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Bespoke nanostars: synthetic strategies, tactics,
Cite this: Nanoscale Adv., 2021, 3,
and uses of tailored branched gold nanoparticles
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3980
Asher L. Siegel and Gary A. Baker *
Interest in branched colloidal gold nanosystems has gained increased traction due to the structures'
outstanding optical and plasmonic properties, resulting in utilization in techniques such as surface-
enhanced spectroscopy and bioimaging, as well as plasmon photocatalysis and photothermal therapy.
The unique morphologies of nanostars, multipods, urchins, and other highly branched nanomaterials
exhibit selective optical and crystallographic features accessible by alterations in the respective wet-
chemical syntheses, opening a vast array of useful applications. Examination of discriminatory reaction
conditions, such as seeded growth (e.g., single-crystalline vs. multiply twinned seeds), underpotential
deposition of Ag(I), galvanic replacement, and the dual use of competing reducing and capping agents, is
shown to reveal conditions necessary for the genesis of assorted branched nanoscale gold frameworks.
By observing diverse approaches, including template-directed, microwave-mediated, and aggregation-
based methods, among others, a schema of synthetic pathways can be constructed to provide a guiding
roadmap for obtaining the full range of desired branched gold nanocrystals. This review presents
Received 18th December 2020
Accepted 20th April 2021
a comprehensive summary of such advances and these nuances of the underlying procedures, as well as
offering mechanistic insights into the directed nanoscale growth. We conclude the review by discussing
DOI: 10.1039/d0na01057j
various applications for these fascinating nanomaterials, particularly surface-enhanced Raman
rsc.li/nanoscale-advances spectroscopy, photothermal and photodynamic therapy, catalysis, drug delivery, and biosensing.
1. Introduction
1.1 Introduction of branched gold nanoparticles
Since Michael Faraday's famous 1857 lecture entitled “Experi-
mental Relations of Gold (and other Metals) to Light” the world
Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211,
USA. E-mail: [email protected]
at large, from scientists to artists, has been fascinated by the
Asher Siegel is pursuing his Gary Baker received his Ph.D. in
Ph.D. in Chemistry at the 2001 from the University at
University of Missouri-Columbia Buffalo under the direction of
under the supervision of Frank Bright. He was a Frederick
Professor Gary Baker. He earned Reines Postdoctoral Fellow at
his B.A. degree in Chemistry Los Alamos National Laboratory
from Skidmore College in Sar- before transitioning in 2005 to
atoga Springs, New York in Oak Ridge National Laboratory
2016. His current research as a Eugene P. Wigner Fellow
focuses on synthesizing aniso- and research scientist. In 2011,
tropic noble metal nano- he relocated to the University of
particles—with particular Missouri where he is Associate
emphasis on photochemically Professor in the Department of
controlled and plasmon-mediated methods—for use in energy, Chemistry. He currently leads a research group focused on two
biomedical, and sensory applications (e.g., SERS, catalysis, and primary areas: (i) ionic liquids and deep eutectic solvents designed
photothermal therapy). for diverse tasks and (ii) the growth of bespoke nanoparticles
exhibiting features tailored to theranostics, photoacoustic bio-
imaging, and catalysis.
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relationship between colloidal metals and optical properties.1,2 made when seeking to design branching AuNPs is that of
Perhaps due to the inherent human interest in precious metals a seeded or seedless growth method. It is even reasonable to
that can be tracked for millennia, this enchantment has resul- categorize all syntheses of these materials into either seeded or
ted, in part, in the eld of nanoscience. For current day seedless growth as the choice is so pivotal to the resulting
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researchers the ever-increasing interest in the eld of nonbulk morphology.31 The advantages and disadvantages of each
materials may be driven by a desire to constantly push the method have been described as well as the underlying consid-
boundaries of control to the atomic level and beyond. erations that must be made with each synthetic route.
