains a vast
and largely unexplored field of research [34].

Lignin Nanoparticles

Lignin is the second most naturally abundant biomass after polysaccharides and it
makes up 15 to 35% of the cell walls of terrestrial plants. Lignin, like chitin, has
always been treated as a waste material from other processes and only used in
low-value applications. However, its antioxidant and antimicrobial properties
along with its UV absorbent capacities, have led to this polymer receiving increasing
1288 C. Rosales et al.

attention from researchers in recent years. Other interesting properties of lignin are
high abundance in nature, ecofriendliness, biocompatibility, ability to biodegrade,
low weight, and reinforcing capability [37].
The polymeric reinforcing effect of lignin strongly depends on the size of the
particles and the interfacial bonding with the matrix. Moreover, it has been studied
that its antioxidant effect increases, decreasing the fillers dimensions [38].
Thus, considerable efforts in the research field are now being made to develop
novel polymer composites through nano-sized lignin as innovative and alternative
packaging materials [39].
Lignin nanoparticles (LNPs) are mainly synthesized by hydrochloric acidolysis
and some studies suggest that individual lignin molecules are compact particles with
elongated non-spherical shapes (ellipsoids, cylinders or discs) and that self-assemble
into larger fractal objects in solutions [39].

Carbon Nanotubes

Carbon nanotubes (CNT) are an industrial nanomaterial formed from a honeycomb

shape layer rolled up as a cylinder. These tubes have diameters in the order of
nanometers and thickness of an atom when present a single wall (SWNT), or can
exhibit several aspect ratios when it comprises multiwalled nanotubes (MWNT), i.e.,
several concentric tubes [40].
CNTs possess extremely high Young’s modulus of 1TPa and tensile strength of
200GPa [24]. For this reason, the addition of CNTs produces a clear improvement in
mechanical properties of pure polymers, as a consequence of its high specific surface
area, as long as the difficulties of interfacial adhesion are overcome. Several
improvements in mechanical properties have been reported for many polymers
matrices like PP, PE, PVC, by incorporating carbon nanotubes [41].

Inorganic Nanoparticles

Inorganic nanoparticles as reinforcing fillers is referenced to metals and metal oxides

such as silver, zinc, titanium oxide, zinc oxide, silicon oxide. Unlike organic fillers,
which are usually more unstable at high temperatures, inorganic materials can
withstand more severe processing conditions. Generally, those particles are added
at 0.1 and 5 wt. % and the usually ways to incorporate them into a matrix polymer are
in melt, in situ polymerization or by solvent.
Nanoparticles produces an improvement in mechanical properties as a conse-
quence of its high surface-to-volume ratio owing nanoscale characteristic, i.e., it is
due to an increase in the number of atoms available to bind to the surrounding
material. However, it should be noted that agglomeration can be a negative conse-
quence, especially when incorporated in non-polar polymers.
The most important characteristic of inorganic nanoparticles is their antimicrobial
activity. They can migrate and react with pathogens present in food [42–44].
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1289

Applications of Nano-Packaging

A variety of food packaging nanomaterials with different functionalities can be

produced by introducing diverse nanoparticles as additives. The applications of the
nanopackaging can be divided into three main categories [45, 46]:

• Improved packaging: The incorporation of nanofillers is intended to improve the

physical properties of the polymer matrix such as the gas, vapor and/or flavor
barrier properties, mechanical strength or flexibility, and temperature and humid-
ity stability.
• Active packaging: The main function of nano-based active packaging is to
offer better protection and durability to the foodstuff by the direct interaction
of the active nanoparticles and the food product or the environment. Addi-
tives can be incorporated directly into the major packaging material or be
introduced into separate sachets as a food contact material. Antimicrobial and
antioxidant activities are among the most sought-after properties in this type
of packaging.
• Intelligent packaging: It involves the use of nanotechnology to monitor changes
in biochemical or microbial components in the food or in the environment
surrounding the product. For example, it is possible to detect a specific pathogen
in the food, or specific gas forming inside the packaging.

Improved Packaging

From the beginning, the research of the biopolymers as alternative materials for food
packaging applications has been directed towards the improvement of their inherent
physical properties, which are generally of a much lower performance than the ones
of conventional plastics. Nanotechnology has proved to be a good and relatively
simple strategy capable of enhancing biopolymers’ features and, consequently,
expanding the shelf life of food. In this way, the incorporation of nanoparticles
into the polymers’ matrices intended to tune mainly their barrier and mechanical
characteristics, gave rise to the so-called improved packaging.
Better barrier properties against gases, volatiles and flavor, moisture stability by
retarding moisture loss, temperature stability, ultraviolet blocking properties, and
enhanced product appearance, are among the properties to be improved in this type
of packaging [47]. Also, package materials need to be resistant during food produc-
tion and filling, capable of withstanding the intended conditions of use and keep
integrity to physical and mechanical forces. Then, the presence of nanostructures
with high aspect ratio might improve mechanical properties of pure polymer, as a
consequence of possessing more specific surface area and transferring the applied
load to the nano-reinforced material [48].
Polymeric packages, unlike other packaging materials, are permeable at different
extents to small molecules or low molecular weight compounds such as gases, water
vapor, aromas or flavor [49]. The permeation process consists in the movement and
1290 C. Rosales et al.

penetration of a permeate (fluid) through a semi-permeable barrier like the wall of a

film or package, and it is directly related to the concentration gradient of permeate on
both wall surfaces. There are several other factors that affect the polymeric packag-
ing permeability behavior, such as polymer degree crystallinity, amorphous phase
free volume, orientation, cohesive and adhesive forces [5]. The study of barrier
behavior has become especially important for polymers used in the food packaging
field because contamination from the external environment could reduce the shelf
life of food by producing foodstuff degradation reactions promoted by oxygen or
microbial growth [49].
Nowadays, the degree of permeability required for packing materials is usually
achieved by using multilayer films, which can impart good barrier properties.
However, the use of adhesives in multilayer film complicates the recycling process
of these materials. Therefore, the use of nano-reinforced biopolymers as monolayer
packaging is one of the preferred alternatives in food packaging due to their
degradable properties [50]. The role of nanoparticles on the polymers’ permeation
and diffusion processes, mainly moisture, oxygen, and carbon dioxide permeation, is
strongly dependent on their dispersion within the polymer matrix and the interfacial
area developed. A uniform dispersion and a higher aspect ratio of the nano-
reinforcements create a tortuous path through the nanocomposite, increasing the
route length for molecules and decreasing the material permeability [50, 51].
Several approaches onto the improvement of biopolymers’ barrier properties for
sustainable food packaging applications include the utilization of nanomaterials such
as nanoclay, cellulosic nanostructures, chitin nanowhiskers, and carbon nanotubes.
The addition of nanoclays into a biopolymer matrix imparts excellent barrier
properties, especially in those exfoliated nanocomposites in which the clay layers are
dispersed at a nanometric level creating a tortuous pathway for the molecular
diffusion. Martino et al. [52] developed bio-nanocomposites based on plasticized
PLA reinforced with 2.1 wt. % of an organo-modified montmorillonite (O-MMT)
and detected a reduction in around 25% in oxygen transmission rate (OTR) without
detriment the tensile properties. An even greater improvement in the barrier proper-
ties of PLA was achieved by Zenkiewicz and co-authors [53]. The incorporation of
5 wt. % of MMT into the PLA matrix caused a decrease in the water vapor
permeability of the film by more than 40%, and a reduction in about 40% and
80% in oxygen and carbon dioxide rate transmission, respectively. Further, incor-
porating clays may improve the mechanical strength and thermal resistance of
biopolymers. Campos-Requena et al. [54] synthesized active films of thermoplastic
starch with essential oils and reinforced them with MMT nanoparticles. The mechan-
ical, thermal, and release properties of films were enhanced with respect to the neat
starch. They found a significant ninefold increase in the Young’s modulus and
twofold increase in the decomposition temperature.
Regarding improvement in the biopolymers’ mechanical properties, carbon nano-
tubes (CNTs) are another nanofiller that have attracted much attention. Improvements
in tensile and impact properties have been reported for starch-based nanocomposites
containing less than 1 wt. % of multi-walled CNTs (MWCNT). Famá et al. [55] have
registered increments in stiffness and ultimate tensile strength of 70% and 35%,
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1291

respectively. They also observed an enhancement of up to 100% in biaxial impact

parameters. In a similar way, Sun et al. [56] reinforced chitosan with MWCNT
obtaining a significant increase in the mechanical strength and elongation by up to
about 40% compared with pure chitosan films. However, the use of CNTs as nano-
fillers for food packaging biomaterials has been somewhat limited by challenges in
processing and dispersion, their high cost and nondegradable nature [14, 22].
Cellulose-based nano-reinforcements have been reported to increase mechanical
properties, improve the thermal stability, and diminish the permeability of biomaterials
[20]. Numerous researchers have incorporated films made from PLA with cellulose
nanoparticles by various approaches to obtain multifunctional properties. Sanchez-
Garcia and Lagaron [57] were able to reduce by up to 90% and 82% the oxygen and
water vapor permeability, respectively, of the PLA matrix by preparing nanocomposites
using CNC contents of 1 to 5 wt. %. They registered the optimum barrier enhancement
for nanocomposites containing a CNC load of 3 wt. %. Fortunati et al. [58] studied the
role of surfactant-modified cellulose nanocrystals (s-CNC) on the barrier and migration
behavior of PLA. The interfacial adhesion between highly polar cellulose and a
hydrophobic polymer matrix is weak, then the presence of hydrophobic surfactant on
the nanocrystal surface may favor the dispersion of s-CNC. The PLA nanocomposite
films containing 1 wt. % of s-CNC presented reductions of 34% in WVP and 26% in
OTR, and migration levels below the overall migration limits required by the European
normative for food packaging materials in both non-polar and polar simulants. The
effects of s-CNC were also investigated in a PLA-PBS polymer blend [59]. Significant
reductions in oxygen and vapor permeability were observed for the formulations
containing 1 and 3 wt. % of modified CNC. PHB based films were also incorporated
with CNCs. Seoane et al. [60] prepared nanocomposites with enhanced mechanical and
water-barrier properties compared to neat PHB, and Dhar et al. [61] observed a drastic
reduction in OTR values.
Chitin nanoparticles have also been used as nanoreinforcement of various bio-
polymers such as starch [34], chitosan [22], PVA [62] and PLA [63]. The tensile
strength of chitosan membrane has been enhanced in about 2.8-fold with respect to
neat chitosan after the introduction of 3 wt. % of rod-like chitin nanowhiskers [22].
Moreover, the water resistance of the nanocomposite membrane was improved and
the film presented effective inhibitory effect on S. aureus, E. coli, and
C. michiganense, respectively, which indicates that it is a promising material for
packaging. Salaberria et al. [34] evaluated the role of chitin nanocrystals and
nanofibers on the properties of thermoplastic starch-based films prepared by
casting method, and discovered that the nanocomposites with contents of
5–20 wt. % presented better mechanical, thermal, barrier and antifungal properties
than the unfilled TPS films. Herrera et al. [63] studied PLA bionanocomposite
blown films filled with 1 wt. % of chitin nanocrystals and demonstrated that the
CHNC increased the tear strength and the puncture strength of PLA film by 175%
and 300%, respectively, hence reinforcing the polymer. Finally, Deng and
co-workers [62] managed to increase in about 100% and 140% the tensile strength
and Young’s modulus, respectively, of PVA films by adding a large content of
chitin nanofibers.
1292 C. Rosales et al.

Active Packaging

The active packaging is a packaging method which is intended to interact with

foodstuff and the internal environment to improve food quality and the shelf life of
food products. Active method is employed to delay microbial growth, oxidation,
moisture migration, and control the respiration rate [48, 64]. Among the active
packaging systems, antioxidant and antimicrobial packaging are the most widely
used in food packaging. This kind of packaging is intentionally designed with
antimicrobial or antioxidant components that would release or absorb material
depending on each function. Particles with active function can operate in two
different ways. The particles may be immobilized on the packaging surface so
they can act by direct contact, or incorporated in the material matrix so they can
migrate slowly and react preferentially with certain organic molecules present in
food. If the particles are entangled in the bulk, there are variables that must be
controlled to ensure the active substance effectiveness, material thickness and
diffusion kinetics of the particles would have great influence to achieve desired
release at the surface material [24, 64].
The antimicrobial packaging is designed to limit or delay the foodstuff spoilage
by the action of microorganism [65]. Antimicrobial activity can be obtained by direct
interaction with microbial cells through the membrane, or by creating secondary
products that impart cell damage. In this way, antimicrobial systems kill microor-
ganisms or limit the growth rate [66].
Another kind of active packaging which has gained attention is antioxidant
packages. The main function of antioxidant activity is to prevent oxidation of the
food product. This activity can be achieved by releasing antioxidant substances to
the food environment or taking up undesired substances like oxygen to improve the
condition of food products [67].
Latest researches into the improvement of antimicrobial activity for biopolymers
used for food packaging applications include the utilization of nanoparticles such as
silver, oxides, and starch, which ensure food safety by slowing down microorganism
growth.
Li et al. [42] studied physical, chemical and mechanical properties of PLA films
with TiO2 and Ag nanoparticles. They observed good antimicrobial activity against
E. coli and L. monocytogenes of nanocomposites, and carried out migration tests
resulting within the standard limits. They also found lower water vapor permeability
(WVP) and an improvement of thermal stability, in comparison with pure PLA film.
Antimicrobial activity of silver nanoparticles was also investigated by Jung et al.
[43] in the development of coated papers for packaging applications. They prepared
different ratios of chitosan, starch and silver solutions and observed a strong
dependence of paper properties with blends’ composition. The studied composition
with less AgNP showed not only the best mechanical properties but also antibacterial
and antifungal activity, making it useful for agricultural food packaging applications.
Al tayyar and co-workers [68] studied the antimicrobial effect of bio nano-
composites films based on chitosan, PVA and inorganic particles (ZnO-SiO2). The
addition of 5 wt. % of nanoparticles showed the best antibacterial property against
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1293

Gram-positive bacteria (S. aureus, S33R) and Gram-negative bacteria (E. coli, IRAQ
3), without detriment of the barrier properties. In a different way, Baysal et al. [44]
investigated modified montmorillonite and corn starch systems, finding excellent
antimicrobial properties of nanofilms against S. aureus and E. coli bacteria.
Regarding antioxidant properties, Iglesias-Montes et al. [19] studied several PLA
systems, finding that lignin nanoparticles enhance antioxidant activity by up to 80%.
In a similar way, Yang et al. [37] found a decrease in water vapor transmission rate as
a consequence of a more circuitous route granted by lignin particles. Also, this
system showed an improvement on migration test and antioxidant behavior,
exhibiting that PLA films with lignin can be a potential material as active food
packaging. Bi et al. [69] analyzed the chitosan-SiO2 system, finding that the inter-
action between components improved mechanical and barrier properties as well as
antioxidant and antibacterial properties.

Intelligent/Smart Packaging

Smart packaging is developed to monitor the condition of food or the environment

surrounding the food package from the production line to the consumer. For this
purpose, nano-sized sensors are incorporated to inform the state of food during
transportation and storage. The smart particles have the ability to detect an external
change and respond in order to assure the supplier or consumer its quality and safety
[25, 67]. The food and its environment are regularly sensed by some mechanism to
identify and communicate that products kept/maintain the appropriate oxygen con-
tent, temperature, and pathogen contamination [4, 70].
The design of smart packaging functions must be taken into account the type and
requirements of the food, as well as conditions of production, transportation, and
storage conditions [71]. Also, intelligent packaging can be also considered the
addition/incorporation of labels inside the main package, that register and inform
with a visible indicator the physicochemical change of the food like pH, temperature,
presence of gases, color change, contaminants, or microbial concentrations [46].
There are three categories to classify intelligent packaging systems, namely, time
temperature indicators (TTIs), gas sensors, and thermochromic inks.
Food deteriorations as a consequence of temperature explorations during the
supply chain is one of the main causes. To monitor temperature changes and ensure
that foodstuff have been stored and distributed at the appropriate temperature, TTIs
are really useful. It is possible to group TTIs into abuse indicators, which commu-
nicate if a particular temperature was reached and full temperature history, which is
continuously monitoring the temperature as a function of time. Depending on the
TTI type, the communication is associated with a chemical reaction or to a migration
of a dye through a porous material [24, 67].
Gases interfere in a destructive way with food, for this reason the aim is to
develop packaging with low permeability to gases. It is necessary to know gas
composition into the food atmosphere, because it can change as a consequence to
the interaction of food with its environment. Gas sensors are helpful to detect any
1294 C. Rosales et al.

modification produced in foodstuff during chain supply. The communication method

used by gas sensors is based on a change chemical reaction that produces a color
change in the indicator [24, 67].
To monitor freshness conditions of minced beef at real time in refrigerator
temperature, Ezati and co-workers [72] developed a colorimetric indicator. For that
purpose, they incorporated alizarin as an indicator in a cellulose-chitosan film. As
deterioration takes place, the indicator interacts with the alkaline gases inside the
packaging and changes from brown to purple. That interaction was successfully
correlated with microbial activity, volatile nitrogen, and pH. The authors ensure that
this smart system could help consumers to visually distinguish the quality of food.
In a different way, using natural pigments as an alternative to synthetic one, Sani
et al. [73] prepared a film based on chitin nanofiber and methylcellulose composite
matrices with immobilizing red barberry anthocyanins (RBAs). The RBAs were
used as a colorimetric indicator to detect changes in pH and ammonia gas due to food
spoilage. The indicator changed from red to pink to yellow with the increase of pH
and ammonia vapor concentrations. Moreover, RBAs and nanofiber pigment pro-
vided a considerable antioxidant and antimicrobial activity, and enhanced mechan-
ical properties, moisture resistance, and optical properties.

Safety Issues of Nanoparticles in Food Packaging

Along with the rapid development of nanotechnology applied in the food packaging
field, concerns emerged about the potential risks or adverse effects that nanoparticles
might cause on human health and/or the environment across their life cycle. Unlike
polymer matrices, nanomaterials exhibit an elevated surface reactivity as a result of
their high surface-to-mass ratio. Although most nanoscale processed foods should
not pose any special health concerns, there are some knowledge gaps in current
understanding of behavior and effects of certain “hard” nanomaterials usually used
in food applications. Therefore, the most important safety concerns about the use of
nanostructures in food packaging is their migration into the food product and/or
penetration of biological barriers, since nanomaterials smaller than 300 nm may
penetrate into individual cells. Hence, biocompatible nanoparticles are preferred for
packaging applications in direct contact with food-stuff. However, it is worth noting
that highly toxic nanomaterials are unlikely to be used in food products [74].
The main risk of consumer’s exposure to packaging nanoproducts is likely due to
the potential migration of low molecular mass constituents of the packaging material
into the packaged food and the consequent oral uptake from food with added
nanoparticles. Migration experimental data for nanoparticles in food contact mate-
rials are still relatively infrequent and little has been published. Migration depends
not only on several physico-chemical properties of both nanoparticles and packaging
polymers, such as the density of the polymer, the size of the nanoparticles, their
density in the polymer macromolecular structure, and the average distance of
nanoparticles from the polymer surface, but also depends on temperature, pH, and
time of exposure, among others [75]. Nonetheless, a number of regulatory
56 Consumer Nanoproducts Based on Polymer Nanocomposites for Food Packaging 1295

frameworks are currently available for food and food contact materials in different
jurisdictions, such as the European Union, the United States, and Australia [76]. For
instance, the European Standard EN 1186–1 (2002) and European Regulation
(EU) N.10/2011, present a guide for plastic materials and articles in contact with
food for the selection of conditions and test methods for overall and specific
migration, and list the allowed substances for the manufacture of plastic materials
and objects suitable for coming into contact with food. In the evaluation of migration
processes, a distinction is made between global migration, which includes all the
compounds in the packaging material that are transferred to food, and specific
migration, which refers to the transfer of specific and well-identified substances. In
this sense, Fortunati et al. [58] showed that migration levels of PLA/CNC
bio-nanocomposites, intended for food packaging applications, were below the
overall migration limits indicated in the current EU legislation in two different
types of food simulants. Likewise, Li et al. [42] studies on PLA films with TiO2
and Ag nanoparticles also showed that NPs migration of the nano-blend films was
within the standard limits.
In summary, the application of nanotechnology in the food packaging field
demands precaution as not much is known about the impact it can have on human
and environmental health. Not all nanoparticles, just like any chemical matter, are
inherently dangerous or harmless. Much more research is still required before
nanoparticles may be tagged as toxic or safe.

Conclusion

Nanotechnology offers huge possibilities related to the improvement of several

relevant properties of biodegradable polymers to be used in packaging applications.
Packaging integrates biodegradable nanocomposites, acting as barrier for
exchange of gases keeping the quality of food, preventing the formation of bacterial
and fungal organisms or other pathogens and toxins, and also producing a real
reduction in waste accumulation being of unlimited potential to environment.
Smart packaging allows the consumers to select accurate products which have
excellent shelf life and giving security and safety to food.
More efforts have to be done in order to incorporate nanotechnology in packaging
industry to reach massive utilization.

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doi.org/10.1016/j.tifs.2011.01.001
Consumer Nanocomposites
for Environmental Pollution Control: 57
A Far-Reaching Review

Sukanchan Palit and Chaudhery Mustansar Hussain

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
The Aim and Objective of This Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1303
What Do You Mean by Nanocomposites? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1303
The Scientific Doctrine of the Science of Environmental Protection . . . . . . . . . . . . . . . . . . . . . . . . . 1304
Significant Scientific Research Pursuit in the Field of Nanocomposites and Composite
Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305
Significant Scientific Research Pursuit in the Field of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . 1306
Significant Research Pursuit in the Field of Nanomaterials and Engineered Nanomaterials . . . 1309
The Status of Groundwater and Drinking Water Treatment in the Global Scenario . . . . . . . . . . 1312
Groundwater Remediation and Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1313
Nanotechnology: The Scientific Vision and the Scientific Sagacity . . . . . . . . . . . . . . . . . . . . . . . . . . . 1314
Environmental Sustainability, Environmental Protection, and the Challenges
of Civilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1314
The Science of Arsenic and Heavy Metal Groundwater Remediation . . . . . . . . . . . . . . . . . . . . . . . . 1315
The Sagacity of Science, Scientific Comprehension, and the March of Modern Science . . . . 1315
Future Recommendations of This Study and Future Flow of Scientific Thoughts . . . . . . . . . . . 1316
Conclusion, Outlook, and Scientific Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1316
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1317

Abstract
The domain of environmental protection, environmental engineering science, and
chemical engineering science is moving towards one visionary challenges to
another. Environmental remediation and water remediation are today undergoing

S. Palit
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Post-Office-Bidholi via Premnagar, Dehradun, Uttarakhand, India
e-mail: [email protected]
C. M. Hussain (*)
Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, USA
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1301

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_104
1302 S. Palit and C. M. Hussain

drastic and dramatic challenges. Global warming, water scarcity, and frequent
environmental catastrophes are urging the scientific community to move towards
more innovation and vast scientific intuition. Mankind’s immense scientific
adjudication, man’s vast scientific grit and determination, and the world of
scientific and technological validation will all lead a visionary way in the true
realization of environmental engineering science. In the similar vein, composite
science and material science are the needs of human scientific progress today.
Nanotechnology is today merged with almost every branch of science and
engineering today. This direction of scientific research is depicted profoundly
by the authors. Fiber-reinforced composites and nanocomposites are the marvels
of composite science today. In this chapter, the authors also rigorously delineate
the success and vision of science in the field of green nanocomposites and fiber-
reinforced composites. The world of material science is slowly moving towards a
new scientific genre and new scientific revelation. Scientific stance, vast scientific
imagination, and the vision of engineering science will all be the forerunners
towards a newer age in the field of composite science and material science. This
well researched treatise profoundly delineates the recent scientific advancements
in the field of nanocomposites, green nanotechnology, composite science, and
material science.

Keywords
Consumer · Nanocomposites · Environment · Pollution · Composites · Water

Introduction

The vast world of chemical engineering science and composite science is today in
the midst of scientific introspection and regeneration. In the similar vein, material
science and green nanotechnology are in the course of scientific vision and deep
scientific understanding and discernment. Green nanotechnology, advanced mate-
rials, and green chemistry are the marvels of science and engineering today. Strin-
gent environmental regulations and the ever-growing concerns for global climate
change are urging the scientific community to gear forward towards newer vision
and new scientific and engineering innovations. In this chapter, the authors deeply
delineate the success and the vision of nanotechnology, composite science, and the
vast world of nanocomposites. The other direction of this well researched treatise is
the mitigation of global environmental pollution. Mankind’s immense scientific
prowess and scientific sapience, the world of technological validation, and the
scientific imagination behind environmental remediation will lead a long and effec-
tive way in unraveling the scientific truth of environmental engineering science. In
the global scientific scenario, global warming, climate change, and frequent envi-
ronmental disasters are destroying the vast scientific fabric of vision, might, and
determination. This chapter will surely open up newer vistas of scientific regenera-
tion and scientific prowess in the field of nanocomposite applications in
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1303

environmental protection. Environmental sustainability is the other side of the

visionary coin. Sustainable development whether it is social, economic, energy, or
environmental are the utmost need of global scientific progress today. This chapter
opens up a new era in the field of nanotechnology, composite science, and environ-
mental protection. Human race will thus usher in a new beginning in the field of
science and engineering as nanotechnology and environmental protection enters a
new age of deep scientific vision and scientific might and forbearance.

The Aim and Objective of This Study

Humanity today stands firm in the midst of vast scientific and engineering advance-
ments. Space exploration, the advancements in nuclear science and engineering, and
the success of science of sustainability will all lead a long and effective way in the
true unraveling of engineering science and technology globally today. The main aim
and objective of this study is to unfold and uncover the scientific vision in the
applications of nanotechnology and composite science in the furtherance of science
and the advancement of human society. The authors pointedly focus on the recent
scientific research pursuit in the field of nanotechnology and composite science with
a deep scientific understanding of environmental remediation. The other areas of
scientific endeavor are the advancements in the science of environmental and energy
sustainability. Systems engineering and reliability engineering are the pillars of
research pursuit in global scenario today. This chapter thus opens up newer thoughts
and newer scientific sapience and pragmatism in the field of systems science and
environmental remediation. The main thrust area of this chapter is to unfold the
scientific intricacies of the applications of nanocomposites in environmental protec-
tion. Science, technology, and engineering are today in the path of newer regener-
ation. Globally, climate change and frequent environmental disasters are urging the
scientific community to gear forwards towards new innovations and new directions.

What Do You Mean by Nanocomposites?

Nanocomposite is a multiphase solid material where one of the phases has one, two,
or three dimensions of less than 100 nanometers (nm) or structures having nano-
scale repeat distances between the different phases that make up the material. The
idea behind nanocomposite is to use building blocks with dimensions in nanometer
range to design and create new materials with improvement in their physical
properties. In the wider sense, this definition can include porous media, colloids,
gels, and copolymers but is more usually taken to mean the solid combination of a
bulk matrix and nano-dimensional phase differing in properties due to dissimilarities
in structure and chemistry. The mechanical, electrical, thermal, optical, electrochem-
ical, catalytic properties of the nanocomposite will widely differ markedly from that
of the component materials. Today, there is an immense vision in application of
nanocomposites in diverse areas of science and engineering. In this treatise, the
1304 S. Palit and C. M. Hussain

authors deeply investigate the application of nanocomposites in the field of environ-

mental protection. The different types of nanocomposites are (1) ceramic matrix
nanocomposites, (2) metal matrix nanocomposites, (3) polymer matrix nano-
composites, (4) magnetic nanocomposites, and (5) heat-resistant nanocomposites.
In mechanical terms, nanocomposites differ from conventional composite materials
due to exceptionally high surface to volume ratio of the reinforcing phase and its
exceptionally high aspect ratio. The reinforcing material can be made of particles
(e.g., minerals), sheets (e.g., exfoliated clay sticks), or fibers (e.g., carbon nanotubes
or electrospun fibers). In this entire treatise, the authors target the visionary research
endeavor in the field of application of consumer nanocomposites in diverse areas of
science and engineering. Scientific vision and scientific ingenuity in the field of
nanocomposites applications are still latent. Thus the need of a detailed research
pursuit in the field of nanocomposites. Humankind’s immense scientific understand-
ing and knowledge prowess in the field of nanomaterials and engineered nano-
materials thus needs to be reenvisioned and reorganized as civilization moves
forward. Today, nanocomposites are a boon and marvel of composite science and
material science. A deep engineering and technological introspection are the needs
of the hour as science, technology, and civilization move forward.

The Scientific Doctrine of the Science of Environmental Protection

The science of environmental protection and remediation are in the avenues of new
scientific sagacity and deep scientific provenance. Global research and development
initiatives in environmental remediation are still latent and undeveloped as global
warming, drinking water contamination, and industrial wastewater treatment are in the
avenues of immense disaster. Arsenic and heavy metal contamination of drinking
water and groundwater are veritably destroying the global scientific fabric. Human
civilization and human scientific progress are thus in a state of immense distress and
devastation. The challenges of environmental protection are thus industrial wastewater
treatment, drinking water treatment, and groundwater decontamination. In such a
situation, chemical process engineering, material science, and polymer science are
the marvels of scientific progress today. In this century, nanotechnology is linked with
every branch scientific research pursuit. The status of environmental and energy
sustainability is equally at a disastrous situation. The target of the scientific domain
and the civil society is to gear towards more innovations in traditional and non-
traditional environmental engineering techniques. Thus there will be a greater scien-
tific emancipation in the field of environmental sustainability and environmental
remediation. The target of science and engineering globally today will be towards
more new technologies and greater emancipation of the science of sustainability. The
scientific doctrine of the science of environmental protection will surely usher in a new
era in the field of drinking water treatment, industrial wastewater treatment, and
groundwater remediation. Developing and developed nations around the world are
in the midst of deep scientific comprehension and vast scientific divination. Here
comes the immense importance of novel separation techniques such as membrane
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1305

science and nonconventional environmental engineering tools such as advanced

oxidation processes. In this well researched treatise, the authors deeply tread through
a weary path in the field of nanotechnology, environmental remediation, and the
science of sustainability.

Significant Scientific Research Pursuit in the Field

of Nanocomposites and Composite Science

Nanocomposites and nanomaterials are revolutionizing the scientific landscape

globally today. Material science and nanotechnology are the immediate needs of
scientific revolution globally today. Composite science as well as polymer science
are changing the research genre in the field of material science, nanomaterials, and
engineered nanomaterials. In this section, the author with immense scientific vision
comprehends the recent scientific research pursuit in the field of nanocomposites and
composite science with a clear view of furtherance of science and engineering.
Bhattacharya (2016) [1] discussed in minute details the polymer nanocomposites
and a comparison between carbon nanotubes, graphene, and clay as nanofillers.
Nanofilled polymeric matrices have demonstrated remarkable mechanical, electrical,
and thermal properties. In this article, the author reviews the processing of carbon
nanotube, graphene, and clay montmorillonite platelet as potential nanofillers to
form nanocomposites [1]. Carbon-based nanofillers are relatively in an early stage of
research and development. Nanoclay-based nanocomposites have immensely met
with success in recent years. The importance of filler dispersion in the polymer
matrix is highlighted. Finally, the challenges and future outlook for nanofilled
polymeric composites are investigated in minute details [1]. The author discussed
in minute details the considerations for developing nanocomposites, interfacial
interactions between filler and polymer, nanocomposite processing, properties of
nanocomposites, and the bigger vision of application of nanocomposites [1]. Car-
bon-based nanofillers are today at a relatively at an early stage of research and
development initiative. Nanoclay-based nanocomposites have met with immense
success in recent years. The domain of consumer nanocomposites are in the avenues
of new scientific rejuvenation. A detailed treatise in the field of carbon nanotubes,
graphene, nanoclays, and other engineered nanomaterials are the utmost need of the
hour [1]. The authors and the scientists in this research paper widely investigate the
scientific intricacies in the field of polymer nanocomposites and its vast and varied
applications in diverse areas of science and technology [1]. A new dawn in the field
of nanotechnology, nanomaterials, and engineered nanomaterials will emerge if
scientific directions in the field of composite and material science are reenvisioned
with the progress of science [1].
Camargo et al. (2009) [2] deeply discussed with scientific vision, scientific grit,
and scientific determination nanocomposites and its synthesis, structure, properties,
and new application opportunities. Nanocomposites, a high-performance material
exhibits unusual property combinations and unique design features [2]. The domain
of science and engineering of nanocomposites is burgeoning. In this detailed
1306 S. Palit and C. M. Hussain

overview, the three types of matrix nanocomposites are deeply investigated,

underlining the needs for these materials, their processing methods, and some results
on structure, properties, and potential applications [2]. Possible uses of natural
materials such as clay-based minerals, chrysotile, and lignocellulosic fibers are
deeply investigated in this paper. Today, the world of composite science and material
science is in the avenues of newer scientific regeneration. Nanocomposites are
composites in which at least one of the phases shows dimension in the nanometer
range (1 nm ¼ 109 m). Nanocomposite materials have emerged as suitable alter-
natives to microcomposites and monolithics [2].
Ingole et al. (2021) [3] discussed deeply polymeric composite/nanocomposite
membranes for diverse applications. The total amount of water on earth is approx-
imately 1.4 billion m3 with 97.5% ocean saline water and 2.5% fresh water [3]. Of
this fresh water, approximately 68% is trapped in glaciers, 30% in the group, 1.7% is
frozen and unusable, and 0.3% is contained in rivers, lakes, streams, and so on. Thus
environmental remediation and water and wastewater treatment are the need of the
hour. Water crisis have been among the top 10 global risks and disaster in each of the
last 8 years [3]. Membrane separation processes and other novel separation processes
are thus the utmost needs of the hour. Membranes can be divided into inorganic and
organic membranes with respect to materials point of view. Inorganic membranes are
made from inorganic materials such as metals, ceramics, or zeolites. The other areas
of research pursuit in this paper are the application of different types of polymeri-
zation in manufacture of membranes [3]. The other areas of scientific research
pursuit are thin film composite membranes, thin film nanocomposite membranes,
manufacture of thin film nanocomposite membranes by incorporating nanomaterials
by interfacial polymerization. Membranes for water purification are the other salient
features of this well researched treatise [3]. Thin film nanocomposite membranes for
enantiomer separation are the other research pursuit. Energy generation with the help
of thin film nanocomposite membranes are also the other avenues of research
pursuit. In this treatise, different nanotechnology applications of thin film nano-
composite membranes are investigated in details [3].
Nanotechnology today has diverse applications in different areas of science and
technology. The status of global water research and development initiatives is
disastrous today. A deep scientific introspection in water purification and application
of nanocomposites are the need of the hour. The authors deeply investigated these
scientific and engineering issues.

Significant Scientific Research Pursuit in the Field

of Nanotechnology

Nanotechnology is the marvel and the vignette of research endeavor globally today.
Global climate change, the monstrous issue of global warming, depletion of fossil
fuel resources, and frequent environmental disasters are urging the scientific com-
munity to gear towards newer innovations and new futuristic thoughts. The domain
of nanotechnology integrated with environmental protection needs to be envisioned
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1307

and broadened with the march of human civilization. There are visionary scientific
endeavors in the field of nanomaterials and engineered nanomaterials today. The
world of science and engineering today stands mesmerized as nanomaterials and
nanocomposites are in the path of new rejuvenation. In this section, the authors
deeply pronounce and pointedly focus on the application of nanotechnology in a
broader sense.
Mansoori et al. (2008) [4] discussed with scientific vision and determination
environmental application of nanotechnology. Nanotechnology is a vastly emerging
field that covers a wide range of technologies which are presently under develop-
ment in nanoscale and microscale. This article gives a deep portrayal and a compre-
hensive review on the ongoing research activities on environmental remediation,
water and wastewater treatment, and nanotechnology [4]. The world of environmen-
tal engineering and nanotechnology is today undergoing vast changes. Nanotech-
nology has vast and versatile applications in the field of water purification, industrial
wastewater treatment, and environmental remediation. In this paper, the essential
aspects of environmental problems are reviewed and then the application of nano-
technology to the compounds which can serve as environmental cleaning and
purification. Various environmental treatments and remediations using different
nanostructured materials from air, contaminated wastewater, groundwater, surface
water, and soil are discussed in minute details [4]. The categories of nanoparticles
studied include those which are based on titanium dioxide, iron, bimetallics, cata-
lytic particles, clays, carbon nanotube, fullerenes, dendrimers, and magnetic nano-
particles [4]. The scientific ingenuity in the field of environmental protection, the
needs of humanity and the world of scientific challenges will all lead a long and
visionary way in true realization of environmental engineering science and chemical
engineering [4]. The authors in this article target these areas. The advantages and
limitations in the field of environmental engineering applications are evaluated and
vastly compared with each other and with the existing tools. The operating condi-
tions such as pH, required doses, initial concentrations, and treatment performances
are also depicted with scientific vision, lucidity, and strong scientific profundity.
Nanotechnology is a field of applied science and applied engineering, strongly
focused on the design, synthesis, characterization, and application of materials and
devices on the nanoscale [4]. Research and development initiatives are needed using
nanoscale science and technology to identify opportunities and applications to
environmental applications and to investigate the potential impacts of nanoscience
and nanotechnology. Early application of nanotechnology is remediation using
nanoscale iron particles [4]. Zero-valent iron nanoparticles are deployed in-situ to
remediate contaminated soil and water with chlorinated compounds and heavy
metals. One of the main environmental applications of nanotechnology is its appli-
cations in the water sector. Freshwater resources are today scarce in the global
scenario due to overconsumption and contamination, and thus scientists and engi-
neers have begun to consider seawater as the alternate resources [4]. Thus the
domain of desalination assumes immense importance. Desalination and membrane
science are today aligned with each other in the field of water, wastewater treatment
and environmental remediation. The science of nanotechnology thus needs to be
1308 S. Palit and C. M. Hussain

reenvisioned as regards its application in environmental and water remediation

[4]. Air pollution is another potential arena where nanotechnology and nano-
engineering has great potential and promise. Scientific stance, vast scientific inge-
nuity, and the validation of environmental protection science will thus open new
doors of innovation and instinct in decades to come [4]. Nanofilters could be applied
to automobile tailpipes and factory smokestacks to purify contaminants and prevent
them from entering atmosphere. Much of the current research is vastly focused on
energy and water technologies and the wide world of environmental sustainability.
Environmental or green sustainability are today’s coinwords in every scientific
research endeavor [4]. Environmental remediation includes the degradation, seques-
tration, or other related approaches. Today, conventional and nonconventional
environmental engineering techniques are the needs of any environmental protection
and environmental engineering endeavor. In this article, the authors have reviewed
processes used for the treatment with the help of the science and engineering of
nanotechnology [4]. The other areas of scientific research endeavor are titanium
oxide-based nanoparticles, iron-based nanoparticles, bimetallic nanoparticles, and
nanoparticle photocatalysts and other catalysts. The areas of application of nano-
clays and dendrimers in environmental protection are the other hallmarks of this
treatise. The domain of application of micelles or self-assembled surfactants in
environmental protection and water remediation stands as a major pillar of this
review [4]. Nanomembrane and nanosieve and its applications in water and waste-
water treatment are technologies of today’s research pursuit in environmental engi-
neering science. These areas are dealt with scientific and engineering vision in this
paper. A new world in the field of nanotechnology will emerge if environmental
engineers and scientists targets a newer direction in research and development
initiatives [4].
Stander et al. (2011) [5] deeply discussed with scientific vision and scientific grit
and determination an update on environmental implications of nanotechnology.
Some of the engineers and scientists globally are either directly or indirectly
involved with nanotechnology and nanoengineering issues. Areas and domains of
particular concern include current/proposed environmental regulations and proce-
dures for quantifying health risks are elucidated in minute details [5]. Nanotechnol-
ogy is concerned with the world of miniscule particles that are highly dominated by
forces of physics, chemistry, and material science that cannot be applied at the
macro- or human-scale level. Today, nanotechnology and nanoengineering are in
the path of newer regeneration [5]. A deep scientific investigation in the field of
nanotechnology is the pillar of this treatise. The term nanotechnology has come to be
defined as those systems or processes that provide goods and services that are
obtained from matter at the nanometer and micrometer level, i.e., from sizes in the
range of one-billionth of a meter. Nanotechnology is the principle of manipulation of
the structure of matter at the molecular level [5]. This treatise deeply elucidates
environmental concerns, environmental risk management, the health risk evaluation
process, the hazard risk evaluation process, regulatory concerns, and the future
vision of the role of nanotechnology in the progress of humankind [5]. The potential
future legislative and regulatory actions in the United States of America are dealt in
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1309

details in this article. The authors believe that nanotechnology is the second coming
of the visionary Industrial Revolution, or as the authors termed it as Industrial
Revolution-II. Environmental risk management is today part and parcel of human
society today [5]. There are two types of environmental risk humanity attached with.
They are health risk and hazard risk [5]. Today, many environmental practitioners,
researchers, and regulators have confused health risks with hazard risks and vice
versa. Environmental health risk and the environmental risk assessment processes
are widely discussed in literature and are the bases of various environmental
management issues. The vision of application of nanotechnology in environmental
protection is dealt in details in this paper [5].
Dhingra et al. (2010) [6] elucidated in minute details the sustainable nanotech-
nology through green methods and life cycle thinking. Citing the myriad applica-
tions of nanotechnology, this paper investigates the need to conduct life cycle-based
assessments as early in the new product development process for a better under-
standing of the potential environmental and health consequences of nanomaterials
over the entire life cycle of a nano-enabled product [6]. This treatise dealt in details
the nanomanufacturing methods and environmental concerns, industrial ecology and
life cycle analysis, and the energy intensity of carbon nanofibers and nanoparticles.
Combination of life cycle and risk assessment in the field of nanotechnology are the
other cornerstones of this paper [6]. Considering that nanotechnology is estimated to
be multitrillion-dollar industry in the next decade, it is important to take a life cycle
approach to evaluate the environmental and human health in a nano-enabled prod-
uct’s life cycle. The application of green chemistry and nanotechnology in human
advancements are dealt in details in this article [6].
Science and technology in the global scenario are moving at a rapid pace. In the
similar vein, nanotechnology and nanoengineering are surpassing vast scientific
boundaries. Technological revalidation, scientific motivation, and deep scientific
revelation are the needs of present-day human civilization. Today, the world stands
in the midst of ever-growing environmental concerns and thus the imminent need of
novel separation processes, and conventional and nonconventional environmental
engineering tools. In this treatise, the authors pointedly focus on the scientific
success, the deep scientific adroitness, and the scientific ingenuity behind application
of nanotechnology in diverse areas of engineering and science.

Significant Research Pursuit in the Field of Nanomaterials

and Engineered Nanomaterials

The world of science and engineering of material science today stands challenged as
human civilization and human scientific profundity gear forward towards newer
vision. Renewable energy is the coinword of today’s scientific endeavor. In this
sphere, application of nanomaterials and engineered nanomaterials will transform
the scientific landscape. In this section, the authors deeply stress on the scientific
facts and the vast scientific ingenuity in the field of nanomaterials and the broad
domain of nanotechnology.
1310 S. Palit and C. M. Hussain

Palit et al. (2020) [7] deeply discussed with vision, scientific forbearance, and
scientific determination functionalization of nanomaterials for industrial applications
and its recent and future perspectives. The authors covered the areas of (1) nanotrends
in industrial development, (2) the use of functionalized nanomaterials in industry,
(3) current research on nanomaterials, (4) recent scientific research in the field of
functionalized nanomaterials, (5) the scientific vision of energy and environmental
sustainability, (6) recent research in environmental protection and industrial ecology,
and (7) groundwater remediation and nanotechnology [7]. Nanotechnology refers to
the categorization, manufacture, and management of structures, devices, and materials
that are smaller than 100 nm. Nanotechnology and nanoengineering are today opposite
sides of the visionary coin [7]. Water purification, drinking water treatment, and
industrial wastewater treatment are some of the current applications of nanotechnol-
ogy. In this chapter, the authors focus on engineering science and technology of
nanomaterials. The vast and varied challenges of water resource management and
wastewater management as well as applications of environmental engineering are
deeply discussed in this chapter [7]. Functionalized nanomaterials and engineered
nanomaterials are next generation smart materials with vast and varied applications in
environmental engineering, water purification, drinking water treatment, industrial
wastewater treatment, and biomedical engineering science [7]. The ingenuity and
revelation of the science of functionalized nanomaterials are today opening new
domains in research endeavor in decades to come.
Palit et al. (2018) [8] elucidated with vision and lucidity of the engineered
nanomaterials for industrial use. Engineered nanomaterials are the next generation
smart materials and have vast and versatile applications. Today, scientific ingenuity
and engineering vision in the field of engineered nanomaterials are at its zenith
[8]. Nanotechnology is today a revolutionary area of global scientific research
pursuit. The authors in this treatise pointedly focus on the vast and varied domains
of engineered nanomaterials such as carbon nanotubes, dendrimers, fullerenes,
graphene sheets, metal oxides, nanoarrays, nanocrystals, and the vast world of
carbon nanotubes [8]. The authors discussed in details the different types of
engineered nanomaterials, scientific doctrine of engineered nanomaterials, scientific
research pursuits in the field of engineered nanomaterials, scientific research pursuit
in the field of nanotechnology, scientific research pursuit in the field of nano-
materials, environmental sustainability, and the vast vision for the future [8]. Water
purification, drinking water treatment and industrial wastewater treatment, and
nanotechnology applications are the other pivots of this article. Biomedical engi-
neering, biotechnology, biological sciences, and medical sciences are today aligned
with the science of nanotechnology [8]. Environmental remediation, environmental
engineering sciences, and water and wastewater treatment are the utmost needs of
humanity today. The application of nanomaterials and engineered nanomaterials in
these areas will surely bolster the global scientific imagination and global research
and development initiatives [8]. Thus diverse areas of science and technology such
as environmental engineering, nanomaterials, engineered nanomaterials, petroleum
engineering, and chemical process technology needs to be revamped and envisioned
with the progress of science and civilization. The authors deeply validate these
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1311

scientific issues. Engineering and technological vision in the areas of engineered

nanomaterials will thus usher in a new era [8].
Chong et al. (2020) [9] described and discussed with scientific vision, scientific
might, and lucidity of the mixed-matrix membranes incorporated with functionalized
nanomaterials for water applications. Membrane science and technology are the
emerging areas of science and engineering globally [9]. Membrane-based technol-
ogy has emerged as one of the effective approaches for producing high quality water
from various sources such as seawater, groundwater, surface water, and drinking
water. The vast scientific grit and scientific determination of novel separation
processes such as membrane science will today veritably open new doors of scien-
tific innovations and engineering vision [9]. In recent decades, nanomaterials have
attracted immense attention among researchers, scientists, and engineers worldwide
due to their unique ability to improve membrane properties with respect to hydro-
philicity, antifouling resistance, permeability, and adsorption capabilities [9]. The
vision and purpose of water and wastewater treatment thus needs to be reenvisioned
and reorganized as regards application of engineered nanomaterials [9]. The authors
discussed in details the mixed-matrix membranes incorporated with carbon-based
nanomaterials, application of carbon nanotubes, application of graphene oxide,
mixed-matrix membranes incorporated with titania-based nanomaterials, and
mixed-matrix membranes incorporated with other nanomaterials [9]. Adsorptive
mixed-matrix membranes for heavy metal removal from contaminated water stands
as a major pillar of this research endeavor. Microporous ultrafiltration membranes
and its application areas has seen remarkable resurgence in recent years. Thus this
article deeply discusses this scientific and engineering issues [9]. To the best of the
knowledge, mixed-matrix membranes are currently unavailable in water and waste-
water treatment [9]. This article vastly investigates these engineering issues. The
status of global water research and development initiatives is witnessing drastic
challenges. Mixed-matrix membranes will thus surely solve these water purification
issues [9].
Rani et al. (2020) [10] discussed with vast scientific vision remediation of organic
pollutants by potential functionalized nanomaterials. During the last few decades,
organic pollutants caused major environmental pollution issues. Its level is contin-
uously increasing due to urbanization, rapid industrialization, and also lack of
awareness on environmental sustainability. The high stability towards heat, light,
and oxidizing agents led to the persistence of pollution by organic substances and
rapid accumulation in environment [10]. Various industries such as the textile,
cosmetics, pulp and paper, food processing, pharmaceutical industries discharge
immense organic and inorganic pollutants to water bodies thus endangering the
human habitat [10]. In this article, the authors stress on environmental concern of
organic pollutants, direct functionalization, non-covalent functionalization, and
green synthesis of functionalized nanomaterials [10]. The importance of green
synthesis in functionalized nanomaterials stands as a major pivot of this chapter.
Degradation of pesticides by functionalized nanomaterials are the other hallmarks of
this article. Functionalization of nanomaterials such as silica, carbonaceous and
metal-based zinc oxide, titanium dioxide, iron, platinum, palladium, and nickel
1312 S. Palit and C. M. Hussain

oxide for environmental applications are deeply reviewed in this chapter. In this
chapter, the application of sustainable functionalized nanomaterials in green synthe-
sis are discussed in details in this chapter [10].
Functionalized nanomaterials and engineered nanomaterials are the hallmarks of
scientific research pursuit in the global scenario today. Deep scientific ingenuity and
technological profundity in the field of nanomaterials will surely validate the appli-
cation of nanomaterials and engineered nanomaterials. In this entire chapter, the
authors stress on the application areas of nanomaterials and its vision.

The Status of Groundwater and Drinking Water Treatment

in the Global Scenario

The status of groundwater and drinking water remediation globally stands in the
midst of scientific ingenuity and vast scientific sagacity. The futuristic vision of
chemical process engineering and environmental engineering is today challenging
the vast scientific firmament. In the similar vision, nanotechnology, composite
science, and material science are the needs of human civilization and in the path of
newer scientific rejuvenation. The global water crisis is unimaginable and in the
same vision groundbreaking. The imminent need of science and technology globally
is environmental protection and further scientific emancipation in the field of
environmental engineering. In India and Bangladesh, arsenic and heavy metal
groundwater contamination are devastating the scientific firmament. The situation
is beyond control and immediate global attention is needed. In such a crucial
juxtaposition, novel separation processes, advanced oxidation processes, conven-
tional and nonconventional environmental engineering techniques assume immense
importance. Nanotechnology, material science, and composite science are the other
scientific avenues of research endeavor. Arsenic groundwater is an immense envi-
ronmental engineering disaster in the global scenario. The scientific landscape is vast
and varies. South Asia particularly India and Bangladesh are in the midst of this
environmental catastrophe that arsenic and heavy metal drinking water and ground
water poisoning. Palit et al. (2019) [11] discussed with immense scientific vision and
scientific provenance arsenic contamination in South Asian regions and the difficul-
ties, challenges, and vision for the future. The authors discussed in minute details the
health problems due to arsenic contamination. Country-wise status of arsenic con-
tamination in South Asia is delineated in this research article. Today, there is
immediate need of scientific innovations and scientific intuition in the field of
environmental protection and water remediation [11]. Arsenic and heavy metal
groundwater contamination are vastly vexing issues in developing and developed
nations around the world [11]. The South Asian countries of Afghanistan,
Bangladesh, India, Nepal, Pakistan, and Sri Lanka face the severest groundwater
contamination issues. The scientific ingenuity in the field of groundwater remedia-
tion techniques needs to be revamped and reorganized as civilization, science, and
technology move forward [11]. The areas of immense introspection are arsenicosis,
cancer, neuropathy, and respiratory disorders. Difficulties and challenges associated
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1313

with arsenic contamination in South Asia are the other cornerstones of this research
pursuit. Remedial measures for removal of arsenic in groundwater are the other
scientific pillars of this article. The techniques of groundwater contamination
discussed in this paper (Palit et al., 2019) [11] are use of natural geologic material,
desalinator, oxidation, coprecipitation, subterranean arsenic removal technology,
hybrid technology based on ion exchange, and electrodialysis. Use of nanoparticles
in removal of arsenic contaminants stands as another major pillar of this research
pursuit [11]. The detrimental effects inflicted by high arsenic concentrations in
groundwater and drinking water are continuously exceeding the maximum limit of
10 ppb set by WHO, sometimes increasing drastically far beyond 10 ppb [11] and
thus the need of a visionary approach in water remediation. Bhardwaj et al. (2019)
[12] discussed in minute details the status of arsenic remediation in India. Arsenic is
a metalloid which occurs in pentavalent (arsenate) and trivalent (arsenite) oxidation
states. Due to its high toxicity and the fact that arsenic occurs in detrimental levels in
water supplies, particularly groundwater, in more than 70 countries, arsenic contam-
ination is a global and worldwide health issue [12]. Continuous exposure to arsenic
could cause damage to the human cardiovascular, gastrointestinal, dermal, hepatic,
pulmonary, renal, neurological, reproductive system, and respiratory system. The
authors discussed in details the metabolism, toxicity, and health effects of arsenic,
sources of arsenic contamination, natural sources, anthropogenic sources, and the
status of arsenic contamination in the global scenario. The status of arsenic contam-
ination in India is also delineated in details [12]. Basic principles involved in arsenic
remediation techniques are the other hallmarks of this paper. Oxidation, precipita-
tion, coagulation, flocculation, adsorption, ion exchange, membrane techniques, and
bioremediation are the other tools of arsenic remediation today. Centralized or
community-type systems for arsenic removal stand as another major yardstick of
this article. Emerging technologies for community-based arsenic removal tools are
today the needs of rural and urban people in India [12]. These areas are discussed in
minute details in this paper (Bhardwaj et al., 2019) [12].
Science, technology, and humankind are today in the avenues of rejuvenation and
regeneration. The status of groundwater and drinking water scenario in India,
Bangladesh, and South Asia is absolutely grave today. Nanotechnology, nano-
materials, and nanocomposites are the recent research and development initiatives
today. This entire article strongly validates these scientific issues and the vast
scientific innovations [13–20].

Groundwater Remediation and Nanocomposites

Groundwater remediation and the application area of nanocomposites are today the
imminent needs of human civilization today. Nanomaterials applications in environ-
mental protection are in the similar vein scientific vision of modern science. Man’s
immense scientific discernment, mankind’s vast scientific acuity, and the futuristic
vision of engineering and science will all lead an effective way in the true emanci-
pation of nanotechnology and environmental engineering. Drinking water issues
1314 S. Palit and C. M. Hussain

globally are destroying the scientific landscape today. Today, groundwater remedi-
ation and water and wastewater treatment are aligned to each other. Groundwater
remediation and nanotechnology are practically new areas of scientific research
pursuit. Nanomaterials and engineered nanomaterials are the present-era scientific
innovations. Drinking water and groundwater contamination in developing and
developed nations around the world are today in a state of disaster. Application of
nanocomposites in drinking water treatment and its vision will surely lead a long
way in opening new windows of innovation in water remediation [21–24].

Nanotechnology: The Scientific Vision and the Scientific Sagacity

The sagacity of science and the ingenuity of engineering science are today changing
the vast scientific frontiers. Nanotechnology and its scientific vision are in the midst
of forbearance and vast astuteness. Global water scarcity and global climate change
are the immediate concerns of human scientific progress today. There is a huge
scientific hiatus in the domains of nanomaterials, engineered nanomaterials, nano-
composites, and environmental protection. Here comes the need of a comprehensive
treatise in the field of nanocomposites and environmental protection. This treatise
will surely open new avenues in research sagacity and research sapience in the field
of environmental protection and environmental engineering science. The world of
scientific challenges in the field of nanotechnology and the scientific vision behind it
will veritably usher in a new era in the field of environmental protection, environ-
mental engineering, composite science, and material science [21–24].

Environmental Sustainability, Environmental Protection,

and the Challenges of Civilization

Environmental sustainability and environmental protection are today in the midst of

immense scientific overhauling and deep scientific provenance. Science, technology,
and engineering have today few answers to the growing environmental engineering
research questions globally. The areas of sustainability are today globally neglected.
The challenges of human civilization need to be reenvisioned and revamped with the
passage of scientific history and time. The target of research pursuit in nanotechnol-
ogy should be more scientific emancipation in the field of nanomaterials and
engineered nanomaterials applications. The success of human civilization and the
success of human scientific progress depends today on the vast world of nanotech-
nology, material science, and environmental remediation. The vision of Dr. Gro
Harlem Brundtland, former Prime Minister of Norway, on the science of “sustain-
ability” needs to be redefined and reenvisioned with the course of scientific history
and vast scientific ingenuity. Environmental sustainability is the utmost need of the
hour as civilization trudges forward towards a new century. Today, environmental
sustainability and the vast world of water purification are the two opposite sides of
the visionary coin. Provision of basic human needs such as water, electricity, food,
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1315

shelter, and education are highly neglected in many developed and developing
nations around the world. In the similar vein, energy and environmental sustainabil-
ity are yet to be envisioned in many governments around the world. In this chapter,
the author reiterates the success and the need of technology and engineering science
in tackling global environmental and energy sustainability. The author rigorously
points towards the integration of environmental protection with nanotechnology.
Nanotechnology is the absolute need of human civilization and human scientific
progress today. Man’s immense scientific prowess and sapience, mankind’s vast
scientific ingenuity, and the needs of environmental sustainability will open newer
thoughts and newer vistas in research and development globally. Water purification,
drinking water treatment, and industrial wastewater treatment are the challenges and
the vision of science and engineering today. This well researched treatise will surely
target the domains of energy and environmental sustainability as a further realization
of science and engineering globally today [21–24].

The Science of Arsenic and Heavy Metal Groundwater

Remediation

The world of science and engineering stands veritably challenged as arsenic and
heavy metal groundwater poisoning destroys the vast global scientific fabric. Devel-
oping and developed nations around the world are in the throes of the world’s largest
environmental engineering disaster that is arsenic drinking water contamination.
Science and technology in the global scenario need to be reenvisioned and
reorganized as research and development initiatives in developing and developed
nations are in the midst of deep scientific intricacies and vast barriers. Today,
research and development initiatives in the field of water science and technology
should be targeted towards innovation and scientific vision in the field of traditional
and nontraditional environmental engineering techniques. Novel separation pro-
cesses such as membrane science needs to be envisioned and envisaged with the
progress of science and technology [21–24].

The Sagacity of Science, Scientific Comprehension, and the March

of Modern Science

Water pollution control, drinking water treatment, and industrial wastewater treat-
ment today stand in the midst of deep scientific introspection and immense scientific
vision. Research and development initiatives globally are entangled in the midst of
immense scientific intricacies. Modern science and water purification science are the
challenges and the vision of human civilization today. The authors deeply compre-
hend the needs of energy and environmental sustainability in the march of human
civilization today. Modern science and modern engineering science need to be
envisioned as regards its integration with nanotechnology, material science, polymer
science, and composite science. The sagacity of science and technology globally
1316 S. Palit and C. M. Hussain

thus needs to be reenvisioned and revamped as civilization moves forward. The ever-
growing concerns of industrial wastewater treatment and integrated water resource
management will surely urge the scientific domain globally to move towards greater
emancipation and greater realization of environmental sustainability. Modern sci-
ence and modern technology are today huge colossus with a vast and definite vision
of its own. This treatise widely redefines the success of environmental remediation
and environmental sustainability in tackling global environmental changes, global
warming, and the vicious domain of global climate change. Scientific sagacity and
scientific vision will thus usher in a new avenue in the field of nanotechnology,
nanomaterials, and composite science in the similar manner. Global water issues are
today moving towards disastrous directions. The civilization has plunged in the deep
whirlpool of comprehension and vast scientific introspection. Technology, engineer-
ing, and science have practically few answers to the intricacies and barriers in
environmental engineering and nanotechnology applications. Here comes the need
of scientific and engineering sagacity globally today. In this chapter, the authors
vastly stress on the needs of sustainability whether it is environmental or energy in
the further emancipation of science and technology.

Future Recommendations of This Study and Future Flow

of Scientific Thoughts

Today, the world of environmental engineering science and nanotechnology is

moving forward at a drastic pace and surpassing one engineering boundary over
another. The questions of environmental and energy sustainability are still today
unanswered as science and technology move forward. Future recommendations of
this study will veritably target the scientific astuteness, the scientific nuances, and the
vast scientific ingenuity in the field of nanocomposites and the vast domain of
nanotechnology. Technological and engineering challenges in the field of nanotech-
nology are today vast and ever-growing. Today, nanoscience and nanotechnology
are in the path of newer scientific regeneration. Nanotechnology is today aligned
with areas of membrane science, composite science, material science, and the vast
world of applied sciences. A new field in the domain of water and wastewater
treatment is slowly emerging. The future of nanotechnology thus needs to be
reenvisioned and revamped as humankind moves forward. The future flow of
scientific thoughts should be thus targeted towards more applications of nanotech-
nology in water and environmental remediation [21–24].

Conclusion, Outlook, and Scientific Perspectives

Modern science and the progress of engineering and technology are in the midst of
deep scientific forbearance and vast scientific astuteness. Today, scientific and
technological challenges of human civilization are vast, versatile, and groundbreak-
ing. Technology has few answers to the ever-growing concerns of provision of pure
57 Consumer Nanocomposites for Environmental Pollution Control: A. . . 1317

drinking water and the concerns of global environmental sustainability. The appli-
cation of chemical process engineering, applied chemistry, biotechnology, and
environmental engineering in human society’s progress are of immense importance
today. In the similar vein, nanotechnology is today making vast inroads in the
avenues of human progress and modern science today. Scientific progress today
globally needs to usher in a new era in the field of environmental engineering, human
factor engineering, and reliability engineering. The success of engineering science
and technology are today changing the face of human society today. The authors
deeply ponder with vision and might the success of nanotechnology, composite
science, and material science in the furtherance and challenge of human civilization
today. This well researched treatise vastly opens new thoughts and newer outcomes
in the futuristic avenues in environmental remediation and industrial waste water
treatment. The vast vision and the challenges of application of nanocomposites in
environmental protection are today changing the face of human civilization. The
future outlook of nanotechnology and composite science needs to be reenvisioned
and revitalized as human civilization and human scientific progress crosses one
boundary over another. Material science and composite science are the marvels
and pantheons of science and engineering today. This chapter unfolds the deep
scientific profundity and the scientific ingenuity in the field of composite science
and the vast holistic world of nanotechnology. Nanotechnology capability, the
scientific validation of the applications of nanotechnology, and the future vision of
composite science and material science will all lead a long and visionary way in the
true realization of nanocomposite science in decades to come. The authors deeply
target the areas of environmental protection and environmental sustainability where
there are vast and versatile applications of nanotechnology. The future outlook and
the future scientific perspectives will surely target the primary needs of human
society such as water, energy, food, shelter, education, and the vast world of
sustainability. The success and the vision of global science lies in the hands of
sustainability. This chapter targets these intricate issues.

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Environmental Aspect on Nanoproducts
58
Saptarshi Roy and Md. Ahmaruzzaman

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1322
Nanoparticles and Their Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1323
Nanoclays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1324
Removal of Water Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1324
Removal of Gaseous Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1326
Large-Scale Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1327
Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1328
Removal of Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1329
Removal of Organic Water Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1329
Large-Scale Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1330
Paper Towel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1330
Self-Cleaning Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1331
Solar Active Cloth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1332
Transparent Polyurethane Nanofiber Air Filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1333
Nanocontact Sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1334
MoS2 Sponge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1334
MoS2 Nanopores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1336
Zeolite Cotton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1336
Future Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1337
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1337
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1338

Abstract
Global deterioration of the quality of air, water, and soil due to the increasing
effects of the toxic emissions can be inextricably linked with rise in industriali-
zation and urbanization and has become a serious threat in the modern world.
Environmental pollution, though not a new problem, has been challenging the
existence of humanity and mankind since the industrial revolution. Therefore, it
becomes important for us to shed light and outline the recent developments in the

S. Roy · M. Ahmaruzzaman (*)

Department of Chemistry, National Institute of Technology, Silchar, Assam, India

© Springer Nature Singapore Pte Ltd. 2022 1321

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_108
1322 S. Roy and M. Ahmaruzzaman

field of nanomaterials that can be used to monitor the increasing hazardous wastes
generated each day with higher efficiency, low cost, time, and energy. Nano-
particles possess unique optical, mechanical, electromagnetic, thermal, and struc-
tural properties which provide an advantageous prospect than their bulk
counterparts and can be utilized for environmental remediation by removal of
toxic gaseous, metal pollutants, and oil spills from water. There has been rapid
development and innovation of new consumer-based nanomaterials worldwide
which is expected to take over the marketplace over the next several years. This
book chapter provides a comprehensive review of these products and the future
prospects to remediate problems relating to the restoration of our environment.
Nanotechnology is the science which is expected to meet the potential challenges
for sustainable environmental protection in the days to come.

Keywords
Nanotechnology · Nanoproducts · Remediation · Fine particulate matter ·
Nanosensors · Cation exchange capacity · Nanoclay

Introduction

The terminology of nanotechnology (NT) was first proposed by an American

physicist, Richard Feynman, in the year 1959. It is the branch of science concerned
with the design, innovation, and application of materials implemented on the
nanoscale. The term NT comprises of a Greek numeral prefix “nano” which means
a billionth and the word “technology,” describing the production and design for the
fabrication of nanometer scale materials with superior characteristic properties [1]. It
is a novel technology that is gaining its popularity extensively in areas ranging from
biochemistry, colloidal science, drug delivery, cancer treatment, food industry and
packaging, nano-based encapsulation of pesticides, and many more [2, 3]. Apart
from these, relevant application of nanoparticles for the remediation of environmen-
tal issues associated with water and soil is speedily progressing originating from the
desperate requirement of a technology which is much cleaner, greener, efficient,
cost-effective, easily available, and environmentally friendly. The success of nano-
scale materials can be visualized both by its potential application of the materials to
detect, prevent, and remove the pollutants and by an indirect way by using nano-
technology to innovate industrial technologies following the green protocol and
create consumer-based products for environment remediation. For example, pollut-
ants from groundwater can be successfully eliminated by the application of iron
nanoparticles making it satisfactory for consumption purpose. Also, nanosensors
offer good prospects in easy detection and monitoring of contaminants [4].
The novel properties of nanoparticles can be attributed to its size and structure.
They have a unique characteristic of possessing “large surface area-to-volume ratio”
unfolding various possibilities for creating many improved potent catalysts to
felicitate chemical reactions. Behavior of materials at nanoscale is not analogous
58 Environmental Aspect on Nanoproducts 1323

to that at macroscale and actually possesses new physicochemical characteristics.

Their physical and chemical characteristics are extensively exploited in a broad
range of fields: biomedicine, textile industry, environmental remediation, agro-
based industries, etc., for the betterment of the society. Due to their interesting
property of increased strength, they can be used in thin films as thermal barriers
and improve the wear-resistant nature of materials.
Nanoscience technology is emerging broadly and holds enormous promising
potential for the continued enhancement of technologies and novel innovative
products for environment remediation. In-depth research and innovation in this
field has to be sought out to identify our existing environmental problems and
evaluate the prospective applications for its remediation. Approaches are welcomed
for the effective monitoring or treatment of toxic pollutants in ways not currently
possible.
Environmental remediation and reclamation are among one of the crucial chal-
lenges faced by the global community in present day. The ever-increasing population
has resulted in the tremendous escalation in activities that compromise and question
the sustainability of our future generations. In addition to this, civilization and
industrialization have not only overexploited the Earth’s natural resources but also
contaminated with deadly chemicals, the impact of which is unforeseen and
unpredictable. These toxic environmental pollutants pose menace to human health
and ecological security. Remediation involves the degradation and removal
approaches for various chemical and radioactive contaminants and toxic heavy
metal ions (e.g., arsenic, mercury, cadmium, lead) from groundwater and soils;
organic compounds (e.g., pesticides, benzene, chlorinated organic solvents) are of
much significant concern. One of the major challenges posed by the environment
remediation strategies is the development of convenient and cost-effective restora-
tion approaches. The application of nanotechnology can play a pivotal role for this
approach as specific control and design of nanomaterials at the molecular scale may
result in the magnification of selectivity and affinity for the sequestration of con-
taminants, thereby cleaning and improving the environment.

Nanoparticles and Their Properties

Nanoparticles possess at least one dimension of 1 to 100 nm. They have distinct
novel properties which can be traced to their high surface area-to-volume ratio
making them more reactive than their bulk counterparts. A material when brought
down to their nano-form manifests interesting properties which are contradictory
from their non-nanoform. Some displays enhanced magnetic and thermal character-
istics. Various plastics designed at the nanometer scale possess increased strength.
For example, tennis racket manufacturers sought to improve the equipment perfor-
mance by utilizing nano-silicon dioxide crystals. These nanosized materials offer a
multitude of advantages for its utilization in fields of biomedicine, textiles, pharma-
ceuticals, agro-based products, cosmetics, and environment.
1324 S. Roy and M. Ahmaruzzaman

Considering the importance of nanoscience technology, we present herein this

chapter some consumer-based nanoproducts and its significant application in
removal of various pollutants from contaminated air, water, and soil media.

Nanoclays

Clay minerals are layered silicates that are formed from silicate materials present on
the Earth’s surface by the natural process of weathering [5–7]. They act as “chemical
sponges” and have the ability to attract and hold water molecules, cations, and
anions in between their layers. Nanoclays are nanoparticles belonging to a class of
layered mineral silicates with structural units such that when these layers are stacked
upon one another, they form complex clay crystallites. Each unit is composed of
tetrahedral and octahedral sheets.
Novel and innovative applications of advanced nanoclay have recently surfaced
as a subject of increased interest for research and development. This can be attributed
to their unique superior properties such as small particle size, high specific strength
and surface area, magnified stiffness, low density, enhanced thermal properties, high
damping, and fatigue endurance. In addition to this, clay minerals are considered
environmentally friendly as they are nontoxic, cheap, and abundant in nature
[8, 9]. As a result of their fascinating properties, nanoclays are crowned as potential
candidates for the elimination of pollutants and heavy metal ions from wastewater,
agricultural leachates, and soil liners [10] (Table 1).
Nanoclays possess the property of cation exchange capacity (CEC) which plays
an interesting role in the sorption of various pollutants and heavy metal ions on the
surface of the clay by covalent bonds. It is not entirely dependent on the CEC of clay
minerals but is also related to other processes depending on the type of metal cation.
Various factors such as pH, ionic strength, and the nature of the anions present in the
solution affect the adsorption capacity of the different heavy metal cation (Table 1).

Removal of Water Pollutants

The global trends of industrialization and urbanization are the main culprits for the
generation of massive amounts of wastewater containing unreasonably high con-
centrations of heavy metals and toxic organic compounds. These persistent pollut-
ants accumulate in the environment and contaminate the food chain causing potential
health threats for the consumers, including mankind.
Among the different kinds of sorbents that are available, nanoclays emerge as the
most potent choice due to their budget-friendly nature and high removal efficiency
and have been employed extensively for the extraction of water contaminants [11].
Babel et al. demonstrated the adsorptive capacities of some low-cost locally avail-
able adsorbents such as bentonite clay, chitosan, and zeolites over commercial
expensive activated carbon. Their high removal performance can be attributed to
58 Environmental Aspect on Nanoproducts 1325

Table 1 Utilization of clay minerals for pollution control and environmental protection [8]
Contaminants for
control Status (actual or potential use) Relevant clay properties
Heavy metal Actual, mainly passive, use (e.g., in soils, Charge, surface area,
cations and simple liners) reactive surface groups
cations
Organic and Potential for water and wastewater treatment, Charge, surface area,
biological cations pesticide control especially interlayer
Nonionic organic Actual, for water and wastewater treatment; Charge, specific surface
molecules potential, for pesticide control, waste liners area, interlayer
Anions Actual, for water and wastewater treatment; Charge, reactive surface
potential, for pesticide and nutrient leaching groups
control
Turbidity and Actual, for treatment of potable water and Colloidal, size and
residual treatment some wastewaters and sewage charge; surface area
chemicals
Leachates Actual, for waste liners and radioactive waste Swelling, charge, surface
storage area, reactive surface
groups

their high surface area, ion exchange capabilities, and the net negative charge on
their structure which gives them the capability to attract the heavy metal ions for the
inorganic effluent treatment [12]. Konig et al. in another study inspected different
berberine-based organoclays as possible flocculants over the conventional pre-
treatment for brine wastewater (BWW) in pickle industry to minimize BWW
turbidity, total and volatile suspended solids (TSS and VSS), and chemical oxygen
demand (COD) [13, 14]. Modification of clays so as to achieve control over the
adsorption of a specific pollutant or to elevate the removal efficiency is of utmost
importance and challenging to the scientific community. Gu et al. investigated and
reported the adsorption data of five different hazardous metal cations, Cd(II), Cu(II),
Pb(II), Ni(II), and Zn(II), by montmorillonite as a function of pH and ionic strength
of the solution. It was found that the ionic strength greatly influenced the adsorption
of the ions in the lower pH range, while at higher pH, the adsorption was indepen-
dent of the ionic strength [15]. The adsorption of lanthanides on clay minerals such
as kaolinite and Na-montmorillonite over a wide range of pH at 22 ̊C was demon-
strated by Coppin et al., and it was inferred that the rare earth element (REE) sorption
is independent of the dissolved carbon dioxide and the background electrolyte but is
largely governed by ionic strength, pH, and the nature of the clay minerals used in
the adsorption study [16]. The efficiency of the adsorption of Pb onto sepiolite from
aqueous solutions for its application in wastewater treatment was studied by Bektas
et al. using the Langmuir and Freundlich equations. The maximum sorption capacity
was observed to be 93.4 mg/g under optimum conditions. The influence of the
agitation speed, size of the particle, and initial concentrations for the kinetic studies
were also determined [17]. Table 2 summarizes recent studies regarding the use of
clay minerals as the sorbents for the elimination of water pollutant removal.
1326 S. Roy and M. Ahmaruzzaman

Table 2 Removal of various water pollutants using different clays [8]

Pollutant Clay mineral Removal (%) References
Cu (II) Bentonite 48% [18]
Cd (II)–Co (II) Kaolinite 100% [19]
Fe (II) Bentonite >98% [20]
Cu (II)–Zn (II) Bentonite 99% Zn (II) [21]
90% Cu (II)
Cd (II) Montmorillonite 90.2% [22]
Pb (II) Zeolite clinoptilolite – [23]
Cu (II) and Cd (II) Na-montmorillonite – [24]
Cu (II) and Cd (II) Bentonite 84.5% Cu (II) [25]
87.2% Cd (II)
NH4 Zeolite clinoptilolite >90% [26]
Phenol Bentonite >45% [27]

Removal of Gaseous Pollutants

With industrialization becoming an increasingly demanding aspect of globalization,

the problem of air pollution aggravated and became much more extensive. The release
of the hazardous air pollutants from industries and emissions from coal-fired power
plants or automobiles is suspected of causing serious harms to humans including
cancer, birth defects, cardiovascular problems and reduced fertility. The release of the
hazardous air pollutants from industries and emissions from coal-fired power plants or
automobiles is suspected of causing serious harms to humans including cancer, birth
defects, cardiovascular problems and reduced fertility. The reduction of these gaseous
pollutants by the application of thermal oxidation requires a large amount of energy
which is not cost-effective and against the protocols of “sustainable chemistry.” Taking
this into consideration, more efficient techniques involving adsorption can be devel-
oped for effective removal of the undesired pollutants from the atmosphere [28]. A
number of studies in this discipline have unveiled the efficiency of nanoclay minerals
in the adsorption of polar and nonpolar gases, and in this regard special mention can be
made to the pillared nanoclays which have gained a wide importance in the pollution
abatement at present time. Nanoclays have emerged as a fascinating choice to grasp
the attention of the scientists and can be applied to minimize and eliminate the gaseous
contaminants due to their hydrophobic and hydrophilic features. Molina-Sabio et al.
investigated the potential utilization of sepiolite, activated carbon, and mixed pellets
and fabricated a novel mixed activated carbon-clay pellet for its application as
adsorbents of polar gas molecules such as NH3 and H2S. The dual role of sepiolite,
as a binder for other materials and also as an adsorbent due to its polar character,
broadens its application discipline [29]. Nguyen-Thanh et al. carried out alteration of
Na-montmorillonite with iron to introduce active centers for selective adsorption of
hydrogen sulfide [30]. The iron doped clay samples within the interlayer space of
aluminum-pillared clay evolved as the most suitable adsorbents for hydrogen sulfide in
spite of the decrease in microporosity than the initial pillared clay. These samples had
58 Environmental Aspect on Nanoproducts 1327

Table 3 Removal of various gaseous contaminants using different clays [8]

Pollutant Clay mineral Removal (%) References
p-Xylene Na-montmorillonite – [31]
n-Hexane Montmorillonite [32]
Benzene –
SO2 Palygorskite – [33]
SO2 Zeolite >95% [34]
SO2 Zeolite clinoptilolite >24% [35]
SO2 Zeolite clinoptilolite – [36]
H2S Zeolite clinoptilolite – [37]
H2S Kaolinite – [38]
H2S Bentonites – [39]
H2S Montmorillonite – [30]

better adsorbent efficiency than the samples modified with iron oxocations. Differ-
ences in the chemistry and the degree of dispersion of the iron species and also the
accessibility of the small pores for H2S result in the variations in the adsorption
capacity of the different clay samples. Table 3 summarizes recent studies of the
application of clay minerals for the removal of various gaseous contaminants. Fur-
thermore, nanoclays are promising alternatives for air pollutant removal which orig-
inate from diverse sources, but their adsorption efficiency depends on the nature of
pollutants, the characteristics of the sorbent, and physicochemical environmental
factors. Besides, application of the hybrid sorbents could be a prospective approach
to elevate the pollutant removal efficiency.

Large-Scale Application

Nanoclays are natural materials with pores in the nanometer dimension that have
gained a considerable attention worldwide. They display advantageous properties
which make them viable alternatives for its utilization as adsorbents of polluting
metals in water, amidst which their affordable cost, easy availability, large surface
area, and ability to exchange ions are mentionable. The possibility for interlamellar
spaces in clay minerals to swell is the underlying reason why they are efficiently
employed in the adsorption of water contaminants.
The calcareous shale of the Soyatal Formation in Zimapàn, Mexico, contains
kaolinite and illite, which adsorb arsenic. This aspect was utilized by the research
community to develop an economical, low-technology remediation system [40]. The
utilization of synthetic hydrotalcite (HT) nanoclay for the removal of arsenic was
demonstrated by Gilmann in order to develop a simple and convenient technology
for the purification of water in domestic or large-scale community levels in under-
developed regions [41]. HT clay underwent modification with ions of chloride,
nitrate, and carbonate. Employment of NO3–HT and Cl–HT in batch experiments
1328 S. Roy and M. Ahmaruzzaman

reduced the As (III) concentrations in water below the recommended permissible

limit of 10μg/L. Cl–HT was finally used to fabricate a cost-effective continuous filter
system involving porous pots or filter candles inserted into the base of vessels. A
novel adsorptive mixed matrix membrane with amino acid modified montmorillonite
was fabricated by Shokri and Yegani that removed arsenic up to 96% with the ability
to recycle [42].
Evaluations of nanoclays as adsorbents have clearly displayed that clay-based
material can be used successfully for remediation of wastewater. They are natural,
cheap, eco-friendly, and nontoxic, which can be used to provide pure consumable
water in developed as well as developing countries. Large-scale commercial water
treatment plants by the employment of natural and modified nanoclays are
envisioned to attain great advancement in the future.

Nanotubes

One-dimensional carbon nanotubes (CNT) are cylindrically straight tubules with

diameters measured in the range of nanometer. The accidental discovery of carbon
nanotubes in 1991 while studying the graphite electrode surfaces in an electric arc
discharge diversified the carbon chemistry and triggered an explosive advancement
of research worldwide. Improvements in the synthesis techniques have resulted in
the scaling up of production of pure nanotubes, assisting a whole range of promising
applications. These tiny carbon nanotubes, in particular, are willing to surpass
fullerenes in its competition to the technological marketplace due to its remarkable
structure, properties, and topology compared to the parent, planar carbon fibers. The
novelty of the nanotubes arises from their size, structure, and topology which
provide them with remarkable mechanical properties of high stability, enhanced
strength, and stiffness in addition to their low density, elastic deformability, signif-
icant adsorption properties, and selectivity [43]. Carbon nanotubes have an inherent
subtlety in their structure which is the helical arrangement of the carbon atoms in
hexagonal arrays on the honeycomb lattices present on the surface. The novel
electronic properties of the carbon nanotubes along the diameter generate a diverse
range of exciting electronic device applications [44]. The surrounding carbon atoms
of the cylindrical pores of the CNTs interact with the adsorbent molecules. This
interaction between the adsorbent molecules and solid surface relies greatly on the
size and geometry of the pores. When a molecule is placed in a slit-shaped pore
between two flat surfaces, it interacts with both its surfaces, and the extent of the
overlap depends on the pore size. However, for pores that are cylindrical and
spherical shaped, the resulting potentials are prominent due to the interaction of
more surface atoms with the adsorbed molecule [43]. Carbon nanotubes are highly
graphitic than activated carbons. Besides, the surface of CNT is highly aromatic
comprising a high density of π electrons. These factors enhance the efficiency of
adsorption of the carbon nanotubes. Hence, in comparison to activated carbons
possessing pores of either wedge or slit-shaped, they can absorb molecules much
more effectively [43].
58 Environmental Aspect on Nanoproducts 1329

Removal of Heavy Metals

Heavy metals are naturally occurring elements with high atomic mass and density. With
the advancement and exponential increase of the applications of heavy metals in
industries and domestic and other various medical sectors, there have been raising
concerns over their acute toxicity on the health of living organisms and environment
contamination [45]. It is associated with several health risks interfering with the
metabolic processes and leads to cancer, disruption of the central nervous system, and
accumulative poisoning [46]. Lead, a particularly insidious hazard, is pervasive in our
environment and has the potential of causing deleterious health effects interfering and
affecting the central nervous system and hepatic and renal systems. It is non-
biodegradable, and hence various strategies of lead removal from wastewater have
been developed, amidst which adsorption with activated carbon is frequently used.
The discovery of carbon nanotubes with high adsorption capability has attracted the
fancy of the research community worldwide. Li et al. reported that CNTs have enhanced
lead adsorption efficiency and can be employed as an adsorbent for lead removal from
contaminated water [47]. It was demonstrated that the efficiency of Pb2+ adsorption of
CNTs elevates after oxidation with nitric acid and greatly depends on the pH of the
solution. In another study, the adsorption thermodynamics of Pb2+ on CNTs and the
thermodynamic parameters (Ko, ΔGo, ΔHo, and ΔSo) at temperatures of 280 K, 298 K,
and 321 K have been obtained [48]. Desorption studies revealed that Pb2+ can be easily
eliminated from carbon nanotubes by changing the pH of the solution by treating with
HCl and HNO3, thus unveiling the promising predominance of CNTs for wastewater
treatment. Lu et al. purified commercially available single-walled carbon nanotubes
(SWCNTs) and multi-walled carbon nanotubes (MWCNTs) with sodium hypochlorite
and demonstrated the adsorption characteristics of zinc from water. There has been a
considerable enhancement in the purity of the nanotubes, structure, and nature of the
surface after their purification which compelled them to be a suitable applicant for
adsorption of Zn2+. The maximum adsorption capacities of Zn2+ calculated by the
Langmuir model are 43.66, 32.68, and 13.04 mg g
1 with SWCNTs, MWCNTs, and
PAC (commercial powdered activated carbon), respectively, at an initial Zn2+-
concentration range of 10–80 mgL
1 [49]. Likewise, amorphous Al2O3 supported on
carbon nanotubes (Al2O3/CNTs) has shown enhanced adsorption efficiency for its
applications in fluoride removal from water at a pH range of 5.0–9.0 [50]. In another
study by Li et al., aligned carbon nanotubes (ACNTs) were demonstrated as promising
candidate for the removal of fluoride from water. This unusual carbon material was
synthesized by catalytic decomposition of xylene using ferrocene as catalyst [51].

Removal of Organic Water Pollutants

Carbon nanotubes have been widely utilized for the removal of organic pollutants
like 1, 2-dichlorobenzene, n-nonane, and CCl4 from water. The spontaneity and high
affinity for the adsorption process has been predicted from thermodynamic calcula-
tions [52]. Unique features of commercial CNTs such as purity, structure, and nature
1330 S. Roy and M. Ahmaruzzaman

of the surface can be greatly intensified after its treatment with acid. This modifica-
tion can provide CNTs advantage over other adsorbents and can be employed for the
effective removal of trihalomethanes from wastewater [53]. Agnihotri et al.
employed gravimetric techniques to determine the adsorption efficiencies of com-
mercially available carbon nanotubes for organic compounds such as toluene,
methyl-ethyl-ketone, hexane, and cyclo-hexane at relative pressures and isothermal
conditions [54].

Large-Scale Applications

CNTs have been crowned as encouraging materials to be utilized in various envi-

ronmental fields. The relatively expensive approach of synthesis is one of the prime
drawbacks for the large-scale applications of CNT. Recently, the possibility of
low-cost mass production of high-quality CNTs was reported. Nanothinx, a spin-
off company of the Institute of Chemical Engineering and High Temperature Chem-
ical Processes (ICE-HT), was able to successfully reduce the cost of CNT production
by employing a low-cost novel catalyst developed by them. Studies showed that
liquefied petroleum gas as carbon source material and the ceramic substrate sphere
could be utilized for the cost-effective synthesis of high-purity CNTs. The mass
production of CNTs has led to the commercialization and field application of this
technology. Freestanding monolithic uniform macroscopic hollow cylinders having
radially aligned carbon nanotube walls, with diameters and lengths up to several
centimeters, are used as filters. They have potential utility for the removal of heavy
hydrocarbon components from petroleum in a single filtration step and the produc-
tion of bacterial free water for consumption [55]. A crucial advantage of these
macro-filters over conventional filters is that they can be reused by simply cleaning
after each filtration process through repeated ultrasonication and autoclaving, hence
regaining their filtration efficiency. Also these filters are robust and devoid of any
cracks or surface defects and gave reproducible results. Because of the exceptional
high thermal stability of the nanotubes, they can also be operated at ~400  C, which
are multiple times higher than that of conventional polymer membrane filters
(~52  C). Enhanced mechanical stability, high surface area, and convenient and
cost-friendly fabrication of the nanotube membranes may allow them to compete
with commercially available ceramic- and polymer-based separation membranes.

Paper Towel

Oil spill is the contamination of seawater due to leakage of petroleum as a result of

human negligence or an accident. This causes long-term environmental damage and
makes the area unsuitable for aquatic habitat. It damages the delicate underwater
ecosystem by killing and contaminating fishes and disturbing the global food chain.
Commercially available conventional materials absorb oil from water but do
not display selectivity. This results in the reduction of oil-capturing efficiency as
58 Environmental Aspect on Nanoproducts 1331

they absorb some water accompanying the oil. Recently, Stellacci and coworkers
of MIT unveiled a mat of nanowire fabric made of potassium manganese oxide
that is thermally stable and is capable of absorbing up to 20 times its weight in oil
while refusing water with its hydrophobic coating [56]. This could be a crucial
invention for its application in the cleanup of oil and also other organic pollutants
towards environmental remediation. This hydrophobic membrane material is
completely impervious to water and remains dry even when soaked in water
medium for over a month. They can also selectively remove lipids like oil from
the ocean. Furthermore, the oil-loaded membrane can be subjected to heating
above the boiling point of oil so that the adsorbed oil evaporates. Once the oil is
removed, the nanowire mesh can be reused and recycled. By condensing the
evaporated oil, the recovery of oil is possible. Both the membrane and the oil
can be put to repeated use. Moreover, production of this nanowire mesh is
economical and can be fabricated in bulk quantities. The interwoven mesh is so
thin that the fabric looks and feels like paper. Like a paper towel, Seaswarm uses
this thin nanofabric to suck up surface spills perfectly. In addition to its applica-
tion in environmental remediation, it can also be successively employed in
filtering and purification of wastewater. This weightless characteristic helped to
come up with the idea to build a vehicle that could smoothly glide over the surface
of the water in the days to come.

Self-Cleaning Glass

After years of continued research and advancement leading glass manufacturer,

Pilkington has made the impossible dream a reality for many households. World’s
first self-cleaning glass was fabricated with a thin microscopic dual action coating
[57]. Pilkington Activ™ range of products aggregates both the properties of self-
cleaning and solar control, making them highly advisable among the modern
generation looking for glass cleaning solutions. External window cleaning and
maintenance has been simplified by the commercial accessibility of glass cleaning
agents but is unable to overpower the potency of the novel “self-cleaning glass.” As
the name suggests, they can clean dirt present on its surface and require least
maintenance. They are coated with transparent and highly reactive nanocatalyst
titanium dioxide using a vacuum coating technique called chemical vapor deposi-
tion. TiO2 exhibits both photocatalytic and photo-induced superhydrophilic proper-
ties. When ultraviolet light hits the glass coated with TiO2 nanoparticles, electrons
are generated which convert water molecules into hydroxyl radicals by chemical
reaction. This can be attributed to the photocatalytic nature of the nanocatalyst.
These radicals degrade the organic dirt. When rainwater hits the glass covered with
dirt, it spreads out evenly, washing away the loosened dirt with it and quickly drying
without leaving any dirt marks. This technology can also be utilized for the manu-
facture of self-cleaning solar panels, exterior of buildings, and ocean exploration
vessels. It was demonstrated that a layer of organic contaminants of a thickness of up
to 10 nm can be cleaned within 1 h exposure to sunlight.
1332 S. Roy and M. Ahmaruzzaman

Solar Active Cloth

Black titania (BT) reaps the benefits of a full-spectrum solar absorption and is much
active than the commercially available photocatalyst, white titania (P25) [58]. Syn-
thesis of BT involves treating of P25 with H2 under high pressure at about 200  C for
5 days. So, there emerged the need for another simplified synthetic route which
would speed up the reaction time and also simultaneously enhance the efficiency of
solar absorption. Treatment of P25 with hydrogen plasma converts it into BT (TiO2-
xHx) of improved solar absorption (83%) in 4–8 h at 500  C. Its nanoparticle
exhibits admirable photocatalytic activity and exceptional stability for the degrada-
tion of methyl orange which can be entirely attributed to its crystalline-core disor-
dered-shell microstructure. Substitution of the conventional gaseous/plasma
hydrogen with hydride powders (NaBH4, N2H4, CaH2, TiH2, etc.) and later releasing
molecular hydrogen under mild calcination conditions oversimplifies the conven-
tional synthetic routes. For example, a gel prepared from TiO2 sol with the use of
NaBH4 and successive calcinations at 500  C in argon atmosphere converts it to BT
in 1.5 h. This method is efficient for the synthesis of black titania in bulk amount and
produces in batches of 100 g. However, the desired product can be achieved after
washing the crude product to remove the residual Na.
Providing fresh and affordable drinking water is one of the challenging obstacles
faced by the global community. The growing population and industrialization has led
to the increase of contamination of water bodies. At this crucial time, nanotechnol-
ogy has come to aid and offered innovative solutions for the practical large-scale
wastewater treatment applications. This requires the employment of a bulk amount
of inexpensive nanomaterials that are also additionally stable, thermally, chemically,
and photochemically. No doubt the commercially available white titania P25 assures
all the abovementioned benchmarks, but BT with comparable cost and much
advanced photocatalytic performance of 83% claims the opportunity. To make the
process of wastewater treatment more cost-effective, the nanomaterials used should
persist for a longer duration and be able to be recovered at ease for its repeated use.
In this regard, immobilization of BT on a high surface area three-dimensional
graphene support (BT/3DG) is highly desirable. It provides preconcentration and
simultaneously enhances the photocatalytic activity including easy, effective solid-
liquid separation and recovery. The use of TiO2-x for BT in BT/3DG revealed
extraordinary photocatalytic activity and light harvesting features as compared to
BT alone. For example, BT/3DG powders efficiently photodegrade MO completely
in only 4 min.
To accomplish field applications of BT/3DG, a solar active cloth was developed
in which BT/3DG hybrids were bonded by a polymeric binder to a nonwoven cloth.
This fabricated cloth was buoyant and easily floated on water. It exhibited interesting
results of MO degradation in only 10 min. Water remediation studies using the cloths
were studied at multiple locations of contaminated water, and it was observed that
there occurred a noticeable decline in the total organic carbon (TOC), nitrogen, and
phosphorus contents of the treated water and also a significant visible variation in the
appearance of the color. This further reduced primary and secondary treatment and
58 Environmental Aspect on Nanoproducts 1333

eventually minimized the cost. So the solar active cloths, which were usually
effective for advanced oxidation process (AOP), can also be employed in water
remediation techniques without any primary or secondary processes. So far, 8 tons of
black titania and 100 kg of 3DG have been utilized to fabricate solar active cloths for
the successful remediation of 600 acres of contaminated water at different locations
in China.

Transparent Polyurethane Nanofiber Air Filter

Fine particulate matter (PM) is an aggregation of numerous solid fine minute

particles and droplets of water-soluble ions and other inorganic and carbon
containing compounds. Fine particulate has been accredited as a serious threat and
is largely released from the combustion of garbage and fossil fuels. PM can be
mainly classified into two categories: PM2.5 and PM10 according to the diameter of
the particulate matter. PM10 has a limited travel distance and stays in the air for
a short time ranging from a few minutes to few hours. Contrastingly, PM2.5 has a
longer residence time in the atmosphere and can persist from a number of days to a
few weeks. It can enter the body through inhalation and accumulates in the respira-
tory system, mainly the trachea and lungs, causing serious health hazards such as
inflammations, vasoconstrictions, malignancies, and premature death. PM2.5 also
affects the ecological environment, disrupting the rainfall patterns and also leading
to hazy weather. It is a destructive factor to climate and ecosystem. In this respect, it
becomes very important and essential to take measures and control against this
particulate matter.
In the present day, professional dust masks are available as an outdoor personal
protection against severe haze that can effectively block the particulate matter
allowing only clean air to pass through. Indoor personal protection equipment
such as ventilation systems and air purifier are expensive, are not easy to install,
and require constant maintenance for the filter elements. To cut it short, they are not
consumer-friendly. The indoor air filters which are used for air protection in com-
mercial buildings rely on a huge cost for pumping systems in exchange for air.
Taking this into account, recently, two transparent air filters for its use in residential
buildings by window passive ventilation have been developed for consumer pur-
pose. One is porous membrane filter which suffers a drawback of low porosity of the
filter, and as a consequence, high ventilation cannot be achieved. The other con-
sumer product to be mentioned is nanofiber air filter with porosity of about 70% and
provides high ventilation. A variety of window screens have also been developed to
safeguard the quality of indoor air with the application of nanofiber. However, as of
today, almost all of the existing nanofiber-based air filters that have been developed
failed to simultaneously meet the obligation of high-performance air PM filtering
and removal efficiency, low resistance to airflow, and long service life. Hence, for the
first time, Chen et al. reported a method for the fabrication of thermoplastic poly-
urethane (TPU) nanofiber air filters using electrospinning method. The TPU con-
centrations in polymeric solutions can be modified for tuning the average diameters
1334 S. Roy and M. Ahmaruzzaman

of TPU nanofibers [59]. Recently, electrospun polymer nanofiber networks have

been developed as transparent air filters for selective removal of PM2.5. Nonetheless,
it still remains a question of challenge to uniformly coat the nanofibers on the
window screens cost-effectively and on a large scale. Khalid et al. demonstrated a
fast and efficient blow-spinning technique that is independent of high voltage
consumption for the large-scale direct coating of nanofibers onto window screens
for indoor PM pollution protection. Air filter of 80% transparency and a standard
removal efficiency of more than 99% were successfully achieved for PM2.5. A
practical test on a real window (1 m  2 m) in Beijing has showed that the nanofiber
transparent air filter acquired exciting PM2.5 removal efficiency of 90.6% over 12 h
under extremely hazy air conditions [60]. The technology of electrospinning has
received extensive praise on account of its minimal energy consumption, easy
operation, and eco-friendly approaches for the fabrication of nanofibers
[61, 62]. Fibers prepared have enhanced porosity and high specific surface area. A
TPU nanofiber air filter has been developed that can be manufactured on a large scale
using a spinning bead spinneret [63]. It exhibited high thermal stability, optical
transparency of 60%, high PM2.5 elimination capacity of 99.6%, long lifetime,
magnified ventilation rate, and weightlessness.

Nanocontact Sensor

Taking into account the difficulties and the obstacles that remain inherent at the
contaminated sites polluted with toxic heavy metals, it becomes very essential and a
pressing demand for the fabrication of an in situ sensor that is sensitive enough to
monitor the heavy metal ion concentration before it extends above the permissible
limit. Nanocontact sensor comprises of an array of pairs of nanoelectrodes on a
silicon chip [64, 65]. The electrodes in each pair are set apart from each other in an
atomic scale gap, which is attained by the technology of quantum tunneling. Any
electrochemical deposition of even a trace amount of metal ions into the gap can
bridge the gap forming a nanocontact between the electrodes, thus stimulating a
quantum jump in the electrical conductance. In addition to its extraordinary sensi-
tivity, it is miniaturized, environmentally benign, and cost-friendly which gives it a
best opportunity to claim its position for the initial on-site screening test of polluted
samples, consequently leading to early threatening and prevention of heavy metal
ion pollution.

MoS2 Sponge

Oil spillage and discharge of organic solvents and chemicals by the industries into
the water bodies have deteriorated the environment resulting in significant energy
losses and ecological problems both to the mankind and other life forms. Super-
hydrophobic sponges have emerged as a potential material and have attracted the
fancy of the scientists by their inherent attractive properties including low density,
58 Environmental Aspect on Nanoproducts 1335

affordable price, and high mechanical flexibility and stability. These characteristics
render them suitable for selective adsorption of oils and solvents. Wang et al. first
reported a convenient and affordable dip coating technique for the fabrication of
superoleophillic and superhydrophobic MoS2 sponges. These sponges absorb a wide
variety of oils and organic solvents with enhanced selectivity and absorption effi-
ciencies, good recyclability, and high chemical inertness. In addition to this, these
sponges can be employed for the continuous absorption and removal of oil pollutants
from aqueous bodies by coupling it with a vacuum.
The proposed preparation method for the fabrication of MoS2 nanosheet sponges
was simple, convenient for scaling up, and cheap and does not insist the use of
expensive complicated treatment. Exfoliation of economically powdered MoS2
crystals by ultrasonification in ethanol was carried out. Then, a commercially
available three-dimensional porous melamine formaldehyde sponge (MF sponge)
was used as a frame for MoS2 coating that has the potentiality to absorb both oil and
organic hazardous solvents. The MF sponge underwent a color change from white
MoS2 sponge to black after it was immersed in the MoS2 solution by squeezing and
degassing method. Finally, after drying, it yielded the MoS2 nanosheet sponge. This
dipping and drying process was repeated a number of times to ensure a homoge-
neous, consistent, and regular MoS2 nanosheet coating. The adhesion of the physical
coating of the MoS2 nanosheets onto the sponge framework can be firmly attributed
to the mechanical flexibility of the nanosheets and strong van der Waals interaction
between the sponge and the MoS2 nanosheets [66–68].
To test the high porosity and the superhydrophobicity of the MoS2 nanosheets
and to validate how they would respond as an effective absorbent to organic
pollutants, two organic solvents with varying densities were chosen. Rapeseed oil,
which served as the first model absorbate as a layer on the aqueous surface, was
entirely absorbed by the MoS2 nanosheet sponge within seconds resulting in clear
transparent water. Chloroform which is denser than water and sinks to the bottom
was also rapidly sucked in by the fabricated sponge. This high absorption capacity
could undoubtedly be attributed to the oleophilic nature, capillary action, and the
enhanced porosity of the nanosheets. Their absorption capacities are potentially
higher than commercially available fabrics, nanowire membranes, and microporous
polymers and are comparable to those of ultraviolet carbon aerogels. Moreover, the
sponges could be mechanically squeezed out to gather the absorbed oils and can be
recycled.
For practical large-scale applications, it became necessary to develop a novel,
continuous, and efficient method for harvesting oil in situ from an aqueous surface
comprising of pipes and peristaltic pump [69, 70]. It was demonstrated how the
absorption of pure oil by the MoS2 nanosheet sponge flowed to the collecting cup
through the pipes allowing the sponge to repeatedly gather the oil for more than 10 h
without any decrease in the working efficiency [71]. This clearly indicated the
working stability of the MoS2 sponges. Disturbing the sponge also did not exert
any influence on the oil removal efficiency. This novel procedure makes the segre-
gation of oil-water emulsions much simpler and brings us a step closer for the
possible applications of remediation of oil spillage.
1336 S. Roy and M. Ahmaruzzaman

MoS2 Nanopores

The engineers of the University of Illinois have developed an energy-efficient

material for the desalination of seawater with the employment of a nanometer
thick sheet of molybdenum disulfide (MoS2) having tiny nanopores [72]. It was
especially fabricated to allow substantial volumes of water through selectively
preventing the salt and various other pollutants. The research team unveiled that
MoS2 sheets had enhanced efficiency (70%) than conventional graphene mem-
branes. Commercially available membranes have pores small enough to prevent
salt or impurities, allowing water slowly through it which is time-consuming. These
membranes are moderately thick and so demand a good amount of pressure to be
administered for filtering at the molecular level. Moreover, reverse osmosis is not
efficient and costly and suffers clogging. In this context, scientists have been
continuously trying to develop graphene nanomembranes despite of its underlying
drawback as it interacts with water.
A MoS2 molecule comprises of a molybdenum atom sandwiched between two
sulfur atoms. The possibility of generating a pore in the sheet will allow an exposed
ring of molybdenum around the center of the pore to be left behind fabricating a
nozzle-like shape that drew water through it. Additionally, the monolayer sheets of
MoS2 are thin and energy efficient which in turn dramatically decreases the opera-
tional costs. MoS2 is a robust material and withstands the necessary pressures and
water volumes. Nanotechnology could play a key part in the designing of desalina-
tion plants, thereby reducing the cost and making them energy efficient.

Zeolite Cotton

It has become very demanding and utmost necessity to develop an economically

viable household water treatment (HWT) for delivering water in an efficient and
robust way for the underdeveloped regions. Chen et al. demonstrated a convenient
flow through filter made by zeolite cotton packing in a tube (ZCT), an affordable
device to filter out heavy metal ions from polluted water [73]. The zeolite cotton is
constructed by an on-site template-free growth of mesoporous single crystal
chabazite zeolite onto the surface of cotton fibers. The device displayed high ion
removal capacity, short flow time, reliable supply, easy operation, and strong
stability simultaneously. A 65 mL 1000 ppm Cu2+ solution was purified and reduced
to its permissible limit (<1 ppm) after allowing it to flow through the device packed
with 10 g of zeolite cotton. Moreover, the simultaneous filtration of several metal
ions did not compromise their performance. In a simulated purification process, 8 L
of water contaminated by hazardous ions Cu2+, Cd2+, and Pb2+ could be made
consumable by a noticeable decrease in the concentrations below a range of 5 ppb
(μg L
1). It is envisioned that this efficient ZCT filter is practical and can be utilized
extensively as an affordable household water treatment throughout the world.
58 Environmental Aspect on Nanoproducts 1337

Future Perspective

Addressing the global issues, it has become an utmost and vital need to orient the
scientific research towards environmental pollution control issues. In this con-
text, nanotechnology provides an important solution vector and gives us new
ways to tackle our problems. Around the world, various research teams are
engaged for the urgent rapid development and innovation of new consumer-
based products and processes to bring into the market place. As a result, nano-
materials and applications are already on the headline, and a large volume of
consumer-based products is expected over the next couple of years. The imple-
mentation of green chemistry principles on the production of nanomaterials must
be crucial for the development of novel materials that are eco-friendly and cost-
effective and can be employed in broad-scale applications in the span of envi-
ronmental remediation. Optimal future use of nanotechnology in recycle
approach should be encouraged. The final goal of future nanotechnology is to
utilize the outputs of one production process for another one and thus carry out
the industrial process chain with minimal waste generation. Crucial advancement
is progressing with a view to meet the long-term environmental protection
challenge.

Conclusion

Environmental nanotechnology involves the wide-scale implementation of nano-

materials in the remediation of environment. They are employed in monitoring
and restoring the existing different pollutants and are also used in the novel
sensing technologies for the detection of pollutants even in trace concentrations.
The capability of coating the nanoparticles with different ligands and the ability to
tune the surface-to-volume ratio permit the designing of sensors with enhanced
selectivity, sensitivity, and stability. They can also be utilized to cleanse our
environment by means of adsorption, filtration, and oxidation. Nanoparticles
have the capability to absorb various contaminants from air or water owing to
its large surface area. They can also degrade the contaminants at a much faster rate
than the bulk material, thereby minimizing the energy consumption rate. Another
approach includes the use of nanostructure membranes and air filtration technol-
ogy to remove bioaerosols and volatile organic compounds. In short, nanoscience
technology holds enormous potential for the continued development and substi-
tution of the already existing ones for better environment protection. This book
chapter is committed to provide further evidence to this issue and has tried to
address all the potential challenges that the global community encounters. Nano-
technology plays a promising crucial role in the improvement of rapid and
accurate environmental process and provides a better understanding of its
innovation.
1338 S. Roy and M. Ahmaruzzaman

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URL

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2. Applications of Nanotechnology-Based Self-Cleaning Glass [Online] Available: https://www.
azonano.com/article.aspx?ArticleID¼5510
3. Nanopores could take the salt out of seawater [Online] Available: https://news.illinois.edu/
view/6367/276449
4. Carbon nanotube ponytails for water purification [Online] Available: https://www.nanowerk.
com/spotlight/spotid¼35742.php
5. MoS2 Nanopores Desalination [Online] Available: https://www.betterworldsolutions.eu/
mos2-nanopores-desalination/
6. Smart sponge could clean up oil spills [Online] Available: https://www.sciencedaily.com/
releases/2020/05/200528160516.htm
7. Zeolite. Nothing new under the sun [Online] Available: https://en.i2owater.com/zeolite-
nothing-new-under-the-sun/
8. Low-cost Nanosensors by IISc Can Help Monitor Air Pollution While Saving Time! [Online]
Available: https://www.thebetterindia.com/107838/low-cost-nano-sensors-iisc-air-pollution/
9. Absorbent Nanomaterials for Environment Remediation [Online] Available: https://www.
azonano.com/article.aspx?ArticleID¼3178
10. Transparent Polyurethane Nanofibre Air Filter for High-Efficiency PM2.5 Capture [Online]
Available: https://www.mbrfilter.com/news-category/filter-news-p6.html
11. Reusable carbon nanotubes could be the water filter of the future [Online] Available: https://
phys.org/news/2017-03-reusable-carbon-nanotubes-filter-future.html
 Part XIV
Advanced Consumer Nanoproducts
(Waterborne Paints, Adhesives, Coatings, and
Dispersible Lattices)
Silver-Nanoparticle-Embedded
Antimicrobial Paints 59
Murodjon Abdukhakimov, Renat Khaydarov,
Praveen Thaggikuppe Krishnamurthy, and Svetlana Evgrafova

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1346
Ag-Nanoparticle-Embedded Paints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1347
Environmental Impact of the AgNPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1351
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1352
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1352

Abstract
In the twenty-first century, silver nanoparticles as antimicrobial agents can be
found in a wide range of commercially available products. This chapter reviews
the latest developments in modifying paints with differently synthesized silver
nanoparticles and studying their antibacterial and antifungal properties. For
carrying out typical microbiological tests, the commercially available water
paint has been mixed with 200 ppm silver nanoparticles solution in different
ratios of 20:1, 50:1, and 100:1 to impart antibacterial and fungicidal properties to
the paint. Escherichia coli, Salmonella typhimurium, Aspergillus niger, Staphy-
lococcus aureus, Pseudomonas aeruginosa, and Candida albicans cultures have
been used to evaluate the antimicrobial properties of Ag nanoparticles in paints.
The experiments performed have demonstrated that synthesized silver nano-
particles added to water paints show a pronounced antibacterial and antifungal

M. Abdukhakimov · R. Khaydarov (*)

Institute of Nuclear Physics, Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan
P. T. Krishnamurthy
JSS College of Pharmacy, Ootacamund, Tamil Nadu, India
S. Evgrafova
Sukachev institute of forest of the Siberian Division of the Russian Academy of Sciences,
Krasnoyarsk, Russian Federation
Institute of Fundamental Biology and Biotechnology, Siberian Federal University, Krasnoyarsk,
Russian Federation

© Springer Nature Singapore Pte Ltd. 2022 1345

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_105
1346 M. Abdukhakimov et al.

effect, although they tend to be agglomerated into colloidal clusters. It has been
shown that larger concentrations of silver nanoparticles have a greater anti-
bacterial/antifungal efficacy in Ag-nanoparticle-embedded paints. Taking into
account the importance of environmental impact of nanotechnologies, potential
environmental risks emerging from nanosilver release from modified paints have
been also discussed.

Keywords
Silver · Paint · Nanoparticles · Bacteria · Fungi

Introduction

Antimicrobial agents are known to be widely included to paint formulations to

preserve the product’s integrity from microbes and to keep any bacterial, fungal,
and algal growth away from the coated surface. The most common commercial dry
film antimicrobial agents added to paints are zinc pyrithione, carbendazim, and
chlorothalonil [29]. Many scientific studies have been conducted to obtain new
additives, for instance, over the last two decades, the scientific and technological
interest in the use of nanosilver-based additives in paint industry has been increased
significantly.
The use of silver for its antimicrobial properties, in bulk and colloidal forms, is
not a recent development [10, 20]. The antimicrobial properties of silver (Ag) date to
3000 years ago, when ancient civilizations used silver-based compounds for water
treatment. The discovery of antibiotics in the early twentieth century led to a
cessation in the development of silver as an antimicrobial agent. The discovery of
increasing levels of bacterial resistance to most antibiotics over the last decades has
led to reexamination of the potential of silver that was engineered into nanoparticles
(AgNP), defined as structures up to 100 nm in size [3, 34]. Current AgNPs are
extensively investigated and have found applications in many areas of science and
technology [27, 28, 33, 39] due to their unique size-dependent optical, electrical, and
magnetic properties. Currently, examples of where nanosilver is used include water
filters, cosmetics, deodorants, clothing, textiles, food packaging, functionalized
plastics, medical devices, wound dressings, detergents, biomedical products, and
electrical appliances such as washing machines and refrigerators [30]. There is also a
promising trend to impregnate commercially available paints with silver nano-
particles [14, 19, 21, 36]. Microbes are known to come into contact with walls in a
number of ways: by deposition of dust and fine aerosols, by human skin contact, and
by splashes from liquids. Microorganisms growing on building materials, such as
algae, bacteria, fungi, and lichens, are using these surfaces as a habitat that provides
them with all necessary nutrients. The exposure to microbial contaminants has been
associated with respiratory symptoms, allergies, asthma, and immunological reac-
tions and associated with the 20% of the documented infected cases with sanitary
assistance. Furthermore, molds growth affects materials causing their deterioration.
59 Silver-Nanoparticle-Embedded Antimicrobial Paints 1347

The nanosilver-based wall paint can potentially prevent the formation of mold inside
buildings and, by conjecture, the growth of algae on outside walls.
The mechanism of antimicrobial action of AgNPs is not well understood yet
[17]. Different postulations were suggested in the literature to elucidate the changes
occur to bacterial cell components after silver nanoparticles (AgNPs) treatment.
Some scientists assume bactericidal effect originates from Ag ions released from
AgNPs [35]. Namely, when exposed to dissolved oxygen in water medium, AgNPs
release small amounts of Ag according to equation

O2ðaqÞ þ 4H3 Oþ þ 4AgðsÞ > 4Agþ ðaqÞ þ 6H2 O ð1Þ

Another approach is based on the work of Morones et al. [31] who found AgNPs
attached to the cell membrane and inside the bacteria by TEM analysis. As Ag
possesses high affinity for sulfur and phosphorus compounds, it can be anticipated
that AgNPs will react with sulfur-rich protein in the bacteria cell membrane and
interior of the cell or with phosphorus-containing compounds such as DNA. There-
fore, detected morphological changes in the cell membrane of bacteria and possible
damage of DNA initiated by reaction with AgNPs have adverse effect on the
respiratory chain or cell division processes, causing a cell death.
This chapter gives an overview of latest developments in application of silver
nanoparticles as an additive in paint industry.

Ag-Nanoparticle-Embedded Paints

The major research on the functionalization of paint with AgNPs is focused on wall
waterborne paints. These paints, commonly acrylic-based, are suitable environment
for bacteria and fungi to grow, due to the fact that they contain cellulosic compounds
as thickeners. These compounds can be used by the microorganisms as carbon
source producing degradation of the paint: stains, color changes, chalking, and
adhesion loosening can be seen in an attacked paint.
Silver is usually added to the paints as nanosilver, silver salts, or silver zeolite.
Although today the technology to use engineered nanomaterials in paints is still in its
infancy, there are quite a number of articles which report about the antimicrobial
effects of nanosilver in paints [8, 11, 13, 26]. It was clearly demonstrated that
nanosilver in paints was very effective in killing resistant microorganisms, such as
Gram-positive and Gram-negative bacteria, fungi, and yeasts. The antibacterial
properties of AgNPs are influenced by morphology, size of NPs, and level of partial
oxidation, and it has been demonstrated that materials with larger surface area show
higher antibacterial activity [16].
The practical applications of AgNPs are limited to some difficulties with getting
NPs free of stabilizing agents. In order to represent typical AgNP-embedded paint,
AgNP synthesized via the cellulose fiber-based technique has been used [23]. The
obtained nanosilver particles suspended in water solution were spherical with
diameter of 13  5 nm. Common household acrylic paint widely used for renovating
1348 M. Abdukhakimov et al.

and decorating purposes has been used in further experiments. Silver-nanoparticle-

containing acrylic paint was obtained by diluting the initial paint sample with the Ag
colloidal solution in such a way as to get the desired value of nanosilver concentra-
tion within the desirable testing range. For the laboratory antibacterial tests, a 22 mm
x 22 mm pasteboard was covered with silver-nanoparticle-containing acrylic paint.
To evaluate the antibacterial and fungicidal properties of silver particles, Escherichia
coli was used as a representative Gram-negative bacterium; Staphylococcus aureus
and Bacillus subtilis were used as Gram-positive bacteria; Aspergillus niger,
Aureobasidium pullulans, and Penicillium phoeniceum were used to represent cos-
mopolitan saprotrophic fungi. Within the laboratory tests in order to evaluate the
antibacterial and fungicidal properties of Ag nanoparticles added to an acrylic paint,
samples with Ag-nanoparticle content as well as control samples were immersed in a
thin layer of beef-extract agar. 1 mL of suspension with approximately 105 CFU/mL
density of the microorganisms to be tested was distributed uniformly on agar surface
and incubated at 28  C (CFU ¼ colony-forming units). Antimicrobial activity was
evaluated according to the presence or absence of microbial growth just above the
sample after a 24-h incubation for bacteria and a 72-h incubation for fungi. All
microbiological tests were performed in triplicate.
For conducting field tests, the commercially available acrylic paint was thor-
oughly mixed with 200 ppm silver nanoparticles solutions in various ratios of 20:1,
50:1, and 100:1 in order to get 10 ppm, 4 ppm, and 2 ppm Ag-nanoparticle-
embedded paint [24]. In field tests building bricks as the surface of putting paints
on have been used. The bricks were painted at the temperature of 20  C by applying
two layers consecutively by the brush over the period of 7 days. The antimicrobial
effect of Ag-nanoparticle-embedded paint has been estimated after 1, 7, and 30 days
of painting. The bactericidal effect of the paint within field tests was studied using
Escherichia Coli ATCC 25922, Klebsiella pneumoniae ATTCC 13833, Staphylo-
coccus aureus Wood-45, and Pseudomonas aeruginosa 508. The antimicrobial
influence of the paints has been checked as follows. Suspension of strains
(0,1 mL), prepared in sterile physiological solution in the concentration of
107 CFU/mL, was coated on the surface of painted bricks. The incubation periods
were chosen to be 1, 3, 6, and 24 hours at room temperature. The sowing was
performed on plates with nutrient medium. SEM measurements have been used to
observe silver nanoparticles on the surface of the modified paint. As one can see
from Fig. 1, most of initial silver nanoparticles had agglomerated into clusters up to
300 nm in size because of attractive interaction forces between them.
The following photographs in Fig. 2 are typical presentation of microbial analysis
of a paint film. They show growth of P. phoeniceum and A. pullulans cultures on
pasteboard samples modified by silver nanoparticles. The absence of visible growth
of the microbes on the sample #2 confirms the antibacterial/antifungal effect of Ag-
nanoparticle-embedded paints. The analogous experiments conducted [22] with
A. niger and S. aureus cultures have also demonstrated a pronounced antifungal/
antibacterial efficacy of the water paint modified by silver nanoparticles of 0.8 μg/
cm2 density. Field tests have been conducted using building bricks as the surface of
putting paints on (see Table 1).
59 Silver-Nanoparticle-Embedded Antimicrobial Paints 1349

Fig. 1 Sample of Ag-nanoparticle-embedded water paint (note the spherical structures

corresponding to nanoparticles)

Fig. 2 Growth of P. phoeniceum (left) and A. pullulans (right) cultures on pasteboard samples
modified by silver nanoparticles. (Note the white spots corresponding to microbial colonies.)
Sample #1 is a control sample, i.e., it was covered with nonmodified paint; sample #2 was covered
with the paint modified by silver nanoparticles of 0.8 μg/cm2 density

As seen from Table 1, all tested Ag-nanoparticle-embedded paint samples

revealed a bactericidal effect on the surface of bricks. Increase of the nanosilver
concentration from 2 ppm up to 10 ppm leads to more pronounced antimicrobial
effect. The revealed antimicrobial efficiency of the paint samples without silver
nanoparticles is connected with the bactericidal influence of some components of
the paint. It is supposed that with the course of time, paint-volatile components will
1350 M. Abdukhakimov et al.

Table 1 The antimicrobial effect of Ag-nanoparticle-embedded paints on different microbial

strains
Amount of bacteria on the surface
of the paint, CFU
Microbe Paint samples 1 3 6 24
Escherichia Coli ATCC 25922 Control sample 150 10 1 0
2 ppm nanosilver 120 10 0 0
4 ppm nanosilver 100 0 0 0
10 pm nanosilver 20 0 0 0
Klebsiella pneumoniae ATTCC 13833 Control sample 300 40 10 1
2 ppm nanosilver 250 30 5 0
4 ppm nanosilver 130 30 12 0
10 pm nanosilver 50 5 0 0
Staphylococcus aureus Wood-45 Control sample 400 100 50 10
2 ppm nanosilver 320 90 20 0
4 ppm nanosilver 200 70 10 0
10 pm nanosilver 50 10 1 0
Pseudomonas aeruginosa 508 Control sample 300 120 50 1
2 ppm nanosilver 270 100 30 0
4 ppm nanosilver 200 80 30 0
10 pm nanosilver 80 30 5 0

be evaporated that will reduce the antimicrobial efficiency of the control samples of
the paint without nanosilver.
Silver-containing paint was able to retard the initial colonization and growth of
L. pneumophila, for up to 14 days (Rogers et al. 1995). Although this paint was
unsuitable for controlling biofouling over extended time periods, the data suggest
that a reformulated paint or electrochemical method of introducing silver ions may
be successful.
AgNPs can also enhance some selected physical and mechanical properties of
emulsion paint [4]. Extensive characterization indicates that the paint containing
equal fraction (0.175 wt%) of AgNPs and benzimidazole carbamate (EPW) gave the
optimal mix for all physical and mechanical properties examined. The specific
gravity was reduced by 16%, the hiding power/opacity increased by 30%, while
the abrasion strength was enhanced by 236%.
AgNP can be also used in paint industry in a combination with other nano-
particles. For instance, in the study of Bellotti et al. [5], they evaluated the incorpo-
ration of silver (of two different sizes), copper, and zinc oxide nanoparticles in
indoor waterborne paints and the bio-resistance imparted by them. This mixture of
nanoparticles inhibited the growth of C. globosum and A. alternata in agar plate
assays, being 10-nm-size silver nanoparticles the more efficient one.
In the interesting study of Tornero et al. [38], hybrid ZnO-AgNPs possessed
significant antimicrobial properties against bacteria (Pseudomonas aeruginosa,
L. monocytogenes, Salmonella spp., S. aureus, and B. subtilis). This waterborne
59 Silver-Nanoparticle-Embedded Antimicrobial Paints 1351

paint accomplishes with the European Ecolabel criteria, with broad-spectrum anti-
microbial effect due to the use of ZnO-AgNPs on its matrix, and with VOC content
100 times less than the limit for indoor decorative paint.

Environmental Impact of the AgNPs

There is still no evidence that humans are being adversely affected by AgNPs while
using paints with AgNPs, but it is very likely that AgNPs will be released into
environment where they persist or bioaccumulate [40]. The levels in the environment
are difficult to determine as they are present at low concentration and AgNPs undergo
complicated reactions which change their speciation including dissolution, aggrega-
tion, and chemical complexation [12, 30]. The proliferation in the use of AgNPs in
different applications hastens the need for the development of inventories of AgNP-
containing products at national and international levels [37]. For instance, the United
States Environmental Protection Agency (US EPA) has developed requirements for
companies that manufacture “chemical substances containing primary particles, aggre-
gates, or agglomerates in the size range of 1 to 100 nm in at least one dimension”
[1]. As for the US Food and Drug Administration, it has issued a series of guidance
documents with respect to the use of nanotechnology in FDA-regulated products [2].
Mueller and Nowack [32] mentioned that paints are among the most important
sources for AgNP released in the environment (comparing with nanosilver-modified
textiles, cosmetics, cleaning agents, and plastics). Despite leakage of silver from
outdoor paints, it is not taken into consideration in many of the existing models of
silver fate in the environment [6].
Release of (nano)silver from outdoor paint (containing 1.5 mg Ag/m2 of painted
surface; average concentration in wet paint—6.2 mg silver nanoparticles/kg) was
investigated by Kaegi et al. [18]. The experiment was conducted over 372 days,
during which 65 runoff events occurred. The authors found significant leaching of
silver nanoparticles (up to 145 μg Ag/L during the initial runoff events). After 1 year
more than 30% (0.5 mg/m2) of the initial mass of silver was released into the
environment, of which 80% was released during the first eight runoff events. In
contrast, only 1% of titania pigments was released during 1 year. Released silver
particles were mostly <15 nm in size, and further analysis revealed that most of the
released metallic silver was transformed into less toxic forms such as Ag2S. Wider
use of silver-containing outdoor paints can thus contribute to a significant increase in
the amount of silver released into the environment since most of the silver nano-
particles from the outdoor paint were gone after 1 year.
Due to their low expected concentration when compared with total silver and
dearth of available capture methods, there have been little to no analytical studies
carried out to quantify the specific contribution of AgNPs to the presence of silver in
the environment. As the concern for environmental and human health risks is
growing and consequently, further research that may discover the real role of
AgNPs in environment is needed.
1352 M. Abdukhakimov et al.

Conclusion

Currently silver nanoparticles are one of the most often explored nanomaterials in the
field of paint industry due to extraordinary antimicrobial activity against numerous
microbes. The tests conducted demonstrate that Ag-nanoparticle-embedded paints
show a pronounced antibacterial/antifungal effect compared to standard paint. The
presence of silver nanoparticles in paints may lead to the inhibition activity of a wide
number of Gram-positive and Gram-negative bacteria, which is very hard to prevent
nowadays. The antibacterial properties of AgNPs are influenced by morphology, size
of nanoparticles, and level of partial oxidation, and it has been demonstrated that
materials with larger surface area show higher antibacterial activity. As the concern for
environmental and human health risks is growing and consequently, further research
that may discover the real role of AgNPs in environment is needed.