As gold-based nanoparticles (AuNPs) continue to amass
attention due to their application in a broad range of scientic
elds, it becomes necessary for those researching the develop- 2.1 Seeded growth
ment of such materials to fully realize their potential. To this The role of seed precursors demands more scrutiny than many
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end, an understanding of the techniques used to precisely tune other procedural choices in the synthesis of these nanosystems.
the morphologies of noble metal nanomaterials is of vital The choice of seed-mediation allows for the temporal separa-
importance. Through the years the synthesis of a great number tion of nucleation and growth processes, leading to better
of gold nanomaterial morphologies has been realized through control over the shape and size of the resulting nano-
careful experimental considerations including spherical nano- systems.32,33 In seed-mediated growth of gold nanosystems,
particles,3 nanorods (AuNRs),4 nanoprisms,5 nanocubes and a typical reaction witnesses small, spherical gold nanoparticles
cages,6 and an assortment of concave7 and hollow8 nano- acting as nucleation centres for the preferential deposition of
materials, as well as the focus of this review, branching additional Au(0) atoms. By adjusting parameters such as
morphologies.9 temperature and pH of the solution as well as the injected
The interest in branching AuNPs largely derives from the Au(III) : seed ratio, spherical citrate-stabilized gold nano-
exhibition of their enhanced optical and catalytic properties, as particles can be grown to sizes exceeding 200 nm.34 In the
well as synthetic methods that demonstrate “greener” and less growth of branching gold nanosystems, isotropic growth can be
toxic reagents than other anisotropic gold nanomaterials.10 stunted by interactions between surfactants or ions with
Branching particles have also demonstrated assembly-based specic crystal faces, driving selective deposition of free gold
plasmonic properties; coupling of plasmon modes can occur onto unblocked surfaces. The roles of such shape-directing
if the particles are separated by a small enough distance, agents will be discussed in later sections; here instead the
expanding the possibilities of application.11 The introduction of choice of seed crystallinity, size, and relative concentration will
thorns, branches, spikes, and petals into a eld mostly led by be described.
ordered and symmetrical morphologies provides inroads for Accordingly, the crystalline structure of the precursor seed
efficiency in various applications that have yet to be realized. As plays a crucial role in the nal morphology of the nanosystem.
such it is worthwhile to dene the parameters that dictate the Wulff's theorem states that a singular fcc metal crystal, like Au,
resulting nanostructures to help provide an experimental would form a truncated octahedron if formed under inert
roadmap towards the specic tuning of these materials. conditions. When formed in solution however, the crystals may
assemble into alternate structures due to differences in facet
1.2 Scope of review surface energies attributed to interactions with capping agents
and the solvent itself. Crystal structures that do follow the Wulff
In this review article we describe common methodologies
construction in solution include Au single crystalline seeds,
towards the synthesis of branching AuNPs such as gold nano-
consisting of a mix of low index [111] and [100] facets. As with
stars (AuNSs),12–14 nanoowers (AuNFs),15–17 nanourchins
most seed-mediated syntheses the growth process can be
(AuNUs),18–20 nanodendrites (AuNDs),21–23 multipods,24–26 and
controlled by selective adsorption of ions and capping agents.
a variety of miscellaneous shapes such as snowakes27,28 and
However, some researchers have proposed that single or
nanoarrows.29,30 In particular, this article focuses on the
multiply twinned seeds are necessary to facilitate the growth of
common synthetic techniques utilized by researchers to achieve
branches in noble metal particles.35,36
greater shape and size control over these nanomaterials
Under this assumption, the pathway for single crystalline
through considerations such as shape-directing agents, solvent,
seed-grown branching nanoparticles comes from the develop-
and reactor conditions. Finally, common uses of branching
ment of twin defects through a coalescence/fusion mecha-
AuNPs have been described with a specic description of the
nism.37 As facet-selective deposition occurs onto the gold seeds
nanomaterial parameters necessitated by each application that
and size begins to increase, structural uctuations in the single
are tuneable through procedural choices.
crystalline species are observed; in order to lower the overall
energy of the enlarged particle, the twinning motif can change,
2. Precursor methodology inducing growth of additional twin planes and resulting in
considerations a seed morphology more suitable for branched particle growth
(Fig. 1).