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Eco-friendly Nanostructured Materials
for Arsenic Removal from Aqueous Basins 60
Estefanía Baigorria, Romina P. Ollier Primiano, and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1356
Arsenic in Water Bodies: Occurrence, Sources, and Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
Occurrence and Environmental Mobility of Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1358
Health Effects Due to Arsenic Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1360
Mechanisms for Arsenic Removal from Water Basins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1362
Nanostructured Materials (NSM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1364
Nanostructured Materials for Arsenic Removal: Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368
Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374

Abstract
The contamination of water basins used as drinking water resources is a topic of
major concern for public health. Arsenic is one of the major sources of aqueous
contamination of broad global-level concern. This metalloid reaches aqueous
basins by natural and anthropogenic activities causing countless problems in
the environment, so its removal is of great importance. Numerous technologies
are used to further reduce or eliminate arsenic from aqueous systems using
various materials as active components. Nanostructured materials offer large
contact surfaces and unique properties for efficient arsenic removal from
E. Baigorria
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina
Institute of Science and Technology, São Paulo State University (UNESP), Sorocaba, Brazil
e-mail: [email protected]
R. P. Ollier Primiano (*) · V. A. Alvarez
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina
e-mail: rominaollier@fi.mdp.edu.ar; alvarezvera@fi.mdp.edu.ar

© Springer Nature Singapore Pte Ltd. 2022 1355

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_107
1356 E. Baigorria et al.

contaminated water by different techniques. Many developments have been

recently proposed as sustainable and environmentally friendly solutions for this
purpose. In addition, there is promising evidence of the use of these nanomaterials
for the removal of toxic metals from aqueous sources.
The aim of this chapter is to present a holistic view of the most recent
eco-friendly nanostructured materials used for arsenic removal from contami-
nated aqueous systems. Different aspects of each approach are discussed, such as
the removal efficiency, the cost-effectiveness, the ease of manipulation, separa-
tion and regeneration, and the suitability for field application and the challenges
that are involved.

Keywords
Arsenic · Nanostructured materials · Nanomaterials · Water remediation

Introduction

Water is the most essential and important component of life on Earth. Only 2.5% of
all the water on Earth is freshwater, of which about 30% is groundwater, which is
used for drinking, irrigation, and industrial purposes globally [1]. Pollution and
degradation of the aquatic environments due to the presence of many harmful
compounds is recognized as one of the main global concerns of our society.
Particularly, arsenic (As) is one of the nonessential metalloids that seriously affects
all living beings including plants and animals. Unfortunately, many people from
various countries across the world are daily exposed to high levels of As by
consuming contaminated water for drinking, food preparation, crop irrigation, and
industrial processes.
Arsenic is a metalloid that belongs to group 15 of the periodic table. It naturally
occurs in air, soil, water, rocks, plants, and animals. This metalloid is the 20th most
abundant element on Earth and comprises 0,0005% of the Earth’s crust. Besides, it is
the 14th most abundant element in seawater [2]. Arsenic occurs in the
3, 0, +3, and
+5 oxidation states and appears in the form of various chemical species. Inorganic
forms of arsenic, based on As(III) or trivalent As and As(V) or pentavalent As, are
predominant in water supplies. Among all the heavy metalloids, arsenic is particu-
larly sensitive to mobilize at pH values in the range of 6.5–8.5, under both oxidizing
and reducing conditions [3]. Arsenic is mobilized in the aquatic environment
through a combination of natural and biological processes as well as through
different anthropogenic activities [4].
Arsenic contamination of surface and groundwater is a serious ongoing public and
environmental health problem that affects hundreds of millions of people worldwide.
In 1993, the World Health Organization (WHO) revised the guideline for drinking
water quality, and the permissible limit of arsenic was reduced from 50 to 10μg/L in
order to minimize the harmful effects of this element on human health [5]. However, it
has been reported the presence of As exceeding this limit in several locations from
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1357

more than 70 countries such as Argentina, Australia, Bangladesh, Chile, China,

Hungary, India, Italy, Mexico, Peru, and the United States [4, 6].
Arsenic is extremely toxic to the human organism, not only in high concentrations
where exposure causes acute effects that can be lethal, but also exposure to low
concentrations over a long period of time has chronic negative effects. Arsenic
poisoning of humans can take place by gradual accumulation of small doses until
lethal levels are reached. Millions of human beings are chronically exposed to
elevated concentrations of As via drinking of As-contaminated water or indirectly
by consumption of vegetables and foodstuff. Low to moderate levels of long-term
arsenic exposure (10–300μg/L) through drinking water lead to several adverse health
complications and illnesses including mortality [7–9]. Arsenic is known for its
carcinogenicity affecting different organs like skin, liver, lung, kidney, and bladder,
as well documented [8, 9].
The prevention of further exposure to arsenic through the provision of safe water
supply is the most important action that should be taken in all the affected commu-
nities. Therefore, there is an imperative need to design water remediation technol-
ogies which can be effectively adopted by the underdeveloped and developing
countries. Nevertheless, arsenic removal from water bodies is a complex task and
represents a great challenge to the scientific community and environmental
engineers. Up to now, numerous technologies have been developed for the treatment
of arsenic-contaminated water bodies, among which are the processes of oxidation/
precipitation, coagulation/electrocoagulation, ion exchange, membrane filtration,
and adsorption, among others. Some of these technologies are commercially avail-
able [10, 11]. However, most of these methods have significant drawbacks, such as
large waste generation, high cost and energy requirements, and high operational and
maintenance requirements [12]. Besides, some of these methodologies can effec-
tively remove arsenic from water bodies containing high initial arsenic concentra-
tions (>100 mg/L) but are not capable of removing small traces found, for example,
in drinking water exceeding the water quality standard [4, 13]. Therefore, effective
and simple technologies for the removal of arsenic from contaminated water bodies
are urgently required. Moreover, there has been an increasing demand from con-
sumers for cost-efficient devices, made from bio-based starting materials by envi-
ronmentally friendly manufacturing processes, which exhibit superior As removal
capacities [4]. In this sense, novel eco-friendly nanomaterials have emerged as
promising alternatives to provide more sustainable solutions, by offering extensive
surface areas, unique functionalities, and tunable properties at the nanoscale, leading
potentially to enhanced As removal. Therefore, a wide spectrum of nanomaterials
based on environmentally friendly raw materials and manufacturing techniques have
been explored for the elimination of arsenic from water bodies by different technical
approaches. However, it is worth to bear in mind that these innovative nanostruc-
tured devices must be easy to handle and adequate for full-scale implementation at
household and community levels in order to provide realistic solutions.
In view of the abovementioned facts, the aim of this chapter is, first, to provide an
overview with a general description of the occurrence, environmental mobility, and
toxicity of arsenic to understand the gravity of this current worldwide problem and
1358 E. Baigorria et al.

then to critically review the most recent products that have been developed to
provide technological solutions for treating or removing arsenic, based on
eco-friendly nanostructured materials. Several techniques for the treatment of
As-contaminated water bodies are deeply discussed, and the removal efficiencies
are compared.

Arsenic in Water Bodies: Occurrence, Sources, and Toxicity

Occurrence and Environmental Mobility of Arsenic

The occurrence, distribution, origin, and mobility of arsenic over a wide range of
redox conditions have recently gained great concern worldwide due to the increasing
awareness of its toxicity. Arsenic is a ubiquitous element that is uniformly distrib-
uted in unpolluted aquatic environments and is naturally present in high concentra-
tions in the groundwater of several countries [4].
The mobilization of arsenic in groundwater is naturally controlled by several
processes such as dissolution/precipitation, adsorption/coprecipitation, reduction/
oxidation, and biological activity. The different processes depend on the geology,
hydrogeology, and geochemistry of the region, and its concentration may vary by
more than four orders of magnitude depending on these factors [3]. It mainly comes
from volcanic rocks, specifically their weathering products and ash, marine sedi-
mentary rocks, hydrothermal ore deposits and associated geothermal waters, and
fossil fuels, including coals and petroleum. Arsenic is naturally present in a wide
range of minerals in soils in several forms of inorganic compounds, for example,
arsenates, sulfides, sulfosalts, oxides, arsenide, and silicates, among others which are
usually the major starting point for the introduction of arsenic into the environment
[7, 14]. It is present as a substitute of S in the crystal lattice of various sulfide
minerals.
Depending on the location, the ubiquity of arsenic in soil and aqueous environ-
ments may be substantially intensified by anthropogenic or nonnatural sources that
arise from several human activities [6] as depicted in Fig. 1. Arsenic has been used
though history for various applications. For example, in the past, inorganic arsenical
fungicides, herbicides, insecticides, and crop desiccants, such as lead arsenate,
calcium arsenate, copper acetoarsenite (Paris green), and sodium arsenate, were
extensively used for debarking trees, to control ticks, fleas, and lice, and in aquatic
weed control. All these compounds were eventually banned because of the toxic
effects of inorganic arsenic and the increasing public awareness about food safety
and environmental contamination [6]. However, because of the environmental
persistence of these compounds, large areas of land are still contaminated. Other
newer organoarsenic-based pesticides began to be used in the 1950s and are still
applied in the present in certain crops with strict limitations on their dose. These
pesticides are based on pentavalent organic arsenic, which are much less toxic than
inorganic arsenic species as mentioned above. Some examples include monosodium
methanearsonate (MSMAsV) and dimethylarsinic acid (DMAsV, known as cacodylic
 60
Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . .

Fig. 1 Natural and anthropogenic As inputs and predominant inorganic As species as a function of Eh and pH (at 25  C and 1 bar total pressure) in aquatic
environments
1359
1360 E. Baigorria et al.

acid). MSMAsV is a broadleaf weed herbicide for use on cotton, and small doses of
cacodylic acid were historically used as herbicides in cotton fields, golf courses,
backyards, and other areas, but its use is now prohibited. Besides, arsenic has been
commonly used in wood preservation treatments since 1940 by impregnating with
chromated copper arsenate or “CCA” (composed of CuO (18.5%), Cr2O3 (47.5%),
and As2O3 (18.5%)) in order to mitigate the deterioration caused by the attack of
insects and microbial agents. Huge amounts of arsenic are released to the environ-
ment by mining and smelting of sulfide ores or by leaching through landfill or waste.
Emission of As also takes place by volatilization of As4O6 due to burning of coal in
thermal power plants and disposal of fly ash, which is ultimately transferred into
water bodies [15]. Arsenic trioxide (As2O3) is widely used as refining agent for the
production of lead glasses. In addition, inorganic arsenic is frequently used as dopant
material in the microelectronics industry for the manufacture of certain semiconduc-
tor devices. Arsenic is also industrially used in pigments, textiles, lead–acid batte-
ries, copper refining process, and a metal alloying agent [6].
One of the most stable and nonradioactive isotopes of arsenic is 75As, and it can
occur in various chemical forms with different oxidation states:
3, 0, +3, and + 5.
Arsenic may appear in inorganic forms as arsenate (As(V)) or arsenite (As(III))
species and in organic derivatives, i.e., monomethylarsonic acid (MMA) and
dimethylarsinic acid (DDA). As(III) and As(V) are usually the main soluble species
in waters, whereas concentrations of organoarsenic compounds are rarely quantita-
tively important. In natural conditions, As inorganic species are subjected to chem-
ically and biologically mediated reactions like oxidation, reduction, and methylation,
and this is the major reason for the diversity of species of arsenic in the aquatic
ecosystem [14].
Arsenic changes its valence state and chemical form in different environmental
conditions. Figure 1 shows the speciation of As in groundwater depending on the pH
and oxidation–reduction potential (Eh) [14]. Proportions of As(III) and As
(V) species are variable and may depend on the source of the water bodies
[3]. Both oxidation states may exist within the pH range of 6–9. In groundwater,
As(III) appears as neutral H3AsO3 (predominantly, the pKa1 of H3AsO3 is 9.2),
H2AsO3
, and HAsO32
, which are not adsorbed efficiently onto mineral surfaces.
In contrast, As(V), existing mainly as charged monovalent H2AsO4
and divalent
HAsO42
species (the pKa1 of H3AsO4 is 2.3; the pKa2 of H3AsO4 is 6.8; the pKa3 of
H3AsO4 is 11.6), is adsorbed easily onto solid surfaces [16]. Regarding the toxicity
and the removability of arsenic species, trivalent forms of As are considered to be
more difficult to remove from water and 25–60 times more mobile pentavalent As
species; therefore, they are more harmful in nature [17].

Health Effects Due to Arsenic Exposure

Ingestion, inhalation, and skin absorption are some of the crucial routes for arsenic
entering the human body. Arsenic is mainly incorporated through contaminated
drinking water and, in a minor extent, ingested in food, i.e., vegetables, fruits,
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1361

cereals, meat, and seafood. Millions of people from over 70 countries around the
globe daily consume As-contaminated drinking water, which is the main way of
exposure to this toxic element. Besides, arsenic and its compounds that are present in
the soil and in the water supply may be absorbed by crops, for example, rice, oat, and
wheat, which then enter into the food chain and are consumed by animals and human
beings. For example, recent effort has been done to reduce the arsenic content in rice,
and several arsenic species have been identified in liver and breast meat of chickens
which were fed with As-containing poultry [18].
Arsenic toxicity in the cell depends on the nature of the species, being inorganic
forms of As generally much more harmful than the organic ones. Both pentavalent
and trivalent arsenic compounds are rapidly and extensively absorbed from the
gastrointestinal tract. Arsenic can interact with several essential biomolecules in
the body, and it may be absorbed and accumulated in living tissues and body
fluids [17].
Excessive and long-term intake of As-contaminated drinking water and food may
result in an illness known as arsenicosis. Inorganic arsenic is considered by the
International Agency for Research of Cancer (IARC) as a potent Group 1 human
carcinogen causing cancers of various organs such as the bladder, lung, skin, kidney,
and liver [8, 9]. Several studies have linked chronic exposure to arsenic via drinking
water to various noncancer illnesses including multi-organ failure, diabetes, and
cardiovascular, dermatological, reproductive, endocrinological, immunological,
neurological, and respiratory problems [8, 9]. Furthermore, it has been shown that
As is a very potent endocrine disruptor that interferes with different hormones by
altering their function [9].
Several biochemical mechanisms have been proposed in order to understand the
ability of arsenic to cause so many diverse disease problems. Overall, arsenic pro-
duces its toxic effects in a variety of ways by altering the cellular metabolism and
signaling, the cell cycle control, growth, and proliferation, thus resulting in diverse
cellular effects such as apoptosis induction, growth inhibition, promotion, or inhi-
bition of differentiation and angiogenesis [9]. Each inorganic form of arsenic enters
and acts in the cell in a different way. As (III) and As (V) are taken up into the cell by
glycerol and phosphate transporters, respectively, due to their similar chemical
structure. On the one hand, trivalent As species have strong reactivity with thiol
groups, and, therefore, they can react with cysteine residues in the proteins, causing
alterations in their conformation and function and affecting the crucial roles of
enzymes, receptors, and transcription factors in several metabolic processes in the
body [8, 9]. Another consequence of As (III) affinity toward thiol groups is the
ability of reacting with glutathione, glutaredoxin, and thioredoxin, which affects
their key functions as antioxidants, in the intracellular redox homeostasis, deoxyri-
bonucleotide synthesis and repair, etc. Another consequence of As (III) reaction with
glutathione is the increment of the oxidative stress and the increased production of
reactive oxygen species (ROS) that may damage important biomolecules, i.e., DNA,
lipids, and proteins [8, 9]. On the other hand, As (V) species are analogues of
inorganic phosphate. Its main interference is indeed related with the metabolism of
phosphorous, by disrupting several biochemical processes, for example, in the
1362 E. Baigorria et al.

phosphorylation process and therefore preventing the synthesis of ATP (adenosine

50 -triphosphate) and altering ATP-dependent pathways. Moreover, arsenic can inter-
fere with normal metabolic processes by displacing Zn and Se from their binding
sites [8].

Mechanisms for Arsenic Removal from Water Basins

The contamination of water basins by arsenic generates numerous environmental

and health problems worldwide as previously pointed out. The treatment of water
contaminated with As is of vital importance and can be carried out by different
methodologies [4, 19, 20] (Fig. 2).
The techniques used for arsenic removal from contaminated aqueous systems can
be classified as follows:

• Biological methods
• Oxidative methods
• Separative methods

Biological environmental remediation methodologies involve the activity of

various microorganisms. These microbes take advantage of their metabolic activities
to carry out different processes on the target pollutant [19, 20]. Biological oxidation
or bio-oxidation caused by fungi, bacteria, or natural flora acts on the removal of
aqueous arsenic in several ways. Mechanisms such as oxidation and methylation of
arsenite, for example, to obtain the least toxic form of arsenate, are efficient for the
removal of aqueous arsenic [19, 20]. On the other hand, phytoremediation
(phyto- means flora) is another biological methodology for the removal of arsenic

Fig. 2 Methodologies for arsenic removal from water

60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1363

from contaminated water. In this case, technologies that rely on natural or genetically
modified plants are used for the removal of such contaminants. Phytoremediation
uses several processes: phytofiltration or rhizofiltration, phytoextraction,
phytodegradation, and phytovolatilization [20].
Oxidative processes achieve arsenic removal by converting As (III) to As (V),
through chemical oxidations and advanced oxidation processes (AOPs) [4, 20]. AOPs
are mainly used for the removal of nonbiodegradable aqueous contaminants such as
As. This methodology generates species with high oxidative potential such as hydroxyl
radicals, which are responsible for oxidations in the pollutants [19, 20]. Among the
AOPs used in the remediation of aqueous As are Fenton, photo-Fenton, photolysis,
photocatalysis, sonochemical methods, zerovalent aluminum/O2 process, electrochem-
ical advanced oxidation processes, and sulfate radical-based AOPs [4, 19, 20].
On the other hand, separation methods commonly used for the removal of
aqueous As include water treatment technologies where the contaminant is trans-
ferred from the aqueous phase to another phase (liquid or solid) [4, 19, 20]. Separa-
tion methods include coagulation (chemical or electrocoagulation), flocculation,
sedimentation, membrane processes, and adsorption [19, 20]. In aqueous decontam-
ination treatments involving coagulation processes, they are generally followed by
flocculation and sedimentation processes [19]. In these processes, a coagulating
agent is added that generates the destruction of the forces that stabilize the colloidal
particles in an aqueous solution so that the suspended solids are agglomerated,
forming larger particles. In this way, the process of elimination of these solids
from the solution is facilitated. These physical removal processes can be flocculation
and filtration [19, 20]. Membrane processes are effective treatments for the removal
of aqueous contaminants such as As. In these techniques, membranes allow the
separation of chemical pollutants depending on their characteristics (size, electrical
charge, etc.), retaining them in the membrane [19, 20]. For arsenic removal, mem-
brane processes depend on several factors such as membrane material, pore size,
concentrations in solution, and membrane surface charge, among others [20]. In
addition, membrane processes commonly used for aqueous As removal can be
pressure-driven such as ultrafiltration, nanofiltration, reverse osmosis, and electro-
dialysis [4, 20]. Finally, adsorption is a process of great technological importance
where a substance such as As is adsorbed to a solid surface. This adsorption process
is the result of different chemical and physical forces between the adsorbent and the
adsorbate [4, 21]. Adsorption techniques are flexible and widely used in the removal
of aqueous pollutants due to their high efficiency in removing aqueous organic
and inorganic substances. In particular, arsenic is able to adsorb on surfaces of
different categories of adsorbent materials such as clays, metal oxides, polymeric
resins, activated carbon, iron-based sorbents, and active alumina, among others
[4, 20, 21].
Compared to all the aforementioned methodologies, adsorption is able to remove
small traces of contaminants that the other techniques mostly leave behind in the
treated aqueous medium [4, 21]. In addition, it is a low-cost, highly versatile
technique that is one of the most suitable processes, together with oxidation, for
the removal of arsenic from contaminated aqueous systems [4, 20].
1364 E. Baigorria et al.

Nanostructured Materials (NSM)

The high costs of water treatment processes are one of the main factors limiting the
availability of water suitable for consumption. The choice of suitable materials for
this purpose is of vital importance in this area. The conventional materials used for
environmental remediation present several limitations for this purpose. The main
problem is that they are larger than a micrometer in size, their physicochemical
properties, and their low capacity to remove small traces of contaminants from the
environment. In this sense, nanostructured materials overcome the restrictions of
other materials and are more efficient for the removal of pollutants, in this case, from
aqueous systems [22–24].
All material that possesses surface and internal structure, composed of structural
elements (crystalline, molecular, or clusters) on the nanometric scale, is called a
nanostructured material. Their nanometer size (<100 nm) and high surface area-to-
volume ratio, among other unique characteristics, make them a nanotechnological
component with multiple applications [23]. The high surface area, the wide
functionalization capacity, and their physicochemical properties make the materials
nano-entities with wide versatility. They also present innumerable applications with
emphasis on environmental remediation, a topic that is attracting worldwide
attention [23].
Nanostructured materials are highly efficient for the removal of complex organic
and inorganic pollutants and contaminants with high volatility, among others.
Depending on the synthetic design used for their formation, these nanomaterials
can show high affinity toward specific target compounds [23]. Modifications in the
peripheral physicochemistry in the design of nanoparticles are a good option before
the synthetic approach of nanoparticles depending on their target molecule. On the
other hand, several interesting aspects of nanostructured materials for environmental
remediation should be taken into account such as low cost, versatility, high envi-
ronmental friendliness, recyclability, structural uniqueness, low toxicity, and a wide
possibility of posttreatment recovery [21, 23].

Classification

In order to understand the large number of existing nanostructured materials, a

classification of these materials must be made. Such classification can be carried
out taking into account several aspects; however, classifying them according to their
preparation method allows to further classify them into different categories.
There are two main approaches to the method used for the preparation of NSMs:
top-down and bottom-up. The top-down method involves physical methods such as
mechanical milling, extrusion, cutting, pounding, and chipping, among others.
Bottom-up frequently uses solution-phase chemistry. Furthermore, the preparation
of such materials can be carried out in solid, liquid, vapor, or combined phases [25].
However, depending on the method of preparation of nanostructured materials,
morphology, dimensions, agglomeration, uniformity, and other aspects vary [23, 25].
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1365

Fig. 3 Nanostructured material classification by chemical composition

Morphologically NSMs can be arranged as helices, zigzag, helically, and as belts. They
can also take oval, spherical, cubic, pillar, and prism shapes. Considering their dimen-
sions, they can be classified as 0-dimensional (0D), one-dimensional (1D),
two-dimensional (2D), and three-dimensional (3D) [25].
Another classification that is widely adopted is according to their chemical
composition (Fig. 3). In this sense, nanostructured materials are classified as
carbon-based nanostructured materials, transition metal oxide-based, super-
paramagnetic, titanium-based, mineral-based, metal-based, hybrid nanostructured
materials, and other nanostructured materials [23, 25].

Carbon-Based Nanostructured Materials

Carbon-based nanostructured materials include carbon allotropes such as amor-
phous carbon, graphite, and diamond. They are widely used in environmental
pollutant removal treatments due to their broad sorption capabilities and naturally
lacking toxicity. They generally take various forms including hollow spheres,
ellipsoid, or tube shapes. Considering their structure and properties, they can be
classified as fullerenes (0D), carbon nanotubes (CNT) (1D), graphite sheets (2D),
and diamond and graphite crystal (3D) [23, 26, 27]. The main nanostructured
materials reported in the literature for use as aqueous purification agents are
1366 E. Baigorria et al.

graphene (G), graphene oxide (GO), single-walled carbon nanotubes (SWNT), and
multi-walled carbon nanotubes (MWNT) [23, 26, 27].

Iron Oxide-Based Nanostructured Materials

Nanomaterials composed of metal oxides are of great interest in various areas due to
their important properties (electrical, electrochemical, adsorbent, magnetic)
[23, 28]. Among the great diversity of existing transition metal oxides, those iron
oxides attract the attention of scientists. Iron oxides are abundant and inexpensive
materials, which is why their utilization is so diverse [23, 28, 29]. Among the iron
oxide-based nanomaterials are hematite (α-Fe2O3), maghemite (γ-Fe2O3), and mag-
netite (Fe3O4). Nanostructured materials based on iron oxides are efficient as
photocatalysts and nano-adsorbents for various inorganic and organic pollutants in
aqueous systems. In addition, they exhibit biomass immobilization capability
[23, 28, 29].

Superparamagnetic Nanostructured Materials

Those nanoparticles formed by magnetic particles without permanent magnetic
moments are called superparamagnetic particles [23, 30]. The use of nanostructured
materials sputtered with superparamagnetic iron oxide for the removal of heavy
metals has been reported in the literature [23, 25]. Besides, surface functionalization
of such nanoparticles with di-mercaptosuccinic acid has been found to be effective
for the sorption of metals such as silver, cadmium, thallium, and mercury [23, 30].

Titanium-Based Nanostructured Materials

Titanium-based nanostructured materials are mainly composed of titanium oxide
(TiO2). These nanomaterials are applied for adsorption and mainly for photo-
degradation of various organic as well as inorganic pollutants [23, 31, 32]. In addition,
hydrated titanium oxides (HOTi) exhibit a broad affinity for heavy metals [33]. HOTi
is a nanomaterial with promising properties as a purifier of polluted water and exhibits
broad stability even under challenging pH conditions [23, 31, 32].

Nanostructured Materials Based on Minerals

Numerous materials are present in nature, such as clays, which exhibit significant
properties and offer constant inspiration for the preparation of nanostructured mate-
rials with broad applications. Nanoclays are sustainable and abundant nanomaterials,
due to the fact that under environmental conditions, such as weathering and hydro-
thermal alteration, they are generated at a constant rate in nature [4, 34]. These
nanostructured minerals, being naturally abundant, present an economic advantage
over other nanomaterials [4, 21].
Nanoclays exhibit significant potential due to their layered structure, high thermal
and mechanical stability, and extensive sorption capabilities [4, 21, 34]. In addition,
they present extensive cation exchange capacity and varied functionalization possi-
bilities due to their interesting structural and surface properties [4, 21, 34]. Due to
these characteristics, nanoclays have been widely studied for the removal of aqueous
contaminants [4, 21, 34]. Their structure consists mainly of hydrated aluminum
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1367

silicates, whose layers contain various cations such as sodium, magnesium, and iron,
among others. Among the most commonly used nanoclays in environmental reme-
diation are bentonite, montmorillonite, goethite, kaolinite, light expanded clay
aggregate (LECA), bauxite, and zeolite [4, 34–36].

Metal-Based Nanostructured Materials

Nanomaterials based on metals have recently presented a wide interest due to their
important physicochemical, optical, and magnetic unique properties [23, 25].
Among these nanostructured materials, those containing iron, titanium, silver,
gold, zinc, and copper are among the most widely used [23, 25]. Silver nano-
particles are very efficient acting as photocatalysts in the degradation of countless
environmental pollutants, mainly aqueous ones [23, 25]. Gold nanoparticles also
present great interest in the area of environmental remediation. It has been
reported that gold nanoparticles coated with 4-aminophenol were found to be
efficient in removing heavy metals as aqueous pollutants [23, 25]. On the other
hand, nanostructured materials based on zero-valent iron nanoparticles exhibit
high aerobic sensitivity and are used for the removal of heavy metals from water
[23, 25].

Hybrid Nanostructured Materials

Many of the aforementioned nanostructured materials present several drawbacks
such as aggregation of their particles, sludge formation, and difficulties in handling
and reuse [19, 21, 37]. Besides these aspects, improvement in contaminant selectiv-
ity, increase in physicochemical properties, improvement in kinetic aspects, regen-
eration, and recovery of nanomaterials have been of importance for the development
of hybrid nanostructured materials [19, 21, 37]. Numerous investigations have been
carried out with the aim of improving nanostructured materials in various aspects as
well as increasing their suitability and feasibility for applications in environmental
remediation [19, 21, 24, 37].
The combination of properties of two or more components in nanostructured
hybrid materials gives them unique physical and chemical properties, different from
those of their individual components. In general, hybrid nanomaterials offer superior
aspects to those of conventional nanomaterials. The development of these nano-
materials provides new opportunities for applications in various environmental
pollutant removal technologies.
Literature reports show the use of hybrid nanomaterials between inorganic
compounds for the removal of heavy metals from contaminated water. Nanostruc-
tured materials are composed of graphene oxides/titanium dioxide, graphene oxides/
magnetite, and graphene oxides/silicon dioxide [38–40]. On the other hand, nano-
structured hybrid materials formed by polymers and inorganic nanocomposites such
as clays or metal oxides have been reported in the literature for heavy metal removal
in waters [19]. Polymeric supports are widely used to increase properties and
stabilize nanoparticles of different types [19, 23]. The polymers used are generally
natural polymers such as carbohydrates, proteins, and nucleic acids, as well as
synthetic chemical polymers [19].
1368 E. Baigorria et al.

Other Nanostructured Materials

In the last 20 years, research in nanomaterials and nanotechnology has advanced
considerably. In 2011, researchers at Drexel University discovered a new class of
nanostructured materials which they called MXenes [41]. These nanomaterials possess
2D structures and are transition metal carbides, nitrides, and carbonitrides. The general
form of these nanostructured materials is Mn+1XnTx [41]. Since their discovery,
MXenes have had a wide range of applications including environmental remediation.
The interesting features of these nanomaterials are due to their high surface area,
active metal hydroxide sites, biocompatibility, ease of functionalization, high metal
content, conductivity, and hydrophilicity that make them the best candidates for
applications in environmental remediation, energy storage, electronics, sensors, and
catalysis. In addition, they offer sites for direction exchange but also have reduction
capabilities for some cations and organic molecules [41]. These specific peculiarities
of MXenes make them ideal candidates for aqueous purification [41]. Nanostructured
polyvinylalcohol/polyacrylic acid/Fe3O4/MXenes/Ag and pure MXene nanostruc-
tured materials have been reported for the removal of aqueous organic pollutants
[42]. In addition, MXene (Ti3C2TX) has been reported for the removal of inorganic
anions from drinking water [41].

Nanostructured Materials for Arsenic Removal: Applications

The wide range of NSM shown above presents extensive fields of application in the area
of environmental remediation. The nanometric size of these materials makes them
superior to many others, and therefore the results obtained, for example, in the treatment
of water contaminated with heavy metals are better. In this sense, the application of
aqueous arsenic removal technologies at the nanoscale exhibits high efficiency.
Carbon-based nanostructured materials show wide advantages over other nano-
materials due to their important physicochemical properties. As mentioned above, they
possess high surface area, mechanical strength, optical and electrical properties,
chemical stability, and high porosity; their structure is layered; they are biodegradable;
and they exhibit high π-π-type electrostatic forces due to their electronic distribution
[23, 25]. Various carbon-based nanomaterials such as CNTs, carbon fibers, activated
carbon, and graphene, among others, play an important role in the efficient removal
processes of metals such as As in aqueous samples. The removal capacity of these
NSMs depends on their surface functionalization and on the experimental conditions
of removal treatments [4, 25]. For example, graphene in aqueous media presents a
large and dispersed surface area, which provides numerous sites of interaction with the
contaminant [23, 25]. On the other hand, graphene oxide contains surface functional
groups such as hydroxyl, epoxides, carbonyls, etc., that increase the π-π- and
electrostatic-type interaction with pollutants in water basins. In the case of CNTs, in
addition to their interesting surface properties, they exhibit significant ion exchange
characteristics and high electrochemical potential [23, 25]. That is why CNTs remove
heavy metals from aqueous systems by precipitation, adsorption, and chemical and
electrostatic interaction processes [27, 43]. Besides, carbon-based NSMs exhibit
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1369

resistance to the implications of experimental conditions such as pH and temperature.

Table 1 exhibits the carbon-based NSMs reported by literature for arsenic removal
from aqueous systems.
The main nanostructured materials used for arsenic removal are based on iron.
This is due to the high remediation efficiency of this pollutant, its natural abundance,
and biocompatibility [4, 44, 45]. Among the iron-based NSMs, there are those of
zerovalent iron, iron oxides, iron oxy-hydroxy, and iron-based bimetallic oxides,
among many others [45].
Many iron, magnesium, and aluminum oxides and hydroxides, for example, are
abundant in various natural environments and highly efficient for the removal of
aqueous pollutants [4]. Arsenic presents the ability to bind to the surface of such
nanomaterials through physical or chemical adsorption processes [28]. The
oxyanions of arsenic in conjunction with the metallic character of As allow com-
plexation to develop on the surface of the nanostructured material. In addition,
ligand exchange can occur leading to the formation of mono- and bidentate com-
plexes between iron and As species. Due to these aspects, metal oxides, in particular,
those containing iron in their structure, present great potential for application in
arsenic removal in aqueous media [28, 46].
Those pure iron oxides, composed of iron and oxygen, are available in nature as they
participate in geological and biological processes. Iron is in two oxidation states +2
(Fe+2) and + 3 (Fe+3) [46, 47]. These chemical structures of iron possess four and five
electrons in the unpaired 3D subshell which makes them magnetic in nature [46, 47]. Of
the 16 types of existing iron oxides, hydrated iron(III) oxide, magnetite, ferrihydrite,
hematite, maghemite, and goethite are the main iron oxides involved in aqueous arsenic
removal nanotechnologies [46, 47]. In addition, many iron-based nanostructured mate-
rials possess superparamagnetic properties that aid in the manipulation and effective
development of As remixing processes from water basins [30]. Table 1 reflects some of
the iron oxides used for As removal from aqueous systems.
Other oxides, such as titanium oxide (TiO2), are widely used in arsenic removal
from contaminated waters. TiO2 functions as a photocatalyst and also as an adsor-
bent. It performs its photocatalytic function in the presence of solar radiation or
ultraviolet light, while it behaves as an adsorbent in its absence [23, 48, 49]. In this
regard, the reactions carried out by titanium oxide are promising technologies for As
removal in waters (Table 1).
While several of the nanostructured materials mentioned above for the remedia-
tion of As from contaminated water show promising results, many of these options
have low economic viability. Mineral-based NSMs offer more sustainable and cost-
effective solutions to the problem of aqueous As contamination [4, 21, 34]. The
worldwide availability of nanoclays is too extensive. Nanoclays containing dolo-
mite, stenvensite, kaolinite, muscovite, and illite were found offshore Morocco and
have been used for As(V) removal from contaminated waters [50]. Meanwhile,
nanoclays found in India were effective for arsenic remediation in contaminated
groundwater [36]. In Argentina, there are several bentonites, montmorillonite, and
kaolinite clay basins that have also shown promising results in As removal in aquifer
basins [4, 21, 34, 35]. Countries such as Mexico, Chile, Tanzania, and Japan, among
Table 1 Nanostructured materials for arsenic removal
1370

Nanostructured material Methodology qe or %R T te C0 Reference

Three-dimensional graphene foam Adsorption 177.6 mg/gAs(V) 328 30 min [26]

K
Chemical activated carbon Adsorption 43 mg/gAs(III) RT 100 mg/L [51]
Physical activated carbon Adsorption 55 mg/gAs(III) RT 100 mg/L [51]
Activated carbon Adsorption 3.08 mg/gAs(V) RT 30 min 15 mg/L [52]
Functionalyzed CNT Adsorption 23.4 mg/gAs(III) RT 30 min 5 mg/L [27]
Magnetite Fe3O4 Adsorption 375μg/gAs(III) RT 12 h 500μg/L [28]
Magnetite Fe3O4 Adsorption 356μg/gAs(V) RT 12 h 500μg/L [28]
Iron oxide-coated sand Adsorption 41.1μg/gAs(III) 22  C 24 h 5μg/L [29]
Iron oxide-coated sand Adsorption 42.6μg/gAs(V) 22  C 24 h 5μg/L [29]
Iron–chitosan Adsorption 16.1 mg/gAs(V) RT 24 h 1 mg/L [46]
Iron–chitosan Adsorption 22.47 mg/gAs(III) RT 24 h [46]
Activated alumina Adsorption 3.5 mg/gAs(III) RT 40 h 12 mg/L [53]
Activated alumina Adsorption 15.9 mg/gAs(V) RT 170 h 12 mg/L [53]
Goethite Adsorption 10.1 mg/gAs(III) RT 50 h 2  10
5 M [54]
Goethite Adsorption 12.1 mg/gAs(V) RT 50 h 2  10
5 M [54]
Hematite Adsorption 10 mg/gAs(III) RT 50 h 2  10
5 M [54]
Hematite Adsorption 31.3 mg/gAs(V) RT 50 h 2  10
5 M [54]
Zero-valent iron Adsorption 3.5 mg/gAs(III) RT 12 h 1000 mg/L [47]
Iron oxide-loaded alginate Adsorption 13.75μg/gAs(V) RT 10 min 50μg/L [55]
Magnesium ferrite (Mg0.27Fe2.5O4) Adsorption 10.1 mg/gAs(III) 25  C 200 min 0.01 mg/L [30]
Magnesium ferrite (Mg0.27Fe2.5O4) Adsorption 11.8 mg/gAs(V) 25  C 200 min 0.01 mg/L [30]
Magnetite
graphene oxide Adsorption 13.10 mg/gAs(III) 20  C 2h 5 ppm [43]
Magnetite
graphene oxide Adsorption 5.83 mg/gAs(V) 20  C 2h 5 ppm [43]
TiO2 Photocatalytic >99.999%As(III) RT 30 min 525μM [56]
oxidation
E. Baigorria et al.
 60

TiO2 Photooxidation >99.999%As(III) RT 250 s 10 mg/L [31]

TiO2 Photocatalytic >97% As(III) RT 1 min 12μM [57]
oxidation
Amorphous iron hydroxide Adsorption 30 mg/gAs(III) RT 4h 20 mg/L [58]
Amorphous iron hydroxide Adsorption 7 mg/gAs(V) RT 4h 20 mg/L [58]
Goethite Adsorption 25 mg/gAs(III) RT 4h 20 mg/L [58]
Goethite Adsorption 4 mg/gAs(V) RT 4h 20 mg/L [58]
TixHy-montmorillonite Adsorption 30%As(III) RT 4h 20 mg/L [58]
TixHy-montmorillonite Adsorption 40%As(V) RT 4h 20 mg/L [58]
Fex(OH)y-montmorillonite Adsorption 95%As(V) RT 4h 20 mg/L [58]
Fex(OH)y-montmorillonite Adsorption 80%As(III) RT 4h 20 mg/L [58]
Fe-LECA Adsorption 3.31 mg/gAs(V) RT 24 h 1 mg/L [44]
Mg/Al-layered double hydroxide Adsorption 114 cmol/KgAs RT 24 h 0.667 mM [59]
(V)

Hydroxyiron-montmorillonite Adsorption 55%As (III) RT 1 min 1 mg/L [45]

Bentonite/alumina–ceramic monolith Adsorption 3.8μg/gAs(V) RT 24 h 2000 μg/L [34]
Three-dimensional Fe3O4/graphene Adsorption 40.048 mg/gAs RT 12 h 100 mg/L [38]
(V)

Amorphous iron oxide–graphene oxide Adsorption 147 mg/gAs(III) 23  c 600 min 110 ppb [39]
Amorphous iron oxide–graphene oxide Adsorption 113 mg/gAs(V) 23  c 600 min 110 ppb [39]
Graphene-carbon nanotube-iron oxide Adsorption 6.3 mg/gAs(III) RT 30 min [40]
Magnetite/graphene/layered double hydroxides Adsorption 73.1 mg/gAs(V) RT 12 h 25 mg/L [60]
Magnetic graphene oxide (Fe3O4–GO) Adsorption 59.6 mg/gAs(V) 298 24 h 25 mg/L [61]

K
Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . .

Graphene nanoplates/Fe–mg binary oxide Adsorption 103.9 mg/gAs(V) RT 90 mg/L [62]

Magnetic iron oxide/graphene oxide Adsorption 54.18 mg/gAs(III) RT 24 h 1000 mg/L [63]
Magnetic iron oxide/graphene oxide Adsorption 26.56 mg/gAs(V) RT 24 h 1000 mg/L [63]
(continued)
1371
 1372

Table 1 (continued)
Nanostructured material Methodology qe or %R T te C0 Reference
Aluminum doped manganese copper ferrite Adsorption 25.5 mg/gAs(III) 313 90 min 1000 mg/L [64]

(Mn0.5Cu0.5Fe1.2Al0.8O4) K
PVA/sodium alginate/bentonite Adsorption >99.99%As(III) RT 12 h 1 mg/L [21]
Poly(4-vinylpyridine)/bromoethylamine/magnetic Adsorption 87.2%As(V) RT 12 h 10 mg/L [65]
CS/clay/Fe3O4 Adsorption 2.2 mg/gAs(V) 23  C 120 min 39.5 mg/L [66]
TiO2.FS/CS Photocatalytic 954μg/ gAs(V) RT 120 min 1000 mg/L [32]
oxidation
Poly(acrylamide)/biochar Adsorption 0.447 mg/g 28  C 6h 1 g/L [67]
Iron(III)-zein Adsorption 1.95 mg/g As(V) RT 8h 1 mg/L [68]
Iron(III)-zein Adsorption 92.5% As(V) RT 16 h 1 mg/L [68]
CS/iron (oxyhydr)oxide Adsorption 54.2 mg/g As(III) RT 30 h 24 mg/L [69]
CS/iron (oxyhydr)oxide Adsorption 39.1 mg/g As(V) RT 30 h 24 mg/L [69]
CS/iron (oxyhydr)oxide Adsorption 0.82 mg/g RT – 233 μg/L [69]
CS/goethite Adsorption 0.0274 mmol/g RT 2000 min 66μmol/L [70]
As(V)

CS/goethite Adsorption 0.0317 mmol/g RT 2000 min 82μmol/L [70]

As(III)

Chitin/TiO2 Sorption 0.05μg/g As(V) RT 4h 10 mg/L [71]

Chitin/TiO2 Sorption 244μg/g As(V) RT 4h 163μg/L [71]
CS/graphene oxide Adsorption 2.75 mg/g As(V) 30  C 30 min 30 mg/L [72]
3mercaptopropyl/silica/polyacrylamide Adsorption 67.71μg/g As(III) RT 60 min 100μg/L [73]
E. Baigorria et al.
60 Eco-friendly Nanostructured Materials for Arsenic Removal from Aqueous. . . 1373

others, show the wide availability of nanostructured natural clays with applications
in the removal of inorganic arsenic from contaminated aqueous media [4]. Table 1
shows some of the mineral-based NSMs used in aqueous As removal.
Some of the nanostructured materials that have received the most attention in
recent times in As remediation of contaminated water are hybrid NSMs. As men-
tioned above, hybrid and nanocomposite materials show even more promising
aspects than their pure components [19, 21, 37]. Their physicochemical properties,
the selectivity of aqueous contaminants, material recovery, regeneration cycles, and
improvement in kinetic aspects are some of the improved factors in these types of
nanostructured materials [19, 21, 37]. There is a wide range of hybrid materials
applied in aqueous arsenic removal (Table 1).

Outlook

Due to the important problems of arsenic in water basins, the development of cost-
effective decontamination treatments to provide safe drinking water is of great rele-
vance in the scientific environment. However, the effective removal of arsenic is a
complicated task due to its physicochemical nature and high mobility. In this chapter,
recent technological solutions based on environmentally friendly nanostructured
materials for the removal of arsenic from water basins have been analyzed. Among
the NSMs, carbon-based nanostructured materials, transition metal oxide-based,
superparamagnetic, titanium-based, mineral-based, metal-based, hybrid nanostruc-
tured materials, and other nanostructured materials were highlighted. While the variety
and quantity of environmentally friendly nanostructured materials are significant, their
utilization on large scales or real field is not. Technologies used for large-scale aqueous
As removal do not utilize many of these nanostructured materials. Operational and
material costs are often discredited compared to the efficiency of these NSMs.
Although the conventional methodologies generate the removal of arsenic from the
environment, they leave small traces of this element which are highly harmful to living
organisms, such as humans, leading to the aforementioned problems. The incorpora-
tion of nanostructured materials in the aqueous arsenic removal technologies already
implemented will allow the total elimination of this contaminant. The performance of
NSMs in aqueous purification is high compared to other materials. However, the initial
investment costs are higher. The incorporation of environmentally friendly nanostruc-
tured materials in small- and large-scale arsenic removal technologies will improve
immediate and future results. In this way, aqueous purification systems could be
improved in the future, with environmentally friendly solutions.

Conclusion

The scarcity of water suitable for human consumption is a social problem of global
importance. Inclement weather and geological conditions together with anthropo-
genic activities have caused more and more water basins to be contaminated with
1374 E. Baigorria et al.

several pollutants such as arsenic. Therefore, effective, practical, and low-cost

aqueous decontamination processes are of great relevance worldwide. The choice
of suitable materials for use in technologies applied in aqueous As removal is a topic
of great interest. The use of environmentally friendly nanostructured materials as the
main component of these As removal technologies in contaminated water has many
advantages over other conventional materials. The nanometric size, their high
surface/volume ratio, their high functionalization capacity, and their unique physi-
cochemical properties make these materials a nanotechnological component with
wide versatility. In the holistic vision carried out, nanostructured materials based on
carbon, transition metals, their respective oxides, minerals, metals, or hybrid or
composite nanostructured materials have been found. It was observed that the
technologies based on separative methods predominated over the others. This is
because it is possible to eliminate a greater amount of aqueous arsenic without
leaving traces of the same remaining in the treated aqueous medium. In addition,
these techniques such as adsorption reflect lower operating costs and high versatility,
making them highly suitable processes for the removal of arsenic from contaminated
aqueous systems.
The increased use of environmentally friendly nanostructured materials in arsenic
removal technologies from water would result in improved aqueous treatments with
significant advantages over other techniques. In addition, the development of new
nanostructured materials with superior aqueous As removal properties at real scale is
a challenge for the current scientific community. In this way, the quality of water
available for human consumption would greatly increase, thus eliminating social
problems worldwide.

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 Part XV
Safety Risk, ELSI, and Economics of Consumer
Nanoproducts
Nanoproducts and Legal Aspects
of Consumer Protections: An Evaluation 61
Mohammad Ershadul Karim

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1382
Consumer, Goods, and Products: Conceptual Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
Nanotechnologies in Consumer Products: Prospects and Concerns . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
Consumer Protection: A Theoretical Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
Consumer Nanoproduct and UN Consumer Protection Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . 1392
Nanotechnologies and Consumer Basic needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1392
Vulnerable Consumers in the Nano-age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1393
Consumers’ Right to Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1394
Consumer Rights to Education . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1395
Consumer Dispute Resolution and Redress Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1396
Consumer Nanoproducts and International Organizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1398
Nanoproducts and Consumer Protection: An Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1400
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1402
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1403

Abstract
Nanomaterials are ubiquitous in nature since time immemorial. The inhabitants of
some ancient societies knew the techniques to use some nanomaterials in a
selected manner, though the idea of exploitation of engineered nanomaterials
(ENMs) in a systematic and controlled manner is relatively new, started only four
decades ago with the invention of scanning tunneling microscope. Six years after
the official inauguration of nanotechnologies in the United States of America
(USA) through the National Nanotechnology Initiative in 2000, the researchers
found nanotechnologies in a stage where ICTs were in the 1960s and biotech-
nology were in the 1980s. This analogy was made to indicate the prospective-
wide use of nanomaterials in both industrial and consumer products in the future.
M. E. Karim (*)
Faculty of Law, University of Malaya, Kuala Lumpur, Malaysia
Bangladesh Supreme Court, Dhaka, Bangladesh
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1381

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_79
1382 M. E. Karim

After almost two decades of the formal beginning, the world, more specifically
the developed countries, is in a stage when supermarket shelves can be located to
have full of thousands of consumer products containing ENMs due to their
unprecedented potentials over traditional materials. Though the long-term behav-
ior of different ENMs in different media of the environment and human health is
yet to be conclusively proved, authoritative scientific and policy reports predicted
that some nanomaterials may harm the environment and human health, albeit the
numbers of permitted products have been growing in the market. This can be an
indication that these products can safely be designed to suit the purpose. There are
already adequately regulated sectors using the experience of which these can be
managed properly as well within a proper regulatory framework. While the
consumers have limited bargaining powers and voice in the regulatory
decision-making, the consumers are an important decisive factor as the ultimate
business success of these products relies on the acceptance and recognition by the
consumers. Therefore, the manufacturers must consider the issue of consumer
protection seriously in a situation even though the international consumer
protection-related legal movement started with the adoption of the United Nations
Guidelines for Consumer Protection, 1985 (finally revised in 2015). To ensure
safe, sustainable, and responsible development of nanotechnologies, numerous
regulatory initiatives or tools, either product based or process based, have been
adopted in different developed countries. Some initiatives have also been taken to
make the consumers aware so that they understand different relevant issues which
will ultimately assist them in understanding the technology better and welcoming
the products which may help in the ultimate success of nanotechnologies in
society. Following the library-based research methodology, this chapter surveys
and provides a preliminary overview of the existing international, regional, and
municipal legal developments on consumer protection and evaluates these in the
context of nanoproducts. Some of the challenges faced by the regulators and
consumers and some innovative initiatives adopted around the world in this
regard are also examined and shared with the aim that the newcomers and
stakeholders will get some insights in settling their future policy directions.

Keywords
Nanoproducts · Consumer protection · Consumer rights · Engineered
nanomaterials · Consumer goods and products · Nanoproduct Registry ·
Precautionary Principle · United Nations Guidelines for Consumer Protection

Introduction

Nanomaterials, a chemical compound or materials having at least one dimension

under 100 nm, are ubiquitous in nature for centuries [1]. Natural nanomaterials are
abundant for the past 4.54 billion years since the beginning of the earth [2]. The
inhabitants of some ancient civilizations, e.g., from India, Greece, Rome, Egypt, and
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1383

China, knew the techniques to exploit some materials such as gold, silver, and
carbon in the nanoscale and developed the expertise to use these in some of the
goods of their daily lives [3]. For example, the inhabitants of ancient India used
nanoparticles as Ayurveda medicine and Kajal, a beauty product used by women in
making their eyebrows dark; the people in China and Egypt knew the techniques to
use gold nanoparticles; Roman people used nanoparticles in ceramics and pottery
[4–6]. Incidental and unintentional use of nanomaterials can be seen since the
beginning of the industrial revolution [2]. Nevertheless, it is uncertain if the
human health and environmental implications of such accidental or incidental use
of nanomaterials were an issue of concern at all for the stakeholders as the legal
regulation of human healthcare and occupational health, environmental protection,
and consumer protection relating to chemical compounds are of recent origin. [Please
be informed that reference nos. 5 & 8 are same. Please use the reference no. 8 in both
places as it looks complete]
The popular modern history of nanotechnology, or more accurately nanotechnol-
ogies, as it was started with the seminal lecture of Richard Feynman, with the
aspiration to exploit things at the atomic scale, delivered in 1959, started to get
better attention in some developed countries after the invention of the scanning
tunneling microscope in 1981. After the official inauguration of nanotechnologies in
the United States of America (USA) through the National Nanotechnology Initiative
(NNI) in 2000 followed by the 21st Century Nanotechnology Research and Devel-
opment Act, 2003, the researchers used to believe that nanotechnologies were in a
stage where ICTs were in the 1960s and biotechnology in the 1980s [7]. This
analogy was shared perhaps to indicate the different prospects and development
stage of this technology. Nanotechnologies are projected as generic technology, i.e.,
technologies having diversified applications like information and communication
technologies, enabling technology, i.e., a technology that can add new features and
functions to existing products, and disruptive technology, i.e., a technology that
works beyond the expectation of the consumers and transformative technology
having a similar effect like the steam engine and electricity [5].
Engineered, manufactured, or man-made nanomaterials (ENMs) have huge com-
mercial prospects to be used in different industrial and consumer products due to
their ability to enhance the product with any feature, i.e., cheap, strong, bright, long-
lasting, etc., as it is intended by the manufacturer based on the needs and demands of
the consumers. All these features make ENMs very lucrative for research and
innovation, and different types of projections as to the commercial prospects of
nanoenhanced products are made regularly by different corners. For example, the
International Labour Organization (ILO) predicted that by the year 2020, approxi-
mately 20% of all goods manufactured in the world will be developed by
nanotechnology [8].
The scholars, predominantly the scientists, from all over the world have also
realized the commercial prospects of ENMs and nanoenhanced products sometimes
after the formal official movement of the US NNI. It was found that between 1997
and 2018, a total of 3546 studies were published and included in Web of Science’s
Science Citation Index Expanded, where 96% of the papers were published between
1384 M. E. Karim

2009 and 2018 and 72% between 2014 and 2018 [9]. It was also found that the main
areas covered in these publications are food science and technology, chemistry
(applied and analytical), spectroscopy, and agriculture [9]. Interestingly, as of
August, 2020, the leading scientific journal Nature listed at least 880,000 nanotech-
nology articles relating to more than 320,000 nanomaterials and 25,000,000 patents
[https://nano.nature.com/]. While there is difference in these projected numbers of
scientific articles, etc. as different methodologies are used, there is doubt about the
commercial prospects of ENMs and nanoenhanced products. The anticipated com-
mercial prospects of ENMs shared in these published literature, based on the findings
of the laboratory research, during the last two decades have been getting life in recent
years as can be identified in the supermarket shelves having full of nanoenabled
products ranging from beauty care products, medicinal and therapeutic goods,
electrical and electronic goods, etc.
With the reaching out of all these nanoenhanced products into the market, there
are also some obvious common human health, environmental, legal, and regulatory
concerns due to our experience of some other products such as tobacco and asbestos
which were initially introduced with high appreciation. One of the reasons of such
concern is that the findings of published literature suggest that human being in
contact with ENMs can be exposed to it in four different ways – dermal penetration,
ingestion, inhalation, and blood circulation [10, 11]; these can be released in
different components of the environment [12] in different stages of their lifecycle.
Even after these concerns, these issues do not get adequate convincing attention from
different stakeholders. The World Health Organization’s regional office for Europe
in its Parma Declaration on Environment and Health, 2010, listed the health impli-
cations of nanotechnology and nanoparticles among the key environment and health
challenges. Nevertheless, even after a decade of the declaration, many of the human
health and environmental exposure-related concerns are unsettled, though the sci-
entific community, as part of an institution or international organization, has been
trying their best to explore and reach an evidence-based conclusion. This is not an
easy task when all activities deserving regulatory attentions have been moving very
fast. The regulators cannot also take any quick decision when they notice that one
group of scientists claim that in the first stage of cradle-to-grave life cycle of ENMs,
the people who come in contact with the ENMs, i.e., the workers, do not face any
confirmed illness relating to their occupational exposure to ENMs [13, 14], whereas
other groups of scholars believe that ENMs can have consequences, both positive
and negative, in the earth system [2]. Such an obvious but healthy competition of
sharing the research findings should make the consumers worried for some valid
reasons due to their inadequate knowledge and understanding, usually shaped by
their socioeconomic and cultural background, about this technology and nano-
enhanced consumer products.
While the consumers have limited bargaining powers and legal remedies, the
ultimate business success of these products relies on the acceptance and recognition
by the consumers, and therefore, the manufacturers must consider the issue of
consumer protection seriously in a situation when international consumer
protection-related legal movement has started very recently with the adoption of
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1385

the United Nations Guidelines for Consumer Protection, 1985 (finally revised in
2015). The absence of a matured and developed consumer protection international
legal framework must have an influence in the development of a comprehensive
consumer protection legal regime within the national jurisdictions. Various countries
have been dealing with relevant consumer protection issues through some sectoral or
through some isolated provisions in some laws; the adequacy and effectiveness of
these provisions are also contested in some jurisdiction almost regularly. The
regulators face the dilemma as activities relating to innovation and commercializa-
tion must be promoted to maintain, continue, and accelerate the development
activities. As a result, the policymakers of different countries, mostly developed
and industrialized, have been constantly trying to evaluate the situation by making a
balance between the promotion of consumer protection, while maintaining innova-
tion activities as they understand the value of respecting the trusts, faiths, and
confidence of the consumers in the commercial success of any technology, the last
glaring example of which is genetically modified organism (GMO) food in Europe.
Yet, while it is evident that the consumers from global south countries have been
suffering various challenges, the situation of the consumers from the global north
countries can be perceived or at least anticipated. The issues and effects of global-
ization and the easy movement of the products have been making the situation more
complex regularly.
Keeping these contexts and the scope of this book in mind, this chapter aims to
share some pertinent legal and regulatory issues relating to consumer nanoproducts.
In so doing, the next part of this chapter discusses some definitional aspects of
consumer, goods, and products followed by sharing a glimpse of prospects and
challenges of nanotechnologies in relation to consumer products. After sharing some
theoretical discussion on consumer protection while introducing the international
legal movement on consumer protection and highlighting the role of some interna-
tional organization, this chapter evaluates their strengths and limitations in the
context of consumer nanoproducts. Some relevant experiences and practices of
different countries are also highlighted.

Consumer, Goods, and Products: Conceptual Analysis

ENMs can be integrated into various consumer products, and thus, the presence of
“consumers” can be found in almost every commercial sector where ENMs are used.
As these consumer nanoproducts may raise different legal and regulatory issues,
both general and very specific to ENMs, an understanding of the relevant terms is
necessary. In the legal sense, the term “consumer” generally denotes a natural person
who purchases, acquires, or uses any goods or services for personal, domestic, or
household use or for consumptions as opposed to business or commercial use. One
exception can be shared here in the context of Europe where, under the Package
Travel Directive (90/314/EEC), the companies and business travelers are also
considered as consumers. Otherwise, a consumer is usually a natural person who
1386 M. E. Karim

remains outside the scope of economic and commercial activities and does not
include a legal person.
The words “goods” and “products,” generally indicating tangible moveable items
as used by the consumers, are used interchangeably in the common parlance. Under
the European Council Directive 85/374/EEC of July 25, 1985, on the liability for
defective products, “product” means all movables even if incorporated into another
movable or into an immovable and includes electricity (Article 2). On the other hand,
under the US federal law, i.e., the Consumer Product Safety Law of 2021 [15 U.S.C.
§ 2052], the word “consumer products” means “any article, or component part,
produced or distributed for the personal use, consumption or enjoyment of a
consumer in or around a permanent or temporary household or residence, a school,
in recreation, or otherwise.” Thus, it is apparent that in the context of the USA, the
definition has mentioned some sectors more specifically where a consumer uses
these products personally. The definition has excluded some articles, e.g.,
non-customary products used by a consumer such as tobacco and tobacco products,
motor vehicles or motor vehicle equipment, pesticides, aircraft, aircraft engines,
propellers, or appliances, drugs, devices, cosmetics and food, etc., from the said
definition as there are separate laws to regulate different aspects of these articles or
products.
One may not find any actual difference between these two words, i.e., “goods”
and “products,” except their usage and context in our daily life. While the common
people prefer to use these words in a different context, e.g., consumer goods,
financial products, petroleum products, etc., these words have different legal impli-
cations, at least in the context of free movement of goods in the European Union as
the word “goods” entails to address different tax- or fiscal-related consequences. In
the case of European Communities v Italian Republic, 1968 (Case 7-68), the
European Court of Justice (now the Court of Justice [CoJ]) defined goods as
products which can be valued in money and which is capable of forming the subjects
of commercial transactions. The term “good” is very broad and depends on the
different contexts. Therefore, a razor-sharp line as to what constitutes a good and
what is not is neither very clear nor straightforward. Moreover, the CoJ has extended
the definition of “goods” and included some otherwise unconventional things
ranging from electricity, gold and silver coins, bees, waste, etc. within the definition
of “goods” [e.g., see Commission v France [1997] ECR I-5815 [Case C-158/94]; R v
Thompson (1978) ECR 2247 [Case 7/78]; Bluhme [1998] ECR I-8033 [Case C-67/
97]; Commission v Belgium [1993] 1 CMLR 365 [Case C-2/90]]. It may be relevant
to share here that in the context of Europe, the word “object” is also used sometimes
as a synonym of goods or products.
From the discussion above, it is evident that these two terms, i.e., “goods” and
“products” are used interchangeably in the legal texts though they may have a
different meaning in a different context. Besides, it is apparent that there are laws
containing general provisions regulating goods or products, whereas, there are
specific laws also the provisions of which govern a specific type of consumer
products or goods such as food, drug, medicine, cosmetics, children toy, etc. This
second category of law, dealing with specific types of consumer goods, is very
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1387

relevant for the purpose of discussion of this chapter as the use of ENMs in these
products is very promising. It can be seen that in the USA, the issues of drugs,
devices, and cosmetics are regulated through the provisions of the Federal Food,
Drug, and Cosmetic Act [21 U.S.C. 321(f)], whereas for regulating food, there are
laws such as the Federal Food, Drug, and Cosmetic Act [21 U.S.C. 321(f)], the
Poultry Products Inspection Act [21 U.S.C. 453(e) and (f)], the Federal Meat
Inspection Act [21 U.S.C. 601(j)], the Egg Products Inspection Act [21 U.S.C.
1033], etc. Similarly, in the EU, there are separate legislations on medical devices,
cosmetics, food, and biocides where nanomaterials can be used. Thus, the idea of
“consumer” is very wide, so is the case of legal provisions, and in a study of 2015
conducted by the European Parliament, it revealed that at least 90 community
legislations contain provisions on consumer protection (European Parliament,
“Consumer Protection in the EU: Policy Overview,” European Parliamentary
Research Service, September 2015, p. 5).
Moreover, in the legal literature, the terms “goods” and “services” are used
regularly as a pair, and many legal disputes arise about “services,” at least in the
context of Europe concerning the free movement of services. As the example of
services include various industry specific services such as legal service, hotel, and
tourism services, where nanomaterials are not directly used as a part of this service,
this chapter will cover the discussion mainly on product-related legal issues.

Nanotechnologies in Consumer Products: Prospects and Concerns

Industrial nanomaterials and nanomaterials used for consumer products have huge
prospects as they promise to improve different features of various types of products.
Rapid advancements propelled by, e.g., IoT, big data, artificial intelligence, synthetic
biology, etc. in this era of fourth industrial revolution in the field of life sciences,
engineering, medicine, etc. have empowered the scientists to experiment with
nanomaterials in different consumer products to improve their various features.
Different organizations have been releasing different statistics on the global market
of nanomaterials featuring different aspects of ENMs and nanoenabled products. It is
evident from the findings of these statistics that the projected market varies perhaps
due to different methodologies, focus, and context used (see, for a general reference,
European Chemical Agency, “Critical review of the relevance and reliability of data
sources, methods, parameters and determining factors to produce market studies on
manufactured nanomaterials on the EU market,” https://euon.echa.europa.eu/
documents/23168237/24095696/170718_critical_review_of_market_studies_nano
materials_final_report_en.pdf/ec77f39e-0918-5984-d7b1-654e3b1f14da). Though
the figures in these statistics vary, one thing is certain that the prospect of ENMs is
simply huge and it’s been growing only.
Nanomaterials have the prospects to assist the stakeholders and policymakers in
attaining many of the United Nations Sustainable Development Goals [15, 16],
including food security (goal 2) [17–20]; good health and well-being by providing
medicine, pharmaceuticals, and health supplements (goal 3) [21–23]; safe,
1388 M. E. Karim

sustainable, clean, and adequate water (goal 6) [24, 25]; affordable and clean energy
(goal 7) [26, 27]; industry, innovation, and infrastructure (goal 9) [28]; sustainable
cities and communities (goal 11) [29–31]; responsible consumption and production
(goal 12) [32, 33]; climate action (goal 17) [34]; life below water (goal 14) [35]; etc.
As nanotechnologies are enabling technologies, the manufacturers have been
using ENMs in various products which may create novel problems, some of which
are complex in nature, for the regulators. This situation has left the regulators in a
real challenge and the manufacturer in an uncertain situation, as in some cases, the
ingredients in the nanoscale forms are used in some of the products, e.g., cosmetics
for decades. In this backdrop, some of the developed countries have already intro-
duced product registry system containing nanoenabled products.
It is neither possible nor desirable to share a list of nanoenabled products here.
Instead, it will be sufficient to mention that nanomaterials are used in various
consumer products, and after a survey of the popular nanoproduct registries, it is
evident that the ENMs are used in various products ranging from cosmetics, textile,
construction, electronic products, beauty and healthcare products, automotive, envi-
ronment, etc. The Statnano database, which appears to be the most comprehensive
nanotechnology products database at the time of writing this chapter, has already
listed 8879 products produced by 2467 companies from 62 countries [https://
product.statnano.com/]. The database categorizes products in groups such as (num-
ber of products in the parenthesis as of August 24, 2020) electronics (1925),
medicine (1065), construction (838), cosmetics (828), textile (765), automotive
(628), environment (547), food (344), renewable energy (317), home appliance
(320), petroleum (284), agriculture (227), printing (153), sports and fitness (141),
and other (397). The database has further listed these products based on industrial
subdivisions such as sensors, masonry materials, skincare, pharmaceuticals, medical
supplies, water and wastewater, maintenance, laser, integrated circuits, processor,
etc. Similar other databases can be found in the context of other countries, mainly
from Europe, too, which will be discussed below.
In the study of consumer nanoproducts, the issue of human health and environ-
mental implications of ENMs are significant, and the findings of scientific studies
published in reputed journals report that with all these projected prospects and
benefits, there are some human health and environment-related concerns too.
Using different methods, the findings of the scientific studies have been reporting
mixed findings relating to ENMs used in consumer products. While some studies
have reported health and environmental concerns out of the exposure and release of
some ENMs, some studies have not [36–38]. Nevertheless, it has already been
agreed unanimously that ENMs can be released to the environmental component
and human beings can be exposed to ENMs. While the actual human health or
environmental concerns are not proved conclusively yet, in all these studies, it has
been generally recommended to conduct more research to reach an evidence-based
regulation though the percentage of research on nanosafety or regulatory issues is
very few compared to the research on scientific prospects and innovation leading to
patents. Similarly, the regulators, mainly from the Europe, have been also evaluating
their decisions regularly in this regard.
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1389

An important concern is that the findings of the conducted researches on nano-

safety do not help the consumers much in reaching to any conclusive decision as to
the precise behavior and effects of these ENMs as these are written mostly in
technical manner. To add to the concern, from the consumer point of view, even
though the researchers found that the regulatory framework on cosmetic in Europe is
almost complete and the safety assessment of nanomaterials in medicine and medical
devices is conducted case by case [39], the European regulators have recently started
the public consultation on the Scientific Committee on Consumer Safety’s Scientific
Advice on the safety of nanomaterials in cosmetics on October 2020. Besides, some
of the products where ENMs are used, e.g., nanofood, are not properly regulated in
countries outside Europe. For example, nanofood is not strictly regulated in India
[40]; the supervision of consumer nanoproducts in China is almost nil [41]. China
and India supply their products to many of the developing and least developed
countries where the regulators do not have the capabilities to understand various
human health and environmental implications of ENMs. Moreover, many of the
multinationals have been using ENMs in foods when some European regulators have
proposed ban on the use of ENMs, e.g., titanium dioxide (E171), an additive partly
made of nanoparticles, in food. There are additional concerns [European Parliament,
Parliament objects to legislation on food products that might be harmful to kids,
https://www.europarl.europa.eu/news/en/press-room/20201002IPR88447/parlia
ment-objects-to-legislation-on-food-products-that-might-be-harmful-to-
kids]. While the regulators in Europe are concerned about the regulation of some of
the products such as medicine, food, cosmetics, and biocide where ENMs are used,
other products are coming to the market which can create real challenges in the long
term. For example, from the Statnano database, it is apparent that the ENMs are
extensively used in textile products. Though their long-term health effect is yet to be
confirmed, studies revealed that ENMs used in textiles can be released in the
environmental components [42].

Consumer Protection: A Theoretical Overview

In the legal and regulatory assessment of human health and environmental implica-
tions of ENMs, the cradle-to-grave life cycle assessment (LCA) is very popularly
used. During the LCA, the consumers will be the stakeholders of the second last
layer just before the product end of use disposal stage. However, they are the most
instrumental and one of the important deciding factors in the success of any product,
though their roles and significances are overlooked in different jurisdictions, mostly
in developing countries as they lack sufficiently loud collective voice against abuse
by the business communities. In the case of nanoenabled products too, it is seen in
some of the developed ad industrialized countries that the consumers’ collective
actions matter their safe, sustainable, and responsible development. History suggests
that some of the technologies and products were introduced in the market with great
projections and excitements, but since the consumers did not accept the product, it
did not get the ultimate success. Therefore, in the development of nanoenabled
1390 M. E. Karim

products, it is very important to understand the needs and demands of the consumers.
With the changing nature of global affairs due to the innovations of ICTs, the effects
of globalization and relaxation of international trade barriers, etc. the nature of
business are also changing [43]. Hence, the entrepreneurs or the manufacturers
who invest a huge amount of money in the production of nanoenabled products
must not take this kind of risks which may invite risks to their investment. The
stakeholders in those industrialized countries have rightly realized this, and they
have been taking some initiatives considering the rights of the consumers as
available in the national legal framework. Therefore, an understanding of the
relevant provisions of the consumer protection laws and ancillary matters is impor-
tant at this stage.
In some ancient civilization, the issue of consumer protection can be found in an
isolated manner. In one of the oldest legal codes, the Code of Hammurabi, an indirect
reference to consumer protection can be located. Around 3,500 years ago, in the
modern-day Turkish region of Anatolia, a consumer food code, containing pro-
visions on food safety and a prohibition on cheating and misleading activities, was
available. Nevertheless, the formal legal recognition of consumer protections and
rights is of a very recent origin. The idea of consumer protection in its modern form
has been developing since the mid-nineteenth century onward, after the advent of
capitalism and trade barrier reduction, initially in Western countries and then in other
parts of the world including Asia (see, for reference, https://consumersinternational.
blogspot.my/2011/03/vision-for-consumer-empowerment.html). Their idea of inter-
national consumer protection law is even novel, merely of less than four decades,
and was started with the support and move of some of the international organizations
such as the World Bank or Organization for Economic Co-operation and Develop-
ment (OECD), mainly in the context of financial products [44].
The year 1962 can be considered as the birth year of modern consumer law and
policy [45] as in this year, when the then American President John F. Kennedy
outlined the “Consumer Bill of Rights,” containing four basic rights of a consumer.
These are (a) the right to safety, (b) right to information, (c) right to choose, and
(d) right to be heard. Consumers International, formerly known as International
Organisation of Consumers Unions, subsequently proposed four additional rights,
i.e., (a) the right to redress or remedy, (b) right to environmental health, (c) right to
service, and (d) right to consumer education.
All or some of these rights are encapsulated in the municipal laws, either in the
national constitutions or in general sectoral laws on, e.g., food, financial sector,
healthcare, etc. or specific law or policy on consumer protection. The United Nations
Conference on Trade and Development (UNCTAD) identified that around 134 coun-
tries in the world have enacted consumer protection laws, whereas 110 countries have
consumer protection laws relating to e-commerce (UNCTAD, “Online Consumer
Protection Legislation Worldwide”; https://unctad.org/en/Pages/DTL/STI_and_ICTs/
ICT4D-Legislation/eCom-Consumer-Protection-Laws.aspx). Besides, some countries
have adopted some strategic or master plan for consumer protection also. In all these
municipal legal frameworks, some sort of regulatory bodies are also formed to
implement the provisions of these laws.
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1391

At the international level, the United Nations encapsulated all the above eight
rights while adopting the United Nations Guidelines for Consumer Protection, 1985
(UNGCP). The UNGCP, “a valuable set of principles that set out the main charac-
teristics of effective consumer protection legislation, enforcement institutions and
redress systems,” can be seen as the beginning of international consumer protection
law movement [44]. The UNGCP are treated as important tools and can assist the
countries in formulating and enforcing national and regional laws on consumer
protection considering their socioeconomic, cultural, and environmental circum-
stances. These guidelines were revised in 1999 and again in 2015 to identify
consumer problems and recommend policy actions. It is pertinent to mention here
that as the title suggests, the UNGCP are mere guidelines, and therefore, it may be
interpreted that these are not legally binding and there was no obligation on the part
of the state parties to observe these. While the interpretation may be true to some
extent, the reality is that in the context of very complex issues surrounding the
consumer protection, e.g., market structure, democratization, harmonization, polit-
ical use of consumer protection laws, etc., the UNGCP are considered to be more
effective than an international treaty [46]. Moreover, guidelines when issued by
authoritative organizations can have some binding force [47].
The UNGCP have identified some of the legitimate needs of the consumers, and
some of these are also relevant in the context of consumer nanoproducts, and these
are, inter alia, (a) access to essential goods and services; (b) protection of vulnerable
and disadvantaged consumers; (c) protection of consumers from hazards to their
health and safety; (d) access by consumers to adequate information which will
enable them to make informed choices according to their individual wishes and
needs; (e) consumer education including education on environmental, social, and
economic consequences of consumers choice; (f) availability of effective consumer
dispute resolution; and (g) freedom to form consumer and other relevant groups or
organization to present their views in decision-making process affecting them
(UNCTAD, United Nations Guidelines for Consumer Protection, https://unctad.
org/en/PublicationsLibrary/ditccplpmisc2016d1_en.pdf).
The UNGCP have also listed some principles for good business practices. Of
these, an important good business practice is disclosure and transparency, which
provides that the business should provide complete, accurate, and not misleading
information regarding the goods and services to enable the consumers make
informed decisions. Besides, the business should also ensure easy access to the
information and develop programs and mechanisms to assist the consumers to
develop the knowledge and skills necessary to understand associated risks which
will help the consumers to take his decisions (UNCTAD, United Nations Guidelines
for Consumer Protection, https://unctad.org/en/PublicationsLibrary/
ditccplpmisc2016d1_en.pdf).
This UNGCP has a huge impact in the development of international consumer
protection. It has encouraged, influenced, and guided many countries to enact
national laws on consumer protection. The UNCTAD subsequently developed the
“Manual on Consumer Protection” to assist countries in implementing the revised
UNGCP. In the absence of any international body on consumer protection, another
1392 M. E. Karim

significant contribution of the revised UNGCP is that it provides for the establish-
ment of an Intergovernmental Group of Experts (IGE) on Consumer Protection Law
and Policy to meet annually, under the auspices of UNCTAD, to monitor the
application and implementation of the guidelines (Section VII, Guideline Nos.
95-99). This forum, with relevant human resources, can play a leading role in
promoting consumer rights in this very connected but complicated world regarding
any scientific and technological innovation, including nanoproducts, having direct
impacts on the consumer. Since 2016, the committee has been meeting every year
and addressing issues ranging from the stakeholders’ responsibilities, consumer
protection-related advocacy and business compliance best practices, needs and
priorities of vulnerable and disadvantaged consumers, to the importance of the
public utilities, energy, and tourism sectors aiming at consumer empowerment, etc.
Besides, the UNGCP have rightly realized the importance of the strategic alliance
between stakeholders to fostering consumer empowerment. It may be relevant to
share that the IGE has already reviewed the consumer-related law and policy of
Morocco and Indonesia in 2018 and 2019, respectively.
It is apparent that under the national legal framework, the consumers have
different rights relating to basic needs, safety, information, selection, redress, edu-
cation, environment, etc. When these are the rights of the consumers, these are, in
converse, obligations on the manufacturers or service providers. Therefore, the
business communities are supposed to take, at least theoretically, initiatives that
will enable the consumer to get these rights, and the regulators should be vigilant to
implement these. However, the reality is that even after having these provisions
encapsulated in the national legal frameworks, since the consumers have very weak
bargaining power, these rights are not respected always generally in the developing
and least developed countries. In terms of implementation of these provisions, this
situation becomes even worse in this hyper-connected world when the stakeholders
in the consumer ecosystem can be based in different jurisdictions, albeit the manu-
facturer or supplier of ENMs should consider consumer protection-related legal
rights and obligations for their business success. In the absence of any binding
international law on consumer protection, the provisions of the UNGCP will be
evaluated in the context of consumer nanoproducts in the following segment, and
some of the rights, e.g., the right to safety, right to be informed, and right to a healthy
environment as included in the UNGCP, will be evaluated for the purpose of
discussion related to this chapter.

Consumer Nanoproduct and UN Consumer Protection Guidelines

Nanotechnologies and Consumer Basic needs

It has already been shared that countries around the world generally consult the
UNGCP and incorporate the principles therein, while enacting their national laws on
consumer protection. Studying the legal framework on consumer protection of
60 countries, the Consumers International found that there are provisions on
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1393

consumers’ basic needs in these countries’ consumer legal frameworks ranging from
social security, water and sanitation, education, healthcare, housing, energy and
food, etc. (Consumer International, The State of Consumer Protection Around the
World, http://www.consumersinternational.org/media/154677/the-state-of-consumer-
protection-around-the-world-full-report-en-revised-april-2013.pdf). If we look at the
legitimate or basic needs of the consumers as identified by the UNGCP in the context
of nanotechnologies and nanomaterials, it can be seen that ENMs or nanotechnol-
ogies have the prospect to provide the consumers essential goods or services and
solve many of their problems, some of which are listed in the United Nations
Sustainable Development Goals as shared above.

Vulnerable Consumers in the Nano-age

The discussion on the protection of the vulnerable and disadvantage consumers in

the nano-age is relevant as we can see that in the developing, least developed, and
even in the developed countries, the consumers are in a disadvantage positions since
they do not have proper bargaining power, an adequate level of education, and
sufficient information which will enable them to make informed choices about
consumer nanoproducts.
One important provision of the UNGCP on the physical safety of the product will
be specifically important and relevant for the discussion of this chapter. The UNGCP
provide that the “member states should adopt or encourage the adoption of appro-
priate measures, including the legal system, safety regulations, national or interna-
tional standards, voluntary standards, and the maintenance of safety reports to ensure
that the products are safe for either intended or normally foreseeable use.” In the
context of consumer nanoproducts, when different scientific studies report or appre-
hend that some of the nanomaterials used in consumer products have the potential to
be harmful in the long run for the human being or environmental component, then,
these findings should be taken into account. The same provision further provides that
the people who are involved in marketing any product should take initiative and care
so that they can introduce a safer product into the market. Moreover, the consumers
should have proper instruction about the use of the products and risk involved from
its intended use.
From the relevant provisions of the consumer protection law as applicable in most
of the countries in the world, there are provisions of product labeling and advertise-
ment. These provisions are included in the law primarily to inform the consumers
about the product since the product labels contain some basic information about the
ingredients of the product, manufacturing and expiry date, and associated risks, if
any. Now, while these provisions in the existing laws are very encouraging, the main
challenge is and will be the proper implementation of such provisions in this
borderless world where the issue of state jurisdiction is present and the parties to a
product, i.e., buyer and seller/supplier, can be based in different jurisdictions. It can
be noticed that even in a developed jurisdiction with better stronger regional
cooperation such as the European Union, there are instances when the product
1394 M. E. Karim

labeling becomes an issue of a debate or contention in the European Court of Justice

[e.g., see the judgment of the Court of Justice of the European Union (CJEU) in the
case of Teekanne, C-195/14 and Neptune Distribution, C-157/14, where the CJEU
found that the companies did not provide correct, neutral, and objective information
in their labeling for the use of the consumers]. Hence, the situation of other
developing countries or least developed countries in terms of proper implementation
of legal provisions can easily be understood. Nevertheless, the accountability, good
governance, and political will of the state machineries can guide the better imple-
mentation of these provisions.

Consumers’ Right to Information

In democratic societies, citizens have the right to know most of the things that
ultimately affect them, both individually and collectively, from the government or
the regulators appointed by the government as the government is a representative
government and primarily runs and manages its activities on the taxpayers’ contri-
butions. However, this is not possible always given the fact that the government
needs to address various development challenges and concerns regularly. With the
aim to inform the stakeholders about the nanoproducts, apart from the nanomaterials
registries developed as a regulatory requirement in different countries, mainly from
Europe, there are also some databases available targeting the interest of the stake-
holders containing relevant information about nanoenabled products. It is a matter of
great concern that when the regulators are experimenting with listing the products,
some of these databases are either updated or stop functioning, and this may be
treated as additional cumbersome for the regulators of the newcomers. Such an
initiative of nanoproduct registry was started in the USA with the establishment of
the Consumer Products Inventory managed by the Project on Emerging Nanotech-
nologies (PEN), based at the Woodrow Wilson International Center for Scholars in
Washington, DC. Though the PEN initially received huge attention and was fre-
quently cited for most of the nanomaterial-related research, the database had some
serious flaws [48], and therefore, initiatives were taken to redesign and redevelop the
register [49].
At present, there are 1833 consumer nanoproducts [http://www.nanotechproject.
tech/cpi/products/] listed in the database, and these are categorized as appliances
[batteries, heating, cooling and air, large kitchen appliances, laundry and Clothing
Care], automotive [exterior, maintenance and accessories, watercraft, lubricants],
crosscutting [coating, bulk], electronics and computers [audio, cameras and film,
computer, hardware, display, mobile devices and communications, television,
video], food and beverage [cooking, food, storage, and supplements], goods for
children [toys and games], health and fitness [clothing, cosmetics, filtration, personal
care, sporting goods, sunscreen, supplements], and home and garden [cleaning,
construction, materials, home furnishings, luggage, luxury, paint, pets]. Even after
the initial limitations of this database, one of the important features of this database
which can be of particular interest of the consumers is that this database contains
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1395

information about the potential exposure pathways into the human body from a
theoretical perspective, without the actual test, taking into account the product’s
intended use [http://www.nanotechproject.tech/cpi/browse/exposures/].
Though some of the flaws are improved, there is still an important concern from
the point of view of the consumers, i.e., in most of the cases, a product is listed as
nanoproduct based on the claim of producers of the product that the product contains
nanomaterials. Thus, these products are not independently reviewed by experts, and
the claim of the producers may not be true ultimately as the producers tend to use the
word “nano” due to its special appeal to the consumers. The Statnano database has
taken some additional measures in this regard which promise to make the consumers
and stakeholders better informed. It is claimed that once anyone submits any product
claiming to be a nanoproduct, the experts verify the product using applicable ISO
standards, i.e., ISO/TS 80004-1:2015 and ISO/TS 18110:2015, before listing this in
the database.
A similar initiative to develop a Europe-wide nanoproduct register was proposed
in 2012 (Concept for a European Register of Products Containing Nanomaterials,
https://www.umweltbundesamt.de/sites/default/files/medien/378/publikationen/
information_concept_nanoregister_npr_e_0.pdf), but it has not been materialized
yet. Already some of the European countries such as Sweden, Belgium, Norway, and
France have introduced national registrars on nanomaterials and/or nanoproducts
[50]. These databases have some common and unique features. For example, Danish
Nanodatabase contains information about 4000 consumer products that contain
ENMs and where it is possible to release ENMs in the environment. Nevertheless,
there are limitations in these product registrars too. While some of these are very
general, some have very selected information available. Moreover, some have very
confidential information not easily accessible for the consumers and primarily
maintained for the use of the regulators.
The issue of information sharing is also ethically very significant [51]. Regarding
ENM-related research, major concerns for the time being is to ensure the safety of
the researcher community, and some innovative initiatives have already been taken
in this regard too. For example, the “Communities of Research” is established, under
a dialogue titled US-EU NanoEHS, comprising the scientists from the European
Union and the USA to meet annually to discuss topics relating to nanosafety and
relevant research needs [52]. While such an initiative is very encouraging, something
similar should be considered in the context of consumer protection also as the
consumer nanoproducts are coming to the market; the consequences of these should
be made clear to the consumer in a better and effective way too for their ultimate
success so that similar fate of GM food in Europe can be avoided.

Consumer Rights to Education

Education has a great role to play in the success of anything including consumer
empowerment. With the aim to, inter alia, educate the consumers, supported by clear
policy directions, about nanoproducts or nanomaterials, different countries or
1396 M. E. Karim

organizations have taken various initiatives starting with the assessment of public
perception, acceptance, understanding, knowledge, etc. Public acceptance, percep-
tion, and understanding study are conducted around the world sometimes as a
regulatory initiative and sometimes for academic interest. These things shaped by
culture are important issues which the entrepreneurs should consider [53] for the
commercial success of any product. It is evident that initiatives were taken to
understand consumers’ risk awareness and relevant information regarding nano-
products in general [54], targeting a specific group such as students [55], and in a
specific sector such as nanofood [56], etc. In the context of some countries, there are
also studies available where the researchers have evaluated the awareness level of
the consumers and the experts [57]. Interestingly, in most of the cases, it was
revealed that the consumers favor nanoenabled products. The manufacturers should
value such support of the consumers and do their best in the safe and sustainable
development of nanoproducts so that the belief of the consumers is not frustrated.
It has already been seen that in different countries, the regulators have started the
process of a product certification system and encourage the nanoproduct manufac-
turers to use such certification system and use the certification logo in their
manufactured products. One of the main purposes of such an initiative is to inform
the consumers about the authenticity of the nanoproducts with the confirmation
about the presence of ENMs there. Besides, some regulators have also been
maintaining product databases of nanoproducts using which the manufacturers can
be identified. With all the information, there are other concerns too. Huge amounts of
information developed using different methodologies are already available in the
public domain that may be confusing for the general consumers to follow. For
example, the US Environmental Protection Agency established Chemical and Prod-
ucts Dataset (CPDat), containing information of 49,000 chemicals used in 16,000
consumer products. Therefore, initiatives should be taken to ensure that the data is
presented in an understandable manner so that the consumers can make informed
decisions before purchasing a consumer nanoproduct based on those data. Previous
studies suggested to develop a communication system to address the expectations
and concerns of the consumers [54]. In line with this, the European Chemicals
Agency, with the funding of European Commission, has taken an initiative, i.e.,
European Union Observatory for Nanomaterials (EU-ON), containing information
about nanomaterials in the European market with the anticipation that using such
information, the consumers will be able to make better and more informed decisions
about nanomaterials and consumer products.

Consumer Dispute Resolution and Redress Mechanisms

The issue of dispute resolution and redress mechanism is extremely important in the
promotion and protection of consumer rights given through the provisions of
national legislations. Though the granting of these rights is welcoming and should
be applauded, there is an apparent lack of effective consumer dispute resolution and
redress mechanisms even within the national level if and when these rights are
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1397

infringed. For the consumers, sometimes it is very difficult to establish product

liability or other related disputes about ordinary products, and this has been recog-
nized or addressed by OECD and UNGCLP.
Legal liabilities of the parties are decided based on the nature of the act committed
because of, inter alia, negligence, breach of contract/warranty, misrepresentation,
strict liability for tort, etc., and these are difficult to establish in the court of law. All
these principles are equally applicable to product liability disputes. It can be seen that
most of the countries in the world have included legal provisions covering these
issues in domestic legislations; nevertheless, the implementation of these is a
challenge even for the developed countries, and this will equally be a challenge
for the rest [58]. The situation will be even more complex concerning consumer
nanoproducts as very different types of ENMs are used in these products, and the
findings of scientific research have been warning that some of these nanomaterials
are released during their life cycle and the consumers may be exposed to these
nanomaterials. Unfortunately, due to the absence or inadequacy of testing materials,
protocol, and guidelines, the consumers may not realize the immediate health effects.
With the issues of limited testing materials and inadequate information, the
consumers have very weak bargaining power and financial ability. These will
again make it difficult for them to bring a suit against the manufacturers, though
the consumers can consider bringing some class action suits in some developed
jurisdictions following standard procedures. Class action suits promise to make the
consumers united and bring a lawsuit against the manufacturer. Nevertheless, this is
not widely practiced in developing countries and in developed jurisdictions, to
prevent the abuse or over use of the class action suit which may discourage
the manufacturers in running the business having adverse economic consequences;
the legal system imposes some additional requirements which may discourage the
consumers to bring class action suits. It is found that even in the developed
jurisdiction, sometimes the courts do not allow class action suit about consumer
products against the manufacturers. For example, in the famous DePuy Pinnacle
Metal on Metal hip litigation case, the English court, by giving strict legal interpre-
tation, ruled in favor of the manufacturer (see Gee v. DePuy International Ltd. (2018)
EWHC 1208 (QB)). Similarly, in the case of Bristol-Myers Squibb Co. v. Superior
Court of California, San Francisco County, 582 U.S.__2017, the US Supreme Court
limited a consumer’s personal jurisdiction to sue the corporations for a purported
injury in a different state where he is not a resident or incorporated. This may
discourage the consumers to move to the court against the manufacturers resulting
in barring the consumers’ right to redress, at least initially. If this is the situation of
the consumers of the developed countries, the situation of the consumers of the
developing or least developed countries can be perceived.
Another important challenge or concern in this regard is the statutory limitation
period. In most cases, the domestic consumer protection law provides for a limitation
period which is generally 3 years, and a consumer must bring a product liability or
defective product-related suit against the manufacturer within these 3 years. How-
ever, as we know the history of asbestos or tobacco, when these were introduced,
these were highly applauded, and it took a few decades to realize that these products
1398 M. E. Karim

have some health-related consequences. Similar things can happen about nano-
enhanced products too. Nevertheless, it can be anticipated that on the ground of
limitation period, some of the consumers will be again barred to get the desirable
remedy. Nevertheless, this demands a special attention as this is a serious policy
question. The manufacturers should not be blamed always for such a situation for
obvious reasons as they will take the risks to make money. However, the regulators
should be careful and consider finding out suitable regulatory options so that the
manufacturers can continue their business while the interest of the consumers are
simultaneously protected. Hence, the product registry system, as can be seen in
Europe and the USA, can assist the regulators and consumers, where relevant
regulatory information will be maintained and updated and the manufacturers will
be reminded to take the responsibilities arising out of strict liability for any future
harms or problems arising out of the nanoenhanced consumer products.

Consumer Nanoproducts and International Organizations

Issues such as law, governance, and trade are significant in international consumer
protection ecosystem. Hence, the World Trade Organization could have been very
instrumental in the protection of consumers’ interests. Unfortunately, as this orga-
nization has somehow failed to play an effective role in this regard [46], UNCTAD’s
UNGCP came into the scene. Almost all the countries in the world, including UN
observer states such as Palestine and the Holy See, are members of UNCTAD.
Therefore, in the absence of an international legal instrument in this regard, the
UNGCP, which was developed by UNCTAD, can be seen to have a significant
impact on the promotion and protection of consumer interest if the guidelines can be
materialized positively. Besides, UNCTAD has also developed three regional pro-
jects in Latin America, Middle East, North Africa, and Central Africa aiming to
protect the consumers.
After evaluating the UNGCP in the context of consumer nanoproducts, this will
be relevant to explore and highlight the activities of some other international
organizations. Some of the specialized agencies of the United Nations, for example,
Food and Agriculture Organization and World Health Organization, have been
playing some limited roles concerning nanotechnologies and ENMs that can be
interpreted to have an impact on consumer protection and empowerment. Besides,
some other specialized agencies such as United Nations Educational, Scientific and
Cultural Organization, International Labour Organization, and United Nations Envi-
ronment Programme, while working within their mandated areas, have also taken
some isolated initiatives that can be related to different aspects of nanotechnologies
or ENMs having implications on consumer protection as the definition and interpre-
tation of the word “consumer” is very wide as shared above.
Apart from these UN specialized agencies, some of the regional organizations
such as the European Union (EU) and Association of Southeast Asian Nations
(ASEAN) have started the process to develop a harmonized framework with the
aim to promote and protect consumer rights within their regions. Like the UN
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1399

specialized agencies, these organizations were established primarily for a different

purpose, and therefore, the issue of consumer protection is not the main priority in
the functioning of these organizations. Though the initiatives of these regional
organizations should be appreciated from the consumer protection point of view,
harmonization of law may not solve the different challenges and problems the
consumers have been facing. Looking at the experience of the EU, one may realize
that finding out of the ideal and an effective legal framework of consumer protection
is a very complex issue as there are countries with different socioeconomic and legal
backgrounds and status. As discussed above, the consumers are protected through
the provisions of general and special laws, and there are around 90 community laws
that contain provisions relating to consumer protection. Therefore, instead of har-
monization, the development and facilitation of cooperation between the parties
seem to be a better and more effective option [46].
In the context of regional organizations, the EU seems to be the most active so far
in terms of regulation of consumer nanoproducts as consumer protection is an
integral part of the organization’s strategic planning. After the EU, for the purpose
of this chapter, some of the initiatives taken by the ASEAN in protecting the interests
of the consumers deserve special attention. ASEAN has established a product safety
system and formed a dedicated committee known as the ASEAN Committee on
Consumer Protection. Even though these are very general in nature, these mecha-
nisms can be considered in the context of consumer nanoproducts. Apart from these
regional organizations, some international organizations have been playing impor-
tant roles in the protection of the consumers. The list of such organizations includes
Consumers International and International Consumer Protection and Enforcement
Network.
The International Consumer Protection and Enforcement Network (ICPEN), an
organization of the consumer protection law enforcement authorities from around
the world, is an important organization which provides for a forum for developing
and maintaining regular contact between consumer protection agencies and focusing
on consumer protection concerns. So far enforcement authorities of 64 countries
along with 6 observer authorities became members of this organization. This forum,
a wonderful idea to encourage international cooperation and collaboration among
consumer law enforcement agencies, can also be considered to share information
about cross-border commercial activities that may affect the consumers. What
ICPEN has been doing with the consumer protection law enforcement authorities,
Consumers International has been playing a similar role with consumer groups from
around the world. Unfortunately, the initiatives of these organizations with consumer
nanoproducts are not significant enough yet.
Apart from the United Nations specialized agencies, some other international
organizations representing mainly the regulators such as OECD and International
Organization for Standardization have been playing an instrumental role in the
development of exposure, testing, characterization protocols, etc. relating to ENMs.
Though these may seem not directly relevant to consumer protection, they will
ultimately assist the consumers by way of empowering them in taking better informed
decisions on consumer nanoproducts. Besides, there are other organizations such as
1400 M. E. Karim

Asia Nano Forum, Asia Pacific Nanotechnology Forum, Nanosciences African Net-
work, etc. that have been playing some roles that can be linked with consumer
protection. Moreover, there are organizations that are representing industry players
such as the Nanotechnology Industries Association. Finally, it may be relevant to share
here that there are some NGOs such as Friends of the Earth, Green Peace, etc. that have
some form of programs that can be interpreted to have some implications on consumer
empowerment in the context of nanoenhanced consumer product.

Nanoproducts and Consumer Protection: An Evaluation

From the discussion above, it is apparent that the nanotechnologies and ENMs have
huge prospects and can be exploited to solve many of the problems of global concern
provided some of the exiting legal and regulatory concerns are addressed properly.
Even though the consumers are an important decisive factor in the commercial
success of any product, the issue of protection of consumer are treated as a domestic
matter, and the international consumer protection law has started to evolve. There are
some very interesting but common or similar things present between the history of
nanotechnologies and the development of consumer protection law. As we have
already discussed that accidental nanomaterials were used in the history by the
people of some ancient civilization, similarly consumer protection-related isolated
provisions can also be seen in some ancient codes of laws. In terms of their modern
history, it can be seen that the history of nanotechnologies was started in 1959 with
the seminal lecture of Richard Feynman, while the concept of consumer protection
began to gain ground in 1962 through the “Consumer Bill of Rights” proposed by J.
F. Kennedy. While the invention of the scanning tunneling microscope in 1981
helped the global community in manipulating things at the atomic scale, the UNGCP
began to shape international consumer protection law after its release in 1985.
While the consumers from around the world have been facing different chal-
lenges on various issues, it can be anticipated that they will face a similar kind of or
more complex situations when more and more nanoenabled consumer products will
reach the market. Nevertheless, the silver lining is that since a movement has already
started to shape and develop international consumer protection law, this will assist
the stakeholders to have some guidelines in regulating and governing nanoenabled
consumer products too even though the regulation of consumer nanoproducts will be
a complicated matter, if not impossible since the word “regulation” is a complex
term and difficult to define as it has context-specific different understandings.
The word “regulations” is used to mean some techniques or tools that the
authorities having regulatory power use to control or monitor the market. Regula-
tions can be process based or product based; it can also be ex ante or ex post facto,
i.e., regulatory checks can be imposed even before and after the occurrence of an
incident. There are various types of regulations – social, administrative, economic,
etc. – and finding out an effective regulatory option is a real challenge in every sector
including product safety. The situation becomes even intricate in the changing
circumstances of this borderless world when products are sold online and can be
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1401

distributed anywhere in the world. The consumers need to face challenges to get
remedies if they receive substandard or defective products. Nevertheless, the regu-
lators need to be very careful in imposing different regulatory tools because too
much regulations can discourage the innovation process; on the other hand, improper
regulation may encourage the market players to control the market in a way
unfavorable to the consumers.
Looking at the regulatory practices of some of the developed jurisdictions, some
of the products containing ENMs such as cosmetics, medical devices, biocides, and
novel food are strictly regulated containing provisions on reporting, labeling, etc. On
the other hand, some of the products, though developed using ENMs are not strictly
regulated. While such regulations can be seen in the context of Europe or the USA
[59, 60], similar regulation is absent in many other parts of the world, perhaps due to
the financial or resource constraints or lack of consumer awareness. As a result,
similar products using similar technology and ENMs may be introduced in the
market.
It is apparent that the issue of consumer protection is considered as a national
issue to be dealt with within the national border, and the international consumer
protection law has been only emerging in the context of world trade primarily. The
situation has been taking a paradigm shift after the Internet age and trade liberaliza-
tion and can easily be anticipated to be very complex in this age of Fourth Industrial
Revolution. At the national level, there are differences of approaches about the
promotion and protection of consumer rights. While in the developed countries,
the interests of the consumers are better protected, this is not the case of the
developing and least developed countries. In the developed countries, the regulators
are relatively active and due to their competence can take immediate measures in
case there is any concern, as it can be seen in the case of Samsung’s nanosilver
washing machines, which were initially banned and later on reintroduced in Sweden
as it was found by the regulators to be safe to use, though the public in other
countries such as Germany and Australia continued the protest [61]. This may not
be the case of the countries in the global south, in the developing and least developed
countries in Asia and Africa, where the regulators do not have such competence
while they need to address other development challenge.
Whatever the case is, the manufacturers must not ignore the interests of the
consumers as we have the history of many failed technologies, such as GMO food
in Europe, that were introduced projecting huge prospects but failed later on. While
consumers have been facing different problems about various products which are in
the marketplace for years or centuries, the case of nanoenabled products is relatively
new. Therefore, even though some of the problems the consumers regularly face in
the context of other products may not be seen in the nanoenhanced products right
now, these will surely be raised triggering a pile of lawsuits in the court of law. That
is why, for the manufacturers or suppliers, the compliance to regulations and
responsible research and innovation will be the key to their ultimate success in the
nano-age.
OECD has developed a Consumer Policy Toolkit, 2010, which the policymakers
can consider to respond to the challenges faced by the consumers in an effective
1402 M. E. Karim

manner. The toolkit, a practical guide intended to help the government authorities
having the responsibility to support consumer interest, provides for a robust frame-
work for examining consumer problems and determining the policy measures that
can be used to improve consumer outcomes [44]. Following the success of the
toolkit, the OECD Council has subsequently adopted a recommendation on con-
sumer policy decision-making. The recommendation provides for a six step frame-
work, the analysis of the problem, determination of the problem whether they are
serious enough to warrant action, setting up of policy objectives, identification and
selection of the best set of policy measures to address problems, and review of
policies to determine whether they had the intended impact. This can also be tested in
the context of consumer nanoproducts.
One policy option targeting the protection of interest of the consumers can be that
the regulators can consider to request the manufacturers, or at least the large
manufacturers or multinational corporations, to spend a small amount from their
annual turnover in the promotion and protection of consumers interest and consumer
education where informative and promotional educational materials can be devel-
oped using which the consumers can make better informed decisions about con-
sumer nanoproducts. Though some ethical issues need to be addressed as to whether
the regulators should use the manufacturers’ contributions or not, these issues can be
solved also as the concept of corporate social responsibility is widely practiced all
over the world now. Thus, using a small contribution from the manufacturers, the
regulators can run some customized programs which will help the consumers build
their confidence in using nanoproducts, and it can be anticipated that such a program
will have an effective desirable consequence in empowering the consumers since
when these programs will be run by the regulators, the consumers will have more
trust and confidence on consumer nanoproducts.
In the absence of any international body directly authorized to deal with con-
sumer protection matters, the Intergovernmental Group of Experts on Consumer
Protection Law and Policy established through UNGCP can be made more func-
tional in this regard by providing sufficient financial support as it does not have
enough. The United Nations Interagency Task Team on Science, Technology and
Innovation for the Sustainable Development Goals, launched as a means to imple-
ment the UN Sustainable Development Goals and the Global Partnership, can also
be utilized in this regard, and the issue of consumer nanoproducts can be included
within their agenda.

Conclusion

Consumer protection is all about respecting people as a human being in a sustainable

and inclusive manner. The understanding of consumer protection is not an isolated
issue in a country, where the rule of law, people’s access to justice, and human rights
issues are respected with due care. In such places, it can be anticipated that the issue
of consumer protection will be also be considered seriously in most of the cases.
Consumers have several rights recognized through the provisions of law. Some of
61 Nanoproducts and Legal Aspects of Consumer Protections: An Evaluation 1403

these are very general and wide in nature, while some of these are very specific.
Under the doctrine of the “inequality of bargaining power,” the consumers are
usually weaker than the manufacturers or suppliers and have very limited bargaining
power, choice, and options. With the weak bargaining power, the consumers have
been facing various types of shocks on a regular basis ranging from the economic
crisis, health crisis, social conflicts, natural disasters, etc. Besides, there are added
frequent newer technology-led challenges as well. For example, in the age of
artificial intelligence, they will suffer from autonomy and subvert reasonable
decision-making. One may find that these all depend on the stands of the courts of
law, legal culture, and legal system of any specific jurisdiction.
ENMs are wonder materials, at least in the theoretical level as using nanotech-
nologies, thighs can be exploited at the atomic level. Like all other technology,
nanotechnologies are also dual dimensions, i.e., have advantages and disadvantages.
Thus, they promise to solve many of the existing problems the global community has
been facing, and if these can be regulated properly, these can be used as an important
catalyst to achieve some of the UN Sustainable Development Goals. Therefore, their
wide use should be encouraged though within an effective regulatory framework.
There is no one-size-fits-all size regulatory tool available which is suitable for the
regulation of ENMs or consumer nanoproducts, and different developed countries
have started to deal with this using different regulatory options. When the interna-
tional legal framework on biotechnology started, only a few members from the
developing countries participated. Besides, there are concerns that nanotechnologies
may be used to exploit the global south, and it will create a similar situation like the
digital divide [62]. Therefore, the active involvement of the industrialized and
developed countries is desired. They should not repeat the experience of biotech-
nology regulation in case of nanotechnologies too as this will not make any
development sustainable and inclusive frustrating the spirit of UN Sustainable
Development Goals.

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 Part XVI
Green and Sustainable Future with Consumer
Nanoproducts
Sustainable Future with Nanoproducts
62
Sukanchan Palit, Chaudhery Mustansar Hussain, and
Shadpour Mallakpour

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1410
The Vision of the Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1411
Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1412
What Do You Mean by Nanoproducts? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1412
Environmental Sustainability and a Vision for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1413
Drinking Water Treatment and Industrial Wastewater Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1413
Integrated Water Resource Management and Wastewater Management . . . . . . . . . . . . . . . . . . 1414
Application of Nanoproducts in the Effective Implementation of Environmental
Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1414
Recent Scientific Research Pursuit in the Field of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1414
Advanced Oxidation Processes, Nanomaterials, and Environmental Protection . . . . . . . . . . . . . . 1417
Novel Separation Processes and Membrane Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1418
Recent Scientific Forays in Environmental Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1419
Arsenic Groundwater Remediation and Its Scientific Vision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1423
The Futuristic Challenges in Application of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Future Research Directions in the Field of Nanoproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1426
Sustainable Development Goals and the Vision for the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1427
Environmental and Energy Sustainability and Scientific Sagacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1427
Future Recommendations and Futuristic Flow of Thoughts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1428

S. Palit
Department of Chemical Engineering, University of Petroleum and Energy Studies, Energy Acres,
Post-Office-Bidholi via Premnagar, Dehradun, Uttarakhand, India
e-mail: [email protected]
C. M. Hussain (*)
Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, USA
e-mail: [email protected]
S. Mallakpour
Chemistry, Isfahan University of Technology, Isfahan, Iran

© Springer Nature Singapore Pte Ltd. 2022 1409

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_80
1410 S. Palit et al.

Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1428
Important Websites for Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1429
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1430

Abstract
The domain of nanotechnology, environmental remediation, and green sustain-
ability is in the avenues of scientific ingenuity and scientific revelation. Science
and technology of nanotechnology, nano-engineering and environmental protec-
tion are highly challenged in the global scenario. Climate change, global
warming, environmental catastrophes, and lack of fossil fuel resources are chal-
lenging the engineering community globally. The utmost requirement for the
human civilization today is the provision of basic needs such as water, electricity,
food, education, and sustainability. Energy and environmental sustainability and
human civilization’s immense scientific and knowledge prowess will all lead a
visionary way in the true emancipation of science globally today. In this chapter
the authors pinpoint the success and the vision of science and engineering in
mitigating global challenges in the application of energy and environmental
sustainability in human society and the application of nanoproducts for a sustain-
able future. Science and technology in the global scenario is highly advanced and
highly envisioned as human civilization moves forward. There are immense
needs of human society. Nanotechnology, chemical process engineering, and
environmental protection science are in the threshold of a new age and newer
introspection. This chapter will open up new areas in the domain of nanoproducts
and environmental engineering. The needs of environmental sustainability are
immense today and in similar vein groundbreaking. Human’s vast knowledge
dimension and prowess in the field of nanotechnology and environmental reme-
diation will veritably open new doors of innovation and profundity in the field of
science and technology today. The authors with vast scientific conscience and
foresight bring to the light to readers these intricate scientific issues and the
applications of nanoproducts for a better and a sustainable future.

Keywords
Nanoproducts · Environment · Water · Arsenic · Metal · Sustainability · Vision

Introduction

Today, in the global scenario science and technology are moving in a drastic pace and
overcoming vast scientific boundaries and barriers. Engineering and technology in the
similar vein should be re-envisioned and revamped with the passage of scientific history
and visionary timeframe. Nanoproducts today are integrated with environmental pro-
tection in diverse areas of scientific research pursuit. Globally, environmental engineer-
ing is in the midst of vision and contemplation. Recalcitrant organic compounds and
hazardous substances in industrial wastewater is a massive scientific issue and replete
62 Sustainable Future with Nanoproducts 1411

with immense intricacies and barriers. Massive industrialization in the global scenario
has brought the human civilization to unending environmental disasters, thus the need of
a sustainable future with the help of nanoproducts. Science and technology has practi-
cally no answers to the heavy metal contamination of groundwater and drinking water in
many developing and industrialized nations around the world. Lack of fossil fuel
resources and petroleum engineering are faced with immense disaster. Here comes the
importance of conventional and nonconventional environmental engineering tech-
niques. So in this treatise, the authors cover the areas of Advanced Oxidation Techniques
and novel separation processes such as membrane separation processes. There are
enough scientific theories to validate that membrane separation processes are the pillars
of mass transfer operations in chemical process engineering. Thus comes the importance
of nonconventional environmental engineering separation processes. Human civiliza-
tion today is bereft of concerted efforts from the civil society as regards mitigation of
global climate change and global warming. This chapter will veritably go a visionary
way in the emancipation of science and engineering of nanotechnology globally.

The Vision of the Study

The vision of this study goes beyond scientific vision and technological profundity.
Global warming, frequent environmental calamities, loss of ecological biodiversity,
and lack of fossil fuel resources are urging the scientific community to gear forward
towards vision, innovation, and scientific instinct. The requirements of human
society and human scientific progress are numerous and in the same vein visionary.
The challenges of environmental remediation and application of nanotechnology are
many today. Today science of chemical process engineering and membrane separa-
tion processes are changing the face of scientific endeavor. The vision of this study is
to pointedly focus on the success of nanoproducts in environmental protection.
Novel materials and eco-materials also include nanoproducts. One of the many
directions of nonconventional environmental engineering processes is degradation
of hazardous and recalcitrant organic and inorganic pollutants. Thus this direction of
research pursuit involves detailed introspection into the area of degradation and
environmental pollution control with the help of nanotechnology. Scientific valida-
tion in the domain of Advanced Oxidation Processes are the other cornerstones of
this well-researched treatise. A detailed discussion on recent scientific endeavor in
the field of nanotechnology, environmental pollution, and Advanced Oxidation
Process are done with immense scientific conscience and deep contemplation.
Today is the age of sustainability. A sustainable future is the utmost need of the
hour. The success of human progress also lies in the hands of energy engineering and
the world of renewable energy. This treatise also deeply discusses the environmental
and energy sustainable goals of human race. A deep discussion of United Nations
Sustainable Development Goals and its re-envisioning are the other cornerstones of
this treatise. The deep scientific profundity and the engineering ingenuity and
subtleties of global environmental protection science are the other main points of
this treatise.
1412 S. Palit et al.

Scope

The domain of science and technology of environmental sustainability and environ-

mental protection is witnessing vast and versatile challenges. The scope of this research
endeavor is immense and groundbreaking in today’s global scenario. Water purifica-
tion, ground water treatment, and industrial wastewater treatment are global scientific
concerns today. Here is the vast scope of science and technology of environmental
remediation and environmental sustainability. The visionary words of Dr Gro Harlem
Brundtland, former Prime Minister of Norway, on the science of “sustainability” needs
to be reframed and reorganized as science and engineering moves forward. The entire
scope of environmental protection and consumer nanoproducts science has no barriers.
Technological and scientific revamping and re-envisioning, the vision of environmental
engineering science and the immediate needs of sustainability will open surely new
doors of scientific profundity and ingenuity in the field of environmental remediation.
The other vast scopes of this research pursuit are the areas of novel separation
processes, conventional and nonconventional environmental engineering techniques.
Technology revamping and scientific redeeming in the field of energy and environ-
mental sustainability as well as the science of renewable energy technology are the
other cornerstones of this treatise. Research pursuit in environmental engineering and
chemical process engineering are in the dawn of new scientific regeneration. Today,
successive generations and the larger scientific community are witnessing vast chal-
lenges due to grave concerns for global warming, loss of ecological biodiversity and
lack of fossil fuel resources. Thus the scope of this study should cover innovations to
ameliorate global climate change and warming. The twenty-first century is a period of
scientific vision and deep provenance. In the similar vein, environmental engineering
science and nanotechnology needs to be re-envisioned and re-organized as civilization
treads forward. Globally, heavy metal groundwater contamination is veritably chal-
lenging the scientific community. This treatise is a veritable reflection to the needs of
energy and environmental sustainability to human society.

What Do You Mean by Nanoproducts?

Nanoproducts, nanomaterials, and nanotechnology are the marvels of science and

engineering today. Graphenes, fullerenes, and carbon nanodots are today revolu-
tionizing the global scientific and engineering scenario. The immediate need of the
hour is the application of newer innovations in nanotechnology and nanomaterials.
Engineered nanomaterials are the other visionary areas of nanoproducts. In this
chapter, the authors elucidate the scientific vision and the scientific divination in
nanotechnology applications in environmental remediation. The areas of sustainable
development and advanced materials are the scientific needs of the global order
today. The success, the intricacies, and the ingenuity in the environmental protection
are brought to light with immense vision in this chapter.
62 Sustainable Future with Nanoproducts 1413

Environmental Sustainability and a Vision for the Future

Environmental sustainability and water purification are today integrated with each
other as science and engineering are confronted with ever-growing concerns of
global climate resilience and frequent environmental calamities. The vast vision
for the future needs to be reframed with the march of human civilization. Provision
of pure drinking water is a challenge of mankind and scientific progress today.
Heavy metal groundwater contamination is a serious global environmental engi-
neering issue. Nations around the world are in the crucial juxtaposition of deep
comprehension and deep scientific ingenuity. The success of science and technol-
ogy thus are in the hands of environmental engineering and chemical engineering
domain. Nanotechnology and nanomaterials are also integrated with scientific
research pursuit in environmental protection. Thus sustainable advanced materials
are also changing the face of human scientific research forays. Material science and
advanced materials are the marvels and vignettes of science and technology today.
The authors with immense scientific rigor delineate the success of science and the
scientific needs of energy and environmental sustainability. The civilization will
thus be in the threshold of a newer scientific age of might, grit, and deep scientific
determination. The challenges and the intricacies are immense as regards water
purification. In such a situation, ever-growing concerns, deep scientific vision, and
newer knowledge prowess will open up a new era in science, technology, and
engineering science.

Drinking Water Treatment and Industrial Wastewater Treatment

Scarcity of pure drinking water is a burden to the scientific progress of human

civilization today. Science and engineering of integrated water resource manage-
ment and industrial wastewater treatment are the utmost needs of human society
today. Heavy metal groundwater contamination is a veritable burden to human
progress today. Millions of people in developing, developed, and industrialized
nations around the world are having serious health effects due to arsenic drinking
water contamination. The challenges and the scientific enquiry lie in the domain
of engineers and scientists. The world of environmental engineering science
stands mesmerized and envisioned as global research and development forays
gears forward. In this chapter, the authors trudge in the field of environmental
engineering innovations such as nanoproducts and nanomaterials. A new dawn in
the field of environmental protection and membrane science will usher in vision,
might, and scientific forbearance in global research and development initiatives.
Human factor engineering and reliability engineering are the other areas of
futuristic vision today. These areas of research pursuit will surely be the
forerunners in the field of water resources engineering and water resource
management.
1414 S. Palit et al.

Integrated Water Resource Management and Wastewater

Management

Water resource engineering and water resource management are in the process of
immense scientific revival today. Technological divination and vast engineering
emancipation in water treatment and wastewater treatment are changing the face of
human scientific progress. In the similar vein, nanoproducts and nanomaterials are
veritably revolutionizing the vast scientific and engineering landscape. Innovations
in membrane science, the futuristic vision and targets of water science are the
torchbearers of environmental protection today. Poor and industrialized nations
around the world are in the threshold of an unmitigated environmental catastrophe,
that is, arsenic groundwater contamination. Thus comes the need of integrated water
resource management. Contamination of industrial wastewater is a scientific burden
to human civilization. In the global scenario, arsenic and heavy metal groundwater
contamination is a major environmental engineering problem. Integrated water
resource management, reliability engineering, and human factor engineering are
the pillars of scientific endeavor in environmental engineering as well as nanotech-
nology. This chapter will surely open up new thoughts and newer future recommen-
dations in the field of environmental science and nanotechnology.

Application of Nanoproducts in the Effective Implementation

of Environmental Sustainability

Nanoproducts, nanomaterials, and the vast avenues of nanotechnology have strong

scientific vision today as regards its applications. In real-world applications of
environmental pollution control, this term usually refers to a subset of chemical
processes that employ nanotechnology and nano-engineering. A visionary area of
such research endeavor is the application of nanotechnology. Advanced Oxidation
Processes rely on in situ production of highly reactive hydroxyl radicals. Techno-
logical stance, the subtleties, and the ingenuity of chemical process engineering will
surely widen the scientific perspectives of environmental sustainability. The whole
gamut of Advanced Oxidation Techniques and nanotechnology today can be inte-
grated with each other thus increasing the efficiency of the separation and purifica-
tion processes. Mankind’s vast and versatile vision and might, the necessity of
scientific vision and the futuristic scientific thoughts will thus open the windows
of scientific aura in environmental engineering and environmental sustainability.

Recent Scientific Research Pursuit in the Field of Nanoproducts

Scientific research forays in the field of nanoproducts are today surpassing and
overcoming vast, versatile, and rigid frontiers. Technological discerning and scien-
tific vision are the hallmarks of nanoproducts and environmental remediation. The
success of science of both environmental protection and environmental engineering
62 Sustainable Future with Nanoproducts 1415

are in the vistas of newer scientific rejuvenation. In this section the authors deeply
pronounce the recent research literature in the field of photocatalytic nanoproducts.
The scientific and academic rigor in the field of nanoproducts and green sustainabil-
ity will surely usher in newer thoughts and newer research recommendations in
decades to come.
Werkneh and Rene [1] deeply discussed with vision, provenance, and deep reve-
lation applications of nanotechnology and biotechnology for sustainable drinking
water and industrial wastewater treatment. The world today stands in the middle of
scientific provenance and deep divination. Nowadays, water pollution and fresh water
scarcity have become a serious problem worldwide [1]. It is veritably creating disaster
to civil engineering, environmental engineering, and public health engineering. Vari-
ous treatment techniques are thus adopted. Nanotechnology- and biotechnology-based
tools are applied for water and wastewater treatment. This treatise focuses on new and
emerging areas of biotechnology and environmental sustainability. The authors
discussed minute details of nanomaterials for the disinfection of pathogenic microbes,
photocatalytic applications of nanomaterials, applications of nanomaterials as adsor-
bent, and bioenergy and environmental biotechnology [1]. Bioremediation and bio-
transformation tools are the other areas of deep scientific introspection. A new
scientific vision will emerge if concerted efforts of scientists and engineers are taken
in the near future [1].
Beydoun et al. [2] discussed and delineated with cogent and lucid insight the role
of nanoparticles in photocatalysis. Science of environmental protection and envi-
ronmental remediation are huge colossuses with a vast and definite vision of its own
[2]. The aim of this chapter is to highlight the development and implications of
nanotechnology in photocatalysis. The chapter deeply discusses the unique proper-
ties of nanoparticles and their relation to photocatalytic properties [2]. Also the
utilization of nanoparticles in doped, coupled, capped, sensitized, and organic-
inorganic nanocomposite semiconductor systems with deep efforts in enhancing
photocatalytic properties are delineated in minute details [2]. Finally the use of
nanoparticles has today made significant contribution in delineating the photo-
catalytic degradation. The science of Advanced Oxidation Processes and nanotech-
nology are elucidated in this chapter with a clear aim in furtherance of global
research initiatives in environmental engineering [2]. Organic chemicals that may
be found as pollutants which are recalcitrant need to be vehemently destroyed before
discharge to the environment [2]. The photocatalytic detoxification of industrial or
domestic wastewater is a process that combines heterogeneous catalysis with solar
technologies. Semiconductor photocatalysis is a cornerstone of scientific research
pursuit in photocatalytic degradation today [2]. The authors also discussed in detail
nanocrystalline photocatalysts. This chapter widens the scientific directions and the
scientific provenance in the field of environmental engineering techniques.
Magalhaes et al. [3] discussed with cogent insight and vast far-sightedness titanium
dioxide photocatalysis, its fundamentals and application on photoinactivation. [3]
Titanium dioxide semiconductor is being deeply investigated and used for different
applications such as energy production, photo-inactivation, photo-abatement, and
water desalination. The progress of global science and engineering is highly
1416 S. Palit et al.

groundbreaking [3]. Sustainability is the utmost need of human scientific progress

today. Technological and scientific ardor, the wide domain of photocatalysis and the
needs of scientific advancement will surely open up new windows in the field of
environmental engineering and nanotechnology in years to come [3]. Till recently,
titanium dioxide/graphene composite proved to be extremely promising material for
photocatalysis purposes, highlighting enhanced energy harvesting properties and vast
photocatalytic properties [3], thus the imminent need of a strong research and devel-
opment initiative in photocatalysis and nanomaterials [3]. The photocatalysis funda-
mentals and the preparation of more efficient titanium dioxide photocatalysts highly
suitable for indoor applications are extensively reviewed with vast scientific insight,
might, and vision. In the past four decades photocatalysis fundamentals and its vast
applications have progressed tremendously [3]. In recent years, there is a deeper
understanding of the photocatalysis fundamentals and the use of photocatalysis in
several emergent and visionary domains such as energy production, environmental
remediation, photo abatement, water purification, photooxidation of micro-pollutants
and for microorganisms inactivation. The authors in this chapter discuss fundamentals
of photocatalysis, doping and decoration, titanium dioxide/graphene composite,
photoinactivation, ultraviolet, and titanium dioxide inactivation. The other areas of
scientific research pursuit are the comparison between photo-inactivation and tradi-
tional disinfection methods [3].
Madhura et al. [4] discussed with immense scientific vision the nanotechnology-
based water quality management for wastewater treatment. The scientific ardor, the
candor, the verve, and the engineering motivation will all lead a visionary way in
opening doors of ingenuity in water resource management in decades to come [4].
Water contamination by pollutants has been a critical issue in the public health
engineering domain in recent times. The needs of science and engineering of
environmental protection are vast and versatile today [4]. The role of nanoscience
and nanotechnology in pollutant remediation, drinking water, and industrial waste-
water treatment has proven to be extremely promising, thought provoking, and
far-reaching. Vast and versatile nanoscale features primarily adsorption properties,
high rate of photocatalysis, and high reactivity are opening up vast and versatile
doors of innovation. The authors deeply discussed emerging and conventional
environmental technologies in terms of production cost and performance of the
photocatalysis properties. The authors in this treatise discussed in deep details
scarcity of water, occurrence of pathogens in industrial and domestic wastewater,
nanotechnology-based water treatment and reuse process, and the vast domain of
nanoadsorbents for environmental remediation [4].
The stance and status of global environmental engineering science is vastly grave
and needs scientific reforming. The targets, the scientific needs, and the scientific
genesis need to be redrawn as regards environmental sciences. Today Advanced
Oxidation Processes is integrated with nanoscience and nanotechnology. Techno-
logical resurgence and vast engineering motivation in environmental science will
surely open a new vista in the field of environmental remediation. The concerted
effort of scientists and engineers will thus usher in a newer eon in scientific
understanding and scientific resurgence in near future.
62 Sustainable Future with Nanoproducts 1417

Advanced Oxidation Processes, Nanomaterials, and

Environmental Protection

Advanced oxidation techniques and integrated advanced oxidation techniques are

today in the avenues of vast scientific revival. Environmental remediation, ground
water treatment, and industrial wastewater treatment are today in the verge of a new
beginning. The necessity of nonconventional environmental science techniques is
today surpassing vast scientific and engineering frontiers. Today the technological
challenges in the field of implementation of environmental science tools such as
Advanced Oxidation Processes are immense and at the same time far-reaching.
Munter [5] discussed with immense engineering insights the current status of
Advanced Oxidation Processes. This paper (Munter [5]) discusses and highlights
theoretical basis, efficiency, economics, laboratory and pilot plant testing, design,
and modeling of different Advanced Oxidation Processes [5]. Vastly hazardous
organic wastes from industrial, military, and commercial operations represent one
of the greatest challenges to both environmental engineers and chemical process
engineers. Advanced oxidation techniques are the promising alternatives to the
incineration of industrial and domestic wastes as well as wastewater [5]. The
Advanced Oxidation Processes are carried along two vital routes: (1) oxidation
with O2 in temperature intermediate between ambient conditions and those found
in waste incinerators which are Wet Air Oxidation processes in the range of
1–20 MPa and 200–300
C, and (2) the use of high energy oxidants such as ozone
and hydrogen peroxide that are able to generate highly reactive intermediates that is
OH’ radicals [5]. Technological vision is the need of the hour in today’s world of
Advanced Oxidation Processes. The other areas of this research pursuit are the
photochemical and non-photochemical processes. The entire gamut of integrated
Advanced Oxidation Processes is dealt in minute details in this paper [5].
Gogate and Pandit [6] reviewed in minute details imperative technologies for
wastewater treatment such as oxidation technologies at ambient conditions. Today,
due to the increasing presence of molecules, recalcitrant to the microorganisms in the
wastewater streams, the conventional biological methods cannot be used for the
treatment of industrial wastewater. [6]. This work depicts with profound insight five
different oxidation processes operating at normal conditions which are cavitation,
photocatalytic oxidation, Fenton’s chemistry and use of ozone and the use of
hydrogen peroxide. The challenges of science and engineering of Advanced Oxida-
tion Processes or other tertiary separation processes are increasing day by day [6].
This research work also highlights the basics of these individual processes including
the operating conditions, and the reactor design aspects with a wide overview of the
various applications to industrial wastewater treatment in the recent years. Advanced
oxidation process is a marvel of environmental engineering today [6]. Scientific rigor
and stance, the vision of environmental protection, and the world of challenges are
all the torchbearers toward a new era of scientific imagination today [6]. In this well-
researched paper, the authors deeply touched on cavitation, acoustic cavitation,
hydrodynamic cavitation, reactors used in cavitation, and the vast area of photo-
catalysis [6]. Reactors used for photocatalytic oxidation are the other important
1418 S. Palit et al.

Table 1 Significant scientific research pursuit in Advanced Oxidation Processes, nanomaterials,

and other environmental engineering techniques
Authors Scientific research pursuit
Munter [5] Current status and prospects of Advanced Oxidation Processes
Gogate and Oxidation Technologies for wastewater treatment
Pandit [6]
Sharma et al. [22] A general review of Advanced Oxidation Processes for wastewater
treatment
Gilmour [23] Water treatment using Advanced Oxidation Processes and application
perspectives
Cesaro et al. [24] Combination of Advanced Oxidation Processes and conventional
Biological Systems
Kunduru et al. Nanotechnology applications in water and wastewater treatment and the
[10] vast vision behind it
Werkneh and Application of nanotechnology and biotechnology for sustainable
Rene [1] wastewater treatment
Das et al. [11] Recent advances in nanomaterials applications in water treatment and
monitoring
Yadav et al. [12] A review of nanoadsorbents for defluoridation of water and wastewater
treatment

features of this treatise. The photocatalytic or photochemical degradation processes

are gaining immense importance in the area of industrial and domestic wastewater
treatment [6]. The photo-activated chemical reactions are characterized by a free
radical mechanism initiated by the interaction of photons of a proper energy level
with the molecules of the chemical species present in the solution, with or without
catalysts. The radicals can be easily produced using Ultraviolet Radiation by the
homogeneous photochemical degradation of oxidizing compounds like hydrogen
peroxide and ozone. This entire paper is a watershed text in the field of Advanced
Oxidation Process and will surely open up newer visionary areas of research pursuit
in years to come [6].
The science and engineering of Advanced Oxidation Techniques and nano-
materials techniques are the challenges of human scientific pursuit in environmental
engineering today. The march of human civilization today is highly challenging and
visionary. This research work will surely uncover the scientific intricacies of envi-
ronmental engineering paradigm (Table 1).

Novel Separation Processes and Membrane Science

Novel separation techniques and membrane science are the marvels of science and
technology. Environmental remediation, nanotechnology, and membrane science are
today integrated with each other. Membrane science applications in environmental
protection encompass reverse osmosis, ultrafiltration, nanofiltration, and micro-
filtration. Food industry today also involves application of ultrafiltration and nano-
filtration. Desalination and membranes are also the needs of water purification and
62 Sustainable Future with Nanoproducts 1419

drinking water treatment. Environmental science is in the verge of new regeneration

and introspection. In the similar manner, environmental remediation stands as a huge
colossus with a wide vision of its own. In this treatise, the author rigorously points
toward the deep scientific vision of novel separation techniques, nanotechnology
tools, and advanced oxidation processes. Scientific re-envisioning and deep redeem-
ing are the cornerstones of research pursuit in the field of membrane science
applications in environmental protection. The challenges of membrane science and
the diffusion processes involved in it is still today unsolved. This chapter with vast
academic and scientific rigor opens up newer thoughts and newer future recommen-
dations in the field of membrane science, nanotechnology, and Advanced Oxidation
Processes. The scientific and technological vision in the field of membrane separa-
tion processes needs to be redrawn and revisited as global water concerns aggra-
vates. Desalination is another vast area of scientific introspection today. In
developing nations around the world, technology and engineering science have no
answers to heavy metal groundwater remediation. Thus comes the applications of
nanoproducts in diverse areas of science and engineering.

Recent Scientific Forays in Environmental Protection

Human challenges in the domain of environmental pollution control are vast as

civilization moves forward. Scientific forays, scientific genesis, and the futuristic
vision of civilization will all be the forerunners toward newer age in the domain of
industrial and environmental pollution control. Today is the age of novel separation
techniques, nanotechnology tools, and advanced oxidation processes. Water purifi-
cation science, groundwater remediation, and industrial wastewater treatment tech-
niques are the needs of scientific progress today. Membrane science and desalination
are today the necessities of scientific progress and human civilization today. Drink-
ing water scarcity and global climate change are the vexing issues facing human
scientific foray today. In this section the author investigates the innovations of
engineering of environmental protection.
Shannon et al. [7] discussed with scientific conscience and deep profundity the
science for water purification in the coming decades. Scientific and engineering
validation, the vast engineering verve, and the futuristic vision of environmental
protection will surely open up newer vistas of innovation in the field of sustainability
in decades to come [7]. One of the most pervasive global issues afflicting people
around the world is inadequate access to clean water and proper sanitation [7].
Problems with water will increase in the recent decades with water scarcity occurring
globally [7]. In this article, the authors deeply elucidate some of the science and
technology being developed to improve the disinfection and decontamination of
water, as well as efforts to increase water supplies through the safe reuse of
wastewater and effective desalination of sea water. The immense problems world-
wide associated with clean and fresh water are very much well known: 1.2 billion
people lack safe access to drinking water, 2.6 billion people have no sanitation, and
millions of people die annually. Besides 3900 children a day from diseases
1420 S. Palit et al.

transmitted with unsafe water [7]. Today science and technology are highly retro-
gressive as regards environmental remediation. This paper widely redefines disin-
fection, decontamination, reuse, and reclamation and the vast world of desalination
[7]. The work highlighted here in addition to the vast research endeavor being
conducted in every continent is veritably sowing the seeds of a revolution in water
purification science. The challenges, the directions, and the vision are the hallmarks
of research pursuit in water pollution control and water purification today [7]. The
sheer enormity of the problems facing the world from lack of clean water and
sanitation implies that much work needs to be done as human civilization moves
forward. This paper opens up newer visionary areas in the field of environmental
protection science [7].
Madhura et al. [8] discussed and described with vast scientific the far-sightedness
membrane technology for water purification. Managing effectively water demands is a
massive challenge in the twenty-first century due to industrial pollution control and the
growing concerns for global climate change [8]. Therefore concerted efforts are
needed for improved tools to purify contaminated waters. The imminent needs of
human scientific progress are immense with the march of human civilization. In this
paper, the use of polymeric membrane materials and polymer brushes are deeply
discussed in minute details. The development of global water is closely associated
with global climate change and the growth of human civilization is estimated to be
twofold from 3.4 billion in 2009 to 6.3 billion people in 2050 [8]. Thus the vision of
science and technology needs to be redefined and re-envisaged as civilization moves
forward. The demand for clean water is increasing drastically as mankind trudges
forward toward a newer visionary era. In this paper, the authors discussed in deep
details membranes and separation processes, fundamentals of separation processes,
fabrication and modification of membranes, nanofiltration membranes, nanocomposite
membranes, self-assembling membranes, nano-fiber membranes, aquaporin-based
membranes, photocatalysis, and polymer brushes as state-of-the-art tools for mem-
brane science. Technological validation and genesis, the world of membranes, and the
vision of environmental protection science will all be the pallbearers toward a new era
in environmental sustainability.
Dhakal et al. [9] discussed with scientific far-sightedness the perspectives and
challenges for desalination in the developing countries. Research directions in the
field of membrane technology and desalination are in the path of new regeneration.
Scarcity of pure drinking water is a big research question in both industrialized and
nonindustrialized nations around the world. Arsenic and heavy metal groundwater
remediation is veritably challenging the scientific domain today [9]. This study
explores the current situation of the membrane desalination market, it encompasses
the issue as to how many countries and which ones will suffer from water scarcity by
2050 and presents three case studies (India, China, and Algeria) [9]. Finally it
highlights some of the challenges for the implementation of desalination in water
scarce nations around the world. The success of science and engineering, the
futuristic vision of environmental sustainability, and the provision of basic human
needs such as energy and water will surely open up new vistas of research pursuit in
the field of energy engineering [9]. The projections in this study indicate that
62 Sustainable Future with Nanoproducts 1421

44 countries (two billion people) will suffer from water shortage by 2050 [9]. In an
increasingly crowded planet, conventional resources such as water and energy are
being fully exploited and the civilization is at a state of immense distress. Thus
technology and engineering needs to be reorganized at civilization moves forward.
The authors in this paper deeply focus on what will be the situation like in 2030 and
2050 in the groundwater and surface water scenario [9]. Desalination is technically
feasible on a large scale, and membrane-based desalination is the need of human
civilization today. This paper deeply discusses the resource savings, green desalina-
tion technology, and processes and methods of operation in the field of desalination
technology [9].
Kunduru et al. [10] described and elucidated in minute details the nanotechnology
for water purification and application of nanotechnology methods in wastewater
treatment. Water is veritably an important asset of human civilization, and potable
water supply is an important human necessity. Today is the age of nanotechnology,
space technology, and nuclear technology [10]. Today the global water demands are
not met and this problem will increase with time. Only 2.5% of the world’s oceans and
seas harness fresh and potable water. However, 70% of fresh water is frozen as eternal
ice [10]. Only less than 1% of fresh water can be used as drinking water [10]. Globally
greater than 700 million people do not have access to clean drinking water. The global
population is expected to reach 7.9 billion by 2020 and therefore the world will have to
face drinking water shortage [10]. Therefore it is utterly necessary to remove these
pollutants from contaminated water to provide good health to global citizens. The most
important water treatment methods are screening, filtration, micro- and ultra-filtration,
crystallization, sedimentation, gravity separation, flotation, precipitation, coagulation,
oxidation, solvent extraction, electrodialysis, fluidization, neutralization, and
remineralization [10]. Any of the above methods can be combined depending on the
type of contaminated water and the end use. These methods work extremely well but
recent harmful anthropogenic pollutants pose a definite challenge to purify the con-
taminated water. Thus the existing technologies are not fully efficient [10]. The authors
in this chapter discussed importance of nanotechnology in water purification. Also the
treatise pointedly focuses on major limitations associated with conventional water
purification methods [10]. The areas of water treatment are nanoadsorption, carbon-
based nanoadsorbents, metal-based nanoadsorbents, polymeric nanoadsorbents, and
membranes and membrane processes [10]. Nanocomposite membranes, thin-film
nanocomposite membranes, and photocatalysis are the other areas of investigation.
The application of antimicrobial nanomaterials in disinfection and microbial control
are other cornerstones of this chapter [10]. Research conducted in the past few decades
discloses a veritable dilemma between effective disinfection and formation of harmful
disinfection products. Here comes the need of innovation and discoveries. The
commonly used chemical disinfectants in the water science industry are chlorine,
chloramines, and ozone. They can react with other contaminants in the water and
generate harmful byproducts [10]. Nano-antimicrobial polymers are the other needs of
environmental remediation today [10]. Safety, toxicity, and environmental impact of
nanomaterials and the research needs are the definite global issues of environmental
engineering and are dealt with effectively in this paper [10].
1422 S. Palit et al.

Werkneh and Rene [1] deeply enunciated applications of nanotechnology and

biotechnology for sustainable water and wastewater treatment. In recent years, water
and wastewater treatment and freshwater scarcity have become a serious problem
worldwide causing concerns to public health engineering [1]. There are immense
challenges behind water and wastewater treatment in the global platform [1]. In order
to eliminate these challenges various water treatment technologies have been
adopted. Among these technologies, nanotechnology- and biotechnology-based
techniques are usually applied separately from water and wastewater treatment.
This chapter with immense academic rigor focuses on new and emerging nano-
and biotechnologies for the sustainable removal of water pollutants [1]. Besides the
toxicological and safety aspects of different nanotechnologies and their future
perspectives are discussed in detail [1]. Environmental pollution along with global
warming is the major cause of environmental catastrophes today. The extensive
industrial development, rapid population growth, and rampant climate change
largely contributes to the deterioration of global ecosystem [1]. The conventional
water treatment technologies used for environmental protection are activated carbon-
based adsorption, membrane filtration, ion-exchange, coagulation and flocculation,
reverse osmosis, flotation and extraction, electrochemical treatment, and biosorption
[1]. Environmental biotechnology is the other cornerstone of this chapter. Bioreme-
diation techniques, biotransformation techniques, and bioreactor configuration in
water and wastewater treatments are the other challenges of this paper [1]. Toxico-
logical aspects of nanomaterials are also dealt with immense foresight in this chapter.
Nanotechnology, nanoproducts, and biotechnology are the two important areas of
scientific introspection and contemplation today. This chapter depicts profoundly the
needs of nanotechnology and biotechnology in the unraveling of scientific
hurdles [1].
Das et al. [11] discussed with vast scientific insight recent advances in nano-
materials and nanoproducts for water protection and monitoring. The effective
handling of wastewater pollutants is a must in the scientific progress of environ-
mental engineering. The vision of this paper is to undertake an exhaustive exami-
nation of current research trends with a deep focus on nanomaterials and
nanoproducts to improve the performance of water treatment technologies [11].
Future directions to inform investigators of potentially disruptive nanomaterial
technologies are dealt with in minute details. The authors discussed in detail
nanomaterials for wastewater treatment [11]. The authors discussed in detail adsorp-
tion, carbon nanostructures, metal and metal-oxide nanoparticles, and the scientific
potential of nanopolymers. The other areas of research are of photocatalysis [11].
Membrane and filtration are the areas of investigations of this paper. Disinfection
and antimicrobial mechanisms are the other areas of introspection and comprehen-
sion of this paper. Summary, optimization, and rediscovery are the hallmarks of each
issue in nanomaterials in this paper [11].
Yadav et al. [12] discussed and comprehended in detail emerging adsorbents and
current demand for defluoridation of water and detailed a bright future for sustain-
ability. Fluoride contamination of groundwater is a burning issue throughout the
world. Geological and anthropogenic factors are highly responsible for the
62 Sustainable Future with Nanoproducts 1423

contamination of groundwater with fluoride. Excess amount of fluoride in drinking

water may cause irreversible demineralization of bone and teeth tissues, an ailment
called fluorosis, and long-term damage to the brain, liver, thyroid, and kidney. In this
water shed text, the adsorption capacities and fluoride removal efficiencies of
different types of adsorbents are compiled from relevant published data available
in the scientific literature and are also represented graphically. Fluoride is a widely
distributed monoatomic anion of fluorine characterized by a small radius (0.133 nm).
The sources of fluorine in water and soil are mostly geogenic and veritably include
various rock forming minerals. This paper highlights technologies for fluoride
removal such as precipitation, membrane processes, and reverse osmosis, nano-
filtration, electrodialysis, and ion-exchange processes [12].
The vast vision of environmental protection science is immense and versatile.
Global water shortage and groundwater heavy metal contamination are challenging
the vast academic rigor of environmental science. In this paper, the authors
suggested the needs of energy and environmental sustainability in the furtherance
of global research and development initiatives.

Arsenic Groundwater Remediation and Its Scientific Vision

Arsenic groundwater contamination is challenging the vast global scientific scenario

today. Millions of people around the world particularly the state of West Bengal,
India, and Bangladesh are in the threshold of the world’s largest environmental
disaster. The disaster is arsenic contamination of drinking water. Here comes the
importance of sound knowledge of environmental protection science and environ-
mental sustainability. The domain of science today stands mesmerized and stands
enigmatic with the larger cause of environmental sustainability. The scientific truth
of environmental remediation science today is in the midst of vision, comprehension,
and vast scientific contemplation. Scientists and engineers around the world are
really grappling this global environmental issue. Now the question of science today
is the application of Advanced Oxidation Processes and nanoproducts in treating
hazardous inorganic and organic pollutants. The state of global environment is
extremely grave, awe-inspiring, and deeply thought-provoking. The challenges
and the vision depend on the scientific and knowledge prowess of environmental
scientists, chemical engineers, and chemical engineers.
Hassan [13] discussed and described with lucid and cogent insight the poisoning
and risk assessment in the domain of arsenic in groundwater. Technological verve,
ingenuity, and the needs of human society are today all the forerunners toward a new
era in the field of environmental protection [13]. This book details the global
scenario of groundwater arsenic catastrophe, groundwater arsenic discontinuity,
spatial mapping, spatial planning and public participation, environmental health
concern of chronic arsenic exposure to drinking water, and the epidemiological
and spatial assessment of groundwater arsenic exposure [13]. The other areas of
the study are arsenic poisoning in Bangladesh and legal issues of responsibility.
Groundwater is the major source of safe drinking water in many countries around the
1424 S. Palit et al.

world but the concern is that much of the groundwater is contaminated with arsenic.
Thus scientific progresses are in a state of scientific regression [13]. It is highly ironic
that so many tubewells have been installed for drinking water that are safe from
water-borne diseases but highly contaminated with toxic levels of arsenic. It is
estimated and understood that 300 million people in 70 countries worldwide are at
the risk of severe groundwater arsenic contamination [13]. Apart from Bangladesh
and the neighboring Indian state of West Bengal, which have between them the
largest problem, there have been also warnings from Argentina, Chile, Taiwan,
Vietnam, China, Pakistan, Thailand, and even the south western parts of USA
[13]. This book gives a detailed approach on the fate of arsenic poisoning in South
Asia [13]. Groundwater arsenic toxicity presents a new dimension of hazard in
Bangladesh beyond the well-known calamities such as floods, cyclones, tidal surges,
famine, and infectious diseases. It has been estimated that as many as 85 million
people in Bangladesh are exposed to toxic levels of arsenic in drinking water,
making it possibly the world’s largest environmental health hazard. The book
deals with the methodological issues of spatial, quantitative, and qualitative enquires
on arsenic poisoning. Use of Geographical Information System (GIS) to investigate
the distribution of arsenic-laced water in space time to uncover the pattern of
variations over larger scales from meters to kilometers [13]. Spatial risk mapping
is an indicator to researchers, policy makers, administrators, and politicians of
possible long-term definite strategies for arsenic mitigation. Arsenic risk mapping
with spatial modeling, social implications, and vast legal issues of arsenic toxicity is
the area where serious discussions are vitally needed [13]. The book is particularly
relevant to the advanced undergraduate and masters’ level. It can vastly contribute to
modules on public health, environmental studies, water quality, GIS methods and
applications, human rights, and the vast legal issues. The micro-level spatial distri-
bution and concentration scenario of groundwater arsenic is deeply discussed in this
book [13]. This book also covers a state-of-the-art review of the literature and
cutting-edge scientific evidence for arsenic-related health effects. The state of sci-
entific endeavor, the immense challenges, and the vast domain of validation of
environmental science are the necessary issues in the true unraveling of environ-
mental sustainability and environmental protection science today. This book is an
eye-opener toward the success of science and engineering in mitigating arsenic
groundwater contamination [13].
Hashim et al. [14] discussed and deliberated with vast scientific conscience the
remediation science and technologies for heavy metal contaminated groundwater. Vast
technological verve and the needs of human society such as water and energy will all
be the forerunners toward a new era in the field of environmental protection. The
contamination of groundwater by heavy metal, originating either from natural
resources or from other sources, is a matter of immense concern to the public health
and public health engineering. Remediation of contaminated groundwater is of
immense priority since billions of people around the world depend on it. In this
paper, 35 approaches for groundwater treatment have been deeply reviewed and
classified under three categories which are chemical, biochemical/biological/
biosorption, and physicochemical treatment processes. The concerns for groundwater
62 Sustainable Future with Nanoproducts 1425

contamination with heavy metal are today immense, path-breaking, and far-reaching.
Scientific research pursuit in the field of groundwater treatment needs to be stream-
lined as scientific and academic rigor in environmental sciences moves forward.
Selection of a suitable technology for contaminant remediation at a particular site is
a matter of immense scientific introspection today. Extremely complex soil chemistry
and aquifer characteristics are the parameters of immense concern in today’s ground-
water remediation science. Keeping the sustainability issues and the environmental
ethics in mind, bioremediation and biosorption are the other challenging areas of deep
engineering introspection. In many contamination sites, two or more processes are
synergistically integrated for groundwater remediation. Processes such as chelate
extraction and chemical soil washings are immensely advisable only for the recovery
of valuable metals in highly contaminated sites of heavy metals. In the environment,
the heavy metals are generally more persistent than organic contaminants such as
pesticides or petroleum products. In this paper, the authors deeply comprehended
sources, chemical property and speciation in heavy metals in ground water, technol-
ogies for treatment of heavy metal contaminated drinking water, in situ treatment by
using reductants, reduction by dithionite, reduction by gaseous hydrogen sulfide,
reduction by iron-based technologies, soil washing, in situ soil flushing, in situ chelate
flushing, and biological, biochemical, and biosorptive treatment technologies. Physi-
cochemical treatment technologies are the other cornerstones of this well-researched
paper. Groundwater and drinking water technologies have come a long way since the
days of their inception. Much research pursuit has been done on numerous technol-
ogies ranging from ex situ physical separation tools to complex in situ microbiological
and adsorption techniques. In modern days, environmental sustainability is the coin
word and jargon of scientific research pursuit today. This immense scientific vision
and profundity of groundwater decontamination along with the numerous techniques
are dealt with in this paper. The challenges, the targets, and the profundity of
technology and engineering science of groundwater remediation are delineated in
detail in this paper [14].
Chakraborti et al. [15] discussed in depth the future danger of arsenic groundwa-
ter contamination in Middle Ganga Plain, Bihar, India [15]. The pandemic of arsenic
poisoning due to contaminated groundwater in West Bengal, India, and all of
Bangladesh has been thought to be limited to the Ganges Delta despite reports of
arsenic contamination in Upper Ganges Plain. This report gives light to the ever-
growing concerns of arsenic contamination in other parts of India. Groundwater
arsenic contamination in the Lower Ganga Plain of West Bengal, India, was first
identified in July 1993. After these scientific findings, the seriousness of this global
crisis was felt and identified. The deep scientific genesis and the futuristic aura of
environmental protection are the utmost necessities of science and engineering of
groundwater remediation today. This paper depicts with vast scientific conscience
the issues of groundwater arsenic contamination of the Ganges plain in India.
Although West Bengal’s arsenic problem reached immense public concern almost
20 years ago, there are still today little achievements as regards solution to the
immense scientific intricacies. Groundwater arsenic contamination surfaced in West
Bengal during 1983 and that in Bangladesh in 1995 and after that year global
1426 S. Palit et al.

attention clearly targeted this world’s largest environmental engineering crisis. The
arsenic catastrophe of Bangladesh is considered to be world’s biggest mass poison-
ing with millions affected and that of West Bengal has been compared with Cher-
nobyl disaster. Technology and engineering has practically few answers to this
burning crisis. Yet chemical engineers and environmental engineers are in the
forefront of global efforts in mitigating this crisis. Human scientific vision’s
immense knowledge dimension and prowess and the domain of basic human
needs such as electricity and water will all be the torchbearers toward a newer
epoch in the field of groundwater remediation and decontamination [15].
Arsenic contamination in groundwater is challenging the vast technological and
engineering fabric. Today is the age of Advanced Oxidation Processes which
includes photocatalytic degradation. Thus environmental remediation science is in
the path of vast vision and contemplation. This chapter rigorously points toward the
success of science and technology in ameliorating this large environmental
catastrophe.

The Futuristic Challenges in Application of Nanoproducts

The futuristic vision and the futuristic challenges of application of nanoproducts and
nanomaterials in human society are immense and far-reaching. Nanomaterial deg-
radation tools and nanoproducts degradation tools are the veritable tools of global
science and engineering. Today nanomaterials and engineered nanomaterials are the
marvels and vignettes of global scientific endeavor. The world of environmental
sustainability is the need of science as well as human society. This well-researched
treatise will surely and veritably open up newer knowledge dimensions and newer
knowledge prowess in the field of conventional and nonconventional environmental
engineering techniques. The aim and objective of environmental engineering
research forays is to gear forward toward more effective and cost-effective processes
[16–20].

Future Research Directions in the Field of Nanoproducts

The world of engineering science today stands in the crucial juncture of vision and
deep scientific introspection. Scientific advancements are the utmost needs of the
hour in the field of environmental remediation. Nanoproducts applications and other
Advanced Oxidation Processes are the scientific and engineering challenges of
scientific research globally today. Today the targets of science and engineering are
nanomaterials and engineered nanomaterials. Environmental sustainability should
be the cornerstones of scientific endeavor of tomorrow. Efficiency and effectivity of
the advanced oxidation processes, membrane separation processes, and other novel
and nanomaterials separation processes should be the targets of scientific research
pursuit in environmental protection today. The other areas of intense research pursuit
are the domain of sustainable materials and eco-materials. The human civilization is
62 Sustainable Future with Nanoproducts 1427

today in the pursuit of new scientific ventures. Water purification and industrial
wastewater treatment should be the forefront of science and engineering endeavor
today. The present status of nanotechnology and its applications is immensely
far-reaching and at the same time thought provoking. Future research directions in
the field of nanotechnology should be directed toward more applications in the field
of environmental engineering and chemical engineering. Thus science and engineer-
ing will surely usher in a new age in the field of environmental engineering science
and sustainable development. The visionary words of Dr. Gro Harlem Brundtland,
former Prime Minister of Norway on the science of “sustainability” will surely be
redefined and reframed as technology and engineering science gears forward toward
a new century [21–26].

Sustainable Development Goals and the Vision for the Future

Sustainable Development Goals and its implementation as devised by United

Nations are changing the face and structure of human civilization today. The vision
for the future in the application of Sustainable Development Goals is vast, versatile,
and groundbreaking. Provision of basic human needs such as electricity and water
are highly neglected in the global research pursuit in sustainability. The concept of
sustainability and water purification are two opposite sides of the coin. Millions of
people around the world have little or no access to clean drinking water. Thus human
civilization’s vast knowledge prowess, the scientific and academic rigor of sustain-
ability, and the needs of human society will surely unravel the scientific intricacies of
global vision in environmental engineering science.

Environmental and Energy Sustainability and Scientific Sagacity

Sustainability is today changing the face of human civilization and the vast scientific
firmament. The sagacity of science and engineering needs to be envisioned and
organized as human civilization moves forward. Technological and scientific verve,
scientific grit, and determination are the cornerstones of research in energy sustain-
ability, energy engineering, and renewable energy. This vast challenge and the vast
ingenuity are brought to light before the scientific community by the authors of this
chapter. Scientific sagacity and technological and engineering validation are of
immense importance in today’s challenging global era. Global climate change and
loss of ecological biodiversity are changing the face of civilization and the social
firmament, thus the need of sustainable development. In the similar vision, energy
sustainability and renewable energy technology should be the cornerstones of
scientific endeavor today. Biofuels and biogas energy are the scientific vision of
today. These are the path-breaking domains of renewable energy today. Wind energy
and solar energy are the other vistas of science globally today. In this entire treatise,
the authors with immense conscience project the need of environmental sustainabil-
ity in the progress of human society. The challenges and the vision of application of
1428 S. Palit et al.

environmental sustainability are immense and at the same time groundbreaking.

Global scientific discernment and redeeming in the field of sustainability will surely
open windows of innovation in the field of environmental engineering and other
diverse areas of science and engineering.

Future Recommendations and Futuristic Flow of Thoughts

Technological and scientific validation of innovations and human instinct are the
veritable needs of the hour. Industrialized and developing nations around the world
are today witnessing immense environmental challenges. The drastic changes of the
global climate, the needs of environmental protection, and the futuristic vision in
nanotechnology and fossil fuel science will surely be the torchbearers toward a new
epoch in the field of science and technology. In this treatise, the authors bring to light
the domains of conventional and nonconventional environmental engineering tech-
niques. Futuristic vision and future recommendations of this study will be targeted
toward more application areas of nanotechnology, biotechnology, nano-biotechnology,
and the vast world of biological science. Future of environmental protection lies in the
hands of the domain of nanobiology. This chapter also highlights the grim and grave
concerns of heavy metal groundwater contamination in diverse nations around the
world. The future of civilization and scientific progress is bleak and vastly retrogres-
sive. Here come the innovations in nanotechnology, environmental protection science,
and other areas of science and engineering. The authors in this well-researched treatise
pointedly focus on the success of environmental sustainability in the furtherance of
science and technology globally. Deep scientific understanding, scientific profundity,
and the needs of the human society will all go a long way in the true unfurling of
science and engineering. Photocatalytic degradation of organic and inorganic pollut-
ants is the scientific requirement of environmental protection today. This chapter will
surely unfold the scientific intricacies of environmental engineering tools and will
widen the futuristic vision of Advanced Oxidation Processes and the application of
nanoproducts and nanotechnology [27, 28].

Conclusion

Engineering and technology are in the critical juncture of deep revamping and
immense revelation. Today the scientific scenario is targeted toward smart materials,
eco materials, and novel materials. Material science and nanotechnology are inte-
grated together with immense vision and engineering redeeming. The needs of
human society are immense and thought provoking. Sustainable development
goals are still not redeemed and not re-envisioned. Here comes the importance of
concerted efforts from the civil society, governments, and the scientific community
to implement energy and environmental sustainability in every walks of human
society. Environmental perspectives should also be redefined and reframed as
human civilization moves forward. Nanoproducts applications are the challenges
62 Sustainable Future with Nanoproducts 1429

of environmental protection science. In this chapter, the authors deeply discuss with
immense scientific divination the needs of nanotechnology degradation tools in the
furtherance of environmental engineering. The domain of science and engineering is
today moving in the visionary directions of application of renewable research, thus
the need of energy and environmental sustainability. The science of “sustainability”
as defined by Dr. Gro Harlem Brundtland, former Prime Minister of Norway, needs
to be redefined and re-envisaged with the progress of human civilization. Also the
United Nations Sustainable Development Goals need to be applied with scientific
might, vision, and provenance. The remit of the study are the areas of nanoproducts
and nanotechnology in industrial pollution control. Thus the scientific prowess of
human mankind, the futuristic vision, and grit will veritably lead a long way in the
true emancipation of environmental engineering and environmental science globally.

Important Websites for Reference

https://www.iaea.org/sites/default/files/18/05/environmental_remediation.pdf
https://en.wikipedia.org/wiki/Environmental_remediation
https://sc-s.si/joomla/images/Environmental%20remediation.pdf
https://www.environmentalscience.org/career/environmental-remediator
https://onlinecourses.nptel.ac.in/noc19_ce05
https://www.ghd.com/en/about-us/what-s-shaping-the-future-of-environmental-
remediation–.aspx
http://www.insituarsenic.org/
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http://www.ipcbee.com/vol94/rp0025_ICWT2016-W0011.pdf
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europepmc.org/abstract/med/24035830
https://en.wikipedia.org/wiki/Photocatalysis
https://www.sciencedirect.com/science/article/pii/S1319610315000393
https://www.sciencedirect.com/topics/chemistry/photocatalyst
https://www.nature.com/subjects/photocatalysis
https://onlinelibrary.wiley.com/doi/toc/10.../(ISSN)2367-0932.hottopic-
photocatalysis
www.greenearthnanoscience.com/what-is-photocatalyst.php
https://www.springer.com/cda/content/document/cda_downloaddocument/
9783319624457-c2.pdf?SGWID¼0-0-45-1616582-p180992849
https://www.researchgate.net/post/what_is_the_main_use_of_photocatalysis
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degradation
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https://www.intechopen.com/books/semiconductor-photocatalysis-materials-
mechanisms-and-applications/photocatalytic-activity-of-quantum-dots
www.mpip-mainz.mpg.de > . . . > Research > Topics
www.academia.edu/Documents/in/Photocatalysis
1430 S. Palit et al.

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Green and Sustainable Approaches
of Nanoparticles 63
A. Ravikumar and K. S. Prakash

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1434
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
Green Synthesis of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1436
Plant-Mediated Synthesis of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1437
Nanomaterials for Environmental Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1442
Water Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1444
Air Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1446
Heavy Metal Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1447
Conclusion and Future Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1448
Related Web Links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1448
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1449

Abstract
Green and sustainable development of consumer products is need for incorpora-
tion of human lifestyle and analyzes the environmental impacts. The ultimate goal
of any development in science is to improve human health and well-being.
Therefore, scientific communities are always eager to develop or apply clean
and green technology in research fields. A branch of green nanotechnology is
highly contributing in the form of green approaches for producing nanoproducts/
nanomaterials, which will not affect or harm the human and environment. In this
chapter, we mainly focus on a current state of technology used in the manufacture
of green nanoproducts in order to develop the materials, and many nanomaterials
are being used for solving environmental issues. It provides a preliminary
A. Ravikumar
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, Tamil Nadu,
India
K. S. Prakash (*)
Department of Chemistry, Bharathidasan Government College for Women (Autonomous)
(Affiliated to Pondicherry University, Pondicherry), Puducherry, India

© Springer Nature Singapore Pte Ltd. 2022 1433

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_81
1434 A. Ravikumar and K. S. Prakash

analysis of significant property of normally used nanomanufacturing techniques

including various parameters. This chapter also deals with the current research in
the development of new nanomaterials for potential applications in the field of
environment concern, such as solar cells, water purifying technology, air pollu-
tion control, etc.
Finally, we highlighted the road map of current technologies, indicated the
future directions, and discussed any drawbacks, if any. We pointed out the
fundamental obstacles in the field of green nanotechnology and argued that the
improvement in green and sustainable technologies has the high potential to solve
the new and challenging problems. We believe that our work greatly increases the
understanding and usability of green nanoproducts.

Keywords
Green approaches · Nanomaterials · Environmental applications · Plant-mediated
synthesis · Water purification

Introduction

The term green nanotechnology refers to the utilization of nanoproducts to improve

environmental sustainability and less hazardousness. In green nanotechnology,
designing green and efficient protocols is the most important. There have been
many efforts in the multifunctional nanomaterials, which are highly useful in various
applications such as sensor for detecting and monitoring the environmental pollut-
ants, production of energy, photocatalysts for effective degradation of organic
pollutants, and preparation of novel membrane for wastewater treatment as well as
in purification of drinking water [56, 72]. Green chemistry confirms that nanotech-
nologies enhance the environmental sustainability of processes in order to lower cost
and decrease the hazardous materials. Green nanotechnology is one of the emerging
fields with various applications due to its environmental friendliness. Hence, it
highly represents novel efforts by researchers to apply the sound knowledge to
remove or decrease the environmental pollution and lead to have good human health.
The combination of nanoscience and green approaches greatly influences the devel-
opment of sustainability, human health, and safety during the preparation of nano-
products and using its applications [2, 21–26, 37].
Environmental pollutants are being released into the environment through differ-
ent anthropogenic processes such as coal conversion, petroleum refining, mining,
textile, and pharmaceutical and paper and pulp manufacturing industries. The large-
scale uses of herbicides, insecticides, and pesticides in agriculture are also consid-
ered as pollutants. Generally, industrial discharges can easily contaminate water, air,
and land, thus putting flora and fauna at risk. The environmental pollution can be
defined as “the contamination of the physical and biological components of the
earth/atmosphere system to such an extent that normal environmental processes are
adversely affected.” Huge efforts are necessary to preserve our environment.
63 Green and Sustainable Approaches of Nanoparticles 1435

Depending on nature of pollutant and component, environmental pollution can be

classified as:

1. Air pollution
2. Water pollution
3. Soil pollution
4. Thermal pollution
5. Radioactive pollution

All the above pollutions majorly occur from the various day-to-day life changes
of human beings, particularly from industrial wastes. Industrialist produces various
useful products and simultaneously hazardous wastes also produced as by-products
(in the form of gas, liquid, or solid).
In the aspect of reducing pollution, green approach is always paid much attention
in researcher’s mind. The increase of populations throughout worldwide, utility of
indispensable materials is also increasing. But we cannot avoid the usage of indis-
pensable materials; instead, it is always good to find a clear solution for pollution-
free environment [10]. To achieve clean environment, a lot of energy is being
expensed worldwide. However, some of the modern technologies are highly active
in achieving the pollution-free environment. For example, carbon materials with
high surface area like graphene, carbon nanotubes, mesoporous carbon, and carbon
fibers can be effectively used as adsorbents for the removal of inorganic pollutants
present in wastewater from industries.
Nowadays, development of nanoscience and related materials plays a vital role.
However, low cost, pollutant-free, and removal and selection of materials are the
major factors in these fields. Nanomaterials such as graphene oxide, transition metal
chalcogenides (MoS2, WS2, and TiS2), graphite nitrite, metal-organic frameworks,
polydopamine nanotubes, and polydopamine nanospheres are some important exam-
ples that are developed and reported in the literature. These kinds of nanostructures
are highly useful in solving many issues of environmental pollution, specifically
removal of heavy metals, degradation of organic pollutants, and wastewater treat-
ment. The applications of nanostructure in the aforesaid fields are discussed in this
chapter later (vide supra). Various metals are being used for the synthesis of
nanoparticles are reported for various applications in the form of zerovalent (Ag,
Au, Fe, Zn, etc.), metal oxide (TiO2, Fe3O4, ZnO, CeO2, etc.), bimetallic (Au-Ag,
Au-Pt, etc.), and trimetallic (Au-Ag-pt, etc.) nanoparticles [43]. In the Fig. 1, green
nanotechnology has many benefits such as atom economy, safer solvents, making
sustainable environment, cost-effective, safe, and eco-friendly. In this chapter,
development of green approaches and nanoparticles for various environment treat-
ments is discussed in forthcoming sections.
It is important to mention that usage of toxic chemical in many conventional
methods makes them not suitable in medical applications. More importantly, in bulk-
scale production of nanomaterials, there are large amount of hazardous materials
being entered into the environment because of usage of organic solvents/chemicals.
To rectify this issue, green synthesis is the best alternative [4, 41]. Mainly, in green
1436 A. Ravikumar and K. S. Prakash

Fig. 1 Green nanotechnology

approach the reducing/capping agents for the reduction of metals are biological
compounds present in the microorganisms and lipids and proteins [50]. Therefore,
the amount of artificial chemicals used is highly reduced. The mechanism for the
formation of nanoparticle is clearly established in the literature. The polar groups
such as –OH or –NH2 act as electron donor for the reduction of metal, which then
leads to the formation of metallic nanoparticles.
In this chapter, green synthesized nanoparticles and applications of the nano-
materials in various fields are discussed in detail. Specifically, plant-mediated
synthesis of nanostructures is summarized. Future challenges and obstacles to the
use of green synthesis of nanoparticles, in the aspect of difficulty in preparations and
application to various fields, are also discussed.

Discussion

Green Synthesis of Nanomaterials

Synthesis of nanoparticles can be mainly classified as top-down and bottom-up

approaches. Classification of nanoparticles preparations is clearly shown in Fig. 2.
Among these synthetic methods, biological methods (green synthesis) have many
advantages like short time, negligible waste, no use of toxic chemicals, etc. Synthe-
sis of NPs via physical or chemical methods is relatively expensive, hazardous, and
also time-consuming. Hence, green approaches for the synthesis of nanomaterials
are highly attractive. Using green methods, a variety of nanomaterials are being
produced in terms of different shapes and also utilizing combination of metals, like
bimetallic or trimetallic nanomaterials.
The concept of green chemistry with its definition and associated with 12 princi-
ples was considered for the synthesis of various materials. Many points are taken
into account for the preparation of materials such as step and atom economy. The
usage of solvents in the preparation is also well presented in the literature. For
example, water, polyethylene glycol, supercritical CO2, and ionic liquids are gaining
traction to alternate many traditional organic solvents. Green synthesis of nano-
materials mainly focused on the improvement of the environmental sustainability,
development of clean technology, ideas for reducing the environmental and human
health problem, etc.
63 Green and Sustainable Approaches of Nanoparticles 1437

Fig. 2 Various approaches for the synthesis of nanoparticles

Plant-Mediated Synthesis of Nanomaterials

Plant-derived synthesis of nanomaterials is a very simple procedure compared with

traditional methods. Metal salts are reduced by biomolecules present in the plant
extract, and this process is completed within minutes to couple of hours at certain
temperature. The biomolecules present in plant extracts are capped around the
nanoparticles; hence the nanoparticles prepared using plant extract are medicinally
valuable. There are many reports found in the literature that these materials are found
to have many applications in the field of medicine because less toxic or toxic-free
nanomaterials are formed. Nowadays, vitamins, amino acids, and some biomasses
are also being utilized for producing various bio-fabricated nanomaterials. The
extracts of blackberry, pomegranate, and turmeric materials have antioxidant agents;
hence these compounds are successfully fabricated with various metals and expected
to have higher anticancer activity. As discussed earlier, using plant extract is a good
alternative for capping/stabilizing/reducing agent. Most of the biosynthesis is
reported as capping/stabilizing/reducing agent-free; in other words, the compounds
present in plants are acting as capping as well as reducing agents. The functional
groups present in biomolecules are acting as reducing as well as capping agents in
biological synthesis of nanoparticles. The interaction between functional groups and
metal nanoparticles is strong and leads to have an excellent stability of
as-synthesized metallic nanoparticles. Moreover, bimetallic and trimetallic nano-
particles can also be prepared in green synthetic approaches and have potential
applications in many fields. Bimetallic nanoparticles are formed by the combination
1438 A. Ravikumar and K. S. Prakash

Fig. 3 Characterization of nanomaterials

of two different metals, because it shows better properties. While combining metals
in nano-level, their electronic properties are completely changed. For example,
Au-Pt NPs are found to have attractive interest and potential applications in the
field of catalysis due to its high catalytic efficiency. Green approaches of mono-, bi-,
and trimetallic NPs are discussed in the following section.
The synthesized nanomaterials are characterized using various instruments as
depicted in Fig. 3. Plant-synthesized nanoparticles are mainly analyzed with the help
of UV-visible absorption spectroscopy, near-field scanning optical microscopy
(NSOM), Fourier transmission infrared (FT-IR) spectroscopy, Raman spectroscopy,
powder X-ray diffraction (PXRD), energy-dispersive X-ray (EDAX) analysis, high-
resolution scanning electron microscope (HR-SEM), transmission electron micros-
copy (TEM), and scanning tunneling microscopy (STM). From these analyses, one
can easily understand the full details of its morphology, optical properties, material
composition, shape, and size.

Green Approaches of Monometallic Nanoparticles

The preparation of nanomaterials using plant extract and biodegradable polymers is
well documented in the literature. Some of the examples are discussed here. Pourya
Mehdizadeh et al. reported spongelike TbFeO3 nanostructure by utilization of green
sonication method. In their work, cherry and orange juices were used for the
preparations of NPs, and the as-synthesized NPs were well characterized, applied
to photocatalytic degradation of various organic dyes (methyl orange, Acid Blue
92, Acid Black 1, Acid Brown 214) under UV light. The obtained results were
clearly compared by natural surfactants (cherry and orange juices) and chemical
surfactants (SDS and CTAB). In addition, different parameters such as pH, dose
concentration, and contaminant concentration were measured. They concluded the
green synthesized TbFeO3 nanostructure is found to have high degradation effi-
ciency compared to other materials [39]. Ramesh Vinayagam et al. summarized a
green synthesis of zinc oxide nanoflowers; the preparation involves aqueous extract
of Calliandra haematocephala leaves. The structure of zinc oxide nanoflowers was
found as wurtzite and crystalline size; surface area of nanoflowers is approximately
63 Green and Sustainable Approaches of Nanoparticles 1439

19.45 nm and 9.18 m2/g, respectively. The prepared material was used to study
degradation of methylene blue (MB) dye under sunlight, and degradation efficiency
was achieved by 88% within 270 min [55]. In another work [17], synthesis of nickel-
substituted copper ferrite nanoparticles (Cu1
xNixFe2O4) using lime juice by sol-gel
method was demonstrated. The synthesized nanoparticles are in spherical shape and
crystalline size was 32 and 37 nm. While changing the concentration of nickel ions,
substituted in the copper ferrite nanoparticles, their emission properties are enor-
mously changed. Their preliminary biological studies are reported using Gram-
positive (Staphylococcus aureus, Bacillus subtilis) and Gram-negative (Klebsiella
pneumoniae, Escherichia coli) bacteria, and antibacterial data was compared with
other ferrite materials (CuFe2O4 and NiFe2O4) [17]. The anatase phase green
synthesized titanium dioxide (TiO2) NPs using Jatropha curcas L leaf extract were
reported by Goutam et al. [18]. In their work, simultaneous removal of chemical
oxygen demand (COD) was studied, and synthesized TiO2 NPs have 82.26%
removal of COD and 76.48% removal of Cr from wastewater [18]. Rosales et al.
[59] reported an efficient green synthesis of zerovalent iron nanoparticles using two
different extracts, green tea (Camellia sinensis) and rooibos (Aspalathus linearis).
Synthesis of iron nanoparticles using plant extract of rooibos (Aspalathus linearis)
has high reactivity and low antioxidant content; but in the case of green tea, NPs
have low reactivity and higher antioxidant. Textile dye degradation was also dem-
onstrated [59]. Another green synthesis was reported by Chaudhary et al. [10] for the
preparation of gold nanoparticles (AuNPs) using Lagerstroemia speciosa leaf
extract. These NPs have strong photocatalytic activity with high degradation effi-
ciency for variety of dyes (methylene blue, methyl orange, bromophenol blue,
bromocresol green, and 4-nitrophenol) under visible light in presence of NaBH4
[10]. The synthesis of iron nanoparticles (Devatha et al. [13]) using different leaf
extracts like Mangifera indica, Murraya koenigii, Azadirachta indica, and Magnolia
champaca were reported in the literature. They applied these materials for the
treatment of domestic wastewater. It was found that there is potential activity for
simultaneous removal of total phosphate, nitrogen, and chemical oxygen demand
from domestic wastewater. Specifically, the plant material Azadirachta indica
showed an excellent result of 98.08% of phosphate removal, 84.32% of ammonia
nitrogen, and 82.35% of chemical oxygen demand [13]. Green synthesis of copper
nanoparticles is reported in the first time by Jayarambabu et al. using Curcuma longa
plant extract. Major benefits of this method were simple approach and less expen-
sive. The particles size is in the range of 5–20 nm. Their preliminary antibacterial
studies were reported [27]. Some important plant-mediated synthesis of monome-
tallic nanoparticles and their applications are given in Table 1.

Green Approaches of Bimetallic Nanoparticles

Bimetallic NPs have many advantages over monometallic NPs; those are (i) mixing
patterns and geometrical architecture, (ii) enhances its functionality, (iii) better
stability, (iv) high selectivity and catalytic activity, (v) better structural behaviors,
etc. These aspects made the bimetallic nanoparticles very good materials in various
applications; if the same is produced from green protocols, their potential is
 1440

Table 1 Plant-derived monometallic nanoparticles and their applications

Sl.
no. Nanoparticles Plant materials Shape Size (nm) Benefits/applications Ref.
1 TiO2 Jatropha curcas L/leaf Spherical/ 10–20 Photocatalytic activity/used in treatment of [18]
anatase tannery wastewater
2 Ag Piliostigma thonningii/leaf Spherical 50–114 Heavy metal removal from textile [47]
wastewater
3 Au Lagerstroemia speciosa/leaf Hexagonal 41–91 Photocatalytic activity reduction of organic [10]
dyes
4 Ag Ficus benjamina/leaf - 60–105 Cd removal [1]
5 Fe Various plants/leaf Spherical 96–150 Degradation studies/treatment of domestic [13]
wastewater
6 Pt Xanthium strumarium/leaf Cubic 22 Preliminary biological studies [70]
7 Ag Ziziphus joazeiro/leaf Spherical 10 Antibacterial activity [40]
8 Ag Moringa oleifera/flower Spherical 8 Antimicrobial activity [5]
9 Cu Curcuma longa Spherical 5–20 Antimicrobial activity [27]
10 Ag Fritillaria/flower Spherical 10 Antibacterial activity
11 Ag NPs Allium ampeloprasum/leaf Spherical 2, 43 Catalyst for reduction of nitrophenol Mehdi Khoshnamvand
et al. (2018)
12 In2O3 Aloe barbadensis Miller Spherical 5–50 Solar cells/gas sensors [36]
(Aloe vera)
13 Au Coriandrum sativum Spherical 6.75–57.91 Drug delivery/tumor imaging/ [44]
(coriander) photothermal therapy
A. Ravikumar and K. S. Prakash
 63

14 Ag Eucalyptus citriodora Spherical 20 Antibacterial [58]

(neelagiri)
15 Ag Mentha piperita Spherical 5–30 To kill microbes [48]
(peppermint)
16 Au Syzygium aromaticum Irregular 5–100 Detection and destruction of cancer cells [53]
(clove buds)
17 Iron oxide Medicago sativa (alfalfa) Crystalline 2–10 Cancer hyperthermia, drug delivery [19]
18 Ag Morus (mulberry) Spherical 15–20 Antimicrobial activity against E. coli, [62]
B. subtilis
19 Au, Ag Camellia sinensis (black tea Spherical, 20 Catalysts, sensors [42]
leaf extracts) prism
Green and Sustainable Approaches of Nanoparticles
1441
1442 A. Ravikumar and K. S. Prakash

relatively huge. For example, Olajire et al. reported a green synthesis of bimetallic
nanoparticles of Pd@Au NPs using A. comosus leaf extract. They isolated core-shell
bimetallic nanoparticles and applied for solid phase photocatalytic activity for the
degradation of low-density polyethylene (LDPE) under solar light. The stability of
nanoparticle and also recyclability were studied for solid phase degradation reaction
of LDPE [46]. Plant-derived bimetallic NPs and their applications are given in
Table 2.

Green Approaches of Trimetallic Nanoparticles

As discussed in the above sections, trimetallic nanoparticles by utilizing plant
materials are being reported in the literature. The combination of various metals is
producing new materials with innovative and surprise properties. Recently, tri-
metallic oxide Cu/Cr/Ni NPs using the aqueous leaf extracts of Eryngium campestre
(E. campestre) and Froriepia subpinnata (F. subpinnata) were reported by Zahra
Vaseghi’s research group. In their protocol, trimetallic NPs were prepared in high
yields and showed potential antibacterial activities [75].

Nanomaterials for Environmental Applications

Recently, various nanomaterials are prepared and those are highly useful in many
fields. Environmental applications of nanomaterials are given in this section, and key
points of environmental applications are depicted in Figure 4.

Solar Cells

Solar cells are the most important in the field of energy conversion in order to make
photovoltaic energy and able to alternate for traditional energies. More specifically,
wide bandgap in the nanomaterials prepared from II-IV and III-V elements are found
to have potential applications in emerging energy. To overcome the limitations of
solid-state physics, the highest conversion efficiency was reported for triple-junction
compound solar cell with 37.9% [66]. While using nanostructures, it is possible to
increase the solar cell conversion efficiency. Due to high surface-to-volume ratio of
atoms in a nanostructure, their physical and chemical properties completely changed
from its bulk state.
Major disadvantages in solar cells are (1) high cost associated with manufacturing
solar cells and (2) loss of acquired power due to surface reflections. Nanomaterials
solve these issues, because nanomaterials present in the solar cells and allow for light
to be precisely guided. Nanostructures have small size and different shape used to
avoid the reflection away.
Various structures of nanomaterials play a major role to improve the light
absorption and carrier collection in solar cells. Improving efficiency of solar cells
is one of the most important, and it can be achieved by utilizing semiconductor
quantum dots. Major benefits of QD solar cells are (1) higher light absorption in
 63

Table 2 Plant-derived bimetallic nanoparticles and their applications

Sl.
no. Nanoparticles Plant materials Shape Size (nm) Benefits/applications Ref.
1 Au-Pt@TiO2 Dahlia/flower Spherical 15–25 Catalytic reduction of organic pollutants [60]
2 Pt@Au NPs Ananas comosus/leaf Cubic 6.83 Photodegradation of low-density polyethylene [46]
film
3 ZVFe/Cu NPs Ficus Benjamina/leaves Semispherical shape 19–63 Carbamazepine removal from aqueous solution
5 Ag-Ni Salvadora persica Cluster 24 Biological applications [68]
6 Ni-Fe Punica granatum/peels Spherical 129 Tetracycline removal from aqueous solution [57]
7 Ag-Pd Terminalia chebula/fruit Cubic 20 Anticancer/antimicrobial activity [3]
Green and Sustainable Approaches of Nanoparticles

8 Ag and Au Apiin extracted from Spherical 39 Hyperthermia of cancer cells and IR absorbing [28]
henna leaves optical coatings
9 Au, Ag, and Azadirachta indica (neem) Spherical, triangular, 5–35; Remediation of toxic metals [61]
Au-Ag hexagonal 50–100
1443
1444 A. Ravikumar and K. S. Prakash

Fig. 4 Environmental applications of nanomaterials

infrared spectral region, (2) introducing silicon solar cell productions, (3) increase of
photocurrent at higher temperature, and (4) improved radiation hardness. Another
important aspect in cost reduction of solar cells is introduction of nanotechnology,
more specifically carbon nanotubes (CNTs) and its network support to anchor light-
harvesting semiconductor particles. For example, when CNTs are fabricated with
CdSe or CdTe, charge transfer process is increased under visible light irradiation. In
similar way, multiwalled CNTs combined with TiO2 film have found to have
improvement of interconnectivity. Production of inexpensive solar cells by utilizing
nanotechnology would give the potential material for environment. Lowering the
usage of fossil fuels will reduce the hazardous material to environment.
Shapes of nanostructures are important in tuning the efficiency. Some important
examples of nanostructure and their benefits are summarized in Table 3.

Water Purification

Water purifying technologies are being developed for making pollutant-free envi-
ronment. The utility of chemical in various forms has been enormously increased in
our day-to-day life. Hence, the development of research in hazardous treatment
technologies will help to make the environment very clean and green. The recent
development of nanotechnology may be collaborated with the field of environment
treatment technologies which will produce effective results.
Adsorption is one of the preferable choices for removing hazardous and dye
material from wastewater due to its simplicity in operation and efficiency for
common organic and inorganic contaminants [11]. This method can otherwise be
called as physical method. Usually, most of the drinking water treatment is done by
this method with the help of ultraviolet irradiation. While discovering the cheap
methods and at the same time equally efficient adsorbents, this technology would
become efficient method for removing organic pollutants from the environment and
water bodies. There are mainly two types of adsorbents: (1) natural adsorbents and
(2) synthetic adsorbents. Natural adsorbents are charcoal, clays, clay minerals,
zeolites, and ores, and synthetic adsorbents are adsorbents prepared from agricultural
products and wastes, household wastes, industrial wastes, sewage sludge, and
polymeric adsorbents. Each adsorbent differs with its pore size and its adsorbing
63 Green and Sustainable Approaches of Nanoparticles 1445

Table 3 Applications of nanomaterials in solar cells

Sl.
no. Nanostructure/shape Benefits Ref.
1 Silicon nanowire Enhance the incident solar radiation path [16]
length up to a factor of 73
2 Ag nanowire Low transparency and sheet resistance/ [30]
increase of 19% in photocurrent
3 Ag nanowire Low cost method/conversion efficiency of [32]
3.231%
4 Graphene-CdSe nanobelt Low cost/different configurations and several [76]
connections from single or multiple nanobelts
5 Semiconducting single-walled Conversion efficiency of 12.6 % [7]
CNTs
6 Acid-treated multiwalled CNTs Conversion efficiency of 3.05% [12]
7 Silicon nanoparticles Enhanced light harvesting in halide perovskite [15]
solar cells
8 TiO2 nanotube/dye-sensitized Conversion efficiency of 7% [49]
solar cells
9 ZnO nanowires coated by Increase the open-circuit voltage of the DSSC/ [29]
10–25-nm-thick TiO2 an enhancement in the conversion efficiency
from 0.85% to 1.7–2.1%
10 CdS nanopillars embedded in a A low-cost nanopillar solar cell [14]
CdTe thin film
11 Aligned ZnO nanopagoda Used in dye-sensitized solar cells [74]
arrays
12 Nanocone solar cells An efficient broadband antireflection property/ [79]
enhance the light traveling path for absorption
13 Graphene sheet based on Large surface area of the hybrid graphene [45]
Mg2CuSnCoO6-gallic acid materials/catalytic capability for iodide
nanomaterials reduction/maximum photoelectric conversion
efficiency of 13.30%
14 Mesoporous anatase TiO2 Conversion efficiency up to 7.78% [31]
nanomaterials

capacity. Carbon-based nanomaterials carbon nanotubes (CNTs) [71], graphene

[78], and carbon aerogels [33] were promising for water technologies. Regeneration
and reuse of carbon-based nanomaterials can be easily achieved by tuning
pH. Powder form of nano-adsorbents is readily integrated into any slurry reactors,
and some modified shapes of adsorbents like in the form of pellets/beads were also
reported in the literature.
Membrane filtration is mainly divided into three types: (1) microfiltration
(MF), (2) ultrafiltration (UF), and (3) nanofiltration (NF) based on their size
[69]. Nano-membrane filtration is a relatively recent membrane filtration process
used most often with low total dissolved solids in water such as surface water and
fresh groundwater, with the purpose of softening and removal of disinfection
by-product precursors such as natural organic matter and synthetic organic
matter.
1446 A. Ravikumar and K. S. Prakash

Many challenges of membrane processes are the energy consumption, lifetime

reduction, and filtration failure that lead to membrane fouling. These issues can be
sorted out by modified nano-membrane. Specifically, inorganic nanoparticles, such
as alumina [38], silica [6], and TiO2 [51], were used to avoid fouling. Ping et al.
demonstrated multilayered inorganic-organic hybrid membranes using metallic
molybdenum disulfide (MoS2) as two-dimensional transition metal dichalcogenide
nanosheets and one-dimensional silk nanofibrils for water purification. This material
possesses negatively charged layers, and interaction sites are the responsible to
adsorb metal ions and dyes from water sources. These kinds of works can open up
effective and green protocols for water treatment technologies.
Another important method is photocatalytic approach in water purification. The
photocatalytic oxidative degradation of pollutants and organic contaminants (pesti-
cides, surfactants, organic fertilizers, humic matter, etc.) in the photic layer of surface
waters is of great importance. Utility of dyes in our routine life and their production
in industries are both increasing alarmingly. These dye wastes from the industries,
more specifically textile manufacturing and other industries, are of great threat to the
environment. Due to these industries, the water sources are highly hazardous to
aquatic organisms and humans. Hence, development of research in the field of dye
degradation by utilizing easy methods is essential in the aspect of protecting water
sources. To be more specific, heterogeneous photocatalysis using nanoparticles that
is capable of providing large surface area is a broad research area that has proven to
be a versatile method for the abatement of organic pollutants from wastewater. Many
organic dyes such as rose bengal, caramine, rhodamine, indigo red, thymol blue, Red
120, Eriochrome Black-T (EBT), and methylene blue have been removed from water
bodies using photocatalytic degradation methods. Silver metal has antibacterial
activity, hence using this metal in nanosize to remove various bacteria in water
bodies. Antibacterial property is analyzed with the help of polyvinyl alcohol (PVA)
and polyacrylonitrile (PAN) nanofibers containing silver nanoparticles and found to
have excellent antimicrobial activities [65].

Air Pollution

Air pollution is one of the major problems to mankind, because mortality and
morbidity were increased and closely related to the ultrafine particle in air [64].
Many issues in various fields are associated with air pollution. Nanotechnology in
air pollution control is used to solve problems in the field of medicine, ecology,
electronics, food industry, clothing, cosmetics, and sporting. Present research in
this field is developing novel and effective protocols, low-cost manufacturing
techniques, etc. Nowadays, nanotechnology provides promising solution to
develop low-cost and effective systems, for example, nanosensor with solid-state
sensor called hybrid sensor, which is used in monitoring air pollution level in
industry. In similar way, nanosized catalyst and nanostructure membrane are
effectively used in controlling air pollution [54]. Mainly, carbon nanotubes
(CNTs) are found to have more adsorption capacity for metal ions than the
63 Green and Sustainable Approaches of Nanoparticles 1447

activated carbon. It also separates methane and carbon dioxide and greenhouse
gases which come from coal mining and power generation [9]. Similarly, many
organic volatile compounds are successfully removed by Au/MgO nano-
composites [63]. Bioactive nanoparticles, mostly silver nanoparticles, act as anti-
bacterial and combined with MgO and cellulose acetate fibers are used in removing
positive/negative spores [52].
Toxic gases in air can be easily cleaned by CNTs and gold particle adsorption.
CNT is a graphene sheet, carbon atoms are arranged in hexagonal shape, and most
importantly, it has strong adsorption potential inside the pores. Strong oxidation
resistance of these carbon nanomaterials has more benefit than others for the
regeneration of adsorbents even at higher temperatures. In CNTs modification can
be done easily by functionalization (covalent or non-covalent) and leads to forming
new and efficient materials for air pollution control. Recently, air filters are being
developed and reported in the literature. For example, high-efficiency (more than
99.5%) polyamide nanofiber was developed and it has high thermal stability, and
removal efficiency was found unchanged when temperature ranged from 25 to
370  C. They checked the efficiency from car exhaust at high temperature
[77]. Ramkumar et al. recently reviewed functional nanofibers and their applications
[34]. Nanofiber materials and their composites were used for making surgical
nanomask [67].

Heavy Metal Adsorption

Heavy metals are highly contaminated the water resources through mining, electro-
plating, metallurgy, chemical industries, agriculture and household wastewater, etc.
Heavy metals pollution inside water is a global environmental issue, and it severely
threats human because they can be incorporated through food chain. Excess heavy
metals in human body damage many organs [8]. Even though many conventional
approaches had been reported, nanomaterials have provided promising effects in the
field of heavy metal adsorption.
Carbon-based nanomaterials, mainly carbon nanotubes and graphene-based mate-
rials, are found in the literature for the alternatives for treating wastewater. CNTs have
large specific surface area, high adsorption ability, and fast adsorption kinetics [35] and
excellent adsorption effects for Mn, Tl, Cu, Pb, Cr, etc. As already discussed,
functionalization of CNTs, heat treatment, and endohedral filling improve the adsorp-
tion efficiency. Other important carbon-based nanomaterials are graphene oxide (GO)
and reduced graphene oxide (rGO). These materials are modified into its derivatives
and used for heavy metal adsorption because the functional groups present in GO/rGO
are responsible for the interaction between metal and materials [73]. Silica-based
nanomaterials are another vital material for removing heavy metals due to their
anomalous properties, such as nontoxicity as well as excellent surface characteristics.
Similarly, nanoscale zerovalent iron (nZVI) has also exhibited potential activity in the
removal of metals and chlorinated compounds [20]. Various metals and metal oxides
are also used in heavy metal adsorption of water treatments.
1448 A. Ravikumar and K. S. Prakash

Conclusion and Future Perspective

This chapter was aimed to provide overview on possibilities and potential

applications of green and sustainable nanoparticles. Important advantages of
biological synthesis over conventional methods are the use of mild synthetic
procedure, biocompatible substrates and environmental friendly, and avoidance
of toxic chemicals as capping/reducing agents. In some cases, innovative shapes
of NPs are produced, which are more challenging/not possible to obtain via
conventional synthetic methods. There is a strong interaction between
bio-support and metal NPs which can give more stability and be applicable in
the field of catalysis also. The materials derived from conventional methods
(physical or chemical synthesis) are costly and produce nanomaterials with
toxic product. So reducing toxicity is a real problem and should be sorted out
for using medicinal fields and also producing pollution-free environment.
In physical and chemical methods, many toxic chemicals were used for the
purpose of capping/stabilizing/reducing agents. Moreover, these chemicals may
also have traces of hazardous compounds which are highly harmful for mankind
and environment. Hence, there is a need for green and sustainable approach for
the synthesis of nanomaterials. Applying biological sources in the synthesis of
nanoparticles is found as a good alternative, and it is easily sorted out the
aforesaid difficulties. Moreover, compared to microbe-derived NPs, biosynthesis
of metal NPs with plant extract has more reducing rate of metal precursors,
and importantly, shapes of NPs are also well controlled. In this chapter,
we focused on the various green approaches of nanoparticles (mono-, bi-,
and trimetallic NPs) and nanomaterials for environmental applications. Recently,
there is an immense interest in the development of green nanotechnology,
and the number of research publications in the literature is expanding ceaselessly.
Utility of metallic nanoparticles are having potential applications in various fields
such as pharmaceutical industry, agricultural engineering, X-ray imaging,
drug delivery systems, etc. The possibilities for innovation in green and sustain-
able nanotechnology are huge and will provide unceasing opportunities in the
future.

Related Web Links

1. https://www.materialstoday.com/nanomaterials/comment/green-nanomaterials-
on-track-for-sustainability/
2. https://link.springer.com/search?query¼Green+and+Sustainable+Approaches
+of+Nanoparticles

Acknowledgment Dr. K. S. Prakash acknowledges Bharathidasan Government College for

Women (Autonomous), Puducherry UT, India, for the infrastructure.
63 Green and Sustainable Approaches of Nanoparticles 1449

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Green and Sustainable Future
with Consumer Nanoproducts 64
Saruchi, Vaneet Kumar, Harsh Kumar, and Diksha Bhatt

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1456
How to Make Green Nanomaterial Sustainable? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1458
Natural, Renewable Sources of Reducing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1458
Natural Sources as Precursors for Carbon Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1459
Green Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1459
Ongoing Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1459
Green Nanotechnology: A Way to Change the Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1460
Nanomanufacturing Methods and Environmental Concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1462
Industrial Ecology and LCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1464
Energy Intensity of Carbon Nanofibers and Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1466
Important Websites About the Topic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1467
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1467

Abstract
The eventual goal of any monetary, industrial, and communal development is to
advance human health and surrounding. Thus, the humanity brings new require-
ments to new technologies, moving toward green and sustainable technology
development. Green and sustainable nanoproduct, as a branch of green and
sustainable technology, significantly contributes to environmental sustainability
by producing nanomaterials and nanoproducts without harming human health

Saruchi · D. Bhatt
Department of Biotechnology, CT Group of Institutions Jalandhar, Jalandhar, Punjab, India
V. Kumar (*)
Department of Applied Sciences, CT Group of Institutions Jalandhar, Jalandhar, Punjab, India
H. Kumar
Department of Chemistry, Dr B R Ambedkar National Institute of Technology Jalandhar, Jalandhar,
Punjab, India

© Springer Nature Singapore Pte Ltd. 2022 1455

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_84
1456 Saruchi et al.

and the environment and by producing nanoproducts that provide solutions to

environmental problems as well.
Sustainability and future studies are connected to each other; the time levels
involved may be unlike from the individual viewpoints of stakeholders,
depending on whether they are futurists or environmentalists. Thinking of futures
calls for planning in the time scale of hundreds of years, whereas the environ-
mental research community may think in terms of a few decades at the most.
In this chapter, we recapitulate green and sustainable nanotechnology—a way
to change the future—methods of nonmanufacturing, and environmental con-
cerns and consumer nanoproduct with green and sustainable future.

Keywords
Nanoproduct · Technology · Sustainable · Green · Environment

Introduction

There are lots of remuneration of the technologies with their negative impacts like
more waste, greenhouse emission, etc., so human health and environment is the main
concern of the new technologies. To achieve this researchers are moving toward
green and sustainable nanoproducts [1]. Nowadays, most of the present products are
replaced by the new environment-friendly, nontoxic, and green nanoproducts. The
techniques that do not harm environment and preserve the natural resources and
produce sustainable development are preferably called as green technology. The
main objective of the green technology is to reduce waste, recycle the material, and
refuse the nonbiodegradable material, utilization of the reusable material, and
responsibility of not to waste electricity, water, food, etc. [2].
Nowadays, nanotechnology is one of the important branches of green technology.
This is the emerging area which utilizes green chemistry principles and encourages
industrial safety and health [3]. The growing field of nanotechnology will take part an
important role in global manufacturing. Diverse applications in the field of agriculture,
pharmaceutics, energy, etc. emerge in each day, with low-cost, energy-saving,
improved productivity and efficacy with lesser harm to environment. Nanotechnology
is the only technology that surpasses the boundaries of the different fields and leads to
the novel benefits of the materials for upgrading the different sphere of life [4].
Nanotechnology is considered an all-pervasive, enabling technology [5] that
transcends sectoral boundaries, resulting in novel applications of nanomaterials
that promise radical improvement in various spheres of life. Examples include
paper-thin, high-energy, nanoengineered batteries. Capable of being folded and cut
like paper and infused with carbon nanotubes, these sheets of nanocomposite paper
serve as ultrathin, flexible batteries and energy storage devices for next-generation
electronics and implantable medical equipment [6]. Nano-enabled miniaturized
diagnostic devices can be implanted in the human body for early diagnosis of
illnesses, and the use of nanotechnology for in vivo drug delivery and imaging
64 Green and Sustainable Future with Consumer Nanoproducts 1457

systems is expanding rapidly [7]. Nano-based coatings can improve the bioactivity
and biocompatibility of implants [8], while nanocoatings are also finding use in
corrosion resistance, dirt repellency, water repellency, thermal insulation, and anti-
microbial applications.
Applications of nanotechnology that directly benefit the environment are nanotech-
nologies for site remediation and wastewater treatment [9], nanomaterial-based solar cells
for improved energy efficiency, and the use of nanocatalysts for air purification [10].
Nanotechnology, as a modern research field encompassing a wide variety of
nanometer-scale technologies, plays a key role in developing novel methods for
manufacturing new items, replacing current manufacturing equipment, and enhanc-
ing efficiency in the reformulation of novel materials and chemical substances
(Vinodn.d.). Any risks to staff that may arise from the realistic implementation of
sustainable chemistry, green processes, and the production and use of green products
should also be considered and discussed in order to better understand all of the
advantages of sustainability [3].
The chapter’s goal is to present the readers to green nanotechnology concepts.
The causes for adoption of green nanotechnology, concepts, advantages, and issues
were discussed (Fig. 1).

DEFENSE
AND
SECURITY

BIOMEDICAL
AND DRUG COSMETICS
DELIVERY AND PAINTS

NANO
TECHNOLOGY
APPLICATIONS
FOOD AND
ELECTRONICS
AGRICULTURE

BIOTECHNOLOGY STORAGE
OF ENERGY

Fig. 1 Nanotechnology application areas

1458 Saruchi et al.

How to Make Green Nanomaterial Sustainable?

Green nanotechnology, integrating of nanoscience with green chemistry concepts

and actions, may be crucial to creating an eco-friendly community in the twenty-
first century [11]. Green chemistry is a collection of guidelines or rather a
chemistry theory that promotes the creation of production processes which min-
imizes usage or eliminates dangerous products and their production [12–15].
The use of renewable materials, innocuous solvents, and energetically effective
methods in nanomaterial manufacturing are currently in practice as green
nanotechnology.

Natural, Renewable Sources of Reducing Agents

Nature gives us various chemical substances, including plant extracts, biopolymers,

vitamins, proteins, peptides (e.g., glutathiones), and sugars (e.g., glucose and fruc-
tose), which are sufficient reductive factors for the nanoparticles synthesis
[11, 16]. Formerly plant extracts are actually the most researched group. Plant
extracts are considered mostly prospective organic reducers, because of their quan-
tity [17]. The fusion of nanomaterials, which are useful in electronics and health
purpose, using extracts from plants as agents to minimize is a specific range of
achievement [13]. Recent time, actively survey has been carried out in the field of
biomedical use like gold and silver nanoparticles for drug as well as gene supply.
The purpose of improved biocompatibility is to use toxic-free green reducing
products, plants, algae, bacteria, and fungi. Elia et al. used four various kinds of
plant extracts to combine the nanoparticles of gold, Salvia officinalis, Lippia
citriodora, Pelargonium graveolens, or Punica granatum as a reducer and
stabilizer [18].
Biopolymers constitute one more class of natural source that is used for metal
nanoparticles reduction and stabilization. Such polymeric molecules of carbohy-
drates were already used in different industries so that they are prepared for
large-sized nanoparticle development. Cellulose, chitosan, and dextran that are
derived from plants, the exoskeletons of crustacean and sugarcane, respectively,
are examples of biopolymer used for the fusion of nanoparticle [19–21].
Vitamin C is a proven natural antioxidant or reducer. Like many other reductive
substances, vitamin C can reduce aqueous metal ions naturally, for the production of
metal nanoparticles [22]. It is also noteworthy that Fe3O4 nanoparticles can be
synthesized by minimizing the iron colloid hydroxides hydrothermally [23]. Another
vitamins B and E are also included for metal nanoparticles fusion [24]. However,
their comparative cost efficiency may be an obstacle to the commercialization, due to
wide range of availability of vitamins. Many organic products, such as proteins and
peptides, are also costly and therefore unsuitable for large nanomaterial development
[25–27].
64 Green and Sustainable Future with Consumer Nanoproducts 1459

Natural Sources as Precursors for Carbon Nanomaterials [28]

The use of natural resources as precursors for carbon nanoparticles is an emergent

field of green nanotechnology science, which in many cases are beneficial because of
their special characteristics. Vegetable oil has proved to be an example of a suitable
option to the use of spray pyrolyses for higher standard carbon nanotubes. Such
process can be used by distinct catalyst to generate both one-walled and multiwalled
carbon nanotubes.

Green Processing

Apart from using organic beginning and manufacturing products for the production
of nanoparticles, the second half of green nanotechnology creates eco-friendly,
renewable methods. Here, water and subcritical carbon dioxide were examined as
substitutes to organic compounds [29, 30]. Diverse alternative solutions to tradi-
tional heating are of specific interest [31]. The most famous green technique is
what’s called the “hydrothermal method,” where water is the source of reactions.
Another fascinating trend recently revealed that Abdelaziz and his associates have
been producing a super-heated and loaded green chemical reaction with the
Leidenfrost influencing the impact to generate and covering of complicated
items [32].
For nanoparticles integration a microwave power and concentrated sole light [33]
have also been considered as thermal sources alternatively. While this method is
successful at the laboratory level, the use of these techniques in industrial manufac-
ture does pose tremendous challenges. For instance, microwave heat’s short reaction
durations are limited to smaller reactions. Inconsistent intensity of the light and the
requirement of a lens restrict the use of concentrated sole light. Flow chemical
methods for improving the efficiency of renewable chemical products have currently
been created [34].

Ongoing Challenges [35]

Many green nanotechnologies have been carried out only on a laboratory level until
now. Proposals must be conducted to assess the potential transition to industrial
output of emerging technologies. For the majority of green nanotech innovations,
economic and legislative obstacles due to uncertain nanotoxicology may be the
biggest obstacle [35]. Green nanotechnology also needs completely novel methods,
which make development initially costly. Green nanotechnology also needs
completely novel methods, to make the development over-priced primarily.
In the last few decades, the government’s environmental regulations have a huge
effect on the chemical industry. So many of these laws are aimed at minimizing the
1460 Saruchi et al.

danger to healthcare as well as atmosphere through exposure reduction. Rather than

investing in green systems, some companies must use their capital for mandatory
measures and end-of-pipe technology to guarantee their goods and systems are
actually safer. This is the positive proof that chemicals production invests more on
pollution reduction instead of any other industries. Of course, in place of risk
reduction, legislative insistence on risk management creates a significant obstacle.
The cooperation of academic scientists and the private companies is crucial to the
effective transition of green technology from laboratory to factory. In fact, by giving
fund to market green nanotechnologies, the government sponsored these partner-
ships. Relating to government rules and directions on green nanomaterial
manufacturing may deliver an important support to green nanotechnology growth
and execution in financial terms.

Green Nanotechnology: A Way to Change the Future

Nanotechnology period was called the Second Industrial Revolution. Apparently,

nanotechnology has less ability to encourage creativity in various applications. In
spite of the expectation and promise that nanotechnology elevates, nanoparticles
produce a tangible apprehension due to their not well-known health and environ-
mental consequences for human [36].
Sustainable chemistry is a balance growth choice for chemical and chemical
technology applications in the industry. It provides a new strategy to chemical
synthesis, manufacturing, and implementation to minimize safety and environmental
treatments [37].
Anastas and Warner originally described 12 theories of green chemistry and
applied to a great variety of design to chemical products and procedure with the
goal of mitigating chemical threats to society as well as environment, waste reduc-
tion, and avoiding pollution [38]. The implications of applying such concepts are
decreased use of dangerous agents and solutions, enhanced materials and energy
performance of chemical methods, and increased end-of-life product design. Using
certain nanoscience concepts can promote the development and processing of
potentially secure nanomaterials and nanostructured devices [39].
The usage of green chemicals to produce nanoscale objects, development of
manufacturing processes of nanomaterials, and implementation of nanoparticles
are included in green nanotechnology. The technique needs to understand the
nanomaterials, containing toxic as well as ecotoxic characteristics, and structure of
nanoscale substances to be integrated as higher level performance materials which
present minimal risk to humans or the surroundings. It seeks to find synthesizing
techniques that remove the necessity of noxious reactants and increase their output
while providing economically sustainable volumes of pure material. Nanomaterials
can be designed for greener purposes, reducing future risks by designing and using
healthier materials. It offers design plans to ensure that the manufactured nano-
materials are ultimately secure by evaluating biological and environmental risks in
accordance with the design. Eventually, green nanotechnology aims to optimize
64 Green and Sustainable Future with Consumer Nanoproducts 1461

nanotechnology benefits in society while reducing ecosystem impacts (Dahl et al.

2007) [40]. Almost all the concepts of green chemistry could be used for nanoscale
product design, biosynthesis, and nanomaterial implementation.
Examples of the variety of green manufactures include methods using
environment-friendly substances with limited power needs for silver or gold nano-
particles with neutral reactives such as vitamin B2, vitamin C, and tea and coffee
extract. The development of various popular nanomaterials has already occurred
(Au, Ag, CdSe, ZnO, FexOy, TiO2, and carbon nanotubes).
Nanomaterials may be coated to keep them from dissolving or joining the organic
cells in water. The reduction of nanomaterials was made of starch, agar, nucleic
acids, extract of tea and coffee, benzoic acid, and even whole species (Mulvihill et al.
2011) [41]. Such nanomaterials can be made from nontoxic sustainable components
or organic waste (Fig. 2).
Including nanomaterials to green up the existing procedures, a subgroup of
greener products. The main nanomaterials for this aim are nanoscale catalyst. They
are very wide depending on their area and can be used more efficiently and without
waste and chemical processes due to pollution. Nanoscale membranes could assist in
dividing the required products of chemical processes from waste products and
illustrate further nano-applications to green the existing procedures. Such trans-
formations can be energizing and unsustainable or induce pollution by themselves.

Fig. 2 Green nanotechnology

1462 Saruchi et al.

Fagan et al. (2013) discusses further use of nanomaterials for water decontamination,
purifying air, as well as deactivation of disease causing pathogens in water. Nano-
materials and nanoproducts are indirectly responsible for underweight nanocomposites,
reducing fuel consumption, reducing energy and environmental damage [4]. For
example, organic film solar panels are more economic and more energetic than standard
silicone solar panels made from the material known as fullerene (C60). Green nano-
technology has been specifically devoted to various developing zones: (i) photovoltaic
(organic, inorganic) nanostructuring, (ii) man-made fuel production photosynthesis,
(iii) energy storage (battery) nanostructures, (iv) solid illumination of state,
(v) thermoelectrical systems, and (vi) desalinization and reuse of water (OECD
2013) [42].

Nanomanufacturing Methods and Environmental Concerns

Nanoscale manufacturing requires two perspectives: top-down or bottom-up.

Through engraving and grinding process including silk screening, printing, and
whirling, the top-down continues into the microsystem and decreases. Bottom-up
practice man-made creation via beginning through atomic or molecular number and
building up by nucleation or rising from solid, liquid, and gas precursor by bio-
chemical and physical methods. Sol-gel and epitaxy are both examples of these
procedures [8, 43]. Usually, top-down approaches are commonly thought to produce
a great deal more waste. However, the bottom-up approach seems to be in its
primitive progressive stage and pledge for drastic changes in the recent system of
development.
Often nanostructured materials are graded as one, two, and three dimensions.
Thin films are example of 1D nanoproducts, whereas 2D include nanowires, and 3D
nanoproducts include fullerenes and bundles of nanowires. In general terms, the
processing of 2D and 3D nanoproducts has tighter criteria for purity. The majority of
the production methods needed have low process efficiency, resulting in unnecessary
waste. Such methods often absorbed a large amount of energy, water, as well as
solvent. Besides having extreme supply and being energy-intensive, few of these
methods may include unexpected acute and a chronic effect on human health
including unintentional exposure to nanoparticles.
Sengül et al. [43] explored different methods of nanomaker processing and
described the features of nanomaker procedures which improve their energy and
resources:

• Requirements for strict purity

• Low product efficiency
• Repeated processing, post-processing, or reprocessing steps of a single process or
batch
• The use of substances and organic solvents toxic, acidic, or basic
• Medium to high vacuum need
• Greenhouse gas use or production
64 Green and Sustainable Future with Consumer Nanoproducts 1463

In a detailed review of the issues concerning the nanometric manufacture of 1D,

2D, and 3D nanostructured materials, the analysts want to describe the narrator to an
article in Sengul et al. This poses the question of finding decent beginning materials
for nanoproduction methods. The amount of production by nanomaterials is sup-
posed to increase when the technology is going to be more prevalent and standard
materials are being replaced. The initial products used in production methods are
typically uncommon and require resource-intensive mining or refining, which places
additional strain on natural resources and raises the effect of the product indirectly on
the atmosphere throughout the total life cycle. This poses the question of seeking
suitable beginning products for methods of nanoproduction (Fig. 3).

TOP DOWN STRATEGY BOTTOM UP STRATEGY

Precursor containing molecule

BULK

Transformation by
energy
Ionization by energy

Powder Formation of ion & radicals

Transformation to smaller fragments

Condensation and formation of clusters

Exfolitation of multilayers to monolayers

Clusters
Synthesized nanoparticles

Fig. 3 Example of top-down and bottom-up strategies for synthesis of NPs

1464 Saruchi et al.

Industrial Ecology and LCA

Industrial ecology is an organization that proceeds toward the complete visibility of

ecological problems and explains how people utilize natural capital to generate
products and services. It highlights the importance to analyze the relationships
between the production processes and the atmosphere and the formation of products
and the process of production in a way that can improve the usage of by-products
[44]. This strategy aims to make industrial development a safe and secure environ-
ment in the coming time. The above discussion leads us straight to the concept of
sustainable development which, according to a 1987 World Commission on Envi-
ronment and Development (WCED) report, is Development that assembles the
demands of the current, where the upcoming era doesn’t have to sacrifice their
ability to fulfill their requirements [45].
Nanotechnology has a broad range of implementation. It has a similar broad
capacity for a negative impact on humans and the environment via different nano-
particle exposure routes along with work exposure [46, 47]. Regarding the early calls
to take measures to guarantee the continued growth of nanotechnology, little has
been done in the relentless effort to quickly introduce ever new nano-applications
[48]. Life cycle assessment is an extremely useful device to evaluate the environ-
mental effects correlated by the complete life cycle of a material. It might not be
possible to execute any kind of declaration toward the advantages of the environ-
ment by any materials or methods of production. Its analyzations depend upon the
result of the environment by the circumstances of the life cycle first. The steps
involved in LCA are as follows: (1) determining the target and scope assessment,
(2) quantification and environmental release for every unit and phase included in a
study (known as LCI) for the material and energy, (3) assessing those possibilities
mankind’s well-being and natural effects connected with those inputs and outputs
recognized in the phase of gathering steps LCI knowledge, and (4) interpretation of
findings, outlining key problems, and drawing conclusions and suggestions
[49]. Material extractions, processing, production, usage, transport, and end of life
(reprocessing) typically involve life cycle stage consideration.
Managing a life cycle assessment of standard product duty is very scary because
of its ages; having limited available resources generally, it occurs to raise the margins
of the assessment with the aim to finalize it up to date. Few methods applicable for
abridging the range of the assessment called LCA streamlining contain the follow-
ing: (i) limiting it to other life cycle phases of importance, such as the use phase;
(ii) classifying different types of environmental effects, such as global warming; and
(iii) only performing a comparative analysis of two separate production processes
leading to the development of otherwise similar materials.
In terms of nanomaterials, the function of operating to evaluate the life cycle gets
to be tougher due to the absence of the registered details of these materials on hand,
as their production methods seem to be new and the themes or topics are restricted
most of the time. Secondly, for ignoring the use of inventory data is similar as in the
situation of unique materials, as nanomaterials never make any judgment on the
basis of volume individually [50]. As well the recent effects assessment strategy
64 Green and Sustainable Future with Consumer Nanoproducts 1465

simply goes without intermingling formulas for calculating the nanomaterial effects
on the heath as well as environment due to unknown effects. Methods of the
nanomaterial productions are still unconventional, but having a progressive stage,
continuously changing. Due to this reason, the effects of the environment which is
related to production method A for a particular material may perhaps very much
differ from method that is related to depletion. In such new cases of technologies
while they are in the stage of developing, a situation analysis may be helpful when
conducting LCAs in order to address ambiguities of possible results in the future.
Despite the dispute faced by nanomaterials LCAs, several LCAs tried [51–55],
whereas complete LCAs could not be carried out, the new technologies suchlike
these must be viewed in a life cycle manner so that any problems and problems
related to any up- and downstream phase might be evasive can be highlighted. This
technique of life cycle thinking is required to get practice in the initial phase to
develop the method of production, to know the environmental impacts of recent
technologies betterly and freely to choose a decision of advantages and disadvan-
tages toward one another. Thousands of proposal are there to use the life cycle
thinking in the development of nanotechnology [46, 56, 57].
Acknowledging the disadvantages of LCA in being insufficient for the study of
nanoparticles’ health impacts and exposure paths, this work later discusses very
effective structures integrating the LCA approach with the Risk Assessment (RA).
NanoLCRA (Life Cycle Risk Assessment) and Systematic Environmental Assess-
ment (CEA) are the two systems explored.
Possibly environmental effects of nano-enabled products at each life cycle phase
are illustrated in Fig. 4.

PRODUCTION Manufacturing
MATERIALS Use End of life

Strong level of Difficult to

energy recycle

Efficient use of Non

Strong energy
resources biodegradable
efficiency
(water and Human and
Possible toxic
solvents Ecological
soil, water, and
included) Performance
Exposure to air releases
Exposure to work
Effects on
work
human health

Environmental concerns

Fig. 4 Nanomaterials life cycle

1466 Saruchi et al.

The obvious advantages of nano-compatible goods, typically in the usage

level, are frequently focused, whereas environmental issues related to the remainder
of up- and downstream life cycles appear to be ignored [58]. The manufacturing and
end-of-life (composting/disposition) phase of the products are of major concern.
Nanomaterials tend to be produced with great intensity of power and resources. At
the end-of-life point, when the material is not completely recycled and/or reused, we
are faced with the question of disposal. Produced nanomaterials may be discharged
into the atmosphere at any point of the entire life cycle [59].

Energy Intensity of Carbon Nanofibers and Nanoparticles

Despite that aluminum is considered as the highest energetic material to manufacture,

having the most beneficial properties, especially underweight and energetic in
comparison to steel material as its competitor, one more disadvantage of aluminum
is its cost as it is very expensive; however, in some critical aerospace, automotive, and
others, it does not generally make any effects in both its price and its great intensity.
Having one of the most energetic intensity aluminum has transformed into a bench-
mark which exactly helped newly discovered materials to assess their intensive energy.
Nanoparticles of carbon and nanofibers are examples of materials producing
excessive energy than aluminum. Two recent surveys, one on nanofibers and another
one on nanoparticles, indicate that carbon nanofibers made of a variety of raw
materials need 13–50 times the amount of energy needed for manufacturing primary
aluminum on an equivalent density [60] and that their force of energy from carbon
nanoparticles is two to a hundred times that of aluminum [61].
While the newly discovered product or application uses traditional (non-nano)
materials, the product developers generally have to tackle some problems such as
durability, execution, price, and theories. Recently, to keep the concept of Design for
the Environment (DfE) in Nuisd, intensive power, recycling of contagious and facility
of disconnecting extra environmental factors have formed their techniques for their
group of design criteria. Yet the advance nanomaterials required to transform the
process of selection of the conventional material as the designer of the product have to
consider the above problems, as well as the welfare and good physical conditions of
whosoever may be revealed these nanoscale materials, which may have the possibility
to consume or to enter the skin and undoubtedly influence the internal organs [62–82].

Conclusion

The green nanotechnology theory is characterized by healthy, energetic products and

methods, minimized waste, emissions elimination of greenhouse gas, and the uses of
renewables. The aim of green nanoscience is to make sure the eco-friendly produc-
tion of nanotechnology materials and to secure that the development and consuming
methods are economically and ecologically sustainable. The environmental-
economic sustainable aspect of green nanoscience emulsion is nevertheless
64 Green and Sustainable Future with Consumer Nanoproducts 1467

combined with the threats to climate, safety, and well-being. Moreover, a range of
obstacles may be limited by progression and usage of such technology, e.g., techni-
cal, economic, social, educational, organizational, or the absence of an adequate
regulated structure. Yet the advantages of green nanoscience tend to be greater than
their potential disadvantages. It is hard to progress and trade green nanotechnology,
and it will take the science, experimental, policy sectors too to focus on obstacles.
Yet the direction forward and the practical steps will provide the stable base for a
forthcoming in nanoscience that is financially viable and eco-friendly.
On view of the fact that nanotechnology is expected to become a multibillion
dollar industry for the upcoming generation, it is necessary to take a life cycle
method to assess the ecological effects as well as public health (both industrial and
end use) at each and every point of the life cycle of a nano-enabled material before
taking any judgments on the possible advantages of environment or making a
judgment about the material. However, the existing technique of life cycle assess-
ment, built for use with standard bulk products, demands to be revised and updated
to make it appropriate for assessing nanomaterials if required. Two systems inte-
grating LCA and risk analysis, NanoLCRA along with extensive environmental
audit, tend to be especially beneficial for accurately evaluating the effects of nano-
materials on human welfare. Therefore, the implementation of green technology
concepts to nanomaterial production methods, the utilization of green technology
measures to determine the greenness of nanomaterials and production of nano-
material procedures, and the implementation of a more constructive strategy when
developing new nanotechnology products are few of the suggested approaches to
insure that nanomaterials have a beneficial effect in the coming decades.

Important Websites About the Topic

https://www.wipro.com/en-IN/blogs/wipro-insights/green-nanotechnology%2D%
2Dmaking-way-for-a-sustainable-future/
https://www.researchgate.net/publication/280836162_Nanotechnology_and_Sus
tainability-_Current_Status_and_Future_Challenges
https://www.springerprofessional.de/en/green-nanotechnology-for-the-environ
ment-and-sustainable-develop/16879594
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6473607/
https://onlinelibrary.wiley.com/doi/full/10.1111/j.1530-9290.2008.00046.x
https://www.forumforthefuture.org/sustainability-and-system-change?
g c l i d ¼C j 0 K C Q j w 7 Z L 6 B R C m A R I s A H 6 X F D J M X t n M G F y M L U o _
LdpTnGv1qN174jIci6yVYtU6fHY5TvgEyDigzuoaAmeYEALw_wcB

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Nanocarriers for Antioxidant Cosmetic
Products 65
Jimena S. Gonzalez, Romina P. Ollier Primiano, and Vera A. Alvarez

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1474
Penetration of Active Compounds into the Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1475
Natural and Biodegradable Polymers as Vehicles for Antioxidant Active Ingredients
in Skin Care . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1479
Antioxidants for Skin Care Cosmetic Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1481
Delivery Systems for Natural Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1487
Commercial Skin Care Products with Antioxidant Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
Conclusions and Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1491
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1493

Abstract
Skin aging occurs as a result of multiple oxidative reactions due to both intrinsic and
external factors which promote wrinkle formation, dryness, tissue elasticity loss, and
thinning, among other visible signs. There are many strategies aiming to reduce
these signs of aging and/or to treat age-related skin problems. Nanovehiculization of
antioxidant ingredients represents one of the most capable technologies of the
twenty-first century. The use of nanocarrier systems has added novel advantages
of improved skin penetration, depot effect with sustained release of active sub-
stances, and targeted site effects. Various innovative formulation types for special
delivery systems like nanocapsules, submicroscopic tiny bits, vesicular, particulate
systems, emulsion type, particulate type, and other delivery systems are discussed in

J. S. Gonzalez
Materiales Compuestos Termoplásticos (CoMP), Instituto de Investigaciones en Ciencia y
Tecnología de Materiales (INTEMA), Universidad Nacional de Mar del Plata (UNMdP) – Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET), Mar del Plata, Argentina
R. P. Ollier Primiano · V. A. Alvarez (*)
Thermoplastic Composite Materials, Institute of Research in Materials Science and Technology
(INTEMA), CONICET –Mar del Plata National University, Mar del Plata, Argentina
e-mail: alvarezvera@fi.mdp.edu.ar

© Springer Nature Singapore Pte Ltd. 2022 1473

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_61
1474 J. S. Gonzalez et al.

this chapter. Special attention is paid to those products based on eco-friendly and
naturally derived ingredients, which might represent interesting raw materials for the
formulation of future innovative nanocosmetics. Thus, several cosmetic delivery
systems for natural antioxidant ingredients are reviewed here and constitute highly
promising technologies with enormous potential as customer products.

Keywords
Skin care · Nanocosmetics · Nanocarriers · Antioxidant · Nanosystems ·
Cosmetic nanoproducts

Introduction

The use of environmentally friendly ingredients in cosmetic formulations has received

rising interest in the cosmetic industry. Such ingredients can be natural products or any
other naturally derived biodegradable substances. Particularly, products with antiaging
properties containing antioxidants in their formulation have been surging in the
market. Nowadays, cosmetic products contemplate an integrative approach, not only
focused on the formulation process but also on the consumer perception and require-
ments, as well as marketing strategies, in order to produce a successful product [1]. In
the cosmetic area, there is an increased interest to develop nanoparticles which are able
to enhance the delivery of active components into and even through the skin barrier,
called nanocarriers. Nanoencapsulation can improve the skin bioavailability of anti-
oxidants for a prolonged period [2]. Nanocapsules with their nanosize and high surface
area are ideal particles in many uses, especially as active ingredient for carrier systems.
The nanocarriers based on biodegradable polymers offer certain advantages over lipid-
based carriers for topical drug delivery. They have flexibility and deformability, which
are important requisites for penetration across tissue barriers, and can be stored for a
long period of time, both hydrophobic and hydrophilic active compounds can be
encapsulated or adsorbed, they can be functionalized, and most importantly their
physicochemical properties can be adjusted in order to achieve a controlled release
of the encapsulated active compound. Polymeric nanocarriers are available in different
sizes ranging from nanometer to submicron and micrometer dimension [3]. Due to a
continuous search for better product efficacy by consumers, the boundary between the
cosmetics and pharmaceuticals field is becoming harder to distinguish [4]. Nano-
carriers are frequently used in cosmetics because of their properties, including a)
stability improvement of the substance, b) modification over the active compound
penetration properties, c) drug protection, d) a reducing risk of irritation (improved
tolerability of the skin to the drug), and e) enhance the appearance of the formulation
(a change of color or odor) [5].
When the natural skin antioxidants (endogenous) are insufficient to reduce
oxidative stress, then antioxidants from different sources can be applied to the
skin in different cosmetic formulations. It is known that free radicals and other
reactive species can cause severe damage to cells and cell components of the skin,
65 Nanocarriers for Antioxidant Cosmetic Products 1475

which results in skin aging and cancer. To prevent these actions on skin, the use
of a topical antioxidant supplementation is a strategy used in the cosmetics
industry, and these antioxidants act on quenching free radicals. However,
antioxidants have some limitations such as low stability (light, pH, temperature,
and oxygen), low ability to penetrate the different layers of the skin, and poor
solubility in water [6].
In this chapter, we briefly discuss antioxidant and antiaging substances encapsu-
lated in different nanocarriers with a special view in the natural and ecological aspect
of the materials and processes involved in their production.

Penetration of Active Compounds into the Skin

To obtain the desired effect, a penetration of the active compound into the skin is
required. This process is influenced by several factors, such as the molecular size, the
degree of ionization, lipophilicity, the compatibility between the polymer of the
nanocarrier and the active substance, and the compatibility between the nanomaterial
and the skin [4].
Skin is the largest organ of the body. The skin has the vital function of keeping the
biochemical and physiological conditions of the body in optimum state. Healthy skin
is very efficient in fulfilling its task as a biobarrier. It is organized as a multilayer
structure, which can roughly be categorized into hypodermis, dermis, and the
non-vascularized epidermis, the latter being covered by the stratum corneum.
Their most important functions are as follows:

1. Releases toxic substances with sweat

2. Protects the body from harmful effects of the sun and radiation
(a) Brings mechanical support
(b) Prevents loss of body fluids and penetration of toxic substances
(c) Regulates body temperature
(d) Acts as sensory organ for touch, cold, heat, sociosexual, and emotional
sensations
(e) Supports for immunological function mediated using Langerhans cells
(f) Produces vitamin D synthesis

Skin acts as a two-way barrier, being able to prevent outward or inward passage
of water and electrolytes. The epidermis mainly assumes a role as skin barrier. If the
epidermis is removed, the remaining dermis becomes permeable.
Firstly, we have to differentiate two delivery processes: dermal and transdermal.
Dermal delivery refers to the process of mass transport of active substances applied
on the skin to several skin layers [7]. However, transdermal delivery refers to the
entire process of mass transport of ingredients applied on the skin surface and
includes their absorption by each strata of the skin, their uptake by microcirculation
of the skin, and distribution in the systemic circulation [7].
1476 J. S. Gonzalez et al.

Fig. 1 Penetration of the nanocarriers throw the skin. 1–3 when the skin barrier is intact. 4, when
the skin barrier is disrupted

Depending on the formulation, shape, and size of carriers, they interact differently
with the skin strata (see Fig. 1). After topical application the process of penetration
can be [as follows (3)]:

(a) Interaction with the stratum corneum (SC)

Stratum corneum (SC) is a very complex barrier. It has been postulated that lipid-
based particles have the tendency to merge with the skin lipid layers, whereas
polymeric particles, being more hydrophilic, might have different interactions with
the extracellular lipids of the SC.

(b) Hair follicle pathway

The hair follicle canal of the pilosebaceous unit represents a reservoir where
materials with micro- and nanosize can penetrate and accumulate.

(c) Translocation across the SC

It is believed that only low-medium molecular weight lipophilic molecules

(below 500 Dalton) can pass the skin barrier, whereas the penetration of nano-
particles is significantly diminished.

(d) Carrier penetration across disrupted skin barriers

In unhealthy skin, where the integrity of the SC is disrupted, carrier systems

might cross the SC barrier and enter the epidermis and dermis. Several methods have
65 Nanocarriers for Antioxidant Cosmetic Products 1477

Fig. 2 Most common nanovehicles used in cosmetic for antioxidant delivery

been developed to bypass the SC, for example, by altering it with adhesive tapes and
abrasion, altering it with permeabilizing agents, or using microneedles.
Once a carrier system has crossed the primary barrier and has reached the
epidermis layers, it can diffuse across the extracellular space and/or be taken up by
epidermis and dermis cells [3].
Numerous nanostructured cues used in cosmetics are shown in Fig. 2 [5]. Nano-
carriers in cosmetic industry are a diverse array of vehicles which serve the dual
purpose of both protecting active compound payloads and enhancing their delivery
to the skin. The most commonly used delivery systems include vesicular delivery
systems (liposomes and niosomes), emulsion delivery systems (microemulsions and
nanoemulsions), dendrimers, nanotubes, particulate systems (microparticles, nano-
particles, polymeric micelles, and solid lipid nanoparticles), and cyclodextrin com-
plexes [5]. Specifically nanocarriers of nanosystems for the cosmetic industry
present many advantages including (a) the protection of sensitive agents, (b) the
controlled release of active compound, (c) improved dermal penetration of active
principle, (d) a reduction in concentration of compound and additives, (e) longer
shelf life, and (f) greater product effectiveness [8].
There is an ample variety of nanocarriers, nanosystems, or nanovehicles. Various
types of nanocarrier systems will be discussed in more detail below [5]. The most
common approved and commercialized nanocarriers in cosmetic industry are the
liposomes. Liposomes are structures which have a hydrophobic lipid bilayer sur-
rounding the aqueous core created by the extrusion of the phospholipids. The lipid
bilayer of liposomes can fuse with other bilayers, such as the cell membrane, and
helps in the transport of the core therapeutic material. Their sizes can be from 15 nm
(called nanosomes) to numerous micrometers, and they can have one or various
layers. It is well known that liposomes have potential applications in cosmetics and
drug delivery owing to spontaneous penetration of the stratum corneum through
intracellular or transcellular routes finding their way to commercial cosmetics.
Moreover, the niosomes are formed mostly by nonionic surfactant (of the alkyl or
dialkyl polyglycerol ether class), and cholesterol is incorporated as an excipient to
1478 J. S. Gonzalez et al.

the lipids to stabilize lipids. Niosomes and ufosomes (made from fatty acids) may be
used in cosmetic products for the delivery of hydrophobic antioxidants such as
vitamin E.
The dendrimers, or fractal polymeric trees, consist of a branched synthetic
polymer, wherein the active ingredient is entrapped in the interstices between the
branches. Dendrimers and hyperbranched polymers have been widely explored in
the cosmetic area. Dendrimers may be recognized as unimolecular, monodisperse,
and micellar nanostructures.
Nanotubes are linear and hollow structures; they could be very effective to
increase the viscosity, while encapsulating the bioactive ingredients to protect
them from degradation, provide on-demand delivery, or mask unpleasant organo-
leptic properties. Carbon nanomaterials, particularly graphene-based ones, are the
most commonly used carriers; they have demonstrated the potential for hair coloring.
The amalgamation of different biopolymers (such as chitosan and graphene)
produces color nanoformulations. This formulation showed high resistance to
various shampoos and is endowed with heat dissipation.
Nanoemulsions and block copolymer micelles are transparent metastable dis-
persions with droplets of one liquid within another and possessing unique tactile and
textural properties. They have specific properties that make them quite attractive for
their application in cosmetic industry. They are organic nanoparticles having a liquid
core. They are made from the same ingredients as classical emulsions, and their
overall organization is also the same. Their structure can be manipulated based on
the method of preparation to give products with distinct characteristics, for example,
water-like fluids or gels. Nanoemulsions possess distinct advantages over large-scale
emulsions. The submicron size brings about important features such as accelerated
skin delivery of active substances, absence of creaming in fluid products, immediate
skin occlusion, transparency, and gloss after spreading [9].
Cyclodextrins (CDs) are nontoxic cyclic oligosaccharides. They are built from
six to eight (α -CD, -CD, γ -CD) D- glucose units and are formed during the
enzymatic degradation of starch. The D-glucose units are covalently linked at the
carbon atoms C1 and C4. These molecules have the capacity to form inclusion
complexes with a broad range of substances. The physical and chemical properties of
the guest molecules change due to complex formation. They offer many advantages.
For Instance, the solubility of slightly soluble molecules increases in a cyclodextrin
complex. All these and further advantages of cyclodextrins and their complexes can
be used for the formulation of cosmetic products.
Polymeric nanoparticles (NPs) consist of a core, in which the active compounds
(the antioxidants in this case) are suspended, and a shell enclosing the core. They are
one of the most studied nanosystems in nanoscience and nanotechnology. The
encapsulation mechanism, the chemical and viscosity properties of ingredients, the
size, and active ingredient-release behavior seem to be the main responsible prop-
erties affecting the form and time to deliver the active compound (antioxidant in this
case). The interest of polymeric nanocapsules is based on their ability to protect the
active ingredients and change the physicochemical properties of the active principle,
controlling, this way, their efficacy. Nanocapsules, a special type of polymeric NPs,
65 Nanocarriers for Antioxidant Cosmetic Products 1479

are capsules constituted of an oily or water core, surrounded by a polymeric wall. If

presenting an oily core, it can be composed by a mixture of solid and liquid lipids or
just liquid lipids. In cosmetics, polymeric NPs are used in skin care products, such as
antiaging and moisturizing creams [10]. It should be mentioned that polymeric
nanocapsule suspensions can be directly applied on the skin as a final product or
incorporated in semisolid formulations as an ingredient. After topical application,
the nanocapsules form a thin film on the skin with water evanescence. This thin film
is related to long-term delivery and the higher storage capacity of the skin in relation
to the active ingredient.
The methods described in the literature to prepare polymeric nanocapsules can be
categorized as chemical and physicochemical methods, depending on whether the
nanocapsules are generated by in situ polymerization or by interfacial precipitation of
the preformed polymer. The former has been less used because undesirable chemical
reactions may occur, which may inactivate the active substance, and also they require
an additional purification step to remove polymerization initiators and residual mono-
mers. Thus, we will focus on the latter which consist of the most commonly employed
methods. Many of the most widely used preformed polymers are biodegradable and
biocompatible and have been approved by the US Food and Drug Administration
(FDA), for instance, poly(D,L-lactide) (PLA), poly(Ɛ-caprolactone) (PCL), poly(D,
L-glycolide) (PLG), and poly(lactide-co-glycolide) (PLGA). Another polymer which
has been employed in this context is poly(hydroxybutyrate-co-hydroxyvalerate)
(PHBV), a promising biopolymer for use in drug delivery systems. Polymers that
are biocompatible and nonbiodegradable, for instance, poly-alkyl-cyanoacrylate, have
also been used for topical application. The natural biodegradable and biocompatible
polymers chitosan, cellulose, pectin, and alginate have also been widely employed in
this area.
An interesting kind of polymeric nanosystems are the environment-responsive
NPs which can off-load their active ingredient (antioxidant) in response to a specific
stimulus, such as temperature, pH, salt concentration, magnetic field, or a specific
molecule, and have also been in focus of research.

Natural and Biodegradable Polymers as Vehicles for Antioxidant

Active Ingredients in Skin Care

Nanocarriers for antioxidant active species can be prepared with natural or synthetic
polymers, preferably biodegradable and biocompatible, in order to minimize skin
toxicity and environmental pollution [11]. The most important biodegradable
polymers that can be used for skin care formulations are presented in Fig. 3 [12].
Aliphatic polyesters such as poly(lactic acid) (PLA) and poly(ε-caprolactone)
(PCL) can be obtained from biomass and petroleum, respectively. They have
attracted much attention for the development of cosmetic and biomedical products
due to their excellent properties, such as biodegradability, biocompatibility, and
mass producibility. Poly(D,L-lactic-co-glycolic acid) (PLGA) is a biodegradable
polyester which is usually synthesized by the ring-opening copolymerization of
 1480

Fig. 3 Types of polymers used as nanocarriers for antioxidant delivery for skin care products
J. S. Gonzalez et al.
65 Nanocarriers for Antioxidant Cosmetic Products 1481

lactide and glycolide. It presents many beneficial properties, including good bio-
compatibility, excellent safety profile, and tunable rate of biodegradation. PLGA has
been approved as an effective carrier for drug delivery and as scaffolds for tissue
engineering [13]. Poly(vinyl alcohol) (PVA) is a nontoxic, biocompatible, and
biodegradable hydrophilic polymer.
Moreover, there are many easily available and low-cost biopolymers, such as
polysaccharides, proteins, and derivatives that can be applied to nanovehiculize
antioxidant species in skin care products [14]. Chitin is an abundant natural polysac-
charide found in the exoskeleton of insects and crustaceans. It is a linear, poly-beta-
(1,4)-N-acetyl-d-glucosamine with an acetamide group at C2 in place of the cellulose’
hydroxyl group. This polymer appears in nature as a highly ordered crystalline/
amorphous structure made of micro/nanofibrils arranged in antiparallel strands [15].
Chitosan can be obtained from the deacetylation of chitin. Taking advance of the
extraordinary technological properties of this polymer, chitosan has been processed
into different formulations such as gels, nanofibrils, and micro- and nanoparticles, for
the delivery of active ingredients [16]. Besides, it has been reported that chitosan has
antioxidant capacity, and this property is higher for low molecular chitosan and
derivates [17]. Carboxymethyl chitosan is a derivate from chitosan that has a better
water solubility in a wider pH range. Gelatin is an inexpensive biopolymer that
consists in a mixture of proteins of high molecular weight. It contains some amino
acid sequences that can act as free radical scavengers [18]. Hyaluronic acid, also
known as hyaluronan, is an anionic polysaccharide that consists of N-acetyl-glucos-
amine and glucuronic acid. It is naturally found in extracellular tissue, cartilage, and
synovial fluid.

Antioxidants for Skin Care Cosmetic Products

Aging of skin is caused by intrinsic and extrinsic factors, as depicted in Fig. 4, which
may act either separately or by synergistically interacting with each other [19]. All
these factors are associated with oxidative stress and the generation reactive oxygen
species (ROS), including free radicals such as superoxide anion radicals, hydroxyl
radicals, and non-free radical species such as hydrogen peroxide and singlet oxygen.
Almost 80% of ROS production is caused by UV radiation, which is composed of
95–98% of UVA and 2–5% UVB [19]. Besides UV, it has also been reported that
visible and near-infrared light induce the production of free radicals in the skin [20].
The interaction of ROS with sensitive cell components and biomolecules, such as
DNA, lipids, and proteins, triggers irreversible damage, and the accumulation of the
altered species over time eventually produces skin aging and, in the worst cases, skin
diseases [21].
Antioxidants are molecules that can interact with free radicals and terminate a
chain reaction preventing them from damaging vital molecules. They are capable of
oxidizing before or instead of other molecules. There are several enzymatic and
nonenzymatic-specific antioxidative endogenous mechanisms present in the skin
that immediately neutralize the free radicals. The most active is considered the
1482 J. S. Gonzalez et al.

Fig. 4 Factors that cause skin aging and effects of oxidative stress

vitamin E homologue, known also as α-tocopherol (tocopherol). It is a membrane-

bound and lipid-soluble antioxidant [22]. Tocopherol acts primarily by two mecha-
nisms as an antioxidant [22]:

• Donating one of its electrons to free radicals and, so that, stabilizing them
• Slowing down the process of collagen breakdown

Supplementing skin with topical antioxidants may strengthen antioxidant capac-

ity and thus reduce ROS-induced skin damage. A good candidate for a topical
antioxidant should fulfill two conditions:
(i) The candidate should permeate through the stratum corneum.
(ii) It should reach the deeper cutaneous layers without significant leakage into
systemic circulation [23].
External antioxidants, either synthetic or natural, can be applied to the skin in
different topical cosmetic formulations in order to attenuate the oxidative stress, by
scavenging ROS and/or enhancing cellular antioxidant capacity [24]. In this regard,
antiaging skin care products to protect the skin against daily exposure to external
factors are highly demanded. In the cosmetic products, different active ingredients
can be combined to prevent skin aging. These include antioxidants, growth factors,
retinoids, sun filters, natural ingredients, and others [25].
Synthetic antioxidants, such as butylated hydroxyanisole, butylated hydroxytoluene,
and propyl gallate, are extensively used in the cosmetic market due to their low cost of
production. However, it has been reported that some synthetic antioxidants may have
potential health risks [26]. Therefore, in the last years, there has been an increasing
demand for cosmetic products containing natural and safer ingredients. Antioxidants
65 Nanocarriers for Antioxidant Cosmetic Products 1483

have two functions in cosmetic preparations: as the active ingredients and as pre-
servatives [27]. As active ingredients, natural antioxidants present many beneficial
properties, for example, antiaging, anti-inflammatory, anticarcinogenic, and antimicro-
bial. Besides, they can also act as preservative ingredients because they protect other
ingredients against oxidation.
Natural antioxidants can be obtained directly from organic sources, for example,
fruits, vegetables, grains, and meat. Natural antioxidants used in the cosmetic market
include a diverse variety of plant extracts and substances that have the capability of
mitigating oxidative processes. They include phytochemicals (flavonoids, catechins,
carotenoids) and vitamins (C, E), among other substances. Some of the most
important natural antioxidants in cosmetic formulations are enlisted and described
in Table 1.
Vitamins and coenzymes with antioxidant capability include vitamin C, K, E
(α-tocopherol), beta-carotene, coenzyme Q, nicotinamide, and lipoic acid. Vitamin
A or retinol is stored in the skin as retinyl ester or is converted into retinoic acid.
Retinoic acid is the biologically active retinoid; however, retinol is less irritating and
produces similar effects as retinoic acid. This quality makes retinol more favorable
for use in cosmetic products. Although trans-retinol is extensively used in the
cosmetic industry, there is insufficient information on its quantitative penetration
and distribution within the different layers of the skin [28]. Vitamin C, or ascorbic
acid, has been used in cosmetic products due to its biological activity as a non-
enzymatic soluble antioxidant and collagen promoter, as in the case of vitamin
E. However, vitamin C is unstable and can be easily oxidized under aerobic
conditions, the rate of which is increased with increasing heat of UV light levels
[29]. To be effective, it has to be functionally refined to enhance its stability and to
increase its cutaneous permeability. Coenzyme Q10 (CoQ10), also known as ubi-
quinone, is a lipophilic cellular antioxidant endogenously synthesized in humans. It
is a cofactor in the mitochondrial respiratory chain, and it is essential to transfer free
electrons from complexes I and II to complex III during oxidative phosphorylation
and ATP synthesis. CoQ10 acts as an antioxidant in the skin with tenfold higher
levels in the epidermis than in the dermis. It has been used in cosmetics due to its
ability to reduce photoaging in vivo, which could be attributed to the capacity to
increase production of basal membrane components, fibroblast proliferation, and
protection against oxidative damage [30]. Alpha lipoic acid (ALA) is a naturally
occurring fatty acid with potent antioxidant activity which exists in the mitochondria
of all kinds of prokaryotic and eukaryotic cells. ALA is known as a network
antioxidant due to its ability to regenerate/recycle itself as well as other antioxidants,
such as vitamins C and E, so that they can continue destroying free radicals
[31]. There is available data of formulations containing 5% ALA producing a
dramatic reduction in facial lines in cases associated with photoaging, and for this
reason, this compound gained the attention of cosmetologists and dermatologists.
Polyphenols are a group of chemical molecules characterized by the presence of
at least one aromatic ring substituted by one or more hydroxyl groups and are the
most abundant antioxidants present in fruits and vegetables. These natural
1484 J. S. Gonzalez et al.

Table 1 Most important natural antioxidants in cosmetic formulations

Antioxidant Antioxidant
substance Chemical structure Natural source action
α-Tocopherol Wheat germ, Via glutathione
sunflower pathway and
chain breaking
lipid
peroxidation
Vitamin E Olives and olive Neutralization
oil, palm oil, of singlet
pumpkin seeds, oxygen in the
sunflower seeds cell membrane;
and sunflower membrane
oil stabilization,
preventing lipid
peroxidation –
oxidation of
unsaturated
fatty acids
Vitamin C Apple, Extensive
bayberry, removal of free
broccoli, citrus radicals and
peel, garlic, repair of
peppermint, oxidized
spearmint vitamin E bound
to the cell
membrane
α-Lipoic acid Spinach, Repair of
broccoli, yams, endogenous
potatoes, yeast, antioxidant
tomatoes, systems, free
brussels sprouts, radical
carrots, beets, neutralizer
rice bran, red
meat
Quercetin Black pepper, Iron chelator,
onions, curly which maintains
kale, leeks, and protects the
broccoli, enzymatic
blueberry, red antioxidant
wine, and tea activity,
sunscreen
Resveratrol Red wine, grape Inhibition of
berry skins and UV-induced
seeds, peanuts, oxidative and
dried roots of mutagenic
plant action to DNA
Polygonum
cuspidatum
(continued)
65 Nanocarriers for Antioxidant Cosmetic Products 1485

Table 1 (continued)
Antioxidant Antioxidant
substance Chemical structure Natural source action
Anthocyanins Berry species Radical
scavenger,
inhibition of
low-density
lipoprotein
oxidation

Rosmarinic acid Peppermint, Free radical

rosemary, scavenger,
marjoram, sage, efficient
thyme antagonist of
lipid
peroxidation
Epigallocatechin Green tea, black Radical
gallate tea (Camellia scavenging,
sinensis) sunscreen

Rutin Buckwheat, ROS scavenger,

apricots, it increases
cherries, grapes, cellular
grapefruit, oxidative
plums, and defense
oranges systems, and it
inhibits
xanthine
oxidase which is
involved
in generating
ROS
Curcumin Curcuma longa Free radical
scavenger
quenching
superoxide
anions, singlet
oxygen, and
hydroxyl
radicals and
inhibiting lipid
peroxidation
(continued)
1486 J. S. Gonzalez et al.

Table 1 (continued)
Antioxidant Antioxidant
substance Chemical structure Natural source action
Lycopene Apricots, Great biological
grapefruit, action in the
guava, neutralization of
watermelon, singlet oxygen
papaya, and
carrots
Lutein Spinach, leaf Protects the
lettuce, peas, fibroblasts from
oranges, kale, UVA-induced
Zea mays, carrot oxidation,
prevents the
decrease of the
antioxidant
enzymes
catalase and
superoxide
dismutase

compounds are structurally diverse and vary from single molecules to highly
polymerized structures. They can be categorized as flavonoids and non-flavonoid
compounds. Moreover, flavonoids can be divided into several subfamilies according
to the degree of oxidation of their oxygenated heterocycle. The efficiency of poly-
phenols as antioxidant compounds greatly depends on their chemical structure [32].
Flavonoids are the most potent antioxidants present in plants. Quercetin has been
demonstrated as the flavonoid with the highest antioxidant activity, characterized by
multiple mechanisms. Moreover, the topical application of quercetin decreases skin
damage induced by exposure to UV radiation [33]. Resveratrol, another polyphenol
that is considered to be an important antioxidant from the family of stilbene [34],
shows geometric isomerism, but only trans-resveratrol presents several biological
effects, such as anticancer, antiaging, and antioxidant activities. It is an interesting
drug to be incorporated in dermal products. Resveratrol has poor oral bioavailability
and short half-life and is extensively metabolized in the body [35]. Curcumin is
another polyphenol commonly used in traditional medications and cosmetics. Stud-
ies have shown that curcumin is also poorly absorbed in the gastrointestinal tract
[36]. Rosmarinic acid is a natural antioxidant which belongs to the family of
hydroxycinnamic acids. It is an ester of 3,4-dihydroxyphenyllactic acid and caffeic
acid. Rutin, also called sophorin, rutoside, and quercetin-3-rutinoside, is a bioflavo-
noid with various important properties such as antioxidant, antibacterial, anti-
inflammatory, and antiallergic, among many other therapeutic qualities. However,
its use in cosmetic dermal products is restricted due to its low water solubility which
limits the penetration rate into the skin [18].
It is possible to design formulations with combinations of antioxidants resulting
in synergistic interactions through free radical transfer mechanisms. As an example,
65 Nanocarriers for Antioxidant Cosmetic Products 1487

the regeneration of oxidized α-tocopherol can be performed by ascorbic acid,

flavonoids, carotenoids, phospholipids, amino acids, and peptides [37].
The attributes of different polyphenols and other antioxidants make them excel-
lent candidates for skin treatment; however, in some cases, their poor water solubil-
ity makes their application difficult. On the other hand, there are good antioxidants
such as vitamin C used in cosmetics and dermatological preparations because of
their favorable effects on skin. However, vitamin C has a poor chemical stability in
heterogeneous systems and may undergo dismutation reactions [38].

Delivery Systems for Natural Antioxidants

One strategy to avoid the abovementioned limitations of natural antioxidants is to

nanovehiculize these active ingredients in the cosmetic formulations, resulting in
improved delivery, stability, bioavailability, and efficiency [5]. Skin interaction with
the nano-delivered system will depend on its size, composition, and elasticity.

Nanocarriers for Resveratrol Delivery

Resveratrol-loaded solid lipid nanoparticles (SLN) have been developed, and the
cellular uptake, transport, and internalization in keratinocytes have been studied. The
particles readily crossed the cell membrane in as little as 15 min, and, in comparison
with free resveratrol in solution, the SLN-encapsulated drug exhibited greater
intracellular delivery, solubility, and stability. SLN were able to protect resveratrol
from photodegradation, enhance its uptake in porcine ear skin, and improve its anti-
lipoperioxidative activity, appearing as a promising delivery system [39].
Liposomes and niosomes can increase the residence time of the drug in the stratum
corneum and epidermis, reducing the systemic absorption of the drug. The advantages
of niosomes over liposomes are their higher chemical stability and their low cost.
Niosomes loaded with resveratrol showed higher delivery of resveratrol in deeper
layers of the skin compared to liposomes; then they are better as carriers of resveratrol.
Niosomes have been prepared with different proportions of polyglyceryl-3 dioleate
(PLU) or glycerol monooleate (PEC) and cholesterol. In particular, niosomes com-
posed by 30 mg/mL of PEC and 30 mg/mL of cholesterol (PEC-niosomes 30:30)
allowed the highest amount of resveratrol to be accumulated in the stratum [40].
Another study has demonstrated the efficacy of that formulation [41].
Another possibility is the simultaneous encapsulation of resveratrol with
curcumin in lipid-core nanocapsules, as has been proposed recently. Skin penetration
studies showed an increased delivery of resveratrol into deeper skin layers upon
co-delivery in comparison to the encapsulation of one individual polyphenol. The
authors demonstrated that the interaction of curcumin with the lipid bilayers of the
stratum corneum facilitated the penetration of the less lipophilic resveratrol across
the skin barrier into the epidermis and dermis [42].
The co-encapsulation of resveratrol and curcumin in niosomal systems affected
the entrapment efficiency values, with respect to the formulations containing the
single antioxidant. The in vitro percutaneous permeation of the antioxidants
1488 J. S. Gonzalez et al.

appeared to be controlled and improved with respect to the corresponding free

solutions used as the control. Moreover, the antioxidant combinations resulted in a
promoted ability to reduce free radicals due to a synergic antioxidant action, and, for
this reason, these niosomal formulations showed potential in the transdermal deliv-
ery of antioxidant molecules and may be useful in the cosmeceutical field [43].

Nanocarriers for Vitamin Delivery

In order to avoid the oxidation of vitamin C, many derivatives have been obtained,
including various esters, such as ascorbyl palmitate (AP) and retinyl ascorbate, bis
(L-ascorbic acid-3,30 )phosphate, and L-ascorbic acid 2-phosphate. AP has been the
most popular ester, used as an antioxidant additive in cosmetic products because of
its improved stability and better skin penetration in comparison to vitamin C. The
deceleration in the AP degradation has been obtained by encapsulation of AP into
microemulsions, bilayer vesicles, polymeric nanoparticles, and solid lipid nano-
particles [44]. To increase the stability of AP, it is possible to make a nanocarrier
with an antioxidative property, attaching the natural dietary antioxidant curcumin
onto PVA. The obtained curcumin-grafted PVA polymer (CUR-PVA) was then
fabricated into a nanocarrier, and AP was encapsulated into the CUR-PVA nano-
carrier. The stability of the encapsulated AP was evaluated, and it demonstrated
better stability compared to free AP [45].
Chitin nanofibrils/bio-lignin nonwoven tissues were electrospun with different
antioxidants along with other active ingredients: sodium ascorbyl phosphate (vita-
min C derived), melatonin, beta-glucan, and nicotinamide. The beauty masks were
controlled for their safeness and effectiveness both in vitro on keratinocyte and
fibroblast cultures and in vivo on 30 volunteer women showing signs of premature
skin aging (photoaging) for a period of 30 days. Results showed that the beauty
masks were not only effective on the aged and sensitive skin but also very safe and
stable for a long period of time because they were free of water [46].
Synthetically available tocopherol is a highly viscous skin irritant and light-
sensitive liquid. This property makes it difficult to incorporate tocopherol in topical/
cosmetic formulations. Therefore, tocopherol acetate, a prodrug ester, is used in most
of the antiaging formulations available on the market [47]. Another option is to
formulate tocopherol into nanocarriers to produce a nonirritant, stable, and cosmet-
ically appealing aqueous formulation. The results confirmed that nanostructured
lipid carriers (NLC) induced a higher release of tocopherol than nanoemulsions;
thus, NLC are promising nanocarriers for cosmetic delivery [22].
Retinol-encapsulated chitosan nanoparticles (100 nm) were produced using a
water-soluble chitosan (18 kDa, DA 0.04) [48]. Retinol was encapsulated in zein
nanoparticles (300 nm) that were coated with chitosan. Chitosan Mw affected the
particle size and polydispersity which increased as the Mw increased. On the
contrary, a slight reduction of encapsulation efficiency was observed when Mw
increased. This system improves retinol photostability [49]. In another example,
retinol was encapsulated into succinic-chitosan nanoparticles by means of retinol
complexation with the chitosan derivatives through H-bonding. The antioxidant
activity of the encapsulated retinol was significantly greater than pure retinol [50].
65 Nanocarriers for Antioxidant Cosmetic Products 1489

Nanocarriers for Quercetin Delivery

The skin protective activity of quercetin is insufficient due to its poor percutaneous
penetration that limits the amount of the compound reaching the site of action in the
epidermis [51]. Different formulations of quercetin based on microemulsions, encap-
sulation in lipid nanoparticles, and silica nanoparticles have been developed in order
to enhance its penetration in the skin. Results of this study demonstrated that the
emulsion containing silica nanoparticles was the only vehicle which could signifi-
cantly enhance the in vivo penetration of quercetin into the human stratum corneum,
with the advantage that the silica particles were confined in the upper layers, limiting
the potential toxicological risks [52]. This study was performed in humans in real
conditions, considering the reported differences between human and animal skin and
the alterations observed in excised human skin when the studies are performed
in vitro [53].
Nanostructured lipid carriers of quercetin have been developed using a solvent
(chloroform/acetone)-based emulsification technique and evaluated for topical
delivery [54]. One of the major disadvantages of a manufacturing method involv-
ing the use of organic solvents can be toxicological issues arising from solvent
residues. For this reason, a solvent-free, solid lipid-based nanosystem of querce-
tin using a probe ultrasonication process has been developed. This process
showed, using in vitro permeation studies with full-thickness human skin, higher
amounts of quercetin to be localized within the skin compared to a control
formulation with particles in the micrometer range. Such an accumulation of
quercetin in the skin is highly desirable since the efficacy of quercetin in delaying
ultraviolet radiation-mediated cell damage and eventual necrosis mainly occurs in
the epidermis [55].

Nanocarriers for Coenzyme Q10 Delivery

The difficulty of CoQ10 in reaching the deeper layers of the skin determines its
inclusion in different carriers. In this sense, liposomes, lipid nanoparticles, solid
nanoparticles, and nanostructured lipid carriers (NLC) are more often used for this
purpose [56]. Among them, nanostructured lipid carriers have been used success-
fully for dermal delivery of CoQ10 due to its highly lipophilic character [57], but the
possible interference with intracellular biochemical processes should be investi-
gated. It has been recently demonstrated that ultrasmall lipid nanoparticles promote
the penetration of coenzyme Q10. In this publication, the cell viability and the
efficiency of these nanocarriers were examined in HaCaT cells [58].
A recent study demonstrated that nanostructured lipid carriers induced some
subtle cytotoxic effects and they did alter the redox state level on human dermal
fibroblasts under normal and oxidative conditions, but genotoxicity was not
observed. The use of reduced CoQ10 decreased these effects because CoQ10 is a
highly active antioxidant and maintains mitochondrial functionality. Then the use of
antioxidants could be considered when preparing NLC for cosmetic delivery pur-
poses in order to prevent undesirable effects on cells by the carrier systems used. The
geno- and cytotoxicity should be evaluated, especially under conditions which
closely mimic their normal usage [59].
1490 J. S. Gonzalez et al.

PLGA nanospheres containing CoQ10 showing increased stability with slow

release and high drug loading efficiency have been developed for cosmetic applica-
tion. 200 nm nanospheres with a loading efficiency of over 90% were obtained at
antioxidant concentrations of 0.1 or 0.2%. The authors reported that after iontophore-
sis, nanospheres were kept onto the horny layer of the skin, even after washing [60].
The combination of CoQ10 and vitamin E plays an important role in many
biological systems. Pegoraro et al. prepared semisolid formulations consisting of
PCL-based nanocapsule suspensions containing the association of CoQ10 and
vitamin E acetate by adding gellan gum to the suspensions [61]. The formulations
presented drug contents above 95% and evidenced increased nonprotein thiol levels
as well as decreased lipid peroxidation induced by UVB radiation. Moreover, the
UVB irradiation-induced effects on the skin were reduced. In another study,
PCL-based nanocapsules containing the association of the coenzyme Q10 and
vitamin E acetate were developed, and three concentrations of vitamin E acetate
were evaluated (1%, 2%, or 3%) [62]. Nanocapsules were able to protect coenzyme
Q10 from photodegradation, and this protection was achieved with higher vitamin E
acetate concentrations. The authors attributed this result to the role of this oil as
coenzyme Q10 photostabilizer.

Nanocarriers for Other Antioxidants

Upon exposure to sunlight, free curcumin degrades rapidly, reducing its antioxidant
capacity. To avoid this effect, one strategy is to encapsulate it into biodegradable,
safe, inexpensive, and commercially available polymeric nanospheres, which offer
protection from photodegradation and retains its antioxidant capacity [36]. Curcumin
has also been incorporated in biodegradable, safe, and inexpensive nanospheres
based on ethyl cellulose and/or methyl cellulose, with a high loading and high
encapsulation efficiency. The authors reported that application on pig ear skin
evidenced a better radical scavenging activity by nanoencapsulated curcumin than
pure curcumin in lotion. The encapsulation of curcumin avoided its photo-
degradation and, therefore, helped to retain its antioxidant capacity [36].
Alpha lipoic acid, ALA, has been formulated as cubosomes, which are discrete,
submicron, nanostructured particles of bicontinuous cubic liquid crystalline phase
which are able to incorporate large amounts of drugs or actives [63]. A recent study
has demonstrated that the formulation of ALA in cubosome dispersion has excellent
results in reducing facial lines with almost complete resolution of fine lines in the
periorbital region and upper lip area and an overall improvement in skin color and
texture in most volunteers [64].
De Oliveira reported the preparation of rutin-loaded gelatin nanoparticles (GNPs)
associated with ethylhexyl dimethyl PABA (EHDP), ethylhexyl methoxycinnamate
(EHMC), and methoxydibenzoylmethane (BMDBM) in sunscreen formulations. The
obtained GNPs evidenced enhanced antioxidant activity by 74% compared with free-
rutin solution. Another important finding was that the incorporation of rutin in the
formulation upgraded the sun protection factor (SPF) by 48% [18].
Astaxanthin is a xanthophyll carotenoid with high antioxidant activity and
scavenging oxygen free radicals, but its application is limited because of poor
65 Nanocarriers for Antioxidant Cosmetic Products 1491

water solubility and low bioavailability. Astaxanthin has been loaded in PLGA
nanoparticles by using the emulsion solvent evaporation technique [65]. The results
obtained from cytotoxicity assay, ROS scavenging, and mitochondrial membrane
potential assay evidenced the advantages of nanoparticles in improving anti-wrinkle
and antioxidation effects of astaxanthin against the free antioxidant.
Chitin nanofibril-hyaluronan nanoparticles (CN-HA) have the ability of easily
loading active ingredients, facilitating penetration through the skin layers, and
increasing their effectiveness and safety as an antiaging agent. CN-HA nanoparticles
were evaluated in vitro measuring their antioxidant capacity, anti-collagenase activ-
ity, and metalloproteinase and pro-inflammatory release. The efficacy was also
shown in vivo by a double-blind vehicle-controlled study for 60 days on
60 women affected by photoaging [15].
Polyphenols with a strong antioxidant activity have also been encapsulated in
nanoparticles and microspheres produced by ionic gelation and by spray-drying,
respectively [66].

Commercial Skin Care Products with Antioxidant Properties

As it has been shown above, there are many ways to nanovehiculize antioxidant
agents for antiage skin care. Nevertheless, only a few types could be commercially
available. Table 2 presents a list of products in the nanocosmetic market, with
antiaging and antioxidant properties containing nanovehiculized active ingredients.
Regarding safety issues, the application of nanomaterials in personal care needs
attention in terms of their assessment and evaluation because they are in direct
contact with the skin [67]. Cosmetic industry is turning into the biggest growth
area. The importance of developing an ever effective formulation relies on the
development of cutting-edge advances such as nanotechnology.
Frequently, it is not easy to identify products containing nanomaterials, because
the manufacturer can choose to declare or not the presence of nanosystems. Now-
adays there is a growing concern of national and international regulatory agencies to
promote the declaration of nanosystems (or nanomaterials) in cosmetic products by
suppliers and manufacturers. However, each country has its own definition of
nanotechnology and legislation [68]. In this way, the World Health Organization
(WHO) and Cosmetics Harmonization and International Cooperation (CHIC) are the
two international bodies which are also concerned about the safety and efficacy of
cosmetic products, and it is expected that some guidelines would be devised for
regulating the nanocosmetics by these bodies.

Conclusions and Final Remarks

As oxidative stress is regarded as one of the main mechanisms involved in skin

aging, natural and synthetic compounds with antioxidant activity could be useful for
preventing and treating skin aging. However, most compounds with proven
1492 J. S. Gonzalez et al.

Table 2 Examples of commercial nanotechnological products used for the skin

Commercial Delivery
product Supplier Active principle system Action
Revitalift L’Oréal Pro-retinol A Nanosome Anti-wrinkle
https://www.
lorealparis.com
Bio- Lancôme Gamma Nanocapsules Antiaging,
performance https://www. linolenic acid wrinkle
Crème lancome.com reduction
Absolue
Rénergie Lancôme Microfilters Nanoparticles Antiaging
Microlift https://www. (silica and moisturizer
lancome.com protein)
Rovisome Rovi Cosmetics Ascorbyl Liposome Antiaging,
ACE Plus International GmbH palmitate, wrinkle
www. tocopherol, reduction
ROVIcosmetics.de retinol
Lipobelle Mibelle Genistein Liposome Antioxidant
Soyaglycone Biochemistry
https://
mibellebiochemistry.
com/
Cutanova Dr. Rimpler GmbH Coenzyme Q10 Nanostructured Revitalizing,
Nano Repair https://www.rimpler. lipid carriers antiaging
Q10 Cream de/
Collagen Cosmetochem Vitamin C Nanocapsules Stimulation of
Stimulator https://www. collagen
Factor MAP ® cosmeticsdesign. production
com/
Nano Gold® Neiman Marcus 24-Karat gold Nanoparticles Antiaging,
Energizing https://www. (natural protein)
Cream neimanmarcus.com/
Platinum DHC Skincare Botanicals and Nanoparticles Anti-wrinkles,
Silver https://www. coenzyme Q10 antiaging
Nanocolloid ® dhccare.com/
line

antioxidant activity do not show suitable properties to achieve adequate concentra-

tions in the skin layers where they should exert their action.
A rationale design of skin delivery systems based on nanocarriers could help
these compounds to be delivered in a more efficient manner and could represent an
undeniable benefit for many antiaging skin care products.

Acknowledgments The authors acknowledge the financial support of CONICET (Consejo

Nacional de Investigaciones Científicas y Técnicas de Argentina), UNMdP (Universidad Nacional
de Mar del Plata), and ANPCyT (Agencia Nacional de Promoción de la Investigación, el Desarrollo
Tecnológico y la Innovación).
65 Nanocarriers for Antioxidant Cosmetic Products 1493

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 Part XVII
Conclusion
Consumer Nanoproducts in Antimicrobial
Application 66
Sujith Ravi and Ishwarya R. Kishore

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1500
Metallic Nanoproducts: Method of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1501
Laser Ablation in Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1502
Wet Chemical Method for Nanoparticle Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1502
Mechanism of Nanoparticles as an Antimicrobial Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1503
Entering the Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1503
Reactive Oxidative Species(ROS) Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1503
Protein Inactivation and DNA Destruction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1504
Detection Methods of NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1504
Viable Plate Count Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1504
Disk Diffusion Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1504
Estimating Bacterial Numbers by Indirect Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1504
Different Types of NPs and Their Action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1505
Silver Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1505
Zinc Oxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1505
Titanium Dioxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1505
Copper Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1506
Gold Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1506
Other Metallic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1506
Effects of NPs on Microbial Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1507
Overcoming the Existing Antibiotic Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1507
Carriers of Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1507
Applications of NPs in Various Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509
Antibacterial Coating of Implantable Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509
Wound Dressings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509

S. Ravi (*) · I. R. Kishore

Faculty of Medicine and Health Sciences, Department of Microbiology, SRM Medical College
Hospital and Research Centre, SRM Institute of Science and Technology, Chengalpet, Tamilnadu,
India
e-mail: [email protected]

© Springer Nature Singapore Pte Ltd. 2022 1499

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6_82
1500 S. Ravi and I. R. Kishore

Bone Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1510

Dental Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1510
Future Perspective of NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511

Abstract
Nanoproducts (NPs) have been materialized as a new option to conquer the big
wall of bacterial resistance to different drugs. Application of NPs in bio-medical
area depends on different exclusive properties which are optical, physical, chem-
ical, thermal, electrical in nature. Few of these properties help it to create a
significant difference in medical field and in other areas.
NPs are materials in which the basic unit in 3-D space falls within the
nanometer scale range (1–100 nm) or at least one dimension is within this
range. NPs have revealed to have wide-spectrum antimicrobial action in oppo-
sition to Gram positive and Gram negative bacteria, mycobacteria, and fungi.
The antibacterial action of NPs vary among the different types of nanoproducts.
The physical structure of the nanoproduct itself may have intrinsic antibacterial
properties due to its membrane damaging abrasiveness. Enhanced release of
antibacterial metal ions from the surface of NPs is another means which has
been recommended. The low surface-to-volume ratio of the NPs can augment
the antimicrobial action allowing superior contact of the nanomaterial with the
neighboring environment. Chemistry, product size, product shape, and the
inherent electric charges are among the most significant factors affecting anti-
bacterial action. Heavy metals such as silver (Ag), copper (Cu), gold (Au),
titanium (Ti), and zinc (Zn) have been known to have antimicrobial activity for
centuries.

Keywords
Nanoproducts · Antimicrobial Nanoparticle · Reactive Oxidative Species ·
Carrier antibiotics · Antimicrobial Nanoparticle coated Implants

Introduction

Contamination with microbes is still a major problem in the field of infections which
contributes substantially towards the morbidity and mortality around the world.
Reports suggested that more than half of the population in developing countries is
infected and death occurs to more than three million people yearly. Regardless of
amazing progress in the field of diagnosis and treatment, the infection with microbes
persist to influence biomedical and health care segment primarily owed to the
appearance of resistance in opposition to a number of accessible antimicrobials.
Several factors including human lifestyle changes, industrialization, civil wars, and
66 Consumer Nanoproducts in Antimicrobial Application 1501

microbe gene modification have been documented for their association in appear-
ance or reemergence of pathogenic organisms. Keeping these factors in mind, there
is a sudden need to find an alternative way to treat the pathogens or to induce a
change in current way of treatment. Other than causing chaos in the health care field,
the microbial particle have been affecting the fields of food production, textiles,
machinery, and the field of agriculture.
Nanoproducts (NPs) have materialize as a new option to conquer the big wall of
bacterial resistance to different drugs. Application of NPs in biomedical area
depends on different exclusive properties which are optical, physical, chemical,
thermal, electrical in nature. Few of these properties helps it to create a significant
difference in medical field and in other areas.
NPs are materials in which the basic unit in three-dimensional (3D) space falls
within the nanometer scale range (1–100 nm) or at least one dimension is within this
range. NPs have revealed to have wide spectrum antimicrobial action in opposition
to Gram positive and Gram negative bacteria, mycobacteria, and fungi. The anti-
bacterial action of NPs vary among the different types of nanoproducts. The physical
structure of the nanoproduct itself may have intrinsic antibacterial properties due to
its membrane damaging abrasiveness. Enhanced release of antibacterial metal ions
from the surface of NPs is another means which has been recommended. The low
surface to volume ratio of the NPs can augment the antimicrobial action allowing
superior contact of the nanomaterial with the neighboring environment. Chemistry,
product size, product shape, and the inherent electric charges are among the most
significant factors affecting antibacterial action. Heavy metals such as silver (Ag),
copper (Cu), gold (Au), titanium (Ti), and zinc (Zn) have been known to have
antimicrobial activity for centuries.

Metallic Nanoproducts: Method of Synthesis

Nanoproducts are fabricated in three ways:

(i) Physical methods

(ii) Chemical methods
(iii) Biological methods

(i) In physical methods, the metallic aggregates are subdivided mechanically by

Laser ablation, vapor deposition, wire discharge, and mechanical milling.
(ii) In chemical methods, the metallic atoms produce nucleation and the growth
occurs.
(iii) In biological methods, the metallic NPs are generally formed by reducing
metallic salts with any plant serum.
1502 S. Ravi and I. R. Kishore

Because of broad distribution of particle size, the physical techniques gain

dispersions. For controlled sized particles, chemical techniques such as salt reduc-
tion are convenient methods.

Laser Ablation in Liquid

Laser-ablated solid metal targets are one of the advance and toxic-free techniques for
synthesis of nanoparticles. In this method, a bulk target is placed in any liquid
environment and ablated by a pulsed laser. A dense plume of vapor and atomic
clusters is released into the liquid environment from ablated portion of the target.
And, thus, nanoparticles are formed.
This method produces nanoparticles which are small, surfactant free, and mono-
disperse having many advantages over chemical reduction technique. In chemical
methods, toxic reducing agents are used which have a negative role in the formation
of nanoparticles. The size, dispersion, and composition of nanoparticles formed by
LAL technique dispersed in liquid medium can be well controlled by adjusting the
target, liquid type, and laser parameters like wavelength, fluence, and pulse duration.

Wet Chemical Method for Nanoparticle Production

Wet chemistry is the second most common method used to fabricate metallic NPs. In
this technique also the NPs are produced with controlled morphology composition
and crystallinity. When compared to the LAL technique here, chemical reduction of
salts produces comparatively larger NPs. In wet chemical method, the NPs formed
have undergone the following processes:

(a) Nucleation
The main process of synthesis starts with the process of nucleation in which a
new phase particle called “Seed” has been formed in a previous system of single
phase. Further growth of NPs is done by additional attachment of metal atoms to
this seed from solution. The shape and growth of NPs depend on the varying
condition of the reaction.
(b) Seeding process
During the process of salt reduction, the metallic atom concentration
increases with the decomposition of precursors till a supersaturated state and
form has been reached. The atoms begin to agglomerate. A nuclei of precise
dimension called “Seed” at this stage which further grow into crystallite. Typ-
ically, metallic atoms which are precursors widely used as reducing agents and
capping agents are used to stabilize metallic seeds by preventing agglomeration
and maintaining the nucleic size. To get the NPs of controlled size and shape,
seed-mediated nuclei growth process act as the most efficient and effective
processes because of the low activation energy requirement for metallic reduc-
tion process on to the preformed seed.
66 Consumer Nanoproducts in Antimicrobial Application 1503

(c) Nanoparticle formation:

The nanoparticles are formed by the controlled competition of surface
energy enhancement and a bulk energy diminution. Dissolution occurs on
enhancement in the surface energy, while the process of growth is en-
hanced by decrease in the bulk energy. Continued addition of atoms
allows the seed to increase in size in the uniform manner. Thus, solutions of
suitable metallic precursor, reducing agent, and capping agent are the basic
necessity for the formation of metallic nanoparticles via chemical reduction
methods.

Mechanism of Nanoparticles as an Antimicrobial Agent

For several centuries, metal and metal salts are well known for antimicrobial
mechanism as silver pots and copper mugs were used for drinking waters.
The toxic effect of bacteria to the metallic nanoparticles is still under debate, but
three main mechanisms are supported which include, firstly, the formation of
reactive oxygen species; secondly; ions are released; and finally, interaction of
NPs with the cell membrane. Metallic nanoparticles as compared to their salts
have enhanced potential to combat bacterial infections. Mostly, the antibacterial
mechanism is influenced by the size of NPs.

Entering the Cell

The metallic ions of nanometer range attaching to the cell via transmembrane
protein is the first step of antibacterial mechanism. After attaching to the
bacterial cells, it produces structural damage in the cell membranes and block
the transport channels. The whole process depends on the size. Larger NPs
have a higher absolute surface area permitting for better adhesion property
while small NPs are more efficient. Then NPs may be internalized, produce
ionization within the cell and damage the intracellular structures resulting in
cell death.

Reactive Oxidative Species(ROS) Generation

The metal NPs producing reactive oxidative species plays a large role in the
antibacterial effectiveness. ROS consist of short-lived oxidants such as superoxide
radicals, hydrogen peroxide, hydroxyl radicals, and singlet oxygen. Because of the
high reactivity of these species, ROS can cause damage to the peptidoglycan and cell
membranes, DNA, messenger RNA, ribosomes, and proteins. ROS also play a key
role in inhibiting transcription, translation, enzymatic activity, and electron transport
chain. In some metal oxide NPs, the main mechanism of toxicity rely on the
generation of ROS.
1504 S. Ravi and I. R. Kishore

Protein Inactivation and DNA Destruction

Metal atoms have great affinity to bind with the thiol group of enzymes and finally
deactivate the function of enzymes. It is also suggested that metal ions attach
themselves within the pyrimidine and purine base pairs disturbing the bonding of
hydrogen between two strands of antiparallel and destruct the molecule of DNA.
Although further investigation is needed in this, but it is true that metal ions have
tendency to attach with DNA, once they go into the cell.

Detection Methods of NPs

The microbial growth measurement are detected by various direct and indirect
methods. In direct method, the growth of microbes are evaluated by viable technique
of plate count, serial dilution, and disk diffusion method, while indirect methods are
usually analyzed by turbidity, dry weight, and by metallic activity. Brief description
of various methods is as follows.

Viable Plate Count Method

Petri dishes are usually used in each reading in plate count techniques. One agar plate
is prepared with inoculum and other agar plates with inoculum and nanoparticle
solutions are spread on it with the help of sterile spreader. Both the plates are
incubated for 24 h at 37  C and colonies are counted on each plate. Then, the
inhibition percentage growth with each reading is calculated.

Disk Diffusion Method

The culture of bacteria which is prepared is mixed in nutrient broth to form liquid
culture. Then sterile nutrient agar solution is prepared and put into dishes and waited
to be solidified. After that, holes are generated in the nutrient agar plate with the help
of cork bores. Bacterial culture is spread on the agar with sterile cotton bud. Holes
are filled with solution of metallic NPs and stabilized. Then the plates are incubated
for 24 h at 37  C. Then, the zones of inhibition are observed on the next day and
calculated with standard error.

Estimating Bacterial Numbers by Indirect Methods

Indirect methods are usually time-consuming methods and a large number of

samples is prepared at a time. The turbidity is analyzed by spectrophotometer
which measures the quantity of light that transmits through a bacterial cell
66 Consumer Nanoproducts in Antimicrobial Application 1505

suspension. As more transmission occurs through suspension, it means

that turbidity decreases indicating the reduction in bacterial cells and vice versa.

Different Types of NPs and Their Action

NPs are generally divided into three divisions, which are categorized into subdivisions.
The inorganic NPs comprise of nanosheets (a 2D nanostructure whose width lies in the
nano range), metal and metal oxide nanoparticle (particles whose width is usually
<100 nm), nanoshells (naturally, spherical nanoparticles with a dielectric core inside a
thin metallic shell), nanowires (wire revealing diameter/thickness of few nanometers),
nanocrystals (material collected of atoms united in single- or polycrystalline collection
with its one dimension usually <100 nm), quantum dots (3D nanocrystals composed of
semiconducting material with their diameter lying in 2–10 nm range), and carbon
nanotubes (cylindrical carbon nanostructures with unusual properties). Organic NPs
include dendrimers (3D, hyperbranched, tree-like polymeric nanostructures), liposomes
(nanovesicles obtained from hydration of dry phospholipids), and nano/microcapsules
(material composed of natural or synthetic polymer shells in order to surround different
active materials, such as drugs, catalysts, biomolecules, etc. as its core).

Silver Nanoparticles

Silver NPs (Ag NPs) are widely used for biosynthesis and has shown to slow down
the growth of Gram negative and Gram positive bacteria as well as yeasts. Silver NPs
function by altering the membrane permeability, interacting with host proteins, and
interfering with cell division and replication of bacterial cells.

Zinc Oxide Nanoparticles

Zinc oxide (ZnO NPs) have marked antimicrobial action due to their high surface to
volume ratio and surface abrasiveness of the nanostructures. ZnO NPs can slow
down the expansion of both Gram positive and Gram negative bacteria. The anti-
microbial properties of ZnO NPs are credited to the intracellular amassing of ZnO
NPs which effect in harm to the cell wall and disturbance of DNA replication. Inside
the cells, the NPs release metal ions, generate reactive oxygen species (ROS), and
accumulate in the bacterial membrane.

Titanium Dioxide Nanoparticles

The photocatalytic action of titanium (TiO2 NPs) and the quantum size effects
make it ideal in antimicrobial applications together with air purification, water
purification, and antimicrobial coatings on biomedical devices. TiO2 NPs can
1506 S. Ravi and I. R. Kishore

wipe out microorganisms upon illumination of light due to its photocatalytic

properties. Reactive oxygen species produced by TiO2 NPs can oxidize the
machinery of the cell membrane leading to destruction. Antimicrobial action of
TiO2 shown in the lack of light point out that apart from the photocatalytic action,
direct contact and adsorption of cells onto TiO2 NPs may lead to breech in
membrane integrity.

Copper Nanoparticles

Copper (Cu NPs) along with other agglomeration produces significant antimicrobial
action. The defect of it is decreasing effect on exposure to air. The Cu NPs causes
toxicity to membrane and thus inducing its antibacterial action.

Gold Nanoparticles

Gold nanoparticles (Au NPs) also show antimicrobial action and even better effi-
ciency along with agglomeration of chemicals. Gold NPs irradiated with laser energy
discharge heat due to the excitation and oscillation of electrons, making them helpful
as anticancer or antibacterial agents.

Other Metallic Nanoparticles

Silica, calcium, magnesium, and aluminum also function as significant NPs through
their significant action on various cell functions like adhesion, differentiation, and
replication. Also the release of superoxide on the surface and increased hydration by
these NPs cause the destruction of bacteria.
Polymeric NPs kill microorganisms either by discharging antibiotics, antimicro-
bial peptides and agents, or By contact killing on cationic surfaces such as quater-
nary ammonium compounds, alkyl pyridiniums, or quaternary phosphonium. The
high levels of positive charge are competent of presenting antimicrobial properties
irrespective of hydrophobic chain length, may be by an ion switch mechanism amid
the bacterial membrane and the charged surface.
Poly-E-lysine is a cationic homopeptide of L-lysine which is effective against
Gram-positive and Gram-negative bacteria. Quaternary ammonium compounds
such as benzalkonium chloride, stearalkonium chloride, and cetrimonium chloride
are renowned disinfectants. Their antimicrobial action is a function of the N-alkyl
chain length and hence lipophilicity. Cationic quaternary polyelectrolytes
employed as antimicrobial polymers are acrylic or methacrylic derivatives, and a
large number of them are synthesized from commercial methacrylic monomers
such as 2-(dimethylamino)ethyl methacrylate.
66 Consumer Nanoproducts in Antimicrobial Application 1507

Effects of NPs on Microbial Resistance

Nanoparticles are an upcoming effective therapeutic method to combat microbial

resistance and multidrug-resistant mutants. They give a highly promising positive
result where the regular antibiotics frequently fail. Nanoparticles can complement
and support as an antimicrobial agent without forming resistance when compared to
traditional antibiotics in following ways.

(i) It can overcome the existing antibiotic resistance mechanism by the disruption
of bacterial cell membrane and by the hindrance of biofilm formation.
(ii) Combatting microbes using multiple mechanisms simultaneously.
(iii) By acting as a good carrier of antibiotics.

Overcoming the Existing Antibiotic Resistance

In contrast to traditional antibiotics, NPs can overcome the existing antibiotic

resistance mechanism by its characteristic dimension <100 nm. Their unique
small size results in novel properties, Such as interaction with cells is highly
influenced because of larger surface area to mass ratio and versatile and control-
lable application.
The further probability of bacterial drug resistance is difficult because of the
conserved nature of a bacteria where bacterial cell membrane change through only a
few genetic mutations.
In addition to the bacterial cell membrane damage, hindrance of biofilm forma-
tion is an important mechanism, as biofilm plays a crucial role in the development of
bacterial resistance. The bacterial biofilms are formed in such a way that they
provide shelter or protection to the microorganisms, helping them to escape from
most antibiotics. In addition, bacterial biofilms also serve as a breeding ground for
frequent resistance mutations and the exchange and alteration of these mutations
among different bacterial cells.
Studies have shown that many NPs can prevent or overcome biofilm formation.
Prevention of biofilm formation is greatly achieved by smaller size and higher
surface area to mass ratio. Even the particle shape of NPs also has a marked effect
on distribution of biofilm. Rod-like shape nanoparticles are more effective than
spherical shape nanoparticles.

Carriers of Antibiotics

As mentioned earlier, NPs can also act as an “Medium and Carrier of antibiotics.”
However, the mechanism of NPs based drug delivery are different from others.
Several types of nanoparticles are currently used for drug delivery.
1508 S. Ravi and I. R. Kishore

(i) Liposomal NPs

(ii) Solid lipid NPs
(iii) Polymer-based NPs
(iv) Polymer micelles
(v) Inorganic nanodrug carriers
(vi) Terpenoid-based NPs
(vii) Dendrimer NPs

NPs as a carrier for the delivery of antibiotics has more advantage over conven-
tional delivery systems. They are as follows.
Size: Verry small and controllable size of NPs is suitable for conducting antimi-
crobial operations and combating intracellular bacteria.
The nanoparticles are so small that are easily phagocytosed by host phagocytes.
Thus, an alternative treatment using drug-loaded NPs serve as intermediaries to
overcome this limitation. Moreover, the structures of many types of NPs are suitable
for carrying drugs and the flexibility of NPs to enter host cells via endocytosis makes
it possible for most of the drug to be released intracellularly.
Precision and security: NP carrier can help to target antibiotics to an infection site
and thereby minimizing side effects.
Without a carrier, it is difficult to deliver high-dose drug absorption at the target
site while preventing adverse effects. But, NP-based antibacterial drug delivery
system can prevent the side effects by delivering the drug only to its affected site.
This method of targeted NP-based drug delivery consists of passive or active
targeting. Passive targeting is achieved by increased time of retention at the infection
site, and active targeting is achieved through surface modification of NPs. This allows
the NP-based drug delivery system to selectively recognize specific ligands on the
cells at the infection site.
Target therapy is achieved by an effective and crucial strategy where the first
target is generally macrophages. Because, at most of the infection site, the bacteria
are targeted and engulfed by macrophages. Therefore, the NPs are then released in
the macrophages in which bacteria are present.
Nanoproducts are also effective in the field of pathogenic control, as a beckon to
identify the change, vaccine design, and treatment. In diabetes mellitus, NPs have
been used for glucose monitoring and closed loop insulin delivery. NPs have shown
to improve glucose sensor technology which makes an instantaneous and major
impact on diabetics, as better sensing will direct to more precise insulin dosing and
diabetes treatment. NPs advanced methods have facilitated extra vigorous insulin
delivery methods that can sense changes in levels of glucose and involuntarily adjust
the rate of insulin discharge to uphold normal glucose level.
NPs have been modulated such a way to regulate autoimmune signals by mod-
ifying antigen-presenting cells and thus can be useful modality of management in
autoimmune diseases as well. In oncology treatment, NPs act as delivery of drug,
thereby improving stability, delay in the degradation, and targeted release to the
affected area. Polymeric NPs, which include nanospheres and nanocapsules,
are concrete carriers ranging from 10 to 1000 nm in diameter made of natural or
66 Consumer Nanoproducts in Antimicrobial Application 1509

artificial polymers which are usually biodegradable and in which therapeutic drugs
can be adsorbed, dissolved, entrapped, encapsulated, or covalently connected.

Applications of NPs in Various Fields

Antibacterial Coating of Implantable Devices

Antibacterial coating on human implantable devices are of two types.

(i) Fully implantable devices

(ii) Partially implantable devices

Fully implantable devices usually consist of heart valves or dental implants. In

case of cardiovascular apparatus, the antimicrobial coating particularly must have
appropriate blood compatibility to prevent thrombosis. The application of a titanium
oxide coating on implants is based on pore morphology, with calcium, silicon,
phosphorous, and silver particle enrichment. This coating inhibits the growth and
adhesion of certain bacteria such as Streptococcus epidermis and Escherichia coli
thus preventing the occurrence of inflammation around the implants. Nanocoating
can also improve the adhesion and proliferation of osteoblast cell lines.
The other type of device is partially implantable devices such as catheters,
neurosurgical catheters, intravenous catheters which are having high risk of bacterial
colonization and more prone for infection in clinical applications. In specific,
nanoparticles can be used as antibacterial coating to decrease the growth of catheter
biofilms. Sustained release of NPs over 6 days can also be achieved which signif-
icantly reduce the growth of Staphylococcus aureus in neurosurgical catheters and
helps in preventing infection and complications.

Wound Dressings

Skin is considered as the protective barrier of the body naturally. The main function of
that is to protect the body from pathogens and foreign bodies and also to maintain the
dynamic equilibrium of water and electrolytes. There are several factors which
damages the skin such as trauma, burns, and certain types of chronic skin ulcer. In
that case, a special cover called dressing is generally used in the process of wound
healing which helps to rebuild the barrier function of skin, to support wound healing,
and to reduce the risk of wound infection. An ideal dressing would have similar
characteristics to skin, such as promoting the proliferation and migration of fibroblasts,
accelerating the formation of epithelial tissue, reducing scar formation, and exhibiting
certain antibacterial and anti-inflammatory effects.
Gram positive bacteria such as Staphylococcus and Streptococcus and Gram
negative such as Escherichia coli and Klebsiella spp can cause wound infections.
Polymicrobes and polymicrobial resistance are also involved in chronic
1510 S. Ravi and I. R. Kishore

infections, but NPs possess broad spectrum antimicrobial properties that can
significantly reduce bacterial growth and reproduction. Recent studies has
suggested a combination of nanosilver and a mixture of poly(vinyl alcohol) and
chitosan (CS) in this regard, and the resulting fiber mat can be used in wound
healing. Because of the high specific surface area of nanosilver particles results in
good contact with bacteria, which significantly inhibit their growth and increase
the rate of wound healing.

Bone Cement

Bone cement is a self-curing plastic at room temperature that is composed of

polymethyl methacrylate (PMMA) or modified PMMA and methyl methacrylate
(MMA). Bone cement is commonly used to fix joint prostheses, such as in hip or
knee replacement surgery, by filling the gap between the bone and implant. A recent
study found that the infection rate following total joint replacement surgery was as
high as 3% and this can be decreased to 0% by administering antibiotic-loaded
PMMA. However, there are other several studies which has shown that bone cement
loaded with antibiotics did not significantly reduce infection rate. Therefore, it is still
unclear whether following arthroplasty infection rate will be reduced by loading
bone cement with antibiotics. Recently the number of resistant bacterial strains are
rapidly increasing and if appropriate effective measures are not taken, even a simple
wound and incurable infectious diseases might lead to death.
NPs have shown a strong killing effect even on certain types of antimicrobial-
resistant bacteria and this effect is becoming a hotspot in research area.
Silver nanoparticles (Ag NPs) mixed with PMMA-based bone cement significantly
reduces the formation of surface biofilms according to the Kirby-Bauer method and the
time-kill method. The main mechanism behind the combination of silver nanoparticles
(Ag NPs) along with PMMA is to prevent bacterial surface colonization. Lower
concentration of 0.05% of nanosilver is enough to significantly reduce the number
of arthroplasty surgery-related infections including methicillin-resistant Staphylococ-
cus aureus (MRSA), Staphylococcus aureus, Staphylococcus epidermidis, and
Acinetobacter baumannii infections.

Dental Materials

Infections are common in the mouth because of plaque which serves as an important
ecological environment that allows microbes to settle on the teeth. Many dental
materials show improved performance after nanocrystallization. For example,
nanodiamond-functionalized amoxicillin in combination with gutta-percha for root
canal treatment can eliminate residual bacteria after root canal filling. In addition,
due to proliferation of bacteria and the reduction in pH in the course of treatment,
orthodontic treatment often leads to the formation of dental plaque chalk, and
brackets coated with CuO and ZnO NPs can effectively inhibit the growth of
66 Consumer Nanoproducts in Antimicrobial Application 1511

Streptococcus mutans; however, the coating also affect the appearance of the
brackets.
Maxillofacial prostheses placed in a complex external environment containing a
variety of flora have been shown to develop biofilms, thereby increasing the inci-
dence of tissue inflammation surrounding the prostheses. The addition of nano-
titanium dioxide to prostheses resulted in antibacterial effects following light
exposure.

Future Perspective of NPs

Surface modification of NPs can be used to advance the stability and antimicrobial
potential. Nanoproducts can perform as a middle man or a carrier for enhanced drug
delivery. Also targeted chemotherapy which brings better tolerance and less side
effects are also an advancement in terms of NPs.
The NPs because of its size can lodge in the mucous membrane and can inflict an
inflammatory response which can affect heart, lungs, and other organs. Also it can
induce an oxidative stress which produces a cytokine reaction and can initiate an
autoimmune response in some individuals. The neuronal uptake of NPs can lead to
the release of inflammatory cytokines which produce the base for various neurolog-
ical diseases.

Conclusion

Antimicrobial resistance poses a serious threat to health care and other industries
currently around the world. The production of various antimicrobials is at a lesser
scale currently due to the difficulty in the production and the testing on humans and
animals. The appearance of nanotechnology has produced new antimicrobial alter-
natives. NPs types have shown marvelous prospective as bactericidal and fungicidal
elements, demonstrating their potential as efficient antibiotic reagents in wound care
and related medical issues. The effectiveness of these NPs changes with their
characteristics which includes size, shape and concentration. These NPs have less
toxicity and prolonged activity making it the current solution for resistance issues.

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Index

A Air pollution, 1308, 1446, 1447

Acalypha indica, 709 Air quality monitoring, 1130–1133
Acrylonitrile butadiene styrene (ABS), 94, 264 Air remediation, 1108, 1109
Activated carbon (AC) Alginate(s), 340, 442
adsorption, 1149, 1150 Alkaline fuel cells (AFC), 366
classification, 1147, 1148 Allantoin, 969
definition, 1141 Alpha-hydroxy acid (AHA), 972
discovery, 1140 Alpha lipoic acid (ALA), 1483, 1490
industrial production, 1141 Alumina, 89
production and activation, 1143, 1146, 1147 silicates, 84
properties, 1141, 1143, 1149, 1150 Aluminium, 883–884, 889, 1206
sources of, 1142, 1144, 1145 cans, 884
Active packaging, 755, 1289, 1292–1293 foil, 884
Acute wounds, 691 matrix, 455
Additive manufacturing, 527 Aluminum oxide nanoparticles
Adhesives, graphene, 490–492 (Al2O3NPs), 817
Adsorption, 1363 Alzheimer’s disease model of Caenorhabditis
Adulterants/toxicants elegans, 683
biosensing, 789 Amino (NH2), 1207
carbon nanofibers, 791 Ammonia (NH3) gas, 1130
definition, 788 Ammonium glycyrrhizinate-loaded ultra
nanoproducts, 790 deformable liposomes, 969
nanosensor, 789 Amylopectin, 893
planning and delivering food, 792 Amylose, 893
types, 789 Analytical hierarchy process (AHP), 1161
ultrathin nanofibers, 791 Angiosarcoma, 883
Adulteration, 754 Animal resources (AR), 340
Advanced oxidation processes (AOPs), 1107, Antiaging creams, 1086
1411, 1415, 1417–1419, 1426, 1428 Antiaging nanocosmetics, 969
Agriculture nanotechnology Anti-aging products, see Nanobiotechnology-
feature, 719 based antiaging products
nanocarriers, 723 Antibacterial properties, nanosilver, 579–580
nano fertilizers, 723 Anti-corrosion coating system, 491
nanoproducts, 725, 726 Antifungal properties, nanosilver, 580
sensors, 724 Anti-inflammatory properties, nanosilver, 581
Agri-nanoproducts, 1112 Anti-microbial nanomaterials, 1421
Agro-nanomaterials, 1213 Antimicrobial property, 893
Agro-nanotechnology, 1207 Antioxidant, 1474, 1475, 1477–1483,
Airborne Nanoparticle Filtration, 150 1486–1491

© Springer Nature Singapore Pte Ltd. 2022 1515

S. Mallakpour, C. M. Hussain, Handbook of Consumer Nanoproducts,
https://doi.org/10.1007/978-981-16-8698-6
1516 Index

Antiperspirants, 1088 Battery, 493, 494, 1116

Antiviral properties, nanosilver, 580–581 Battery-powered vehicles, 361
Anti-wrinkling finishing, 919 3,3',4,4'-Benzophenonetetracarboxylic acid
AgNPs, 920–921 (BPTCA), 916
chitosan nanoparticles, 922 Bimetallic NPs, 555
CNTs, 921 Bioactive agent-loaded liposomes, 565
SiO2 nanoparticles, 922–923 Bioavailability of nutrients, 770
TiO2 nanoparticles, 918–920 Bio-barcode method, 626–627
ZnO nanoparticles, 921–922 Bio-based nanoformulation, 1227
Apolipoprotein E4, 681 Bio-based nanoproducts
Aquatic ecosystem, NPs on, 1261–1264 antimicrobials, 381
Aquatic nano toxicity, 1267 fertilizers, 382
Argentum, 1224 food packaging, 381
Aros, 494 pesticides, 383
Arsenic, 21, 31, 420, 430–431, 1356 Bio-based polyester (BE), 301
contamination, 1356 Bio-based polymers, 252, 1203
exposure, 1357 Biocompatibility, 338, 341–343, 347, 349
health effects due to exposure, 1360–1362 Biodegradability, 755
nanostructured materials for the removal of, Biodegradable films, 1203
1368–1372 Biodegradable nanomaterials, 1207
occurrence and environmental mobility of, Biodegradable polyesters, 1203
1358–1360 Biodegradable polymer, 149, 892–893, 902,
removal from water, 1362–1363 1281–1284
stable and non-radioactive isotopes of, 1360 Biofuels, 1427
Arsenic groundwater contamination, 1248 Biogas energy, 1427
Arsenic groundwater remediation, and scientific Bio-ink, 528, 530
vision, 1423–1426 Biological environmental remediation, 1362
Arsenicosis, 1361 Biologically active molecules, 531
Arsenic risk mapping, 1424 Biological sensors, 705
Arsenic trioxide, 1360 Biomedical applications, 148
Asahi Kasei Group, 327–329 Biomedicine, 527, 530, 531, 543
Ascorbic acid, 1483 Biomineral composition, 663
Association of Southeast Asian Nations Bionanocomposite materials (BM), 339, 344
(ASEAN), 1398 Bio-nanocomposites, 811, 1211
Astaxanthin, 1082, 1490 as controlled release systems for
Atomic force microscope (AFM), 658, 661, agrochemicals, 1215–1219
662, 665–667, 669 properties, 1208–1215
Attenuated total reflection (ATR)-FTIR, Biopolymer based nanotechnology, 540
648–650, 668–669 Biopolymer-coated nano-imidacloprid
Attritor milling, 93 formulations, 1229
Au/Ag core-shell nanoparticles, 569 Biopolymers, 1278, 1281–1284, 1286, 1287,
Au NP-poly(para-phenyleneethynylene), 569 1289–1292
Azobenzene derivative, 623 Bioprinted three dimensional
nanomaterials, 538
Bioprinted three-dimensional scaffolds, 541
B Biosensors, 392, 568–569
Backscattering, 662 Biotechnology, 1422
Bacteria, 1346–1348, 1350, 1352 Biozar Nano-Fertilizer ®, 1224
Bacterial cellulose, 245, 247 Blender, 530
Ball milling, 87 Blending, 232
Ball to Powder Weight Ratio (BPR), 89 Block copolymer micelles, 1478
Basic carbonate of zinc (BCZ), 1068 Blood brain barrier (BBB), 1266
BaTiO3-filled composites, 169 Blow-spinning technique, 1334
Index 1517

Bone cement, 589–590, 1510 Cardiovascular implants, 586–588

Boron (B), 1221 Carrageenans, 343
Boron nitride (BN), 92 Carriers antibiotics, 1507, 1508
nanotubes, 349 Cartilage, 536
Brain-computer interfaces (BCIs), 781 Cassia fistula, 709
Britannica, 37 Catalytic chemical vapor deposition
Brownian relaxation, 629 (CCVD), 63
Brunauer-Emmett-Teller method, 838 Catheters, 588–589
Brunauer–Emmett–Teller (BET) technique, 119 CATIA, 530
Brust and Schiffrin method, 700 Cation exchange capacity (CEC) of clay, 1324
Buckminsterfullerene, 552, 1079 Cationic emulsion, 939
Buckyball, 995 Cationization, 900
Bullet proof vest, 488 CdS nanocrystals, 620
1,2,3,4-Butanetetracarboxylic acid Celite, 290
(BTCA), 916 Cell-laden hydrogels, 533
Cell loaded hydrogel bioink formulations, 531
Cell search device, 632–633
C Cellulite, 942, 944
Cadmium oxide nanoparticles (CdONPs), 818 Cellulose, 340, 341, 442
Calcium (Ca), 347, 1227 fibrils, 247
Calcium carbonate (CaCO3), 93, 267 Cellulose nanocrystals (CNCs), 1211, 1213,
Cancer treatment, 679 1286
(ε-caprolactone) (PCL), 1211 Cellulose nanofibrils, 1286
Carbonaceous materials, 174 Cellulose nanowhiskers (CNWs), 91
Carbon-based nanomaterial, 39, 474–475, 559 Central nervous system (CNS), 349
Carbon based nanoparticles, 1267–1268 Central venous catheters (CVC), 588
carbon-based quantum dots, 553 Ceramic(s), 81, 83, 344
carbon nano tubes, 553–554 chemical bonding, 83
fullerenes, 552 nano composites, 85
graphenes, 552 nanofillers, 170
mesoporous carbon nanoparticles, 554 nanoparticles, 345, 346
nanodiamonds, 552 raw materials, 84
Carbon-based nanostructured materials, 1228, Ceramic matrix composites (CMCs), 81, 458,
1365 462–463
Carbon-based quantum dots (CQDs), 553 Cerium oxide (CeO), 1040
Carbon black, 174 Cerium oxide nanoparticles (CeO2NPs), 556,
Carbon dioxide barrier, 905 563, 569, 818
Carbon nanodots, 1412 Changchun Foliaplast Bio-Tech Co., Ltd, 328
Carbon nanofibers (CNFs), 63, 1466 Chemical digestion, 112
Carbon nanoparticles, 1459 Chemical Health Risk Assessment
Carbon nanosensors, 790 (CHRA), 1160
Carbon nanostructure, 109, 110 Chemically converted graphene (CCG), 375
Carbon nanotubes (CNTs), 38, 63, 342, 374, Chemically modified graphene (CMG), 374,
410, 553–554, 921, 1039, 1079–1080, 377, 379
1099, 1106, 1109, 1111, 1177, Chemical modification, starch
1288, 1328 cationization, 900
electronic properties of, 1328 esterification, 900
heavy metal removal, 1329 etherification, 900
larges cale applications, 1330 oxidation, 900
organic water pollutant removal, 1329–1330 Chemical process engineering, 1412
polyvinyl alcohol, 290 Chemical sunscreens, 971
Carbon-reinforced nanomaterials, 173 Chemical vapor deposition (CVD), 63, 376,
Carboxymethyl chitosan (CMCS), 743 402, 405, 406, 478, 1127, 1128
1518 Index

Chemiresistive single-walled carbon Co-Fe@hemin nanoparticles, 679

nanotubes, 790 Commercial nanobiotechnology products,
Chemometric models, 780 1008–1009
Chitin, 341, 596, 1481 Commercial nanoproducts, 181–183
nanowhiskers, 1287 Composite, 80, 81
NPs, 1209 definition, 244
Chitin Nanofibril-Hyaluronan nanoparticles fabrication, 454–458
(CN-HA), 1491 material, 162
Chitosan, 443, 922, 1103, 1106, 1207, Composite Technology Development, Inc.,
1283, 1481 329–330
bi-carboxylic acids, 601, 602 Compton scattering, 637
bio-medical uses, 596, 597 Computer-aided design (CAD), 260
cationic properties, 605 Conducting polymer, 440
characterization, 602, 603 Conductive inks, 514–516
degree of acetylation (DA), 596 Conductive polymers, 147, 149, 151
degree of deacetylation (DD), 596 Conductivity measurement (CDM), 1069
drug loading, 605 Conjugated polymers, 146
fluorescence properties, 603, 604 Consumer acceptability, food nanotechnology
ionic gelation technique, 600 consumer safety, 728, 729
method of emulsification, 605 health implications, 725, 728
method of micelle formation, 606 Consumer market, 53
NPs, 1209 Consumer nanocomposites, 1304, 1305
pH, ratio of chitosan, 600 groundwater and drinking water treatment,
poly-electrolyte complex formation, 606 1312–1313
reverse micelle method, 602 and groundwater remediation, 1313
scaffolds, 542 Consumer nano industry, 40, 41
spray-drying method, 605 Consumer nanoproducts, 1172, 1242–1243,
structures, 596, 597 1255, 1412
water soluble chitosan nano particles, 597 characteristics, 62
water soluble depolymerized chitosan, database/inventories, 69
597–600 definition, 60, 61
zeta potential, 601 development/marketing regulation, 62
Chitosan-based nanocomposites, 1207, effects/environmental safety, 64
1214–1215, 1218–1219 in environmental pollution control,
Chronic wounds, 691 1248–1249
Circulating tumour cells, 632 expert committees, 72
Citric acid (CA), 916 GHS/labelling, 71
Clay, 344, 345 international organisations, 71
Clay nanomaterials, 109 marketing, 70
Cleavable amplified polymorphic sequences material-based categories, 63
(CAPS), 779 NM, 61
Climate change, 1174, 1175 scientific advancements in, 1243–1245
Climate change mitigation, 423 Consumer product inventory (CPI), 4, 6, 8, 69
Clustered regularly interspaced short Consumer protections
palindromic repeats (CRISPR), 1111 acceptance and recognition, 1384
CO2 sensor, 756 ENMs, 1383, 1384, 1388
Coacervation, 769 features, 1387
Coagulation, 1363 ‘goods’ and ‘products, 1385–1387
Coatings, graphene, 490–492 history, 1383
Cobalt (Co), 1227 international organisations, 1398–1400
Co-condensation, 622 nanoproducts, 1400–1402
Coefficient of thermal expansion (CTE), 164 natural nanomaterials, 1382
Coenzyme Q10 (CoQ10), 1483 regulation, 1389
Index 1519

stakeholders and policymakers, 1387 nanopigments, 937, 938

Statnano Database, 1388 nanosponges, 936
theoretical overview, 1389–1392 NLCs, 936
UNGCP, 1392–1398 patents, 957
Controlled-release (CR), 1215, 1221 preparation, 932, 933
Conventional plastics, 1279–1281 regulation, 955, 958
Copper (Cu), 1206, 1221 safety assessment, 955
nanoparticles, 697, 1506 SLN, 935, 936
oxide, 557 types, 933, 934
Copper/copper oxide nanoparticles (CuNPs/ Cosmetic products
CuONPs), 819 deodorant, 1088
Coprecipitation, iron oxide based hair care, 1086–1087
nanoparticles, 835 lip care, 1088
Cornerstone Research Group Co., 324–325 nail care, 1087–1088
Corn protein, 737 perfumes, 1089–1090
Cosmeceuticals, 987–995, 997 skin, 1084–1086
hair care, 1036 Cosmetics Harmonization and International
lip care, 1036 Cooperation (CHIC), 1491
nail care, 1034–1035 Cotton gauze bandages, 693
skin care, 1036 Coumarin molecules, 620
Cosmeceuticals, nanoproducts (NPs) Creams, 1086
anti aging products, 47, 48 Creo, 530
exposure and penetration to skin and body, Cross-linking, 913, 916, 918, 920–923
49, 50 Cubosomes, 1078
haircare, 48 Curcumin, 1486, 1490
lip and nail care, 49 Curcumin-based liposomes, 973
moisturizers, 47 Curing, 80
skin cleaning application, 48, 49 Cyanoethyl ester of polyvinylalcohol
sunscreens, 47 (CEPVA), 169
Cosmetic(s), 964 Cyclin D1, 617
hair growth and removal products, 953, 954 Cycling G+ graphene aero jersey, 483
industry, 1491 Cycling helmets, 482
liposomes, 935 Cyclodextrins (CDs), 624, 1478
manufacturing details, 956 Cyfuse Biomedical, 543
nanocapsules, 937
nanocrystals, 936
nanodiamonds, 937 D
nano emulsions, 934, 935 3D additive micromanufacturing, 527
nanofibers, 938 DAZ Studio, 530
nanoform anti-cellulite creams, 942, Defluoridation, 1422
944–946 Dendrimers, 967, 1039–1040, 1078, 1478
nanoform anti-wrinkle creams, 942, 943 Dental materials, 1510, 1511
nanoform deodorants, 948, 949 Deodorants, 1088
nanoform hair color products, 939, 940 Desalination, 1419
nanoform lipsticks, 953 and membrane science, 21
nanoform moisturizers and cleansers, process, 235
945–948 Design for the Environment (DfE), 1466
nanoform nail polishes, 952–954 Detonation nanodiamond (DND), 988
nanoform perfumes, 951–953 3D hydroxyapatite hydrogel scaffold, 541
nanoform shampoos and conditioners, 939 Diabetic foot, 542
nanoform soaps, 948, 949 Diagnostic magnetic resonance, 629
nanoform sunscreens, 948–951 Dielectric nanocomposites, 150
nanoform toothpastes, 940–942 Differential scanning calorimetry (DSC), 1211
1520 Index

Diffusion coefficient (Dτ), 115 colored sample, 115

Digital light processing (DLP) technology, 294 concentration effects, 116
Digital light processing stereolithography 3D definition, 114
printing, 311 diffusion coefficient (Dτ), 115
Dihydroxydimethylolethyleneurea dimensionless constant, 114
(DMDHEU), 915, 916 equipment handling and sample
3 Dimension (3D) printing technique preparation, 116
additive manufacturing, 527 geometric scattering, 114
advantage, 528 intensity fluctuations, 115
applications, 535–538 Mie scattering, 114
characteristic, 528 nanomaterials analysis, 116, 117
combination of technologies, 541–542 Rayleigh scattering, 114
inkjet bioprinting, 529 salt concentration, 116
limitation, 528 sample concentration, 115
market and marketing, 543 signal-to-noise ratio, 115
materials, 529–534 Dynamic mechanical analysis (DMA), 895
microfabrication, 527
micromanufacturing categories and
methods, 527 E
nanotechnology and nanomedicine, Earphones, graphene-based, 506
538–540 Eco-friendly bio-nanocomposites, 1210
oxidative stress, 528 Eco-friendly nanomaterials, 1357
scaffolds, 528 Ecofriendly polymer nocomposite (EPN),
stereolithography (SL) process, 528 244–245
Dimethyl sulfoxide (DMSO), 618 Ecological biodiversity, 1411
Dimethylurea glyoxalate (DMG), 916 Ecological hazards, 1051
Directed amplification of minisatellite-region Eco-materials, 1411
DNA (DAMD), 779 Edible coatings (ECs), 807
Direct methanol fuel cells (DMFC), 367 Elastic memory composite (EMC)
Disk diffusion method, 1504 materials, 304
DNA amplification fingerprinting (DAF), 779 Electrical conductivity, 476, 479
Dose metric, 1271 Electrical double layer (EDL), 385
Double wall CNTs (DWCNTs), 174 Electric double layer capacitors (EDLCs), 403
3D printing, 494 Electric double layer charge (EDLC) based
Dressings, 540 supercapacitor, 493
Drinking water crisis, 430–431 Electroactive polymer, 147
Drinking water remediation, 1312–1313 Electro-active shape memory, 293
Drinking water treatment, 1413 Electrochemical capacitor, 1118
Drug delivery, 148, 612 Electrodeposition, 1127, 1129
Alzheimer’s disease, 613 Electrolytic chromium/chromium oxide coated
mesoporous silica nanoparticles, 620–625 steel (ECCS), 885
pH-responsive, 621 Electrolytic tinplate (ETP), 884–885
site-specific, 623 Electromagnetic interference (EMI), 153
Drug delivery systems (DDSs), 559–564 Electron beam lithography, iron oxide based
Drug reservoir gradient-controlled TDDS, 863 nanoparticles, 833
Dry-jet wet spinning, 441 Electronic nanoproducts
3D Slicer, 530 integrated circuits, 390
Durability, graphene, 478, 482 piezoelectric materials, 388
Durable press (DP), 913, 914, 916 transistors, 389
Dye-sensitized solar cells (DSSCs), 387 Electropolymerization, 403
Dynamic light scattering (DLS) Electrospun bio-nanocomposite mats, 1213
advantages, 115 Electrostatic tires, 512
Brownian motion, 114 Electrostatic tires with graphene composites, 487
Index 1521

Electro-thermoacoustic (ETA) device, 505 Enzyme-based nanosensors, 790

EMotion, 493 Enzyme immobilization, 755
EndoShape, 329 Epoxy-clay nanocomposites, 168
Endurance time test, 369 Epoxy resin, 175, 440
Energy conservation, 1174–1178 Essential oils (EOs), 799, 807
Energy generation, 1174–1178 Estane, 330
Energy storage, 403–405 ESTANE® thermoplastic polyurethane, 330
fuel storage, 386 Esterification, 900
supercapacitors, 384, 385 e-textile, 152
Energy storage applications Etherification, 900
ionic liquid-based P(VdF-HFP)-layered silicate Ethylcellulose (EC), 442
nanocomposite electrolytes (see Ionic Ethylene vinyl acetate (EVA), 95
liquid-based P(VdF-HFP)-layered silicate Ethylene vinyl alcohol (EVOH), 782
nanocomposite electrolytes) Ethylhexyl dimethyl PABA (EHDP), 1490
ionic liquids, 197 Ethylhexyl methoxycinnamate (EHMC), 1490
layered silicates, 195 European Medicines Agency (EMA), 814
liquid-based polymer electrolytes, 198 European Union (EU), 1050
polymer electrolyte, 191, 192, 194 European Union Observatory for
P(VdF-HFP)-BMIMBr-MMT intercalated Nanomaterials (EUON), 1059
nanocomposite electrolyte, 200 Exfoliated nanocomposite, 195
rechargeable batteries, 190 Exfoliation, 477
selected area electron diffraction pattern method, 477
(SAED), 201 External antioxidants, 1482
Energy sustainability, 22, 1427 Extrusion-based printers, 528
Engineered, manufactured or manmade Eye mask, 490
nanomaterials (ENMs), 1383, 1384
Engineered nanomaterials, 421, 422, 431, 1310
Engineered nanoparticles, 1171, 1254, 1263 F
Engine oil product, 487 Fabrication process, 154, 444
Environment, 244, 249–251 Fe3O4 magnetic nanoparticles, 679
Environmental biotechnology, 26 Fellgett advantage, 651
Environmental calamities, 1413 Ferroelectric ceramics, 169
Environmental engineering, 428, 1410–1412, FG-based bio-nanocomposite films, 1213
1418, 1427 FiiO F3 earphones, 485
Environmental hazards of nanomaterials Fillers
assessment of nanoparticles in air, 1164 CaCO3, 267
assessment of nanoparticles in soil, 1165 carbon fibers, 270
life cycle risk assessment, 1165 fly ash, 266
risk of nanoparticles in water, 1165 montmorillonite, 267, 268
Environmental Health and Safety (EHS), 65 Fine particulate matter, 1333
Environmental pollution, 1411, 1435 Fish gelatin (FG), 1209
Environmental pollution control, 1245–1247 Fishing rods, 515
Environmental protection, 1412, 1415, Flavonoids, 1486
1417–1420, 1422–1426, 1428, 1429 Flexible electronics, 504
Environmental remediation, 1411, 1418, 1420 Fluorescent gold nanoparticles, 562
Environmental remediation nanoparticles, Fluoride contamination, 1422
1323–1324 Food Adulteration/Food fraud
Environmental Risk Assessment (ERA), 1164 conventional methods, 778–780
Environmental science, 1419 definition, 776
Environmental sustainability, 22, 23, 423, 1242, drawbacks, conventional methods, 780
1314, 1412, 1413, 1426, 1427 health risks, 777
Envision TEC, 543 metallic compounds, 776
Enzymatic modification, 902 methods, 779
1522 Index

Food and Drug Administration (FDA), conventional strategies, 820

814, 1050 food processing, 812
Food industry indirect methods, 808, 809
definition, 780 mechanisms, 801
problems, 781 microorganism contamination, 801
smart technologies/smart products, 781 nanomaterials, 804
technological advancement, 781 needs, 801
Food industry, nanoproducts (Nps) packaging material, 810
silica (SiO2), 42 Food processing
silver-Ag nanoparticles, 42, 43 definition, 812
titanium dioxide (TiO2), 43 nanoparticles, 812
zinc oxide (ZnO), 43 nanotechnology, 812
Food nanotechnology techniques, 812, 813
components, 720 Food-related applications, 798
consumer safety, 728, 729 Formaldehyde-based reagents, 914–915
feature, 719 Fourier transform infrared (FTIR),
health implications, 725, 728 647–649
nanoproducts, 725, 726 antimicrobial mechanisms, 650
packaging, 722, 723 ATR–FTIR, 648–650
preservation and shelf life of benefits, advantages and disadvantages, 651
foods, 724 FTIR imaging, 652–658
processing, 720–722 iron oxide nanoparticles, on liver and
regulations, 725, 729 kidneys, 656–658
safety, 724 micro-spectroscopy FTIR, 648, 652,
Food packaging, 882, 1278 656, 657
active packaging, 1289, 1292–1293 monitoring molecular changes, in
aluminium cans, 884 microorganisms, 650–651
aluminium foil, 884 nano-FTIR spectroscopy, 658–668
biodegradable polymers, 1281–1284 silver nanoparticles, on terrestrial isopods,
bugs, 810 653–654
carbon nanotubes, 1288 synchrotron FTIR, 668–671
cellulose nanocrystals/nanofibrils, 1286 transmittance FTIR, 648, 649
chitin nanowhiskers, 1287 tungsten oxide (WOx) nanofibers, on
conventional plastics, 1279–1281 digestive gland tissue of Porcellio
definition, 809 scaber, 655
glass, 886–887, 890 ZnO nanoparticles, on crustacean digestive
improved packaging, 1289–1291 glands, 655–656
inorganic nanoparticles, 1288 Fourier transforms infrared spectroscopy
intelligent/smart packaging, 1293–1294 (FTIR), 779
lignin nanoparticles, 1287–1288 Freeze drying, 769
nanoclay/nano-layered silicate, Friction, 481, 487
1285–1286 FSL, 530
paper, 887–889, 891 Fuel cell technology, 365–369, 386
plastics, 885–886, 889 Fullerene(s), 10, 552, 968, 1412
safety issues of nanoparticles, 1294–1295 based immunomodulators, 552
starch (see Starch, food packaging) buckyballs, 1040–1041
steel, 884–885 Full width at half maximum (FWHM), 1061
strategies, 809 Functionalized Au nanoparticles, 634–636
wood, 890–891 Functionalized nanoparticles, 1171
Food pathogen detection, 756 Fungi, 1346–1348
Food preservation Furnace graphene, 483
biobased packaging, 811 Fused d0eposition modelling (FDM)
conventional methods, 802 technique, 168
Index 1523

G chemical modification, 402

Gamma radiation, 901 coatings adhesives and oil and gas
Gas sensors, 756 industries, 490–492
G6E-GSTMepoxy, 492 consumer applications, 478–479
Gelatin, 341, 381, 443, 1481 creative process, 445
Gelatin-based nanocomposite films, 1211 derivatives of, 476
Gelatin nanoparticles (GNPs), 1490 electrical/electronic/thermal applications,
Gel formation process, 207 479–481
Gemcitabine hydrochloride-loaded colloidal energy, 492–494
gold NPs, 562 fishing rods, 515
Geotextiles, 494 Flagship project, 510
G3-fireshield technology, 495 future prospects of, 496–497
G-King, 494 growth of, 479
Glass, 890 isolation of, 503
fiber, 270 jacket, 515
food packaging, 886–887 processing of, 477–478
Glass transition temperature (Tg), 1211 properties, 476–477, 503
Global climate resilience, 1413 sensors, 484
Global environmental engineering science, 1416 sports, safety and outdoor activities,
Global warming, 1411 481–484
Gluconacetobacter strains, 247 in sports equipment, 507–509
Glycerin, 896 suspension/substrate, 445
Glycerol, 898 textiles/outfits and filtration/membranes,
Glycerol-plasticized potato starch (GPPS), 1209 488–489
Gold nanoparticles (AuNPs), 291, 555, 568, top-down approach, 477
624, 690, 697, 698, 799, 818, in touch screen displays, 504–505
1041–1042, 1103, 1506 in wireless communication, 505–507
antibacterial properties, 706 Graphene-based composites
applications, 705–707 in autoobile parts, 511
bottom-up approach, 699 in packaging applications, 512–514
Brust and Schiffrin method, 700 Graphene based nanoproducts, 421
green synthesis, 701–705 description, 422
Navarro method, 700 scientific advances in, 424–426
physical methods, 700 Graphene-based nanostructured sensors, 1228
properties of, 698–699 Graphene contact enhancers (GCE), 485
seed-based method, 701 Graphene-enhanced antibacterial face
sonolysis, 700 masks, 489
synthesis using phytochemicals, 702 Graphene-enhanced audio equipment, 486
synthetic approaches of, 700 Graphene-enhanced Lacrosse gear, 482
top-down approach, 699 Graphene hybrid material (GHM), 441
toxicological effects, 1264–1266 GrapheneLin conductive inks, 514–516
Turkevich method, 700 Graphene nanocomposites
GRAFYLON 3D, 495 applications, 395
Graphene(s), 39, 375, 402, 444, 502, 552, 1412 battery-powered vehicles, 361
applications, 447 biocompatiblity, 380
audio applications, 485–486 electrical property, 379
automobile application, 486–488 environmental remediation, 394, 395
in automobile parts, 510–512 fuel cell technology, 365–369
in batteries, 509–510 mechanical property, 376
based biosensors, 568 nanoproducts, 380
based hydrogen storage systems, 386 preparation, 376
biotech, 489–490 separators, 394
bottom-up approach, 477 solar cell technology, 364–367
1524 Index

Graphene nanocomposites (cont.) waste reduction, 1182–1184

supercapacitors, 362–364 in water treatment, 1178, 1179
thermal property, 379 Green sustainability, 23
Graphene nanomaterial (GM), 438, 439 Green synthesis, 1436, 1437
Graphene-nanoparticle composite, 444 iron oxide based nanoparticles, 836–837
Graphene nanoparticles, 359–361 Green synthesis of nanoparticles, 701
Graphene nano-ribbons (GNRs), 379 advantages, 702–703
Graphene oxide (GO), 374, 376, 403, 406, 440, factors affecting quality of, 704–705
455–461, 463, 552, 1447 Green tea polyphenols (GTP), 1107
Graphene oxide–reinforced poly( l-lactide- Groundwater remediation
co-ε-caprolactone) nanocomposites, 295 and drinking water remediation, 1312–1313
Graphene quantum dots (GQD), 359, 552 and nanocomposites, 1313
Graphene reinforcement
ceramic matrix composites and properties,
462–463 H
metal matrix composites and properties, Hair care, 973–974, 1036
455–460 Hair discoloration, 974
polymer matrix composites and properties, Hair grease, 973
460–462 Hazard assessment, for nanoproducts
Graphene security (GS), 481 dose metric, 1271
Graphene sheets (GS), 440 nano specific risk assessment, challenges
Graphene ultra fuel efficient tires (GUET) for, 1272–1273
tires, 482 physical chemical properties, 1272
Green alternatives, 1164 target tissue, 1272
Green approaches Hazard identification and risk assessment
bimetallic nanoparticles, 1439, 1442, 1443 technique (HIRA)
monometallic nanoparticles, 1438–1441 basic mitigation measures for the workers,
trimetallic nanoparticles, 1442 1161
Green chemicals, 1460 control strategies, 1163–1164
Green manufacturing, 1182 green alternatives, 1164
Green nanocomposites, 1209 human health risk assessment, 1161
Green nanoproducts likelihood rating, 1160
and green nanotechnology, 21 risk category, 1160
scientific advancements in, 23–25 severity rating, 1160
Green nanotechnology, 1220, 1458–1462 HEAD ® Youtek Graphene Instinct Junior
application, 1184 Tennis Racquet, 508
benefits, 1435, 1436 Health and environment safety
in energy generation and conservation, nanotech/nanoproducts, 64
1174–1178 NMs, 66
in environmental remediation, 1179, 1180 profile judging tools, 66
goals, 1174 risk assessment, sources, 67
LCA, 1185 toxicology data, NMs, 65
manufacturing, 1182–1184 Health hazards, 1051–1052
NADPH dependent reductase enzyme, 1174 Heart attack, 680
nanocontact-sensors, 1181 Heat moisture treatment, 901
nanotoxicology, 1185, 1186 Heavy metal(s), 430–431, 1447
nano waste management, 1190–1193 activated carbon, 1140–1143, 1146–1150,
optical properties, 1184 1153
phytoformulation methods, 1173 adsorption capacity, 1154
pollution prevention, 1182–1184 carbon and allotropes, 1141, 1142
potential hazards, 1188–1190 charcoal, 1140
properties and issues, 1187, 1188 classification, 1150, 1151
toxic byproducts, 1173 effect of, 1151–1153
Index 1525

groundwater remediation, 1247 2-Hydroxypropyl methacrylate (HPMA), 923

lead, chromium and copper ions, 1154 HyperMesh, 530
properties, 1151
removal of, 1153
toxic symptoms, 1154 I
Helmet, graphene-enhanced, 484 Ibuprofen, 560
Helmets, 508 Imaging/spectroscopy, 779
Hemostasis, 692 Imidacloprid-loaded chitosan-PLA
Hemp nanocrystals (HNCs), 1209 nanoformulations, 1217
Henry equation, 118 Immune-checkpoint inhibition (ICI), 613
Hexagonal boron nitride (h-BN), 172 Immunoassay, 678
Hexamethylol melamine (HMM), 915 Immunogenic cell death (ICD), 615
HexaShield, 481 Immunotherapy, 614
High-density polyethylene (HDPE), 1280 Immunotherapy-related adverse events, 625
High energy ball milling (HEBM), 86, 90 IMPEDE Embolization Plug, 325
methods, 87 Improved packaging, 1289–1291
nanocrystalline grains, 89 Incidental nanoparticles, 1171
polymer–ceramic composite, 89 India, 1050
polymer metal matrix composites, 94 Indium tin oxide (ITO), 504
thermoplastics matrix composite, 89 Industrial ecology, 1464
thermosets matrix composites, 94 Industrial wastewater treatment, 1413,
Highly reduced graphene (HrGO), 374 1415–1417, 1419, 1427
High-performance polymer nanocomposites, Inflammation, 692
164 Infrared spectroscopy, 648
High-speed ball milling (HSM), 88 Inkjet bioprinting, 529
High-speed vibrational ball milling (HSVM), 88 Inkjet printing, 514
Hispo-pathologic analysis, 1268 Inks, 480, 489
Hockey sticks with graphene, 482 Innovations in nanoproducts, 38, 39
H2O2 mediated depolymerization, 599 Inorganic nanoparticles, 12, 1288
Home fragrance products, 1089 In situ polymerization, 167
Honor’sHonor X10, 480 Integrated water resource management and
Human health risk assessment, 1161 wastewater management, 1414
Human mesenchymal stem cells (hMSCs), 682 Intelligent/smart packaging, 1293–1294
Hyaluronan, 1481 Intercalated nanocomposite, 195
Hyaluronic acid, 1481 Interfacial polymerization process, 232
Hybrid nanostructured materials, 1367 International Consumer Protection
Hycote, 491 Enforcement Network (ICPEN), 1399
Hydrated titanium oxides, 1366 Inter simple sequence repeat (ISSR), 779
Hydrogels, 531, 967, 1075 InVesalius, 530
Hydrogen fuel cells, 1177 Ionic liquid-based P(VdF-HFP)-layered silicate
Hydrogen gas sensor, 146 nanocomposite electrolytes
Hydrogen sulfide (H2S), 1130 advantages, 197
Hydrophilic membranes, 229 amorphous hexafluoropropylene (HFP)
Hydrophobic compounds, 618 units, 199
Hydrophobic membranes, 229 aprotic ionic liquids, 196
Hydrotalcite (HT) nanoclay, 1327 bulk resistance and capacitance, 206
Hydrothermal method, 835, 1459 compatibility, 210
Hydroxyapatite-graft-poly(D,L-lactide) composite polymer electrolytes, 192
nanocomposites, 307 constant phase element (CPE), 205, 206
Hydroxyapatite (HAP), 347, 975 contact angle measurements, 204, 205
Hydroxyl (OH), 1207 crystalline vinylidene fluoride (VdF), 199
Hydroxypropyl chitosan (HCS) decomposition voltage limit, 209
nanoparticles, 922 elastic collisions, 194
1526 Index

Ionic liquid-based P(VdF-HFP)-layered silicate biological-based synthesis method,

nanocomposite electrolytes (cont.) 836–837
electrical properties, 190 chemical and physical properties, 831–832
electrochemical and thermal properties, 200 chemical-based synthesis methods,
electrochemical properties, 192 834–836
electrochemical stability, 192, 209 coprecipitation, 835
elemental analysis, 204 electron beam lithography, 833
exfoliated nanocomposite, 195 functionalization of, 838–840
gel formation process, 207 hydrothermal method, 835
gel polymer electrolytes, 192 in vivo and in vitro studies, 830
history of, 190 laser pyrolysis method, 834
inelastic collisions, 194 magnetic characterisation, 838
in-situ polymerization, 195, 198 microemulsion method, 835
intercalated nanocomposite electrolyte, microscopic characterisation, 837
195, 210 physical-based synthesis methods, 832–834
interfacial stability, 210 physical vapor deposition, 833
ionic conductivity, 191, 192, 203, 205 sol-gel method, 834
ionic transport and electrochemical sonochemical synthesis, 836
properties, 199–202, 204, 206, spectroscopic characterisation, 838
210, 211 synthesis and design of, 832–837
Li-MMT/Na-MMT, 196 Iron oxide-based nanostructured materials,
linear sweep voltammetry plots, 209 1366
mechanical strength, 192 Iron oxide nanoparticles (Fe2O3NPs), 568,
montmorillonite (MMT), 193 791, 820
montmorillonite, hectorite and saponite, 194 on liver and kidneys, 656–658
onset decomposition (Tonset) and rapidest IR scattering scanning near-field optical
decomposition (Trpd), 211, 212 microscopy (IR s-SNOM), 658
organoclay, 195 Isocyanate-modified graphene (ICG), 440
PEO16LiClO4 composites, 196 Itaconic acid (ITA), 916
phase separated, 195
polymer gel electrolytes, 193
properties, 193, 197 J
protic ionic liquids, 196 Jacquinot advantage, 651
room temperature ionic conductivity, 207 Job hazard analysis (JHA), 1160
room temperature Nyquist plots, 205 Job safety analysis (JSA), 1160
SAED, 201
Scanning Electron Microscope (SEM)
micrographs, 203 K
solid polymer electrolytes, 192 Kenaf seed oil-NLC (KSO-NLC), 970
d-spacing, 202 Kevlar fiber, 269
swift heavy ion irradiation effects, 212–222
swift heavy ion (SHI) irradiation, 194,
198, 199 L
temperature dependence, 208 Landfills, 428
thermogravimetric (TG) analysis, 210–212 Langmuir and Freundlich equations, 1325
total transference number, 208 Langmuir–Blodgett (LB) coating
XRD studies, 201 technique, 1131
zwitterionic ionic liquids, 196 Langmuir model, 1153, 1329
Iron (Fe), 1221 Laser based bioprinting, 528
Iron oxide based nanoparticles, 829 Laser pyrolysis method, iron oxide based
advantages and disadvantages of synthesis nanoparticles, 834
methods, 833 Laser scribing method, 506
applications, 840–842 Lemongrass nanoemulsion, 808
Index 1527

Life cycle assessment (LCA), 1185, 1464 Mechanical alloying (MA), 86, 95, 96
Life Cycle Assessment and Risk Assessment Mechanical Characteristics of nanosystems, 40
of Nanoproducts (LICARA) Mechanical treatment, 901
nanoSCAN, 68 Medicine and Healthcare, 1102, 1118
Life cycle risk assessment (LCRA), 1165 Medium density polyethylene (MDPE), 89
Ligand exchange method, 839 MedShape Co., 325
Light barrier, 905 Melamine-formaldehyde resins, 915
Lignin nanoparticles (LNPs), 1287–1288 Melt intercalation, 167
Linear low-density polyethylene (LLDPE), Membrane filtration, 1445, 1446
1280 Membrane processes, 1363
Lip care, 971–972, 1036, 1088 Membrane science, 1418
Lipid carriers, 970 and technology, 1311
Lipid nanoparticles, 14 Membrane separation processes, 21
Lipo/octyl p-methoxycinnamate system Memory-foam pillow, 484
formulation, 969 Mentha piperita, 709
Lipophilic nanoencapsulated molecules, 767 Mercury cadmium telluride (MCT), 653
Liposomes, 14, 558–559, 965, 1042, MeshLab, 530
1081–1082, 1477, 1487 Mesoporous carbon nanoparticles (MCN), 554
cosmetics, 935 Mesoporous silica nanoparticles (MSNs), 349,
Liposome–scaffolds, 565 620–625, 1046
Liquid phase epitaxy method, 232 Metal, 1411–1414, 1419–1425
Li-S batteries, 509 Metalaxyl (Me), 1214
Lithium ion battery(ies), 509 Metal based nanoparticles
cathode, 362 bimetallic NPs, 555
Lithium-sulfur (Li-S) batteries, 1175 metallic NPs, 555
Lithium titanate spinel oxide (LTO), 1117 Metallic nanomaterials, 991
“Little wonders: the world of nanoscience”, 37 Metallic nanoparticles, 12, 109, 555
Local Exhaust Ventilation System Metal matrix composites, 81, 455–460
(LEVS), 1163 Metal NPs–polymer composites, 569
Loop-mediated isothermal amplification Metal-organic frameworks (MOFs), 229
(LAMP) technique, 780 factors affecting properties of, 230–231
future research, 236
incorporation into polymer, 231–233
M Metal-organic frameworks (MOFs) membranes
Magnetic glyco-NPs, 632 desalination process, 235
Magnetic iron oxide nanoparticles, 563 pervaporation, 232–234
Magnetic nanocrystals, 623 Metal oxide NPs, 556–557
Magnetic nanoparticles, 635, 791 Methylene blue (MB), 1068
Magnetic NP-based DNA extraction, 791 Micellar nanoparticles, 993
Magnetotactic bacteria, 836 Michaelis-Menton reaction kinetics, 676
Maleic acid (MA), 921 Microbial polyesters, 176
Malic acid (MLA), 916 Microcomposite-aggregate morphology, 167
Manborui, 323–324 Microcomposites, 85
Manganese (Mn), 1221 Microemulsion method, iron oxide based
Manganese-based NPs, 557 nanoparticles, 835
Manganese oxide NPs, 557 Microfibrillated cellulose (MFC), 247
Man-made composite materials, 162 Microfiltration (MF), 1445
Master model manufacturing technique Microfluidic device, 631–632
SL, 264 Micronutrients, 767, 768
three-dimensional printing, 263 Microreservoir dissolution-controlled
Master models, 259 TDDS, 863
Matrix materials, 81 Micro-spectroscopy FTIR, 648, 652, 656, 657
MeadWestvaco, 480 Microwave irradiation, 901
1528 Index

Milling, 901 industrial effluents and contaminated

Mills, types of, 88 waters, 249–250
Mirabilis jalapa, 709 microfibrillated cellulose, 247
Mixed-matrix membranes, 229 nanocrystalline cellulose, 245, 246
Moisture treatment, 901 nanofibrillated celluloses, 245
Molecular imaging (MI), 566–567 Nanoceramics, 345–348
Molten carbonate fuel cell (MCFC), 366 Nano-cerium oxide, 683
Molybdenum disulfide (MoS2) Nanochitin crystal particles, 1225
nanopores, 1336 Nanoclay/nano-layered silicate, 1285–1286
sponges, 1334–1335 Nanoclay based nanocomposites, 1305
Molybdenum (Mo), 1224 Nanoclays, 165, 754, 1324, 1366
Monosodium methanearsonate, 1358 cation exchange capacity, 1324
Mono-walled carbon nanotubes, 39 large scale applications, 1327–1328
Montmorillonite (MMT), 90, 165, 267 removal of gaseous pollutants, 1326–1327
MS Technology, 495 removal of water pollutants, 1324–1325
Multi-attribute utility theory (MAUT), 1161 Nanocolorants, 972
Multi-criteria decision analysis Nanocomposite coatings
(MCDA), 1161 advantage, 1135
Multidrug-resistant (MDR) microbes, advantages, 1124
1183, 1184 air quality monitoring, 1130–1133
Multifunctional finishing, 923–924 CVD, 1127, 1128
Multi-layered packaging strategies, 782 electrodeposition, 1127, 1129
Multi-layer graphene (MLG), 455 environmental pollution, 1130
Multi-walled carbon nanotubes (MWCNTs), feasible technologies, 1125
174, 342, 554 hardness verses grain size, 1125, 1126
MXenes, 1368 nanocrystalline and amorphous
Myocardial infarction, 680 phases, 1125
properties, 1124
PVD, 1127, 1128
N sensor, 1130
Nafion, 441 spray coatings, 1129
Nail care, 1034–1035 water quality monitoring and treatment,
NaNO2 mediated depolymerization, 599 1133–1135
Nano-based consumer products, 550 wet chemical synthesis, 1129
Nanobiotechnology, 559 Nanocomposite-exfoliated morphology, 168
Nanobiotechnology-based antiaging products Nanocomposite hydrogel, 1218
benefits of, 1006 Nanocomposite-intercalated
commercial nanobiotechnology products, morphology, 168
1008–1009 Nanocomposites, 85, 1099, 1284, 1287,
nano cosmetics on the skin, 1006 1290–1292, 1295
safety and efficacy, 1006–1008 Nanocomposites of polymer matrix, 164–168
Nanobiotechnology based materials, 1006 Nano consumer industry
lists, 1008 anti-fingerprint, 51
Nanocapsules (NC), 754, 937, 966, 1043, 1076, antifog, 51
1216, 1474, 1490 anti-Graffiti, 50
Nanocarriers, 1474, 1475, 1477, 1479, 1480, antimicrobial coating, 51
1488, 1489, 1492 anti-reflective coating, 53
antioxidants, 1490 corrosion protection, 51
CoQ10, 1489 easy-to-clean products, 50
quercetin, 1489 insulation, 52
vitamins, 1488 photocatalytic surfaces, 52, 53
Nano catalyst, 1101, 1105, 1108, 1109 scratch resistance, 52
Nanocellulose (NC), 178, 245–246, 442, 811 tensile strength, 52
bacterial cellulose, 245, 247 wear and tear protection, 51
Index 1529

Nanocontact sensor, 1334 Nanoemulsions, 770, 807, 934, 935, 966, 989,
Nanocontact-sensors, 1181 1044–1045, 1077, 1087, 1221, 1478
Nano-cosmeceuticals, 1006, 1038 Nanoencapsulation, 721, 769, 804, 821,
advantages, 1038 1089, 1474
cerium oxide, 1040 coacervation, 769
CNTs, 1039 core and wall materials, 767
dendrimers, 1039–1040 drying methods after, 769–770
ecological hazards, 1051 emulsification, 767
EU regulations, 1050 emulsification–solvent evaporation, 768
FDA, 1050 fortification through nanoencapsulation, 770
fullerenes/buckyballs, 1041 improvement of vitamin and mineral
gold nanoparticles, 1041–1042 delivery, 770
health hazards, 1051–1052 inclusion complexation, 768
India, 1050 nano approaches for improving
liposomes, 1042 bioavailability of nutrients, 770
nano-capsules, 1043 nanoprecipitation/solvent
nanocrystals, 1047 displacement, 769
nano-emulsions, 1045 safety issues with nanoencapsulation, 771
NLCs, 1044 supercritical fluid method, 768
quantum dots, 1045–1046 Nanofabrication, 1175
silica nanoparticles, 1046 Nanofertilizers (NFs), 1111, 1206, 1221
silver nanoparticles, 1046 Nanofibers, 938, 1216
SLN, 1044 Nanofibers composites, 147
titanium dioxide, 1046 Nanofibrillated celluloses, 245
zinc oxide, 1047 Nanofilled polymeric matrices, 1305
Nanocosmetics Nanofillers, 440, 1208, 1284, 1285,
dendrimers, 967 1289–1291
fullerenes, 968 Nanofiltration (NF), 1133, 1178, 1179, 1445
hair care, 973–974 Nanofluid, 1116
hydrogels, 967 Nano-food packaging, 753–754
lip care, 971–972 active packaging, 755
liposomes, 965 challenges assessment of nanomaterials,
nanocapsules, 966 759–760
nanoemulsions, 966 consumer acceptability in, 757–759
niosomes, 967 efficient packaging, 754–755
oral care, 974–975 in India, 761
skin care, 968–971 role by stakeholders and regulatory
solid lipid nanoparticles, 967 agencies, 760–761
toxic effect of nanotechnology, smart/intelligent packaging, 756–757
975–976 Nano-FTIR spectroscopy, 658–659
Nano cosmetics on the skin, 1006 AFM-IR spectroscopic imaging benefits and
Nanocrystalline cellulose, 245, 246 disadvantages, 659
Nanocrystals, 936, 1047, 1075 carbonate-forming organism, 662–664
Nanocu ®, 1224 chemical mapping of minerals, in biological
Nanodatabase, 69 materials, 661–662
Nanodiamonds, 937, 987, 988 closed-loop, 659–661
Nanodiamonds (ND), 552 probe single bacterium, 666–667
Nanodimension drug delivery tools, 551 subsurface chemical nano-identification,
Nano drug delivery approach, 559 664–666
Nano-edible coatings, 758 Nanogels, 1216
Nanoelectronics, 45 NanoGreen ®, 1224
applications, 45, 46 Nano Guidance for Risk Informed Deployment
definition, 45 (NanoGRID), 68
implications, 45 Nano-imidacloprid, 1229
1530 Index

Nanoliposomes, 559, 767, 806 carbon-based quantum dots (CQDs), 553

Nanomaker procedures, 1462 carbon nano tubes, 553–554
Nanomaterial-based detection, 791 fullerenes, 552
Nanomaterial-based electrochemical global market of nanomedicine, 569
immunosensors, 790 graphenes, 552
Nanomaterials, 39, 163, 374, 377, 438, 472, liposomes, 558–559
539, 656, 1099, 1101, 1412, 1413, 1415, mesoporous carbon nanoparticles
1418, 1421, 1422, 1426, 1460 (MCN), 554
advantages, 103 metallic NPs, 555
adverse effects, 103 metal oxide NPs, 556–557
in anti-wrinkling finishing, 917–923 nanodiamonds (ND), 552
applications, 105, 106 polymeric nanoparticles, 557–558
BET-surface area analysis, 119 solid lipid nanoparticles, 558
carbon based, 474–475 Nanomaterials, in construction sites
characteristic properties, 103 environmental hazards of nanomaterials,
characterization techniques, 113, 114 1164–1166
classification of, 472 evolution of nanoproducts, 1158
in consumer products, 105, 107–111 HIRA, 1160–1164
DLS, 114–117 usage and improvements of, 1158
elemental compositions and crystal Nanomedicine, 539, 785
structures, 103 aims, 614
engineered, 20 blood–brain barrier, 613
environmental applications, 1442, cancer, 613–614
1444–1447 cancer-immune, 626
environmental impact, 925–926 in market, 637–640
FTIR and UV-Visible spectroscopy, 120, 121 uses, 616
green synthesis, 1436, 1437 Nanomicelles, 1216
life-cycle, 1465 Nanoparticles (NPs), 10, 792, 1099, 1206,
material-based categories, 63 1257, 1323–1324
nano-scale properties, 103 AgNPs, 920–921
one-dimension nano-structure, 103 in animals and humans, 1257–1258
physical and chemical properties, 103 on aquatic animals, 1264
plant-mediated synthesis, 1437–1443 on aquatic microbes, 1263–1264
potential health risk, 110, 111 on aquatic plants and algae, 1263
products/applications, 63, 64 bimetallic, 1439, 1442, 1443
properties, 63, 104 bio-barcode method, 626–627
reduction, 1461 cell search device, 632–633
sample preparations, 111–113 chemical nose mechanism, 626
scanning electron microscopy (SEM), chitosan, 922
126–128 chitosan-encapsulated Au, 634
scientific advances in, 25–28 classes, 1256
sources, 63 containing magnetic elements, 791
surface charge (Zeta potential (ζ)), 117–119 in cosmetics and efficacy of herbal
three dimensional nanostructure, 103 nanocosmeceuticals, 1090
transmission electron microscopy (TEM), on crops, 1258–1260
126–130 definition, 1254
two-dimension nanostructure, 103 dermal routes, 1049
types, 106 diagnostic magnetic resonance, 629
X-ray diffraction, 122–126 functionalized Au, 634–636
zero-dimensional nanostructure, 103 hazards of, 640
Nanomaterials, in biomedical field health, safety and environmental impacts,
bimetallic NPs, 555 1090–1091
biomedical applications, 559–569 on humans and animals, 1260–1262
Index 1531

ingestion, 1049 functions, 8–9

inhalation, 1048, 1049 gold nanoparticles, 1506
inorganic, 12 hazard assessment for, 1271–1273
lipid, 14 indirect methods, 1504
magnetic NP relaxation sensors, 629 laser ablation, 1502
mesoporous silica, 620–625 microbial resistance, 1507
metallic, 12 nanoelectronics (see Nanoelectronics)
microfluidic device, 631–632 nanoparticles, 10–14
monometallic, 1438–1441 natural source of, 10
nanomaterials, 1099 polymeric nanoparticles, 1506
opening and closing of the core-shell reactive oxidative species, 1503
structured, 621 scientific research pursuit, 1414–1416
pathways for cellular internalization, 616 silver nanoparticles, 1505
photodynamic therapy, 636–637 in textile industry, 44
polymer based, 13 titanium dioxide, 1505
Raman scattering with surface uses, 6
enhancement, 628 viable plate count method, 1504
as sensors, 626–633 waste water treatment, 1104
SiO2, 922–923 wet chemical method, 1502, 1503
in soil and plants, 1256–1257 zinc Oxide, 1505
subcellular organelles, 618–619 Nanoproducts, commercial and emerging,
surface plasmon resonance (SPR), 629–631 1220–1228
therapeutics, 614 Nanoproducts, environmental protection
TiO2, 918–920 carbon nanotubes, 1328–1330
trimetallic, 1442 future research, 1337
ZnO, 921–922 molybdenum disulfide sponges and
Nanoparticulated nutrients, 1219 nanopores, 1334–1336
Nanopesticides, 1206, 1227 MoS2, 1334–1336
Nanophotonics, 45, 53, 54 nanoclays, 1324
Nanopigments, 937, 938 nanocontact sensor, 1334
Nano-powders, 86 self-cleaning glass, 1331
Nanoproducts (NPs), 1099–1101, 1410–1412, solar active cloth, 1332–1333
1422, 1456, 1501 transparent polyurethane nanofiber air filter,
agricultural applications, 1110 1333–1334
applications, 1426, 1428, 1509, 1510 zeolite cotton, 1336
biomedical applications, 1102 Nanoproducts, of 3DGPNs
categories, 374 conducting applications, 406–407
challenges, 375, 1426 energy storage, 403–405
commercialization of, 1101 environmental protection, 409–411
composition of, 6–7 sensitive detection, 408–409
consumer, 782, 783 Nanoproducts, in cosmetic industry
in consumer industry, 41 bucky balls, 1079
copper, 1506 carbon nanotubes, 1079–1080
in cosmeceuticals, 46–50 cubosomes, 1078
CPI growth, 8 dendrimers, 1078
definition, 374 hydrogels, 1075
disk diffusion method, 1504 liposomes, 1081–1082
DNA destruction, 1504 nanocapsules, 1076
energy, 1112 nanocrystals, 1075
entering cell, 1503 nanoemulsions, 1077
environmental sustainability, niosomes, 1082
implementation of, 1414 polymersomes, 1083
food industry, 41–43 solid lipid nanoparticles, 1080
1532 Index

Nanoproducts, in cosmetic industry (cont.) composite-based NM, 1102

titanium dioxide, 1083 inorganic-based NM, 1102
zinc oxide, 1083 organic-based NM, 1102
Nano-remediation, 251, 1179, 1180 Nanotechnological techniques, 780
NanoRiskCat, 68 Nanotechnology, 5, 37, 162, 577, 798, 912,
Nanorods, 1108 926, 964, 1037–1038, 1098, 1099, 1158,
Nanoscale, 1099 1279, 1411–1413, 1419, 1422, 1456,
manufacturing, 1462 1457, 1460
membranes, 1461 advancements in green, 28–30
technology, 539 advantages, 54, 55
Nano-scaling, 60 and arsenic and heavy metal groundwater
Nanoscience, 1098, 1099 remediation, 31
nanotechnology, 374 chemical composition, 775
Nano-semiconductor catalyst, 1109 conventional methods, 775
Nanosensors, 756, 787, 1227 definition, 774
Nanoshel LLC, 330 disadvantages, 55, 56
Nanosilver (NS), 576–579, 587, 591 in environmental pollution control, 1248
antibacterial properties, 579–580 in food packaging, 1284–1288
antifungal properties, 580 food preservation, 804
anti-inflammatory properties, 581 food science, 802, 803
antiviral properties, 580–581 food sector, 786, 787
biological method of synthesis, 583–584 future recommendations, 1249
biomedical products and effects, 588 future scientific directions and
bone cement, 589–590 recommendations, 31–32
cardiovascular implants, 587–588 and green sustainability, 23
catheters, 588–589 in groundwater remediation and drinking
chemical method of synthesis, 581–582 water treatment, 22
mechanisms of biological interactions, 584 in health products, 11
physical method of synthesis, 582 human health, 799, 802
toxicology, 585–586 instruments, 775
wound dressing, 590–591 merits, 784, 785
Nanosomes, 989, 1477 methods, 775
Nanospheres, 1216 and nanomedicine, 538–540
Nanosponges, 936 nanoscale, 774
Nanostructure, 1099 and nano-science, 1243
Nanostructured lipid carriers (NLCs), 936, 970, properties, 774
1044, 1488, 1489 scientific research in, 1306–1309
Nanostructured materials, 86, 539, 1364 and scientific vision, 1314
for arsenic removal, 1368–1372 Nanotechnology-based agroproducts
based on minerals, 1366 challenges
carbon-based, 1365 commercial and emerging nanoproducts,
classification, 1364–1365 1220–1228
hybrid nanomaterials, 1367 multiple challenges, 1220
iron oxide-based, 1366 nanotoxicity and environmental safety,
metal-based, 1367 1228–1229
MXenes, 1368 public awareness and acceptance, 1232
superparamagnetic materials, 1366 regulation and legislation, 1229–1232
titanium-based, 1366 smart-agroformulations, 1220
Nanostructured polymeric lipid carriers Nanotechnology-based water quality
(NPLC), 970 management, 1416
Nanosystems, 1477–1479, 1491 Nanotechnology Products Database (NPD), 1104
Nanotechnological products, 1101 Nanotechnology Research Centre (NTRC), 1255
carbon-based NM, 1102 Nanotheranostics, 679
Index 1533

Nanothinx, 1330 n-Hexylphosphonic acid (HPA), 170

Nanotools-based agrochemical Niosomal carriers, 971
formulations, 1206 Niosomes, 967, 1082, 1487
Nanotoxicity, 1229 Nitric oxide-releasing nanoparticles
and environmental safety, 1228–1229 (NO NPs), 1184
Nanotoxicology, 1185, 1186 Nitrogen dioxide (NO2), 1131
Nanotubes, 443, 1478 Nitrogen (N), 1219
Nano wastes Noble metal NPs, 565
consumer product applications, 1192–1194 Non-formaldehyde-based reagents, 916–917
disposal procedures, 1191 Normal wound repair mechanism, 696
environmental risks, 1191 NovaLand-Nano, 1224
production, storage, and distribution, 1190 Novel separation techniques, 1418
public awareness, 1191, 1192 nScrypt, 543
Nanowires, 38 Nubiotek ®, 1224
Nanozeolites, 1106 Nuclear localization signal (NLS), 619
Nanozymes, 676 Numerous methods, 778
antibacterial effects, 683 Nutraceuticals, encapsulation of, 742
antioxidation and antinflammation therapy, Nylons, 342
681–682
applications of, 677
biorthogonal chemistry and living cells, 683 O
cardiovascular medicine, 684 Octyl methoxycinnamate (OMC), 970
in diagnosis applications, 677–681 Oil–water separation process, 149
factors affecting properties of, 684–685 Olive oil, 1077
glucose and antioxidant detection, 680 Optical nanoproducts
gold nanoparticles of therapeutic PD, 393
applications, 682 polarizers, 393
H2O2 detection, 681 Optical spectroscopy, 646
imaging, 677–678 Oral care, 974–975
immunoassay, 678 Organic dyes, 1107
myocardial infarction, 680 Organic Matrix Composites (OMCs), 81
neuroprotection, 683 Organic solar cells, 364
status and challenges of practical Organisation for Economic Co-operation and
applications of, 685 Development (OECD), 72,
stem cell growth, 682 1399, 1401
superoxide anion detection, 680 Organophilic montmorillonite (OMMT), 91
therapeutic applications, 681–684 Organovo Holding, 543
tumortheranostics, 679, 684 Organ printing, 537
National Institute for Occupational Safety and O2 sensors, 756
Health (NIOSH), 1048, 1255 OsiriX, 530
National Nanotechnology Initiative Osteopore, 543
(NNI), 1037 Oxford Performance Materials, 543
Natural adsorbents, 1444 Oxidation, 900
Natural antioxidants, 1483, 1484, 1487 Oxidative depolymerization, 599
Natural hydrogels, 531 Oxidative processes, 1363
Natural modes of vibration, 647 Oxidative stress, 528
Natural nanoparticles, 1171 OxSyBio, 543
Natural polymers, 557 Oxygen barrier, 904
Navarro method, 700 Oxygen containing functional (OCF), 379
ND-insulin system, 561 Oxygen dispersion strengthened (ODS), 87
Near-field spectroscopic methods, 658 Oxygen permeability coefficient
NeuCombi ®, 1224 (OPC), 904
Neurotoxicity, 1266 Oxygen scavengers, 755
1534 Index

P Phytochemically synthesized gold

PAA nanoshell, 622 nanoparticles, 701–705
PA-6/CNT compounds, 175 wound healing applications of, 707–710
Paints, Ag-nanoparticle-embedded, 1347–1351 Phytoformulations, 24
Palm oil esters, 1077 Phytopathogens, 816
Paper, food packaging, 887, 891 Phytoremediation, 1362
corrugated cardboard, 888 Pickering emulsions, 742
kraft paper, 888 PLA based nanocomposites, 178–180
parchment/baking paper, 888 PLA-based silicate nanocomposites, 179
Paper towel, 1330–1331 Plant-based nanomaterials
PCL based nanocomposites, 180 food/deterioration, 799, 800
PCR restriction fragment length polymorphism food preservation, 801
(PCR-RFLP), 779 plant-derived formulations, 799
PEEK Altera ®, 325 Plant-based particles
Peptide capped gold NPs, 562 antimicrobial activity, 816
Permanent hair dyes, 974 food preservation, 814, 815
Peroxidase (POD), 813 Plant-based products, 10
nanozymes, 678 Plant-mediated gold nanoparticles, 701–705
Personal protective equipment (PPE), 1141, 1163 Plant-mediated synthesis
Pervaporation, 232–234 bimetallic nanoparticles, 1439, 1442, 1443
Petrochemical-based biopolymers, 1283 bio-fabricated nanomaterials, 1437
Petroleum-based plastic, 882, 883 characterization, 1438
pH5®, 1224 functional groups, 1437, 1438
Phase separated nanocomposites, 195 metal salts, 1437
Phase-separated polymer blends, 163 monometallic nanoparticles, 1438–1441
Phosphoric acid fuel cell (PAFC), 367 trimetallic nanoparticles, 1442
Phosphorus (P), 1219 Plant resources (PR), 340
Photocatalysis, 1415, 1416, 1422 Plasmonic nanoparticles, 301
Photocatalytic approach, 1446 Plastics, food packaging, 885, 889
Photocatalytic degradation, 1428 PET, 886
Photocatalytic nanoproducts, 1415 PP, 886
Photocatalytic oxidation (PCO), 1109, 1417 PS, 886
Photoctalyst, 1108 Plastic wastes, 1203
Photodetector (PD), 393 PlatDrill, 491
Photoelastic modulator, 630 Poly(3-hydroxybutyrate) (PHB), 1283
Photoelectrochemical (PEC), 387 Polyacrylonitrile (PAN), 175
Photoinactivation, 1415, 1416 Polyamide (PA), 151, 166, 342, 443
Photo-induced force microscopy (PiFM), 659 Polyamide-6 (PA-6), 175
Photooxidation, 1416 Polyaniline (PANI), 342, 403, 405, 440
Photopolymerized SMP, 329 Polybutylene adipate terephthalate (PBAT), 1214
Photoprotective niosomes, 971 Polybutylene succinate, 755
Photovoltaic (PV) cell, 1113 Poly(butylene terephthalate) (PBT), 90, 151
Photovoltaic (PV) devices, 1176 Poly(ε-caprolactone) (PCL)-based
Phyllosilicates, 165 nanocomposites
Physical modification, starch chitosan flakes, 301
gamma radiation, 901 3D finger-print, 320
heat moisture treatment, 901 functionalization, 302
mechanical treatment, 901 molecular scale of, 299
microwave irradiation, 901 shape memory properties of, 297
moisture treatment, 901 voltage and flow rate, 303
ultrasound treatment, 902 Polycarbonate (PC), 175
Physical vapor deposition (PVD), 1127, 1128 carbon nanotubes, 272, 273
iron oxide based nanoparticles, 833 definition, 266
Index 1535

fillers, 266 Polymeric matrix (PMMA), 93

glass fiber, 270 Polymeric nanocomposites, 165
glass transition temperature, 259 Polymeric nanomaterials, 251
graphene and graphene oxide, 272 Polymeric nanoparticles (NPs), 557–558, 1478
Kevlar fiber, 268, 269 Polymeric surfactants, 171
nanocomposites, techniques, 273 Polymer inorganic hybrid composite film, 145
pinapple leaf fiber, 271 Polymer intercalation, 166
polymer products, 258 Polymer matrices from sustainable renewable
vacuum casting, 258, 259 sources, 176
Poly-carboxylic acids (PCAs), 916, 917 Polymer matrix, 339, 342
Poly(D,L-glycolide) (PLG), 1479 Polymer matrix composites (PMC), 81, 82, 457,
Poly(D,L-lactic-co-glycolic acid) 460–462
(PLGA), 1479 Polymer matrix diffusion-controlled
Poly(D,L-lactide) (PLA), 1479 TDDS, 863
Poly(e-caprolactone) (PCL), 180, 1479 Polymer membrane permeation-controlled
carbon nanotubes (CNT), 180 TDDS, 862
Poly epoxidized soybean Polymer nanocomposite (PNC), 82, 89, 96,
oil/polycaprolactone, 296 244, 402, 806
Polyethylene glycol (PEG), 96, 920, 1225 EPN, 244–245
Poly (ethylene oxide), 166 WPNC, 251–252
Polyethylene (PE), 166, 175, 1202 Polymer nanoparticles, 13
Polyethylene terephthalate (PET), 408, 440, Polymer nanotechnology, 163
782, 886, 1281 Polymer packaging films, 145
Polyhydroxyalkanoate (PHA), 1205 Polymersomes, 1083
Poly(hydroxybutyrate-cohydroxyvalerate) Poly(methyl methacrylate) (PMMA), 96,
(PHBV), 1479 175, 406
Polyimide (PI), 175 Polypeptide, 341
Polylactic acid-graphene composite films, 513 Polyphenoloxidase (PPO), 813
Polylactic acid (PLA), 178, 382, 1205, Polyphenols, 1483, 1491
1283, 1479 Poly(phenylene sulfide) (PPS), 92
Poly(lactide-co-gycolide) (PLGA), 1479 Polypropylene (PP), 151, 166, 175, 886
Poly-ε-lysine, 1506 Poly pyrrole (PPy), 403
Polymer/BaTiO3 nanocomposites, 169–172 Polystyrene (PS), 175, 342, 440, 886
Polymer/BaTiO3 systems, 170 Poly-styrene-co-methyl methacrylate
Polymer/carbon nanotubes nanocomposites, (PMMA/PS) NPs, 969
173–176 Polystyrene-graphene based
Polymer/ceramic nanocomposites, 169 nanocomposites, 513
Polymer/clay nanocomposites, 165–168 Polystyrene nanoparticles, 1260
Polymer/CNT compounds, 175 Polyurethane (PU), 166, 175, 440
Polymer/hexagonal boron nitride Poly(vinyl alcohol) (PVA), 95, 166, 175, 343,
nanocomposites, 171–173 462, 1481
Polymer/layered silicate (PLS), 91 Poly(vinyl alcohol)/organic montmorillonite
Polymer-based hydrogels, 968 (PVA/OMMT), 91
Polymer blends, 300, 303, 308 Polyvinylidene fluoride (PVDF), 169, 440
Polymer electrolyte, 190, 192–194, 196–199, BaTiO3nanocomposites, 170
201–213, 215–222 Pomegranate seed oil based cream, 971
Polymer-graphene nanocomposites, 512 Porcine serum albumin (PSA), 791
Polymer hybrid nanocomposite film, 144, 146 Porous structure, 402, 405, 410, 412
Polymer hybrid nanomembrane, 149 Potassium (K), 1219
Polymeric composite/nanocomposite PowerBooster, 480
membranes, 1306 Pristine CNTs (P-CNTs), 176
Polymeric electrolyte membrane fuel cells Pristine membranes, 231
(PEMFC), 366 Professional dust masks, 1333
1536 Index

Project on emerging Nanotechnologies Resource-intensive mining, 1463

(PEN), 69 Respiratory toxicity, 1267
Proliposomes, 770 Resveratrol, 1486
Protein, 443 Reticuloendothelial system (RES), 1187
inactivation, 1504 Retinol, 1483
nano-bioengineering, 784 Reverse micelle method, 602
Proton sponge effect, 617 Reverse micelle system, 836
Pt hollow nanodendrites, 684 Reversible addition-fragmentation chain
Public health engineering, 1416 transfer (RAFT) polymerization, 622
PuFF, 494 Risk assessment (RA), 1270–1273, 1465
Pulmonary cytotoxicity, 1268 Risk management, 1269
Pulmonary toxicity, 1268 RNA interference, 616
Pulsed laser irradiation, 988 Rockwell hardness tester DXT-3, 321
Rosmarinic acid, 1486
Rosmarinus officinalis-nanocapsules, 1218
Q Round silica particles, 174
Quantum dot(s) (QDs), 1045–1046, 1084 Rutin, 1486
Quantum dot-sensitized solar cells
(QDSSC), 1113
Quantum mechanical impacts, 40 S
Quarno, 481 Sanitary napkins, graphene-based, 489
Quenching method, 637 Saula ®, 1221
Quercetin, 1486, 1489 Scaffolds, 528
Quinoa seed, 895 Scanning electron microscopy (SEM),
Quinoa starch, 895 126–128, 1061, 1068
Scanning probe microscopy, 658
Scanning tunnelling microscope (STM), 658
R Scanometric assay, 626
Radiation treatment, 901 Scattering-type scanning near-field optical
Radical Status Factor (RSF), 1040 microscopy (s-SNOM), 661, 662,
Raman scattering with surface 664–666
enhancement, 628 Science and technology, 1411, 1412
Random amplified polymorphic DNA Scientific Committee on Consumer Safety
(RAPD), 779 (SCCS), 72, 1060
Reactive oxygen species (ROS), 579, 650, Scientific Committee on Emerging and
1058, 1259, 1273, 1481, 1503 Newly Identified Health Risks
Receptor-mediated endocytosis (RME) (SCENIHR), 72, 729
peptides, 619 Scientific genesis, 1419
Rechargeable batteries, 190 Scientific redeeming, 1412
Recombinase polymerase amplification Scientific sagacity, 1427
(RPA), 790 Screening-based strategy, 65
Recycling, 1203 SEC-S801BT, 486
Red barberry anthocyanins (RBAs), 1294 Sedimentation, 1363
Reduced graphene oxide (rGO), 374, 406, Seed-based method, 701
552, 1447 Selenium nanoparticles (SeNPs), 819
effect, 306 Self-assembled monolayers (SAM), 660
RegenHU, 543 Sensors, 146
Relative humidity (RH), 904 biosensors, 390, 391
Remodelling, wound healing, 693 gas, 392
Renewability, 246 properties, 390
Renewable energy, 358, 1309 Separation methods, 1363
Renewable resources (RR), 339 Shandong Yabin Medical Technology Co., Ltd.,
Resins, 913–915, 924 326–327
Index 1537

Shape fixity, 294, 295, 309 Silver nanoparticles (SNPs), 555, 697, 799,
Shape memory alloy nanocomposites, 288 806, 815, 920–921, 1046, 1103,
Shape memory behavior, 294, 301, 303 1347, 1505
Shape memory effect (SME), 287 Ag-nanoparticle-embedded paints,
acrylate-based photosensitive resins, 294 1347–1351
in Fresnel lens, 322 antimicrobial uses and antimicrobial
graphene oxide–reinforced resistances, 1269
poly( l-lactide-co-ε-caprolactone) benefits, 855
nanocomposites, 295 characterization and application, 859, 860
heating-responsive, 293 chemical reduction, 858, 859
Moiré pattern based on, 317 environmental impact, 1351
PCL-PU-Chitosan biocomposite, 302 history, 855, 856
in PET lenticular lens sheet, 321 properties, 856–858
in polymeric materials, 318 on terrestrial isopods, 653–654
Shape Memory Medical, 325–327 toxicological effects, 1267–1269
Shape memory polymer (SMP) types, 858
Changchun Foliaplast Bio-Tech Silver oxide (Ag2O), 1206
Co., Ltd, 328 SimpleBox4Nano (SB4N) model, 1164
Composite Technology Development, Inc., Simple harmonic oscillator model, 647
329–330 Single layer graphene (SLG), 393
Cornerstone Research Group Co., Single nucleotide polymorphism (SNP), 779
324–325 Single-strand conformation polymorphism
EndoShape, 329 (SSCP), 779
Lubrizol Advanced Materials Co., 330 Single-walled carbon nanotubes (SWCNTs),
Manborui, 323–324 174, 554, 1109
market, 287–288 Single-walled nanotubes, 790
MedShape Co., 325 Sintered tricalcium phosphate scaffold, 541
nanocomposites, 289–312 SiO2 nanomaterials, 107, 108
Nanoshel LLC, 330 SiO2/PCL macroparticles, 290
sensor applications, 313–323 SkelMod 160V supercapacitor, 494
Shandong Yabin Medical Technology Co., SkelStart Engine Start Module 2.0, 493
Ltd., 326–327 Skin
Shape Memory Medical, 325–327 cleansers, 1086
Shape recovery functions, 1475
of composites, 309 lightening creams, 945, 946
and cross linking, 300 penetration, 1475
in ether–vinyl acetate copolymer, 295 two-way barrier, 1475
of gold nanoparticles filled SMP, 291 Skin care, 968–971, 1036, 1479–1482, 1492
kinetics, 310 commercial, 1491
process, 299 SLN-safranal formulations, 970
rate, 294 Small-Angle X-ray Scattering (SAXS)
test, 307, 308 techniques, 124, 125
Shape-retaining doll hair, 328 Smart aerial vehicles, 782
Shear-exfoliation process, 515 Smart-agroformulations, 1220
Shielding efficiency (SE), 153 Smart/intelligent packaging, 756
Signal-to-noise ratio (SNR), 648, 651, 653 freshness indicators, 757
Silica (SiO2) nanoparticles, 922–923, 992, 993, spoilage and pathogenic microbe
1046, 1088 detection, 756
Silicon/silicon dioxide nanoparticles (SiNPs/ time-temperature indicators, 757
SiO2NPs), 819 SMPresin, 327
Silicone oil nanoemulsion, 973 Sodium hypophosphite (SHP), 916–918, 920
Silicon nanaoparticles, 697 Solar active cloth, 1332–1333
Silver (Ag), 8, 1206, 1224 Solar cells, 387, 1113, 1115, 1442, 1444, 1445
1538 Index

Solar cell technology, 364–365 Strength, graphene, 488, 495

Solar collectors, 1116 Succinic acid (SA), 916
Solar protection factor (SPF), 969 Sulfonated graphene (SR), 440
Sol-gel method, 834, 1069 Sulfur dioxide (SO2), 1131
Solid lipid nanoparticles (SLN), 558, Sun protection factor (SPF), 1490
563, 935, 936, 967, 994, 1044, Supercapacitors (SC), 362–364, 384, 1118
1080, 1487 Supercritical fluid method, 768
Solid oxide fuel cell (SOFC), 365 Superhydrophobic sponges, 1334
Solid state ball milling (SSBM), 91 Super magnetic iron oxide nanoparticles
Solid-state gas sensors (SGSs), 1181 (SPIONs), 628–629, 831
SolidWorks, 530 Superoxide anion, 680
Solution enhanced dispersion by supercritical Superoxide dismutase, 682
fluid method (SEDS), 742 Super paramagnetic iron oxide (SPIO)
Solution mixing, 440 nanoparticles, 682
Solvent displacement, 769 Super paramagnetic nanostructured materials,
Sonochemical synthesis, iron oxide based 1366
nanoparticles, 836 Surface-modified gold NPs, 562
Sonolysis, 700 Surface plasmon resonance (SPR), 629–631,
Sophorin, 1486 699
Soy protein isolate (SPI), 1208 Surfactant, 166
Sports watch, 483 Sustainability
Sportswear, 484 and education, 1249
Spray coatings, 1129 environmental and energy, 1242
Starch, 341, 442, 1207, 1283 Sustainable agriculture, 1206, 1220
based nanocomposites, 177 Sustainable development goals, 1427
Starch, food packaging, 891–893 Sustainable nanoproducts
antimicrobial property, 893 energy conversion, 384, 386–388
barrier property, 894, 903–905 energy storage, 383, 384
biodegradable polymer, 893, 902 Sustainable resource management, 431
botanical sources, 893–894 Synchrotron FTIR
carbon dioxide barrier, 905 macro ATR-FTIR microspectroscopic
chemical modification, 899–900 analysis, of silica nanoparticle-
edible property, 894 embedded polyester coated steel
enzymatic modification, 902 surfaces, 668–669
light barrier, 905 signal changes, of biofunctionalized
mechanical property, 905 magnetic nanoparticle attachment on
oxygen barrier, 904 Salmonella sp., 669–671
physical modification, 901–902 Synthetic adsorbents, 1444
starch-based films, 894–896 Synthetic antioxidants, 1482
thermal property, 905 Synthetic hydrogels, 531
TPS, 897–898 Synthetic polymers, 557
water barrier, 904 Synthetic skin, 706
Starch-based nanoparticles (SNPs), 180
Stratum basale, 1061
Stratum corneum, 1476, 1477, 1062–1063 T
Stratum granulosum, 1062 Tailor-made nanosensors, 791
Stratum lucidum, 1062 Tanaka’s approach, 620
Stratum spinosum, 1062 Tangible user interfaces (TUIs), 781
Steel, 884–885 Technology revamping, 1412
Stereolithography (SL) process, 264, 528 Terrestrial ecosystem, NPs on, 1258–1262
Sterilization, 813 Tetraoctylammonium bromide, 700
Stober’s method, 992 TeVidoBioDevices, 543
Strategic controls, 1163 Textile materials, 151
Index 1539

Theranostics, 567–568 Toxicity

Therapeutic molecules, 531 iron oxide nanoparticles, on liver and
Thermal barrier material, 152, 153 kidneys, 656–658
Thermal gravimetric analyzer (TGA), 266 silver nanoparticles, on terrestrial isopods,
Thermal outerwear, 489 653–654
Thermal paste, 490 Toxicological effects
Thermogravimetric analysis (TGA), 895, 1210 of AgNPs, 1267–1269
Thermoplastic polyurethane (TPU), 299, of carbon-based nanoparticles, 1267–1268
308, 440 of gold nanoparticles, 1264–1266
nanofiber air filters, 1333 of titanium dioxide nanoparticles,
polylactide (PLA) SMP blends, 303 1266–1267
Thermoplastic starch (TPS), 177, 894, 897, 903, Toxicology, of nanosilver, 585–586
904, 1209 Transdermal drug delivery system (TDDS)
blends, 898 advantages, 861
composites, 898 backing membrane, 869
starch plasticizers, 898 characteristics, 861, 862
The Team Group, 480 characterization and evaluation, 871–876
Thioglycerol, 1060 drug administration, 860
Three-dimensional carbon nanotube drug characteristics, 869
(3D-CNT), 413 drug matrix, 864, 866
Three-dimensional graphene networks drug reservoir, 864, 865
(3DGNs), 402, 406 drug reservoir gradient-controlled TDDS,
Three-dimensional graphene-polymer networks 863
(3DGPNs), nanoproducts limitation, 861
conducting applications, 406–407 microreservoir dissolution-controlled
energy storage, 403–405 TDDS, 863
environmental protection, 409–411 multiple layer drugs adhesive, 864, 865
sensitive detection, 408–409 nanoparticles, 870, 872, 874
Three dimensional graphene support nano-size drug, 870, 871
(BT/3DG), 1332 patches, 861
Time-temperature indicators, 757 plasticizers, 870
Tip-enhanced Raman spectroscopy (TERS), polymer matrix diffusion-controlled
658, 666 TDDS, 863
Tires, 482, 487 polymer membrane permeation-controlled
TisconSuperlinks+, 491 TDDS, 862
Tissue engineering, 535, 564–565 polymers selection, 868, 869
Tissue scaffolds, 552 protein enhancers, 869, 870
Titana nano-shells, 569 release liners, 869
Titanate nanotubes, 1105 single layer drug adhesive, 863, 864
Titanium-based nanostructured materials, 1366 skin loss, 860
Titanium dioxide (TiO2), 12, 941, 1046, 1083, skin permeation, 865–868
1206, 1505 solvents, 870
nanomaterials, 105, 107 therapeutic options, 860
Titanium dioxide nanoparticles (TiO2NPs), Transmission electron microscopy (TEM),
556, 820, 918–920, 1266 126–130
aquatic nano toxicity, 1267 Transmittance FTIR, 648, 649
neurotoxicity, 1266 TrelliX Embolic Coil, 325
respiratory toxicity, 1267 Trigonella-foenum graecum, 709
α-Tocopherol, 1482 Trimethylol melamine (TMM), 915
Tocopherol, 1488 Triphenyl phosphonium (TPP) cation, 619
Touchless gesture user interfaces (TGUIs), 781 Triple wall CNTs, 174
Touch screen(s), 480, 485 Tri-stimuli sensitive delivery system, 623
displays, 504–505 Tumortheranostics, 679, 684
1540 Index

Tungsten oxide (WOx) nanofibers, on digestive Vitasoil, 1224

gland tissue of Porcellio scaber, 655 Voice user interfaces (VUIs), 781
Turkevich method, 700 Volatile organic compounds (VOCs),
1131, 1132
Vorbeck materials, 480
U Vor-Power straps, 510
Ubiquinone, 1483
Ultra and Nubiotek ®, 1224
Ultrafiltration (UF), 1445 W
Ultra high molecular weight polyethylene Waste management, 1158
(UHMWPE), 175 Waste particles, 1171
Ultrasonication process, 1489 Wastewater treatment methods, 1106, 1107
Ultrasonic cavitation, 988 Water, 1104
Ultrasound treatment, 902 barrier, 904
Ultra-violet (UV) attenuation, 1064–1065 crisis, 1306
Ultraviolet light emitting diode (UVLED), 1109 groundwater remediation, 31
United Nations Guidelines for Consumer and industrial wastewater treatment, 31
Protection, 1985 (UNGCP), 1391, 1392 pollution, 25
consumer basic needs, 1392, 1393 purification, 249, 1412, 1413, 1444, 1446
Consumers’ Right to Education, 1395, 1396 quality monitoring, 1133–1135
Consumers’ Right to Information, remediation, 424, 1312, 1357
1394, 1395 resource management, 1310
dispute resolution and redress mechanism, shortage, 21
1396–1398 softening, 1179
vulnerable consumers, 1393, 1394 treatment, 1178, 1179
United States Environmental Protection treatment technologies, 26
Agency, 1351 and wastewater treatment, 426–429
Urea-formaldehyde resins, 914 Water vapor permeability (WVP), 1205
Urucum oil, 970 Wearables, 488, 496
US National Science Foundation, 39 Wet chemical method, 1502, 1503
Wireless pressure sensor monitoring
system, 144
V Wood, 890
Vaccine carriers, 552 carpenter ants, 891
Vacuum casting carpenter bees, 891
ABS, 264, 265 fungi as agent, 890
conventional methodologies, 274 marine borers, 891
definition, 260 powder post beetles, 891
indirect tooling methodology, 260 termites, 890
material and mould, 260 Wood polymer nanocomposites (WPNC), 251
mould materials, 262, 263, 277 application, 252
products & application, 261 bio-based polymers, 252
vaccum pressure, 260, 262 World Commission on Environment and
Vapor-gas separation, 149 Development (WCED), 1464
Veriflex ®, 324 World Health Organization (WHO), 1059
Vesicular delivery systems, 1477 Wound(s), 691
Vibrational energy characterization, 649 dressing, 565–566, 590–591, 1509
Vibrational energy levels, 648 types of, 691
Vision, 423, 430–433 Wound healing, 691
Visionary future of sustainability, 1242 bottom up approach, 854, 855
Vitamin A, 1483 extrinsic factors, 854
Vitamin C, 1458, 1483, 1487 gold nanoparticles, 698–710
Vitamins, 770 intrinsic factors, 850, 852, 853
Index 1541

mechanisms, 849 nano-particles, 740, 741

metallic nanoparticles in, 696–698 processing, 738, 739
micro-nano, 855 sensor developments, 745, 746
nano formulations in, 694–698 shelf life, 742, 743
nanoparticles, 694–695 Zeolite, 1347
phases, 850, 852 cotton, 1336
silver nanoparticles, 855–860 Zero dimensional materials, 473
stages of, 692–693 Zeta potential (ζ), 117–119
strategies for, 693–694 Zinc (Zn), 1206, 1221
TDDS, 860–872 Zinc oxide, 1047, 1083, 1505
top down approach, 855 Zinc oxide (ZnO) nanoparticles, 556, 697,
types, 850, 851 921–922, 1206
Wrinkle recovery angle (WRA), 918, 921, 922 benefits, 1058
Wrinkle-resistant fabrics cosmetic applications, 1069
conventional methods, 914–917 cosmetic products, 1058
multifunctional finishing, 923–924 cosmetics, 1059
nanomaterials, in anti-wrinkling finishing, inorganic applications, 1066–1069
917–919 light interactions, human skin, 1064
permeability, human skin, 1063
preparation, 1060
X skin blockage characteristics, human,
X-ray diffraction (XRD), 1060 1061–1063
X-ray powder diffraction (XRD), 1068 structure analysis, 1060–1061
sunscreen, 1059, 1065, 1070
synthesis technique, 1070
Z toxicity, 1065–1066
Zea mays, 736 UV attenuation, 1064–1065
Zein Zirconia, 349
biodegradable films, 744, 745 ZnO nanomaterials, 108, 109
corn/maize, 736–738 Zno nanoparticles (Zno), cosmetic applications,
food and non-food sectors, 739, 740 see Zinc oxide (ZnO) nanoparticles
food and nutritional applications, 741, 742 ZnO nanoparticles, on crustacean digestive
micronutrient encapsulation, 743 glands, 655–656