While a scrutinizing eye must be used in selecting from the This process of single crystalline seed evolution was recently
large variety of synthetic parameters, experimental methods, investigated in detail through the synthesis of multi- and six-
and reaction vessels, the most fundamental choice that must be branched gold nanostars by Atta et al.38 A typical creation of
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Fig. 1 Models and STEM images depicting the proposed growth
pathway of a single-crystalline seed in a plasmon-mediated reaction,
taken at various points in the same reaction. (A) STEM image of the
Fig. 2 (a) TEM micrograph of the seeds with an average diameter of
pseudo-spherical single-crystalline Au seeds. (B to J) STEM images of
3 nm. The HRTEM micrograph (inset) shows the single crystalline
bimetallic particles with (B) octahedral, (C) truncated tetrahedral, (D)
morphology of the seed, with an interplanar spacing characteristic of
tetrahedral, (E) truncated bitetrahedral, (F) bitetrahedral, (G) truncated
the {111} plane in FCC gold. (b and c) TEM and STEM micrographs of
decahedral, (H) decahedral, (I) decahedral with an additional tetrahe-
penta-twinned intermediate seeds isolated within the first instance of
dral growth, and (J) icosahedral morphologies. Scale bars, 25 nm;
growth of the 6-branched stars. (d) High resolution STEM image of the
reprinted with permission from ref. 37. Copyright © 2012 American
selected area of (c) exhibiting a fivefold symmetry. (e) STEM image of
Association for the Advancement of Science.
a typical penta-twinned intermediate seed showing one five-fold
symmetry and two four-fold symmetry defects, which correlates with
the 3D construction of the decahedral morphology of the penta-
the AuNSs in question consisted of the synthesis of single twinned intermediate seeds. (f) Representation of spike growth from
crystalline seeds with (111) planes by reduction of HAuCl4 by decahedral seeds. Top image: Schematic side view identifying the
spike growth directions on seeds such as that shown in (e). Bottom
NaBH4 in the presence of surface Triton X-100 at various
image: Schematic top view representing five neighbouring facets. (g–i)
concentrations. The seeds, AgNO3, and ascorbic acid were TEM and HRTEM images of multiply twinned intermediate seeds iso-
added to a growth solution of HAuCl4 in Triton X-100, the lated within the first instance of growth of the multibranched stars.
concentration of which was equal to that of the seed solution. By Reprinted from ref. 38 with permission from the Royal Society of
arresting the nanoparticle growth with n-pentane thiol at 10 s Chemistry.
aer reagent addition to the growth solution, the evolution of
the seeds could be observed (Fig. 2). solution under acidic conditions. 5 s aer the seed addition,
At high ascorbic acid concentrations, the seeds develop into a small aliquot of AgNO3 was injected followed by, 5 s later, AA.
multiply twinned intermediates, resulting in multi-branched The AuNSs synthesized with the smaller seeds yielded smaller
AuNSs. The excess reducing agent is believed to cause the core and tip-to-tip diameters than those with the 12 nm seed.
migration of gold atoms to low energy facets such as {111} by Meanwhile the branches resulting from the 5 nm seeds are
increasing the negative charge on the seeds. Conversely, at relatively longer, but no differences in the number of branches
lower ascorbic acid concentrations, a slower reduction of Au(III) were observed despite the assumed increase in defects in the
takes place, resulting in penta-twinned intermediates appro- 12 nm seeds (Table 1).
priate for the growth of the six-branched AuNSs. These results A more dramatically signicant parameter to consider in
strongly suggest that while crystalline defects may be necessary seeded-growth structures is the ratio of seeds to Au(III) (Rseed). In
for such branching anisotropic growth, such twinning can be the same work by Indrasekara et al. an increase in this ratio,
both induced and specically tuned by altering the reactant. regardless of seed size, resulted in a branch length : core size
The number of surface defects in polycrystalline seeds decrease, core size decrease, and a branch density decrease. As
however depends on their size.39,40 A recent publication by the number of seeds increases relative to the free Au(III) ions the
Indrasekara et al. on the synthesis of surfactant- and capping- amount of free-gold that can be deposited onto each seed
agent-free AuNSs can serve as a model system to study the decreases, understandably limiting growth. Consequently, at
effect of seed size on the resulting morphologies as it eliminates lower Rseed values, the abundance of Au(III) leads to increased
the inuence additional shape directing-agents may have on branch density and overall length, resulting in a red-shiing of
pre-branch-growth.41 the main LSPR mode. An increased number of branches and
The researchers synthesized 5 nm and 12 nm gold nano- length inevitably leads to more dispersity in the branch
particles capped by citrate, through modied Turkevich morphologies themselves, causing broadening of the LSPR
methods. The chosen seeds were added to a gold chloride band (Fig. 3).
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Table 1 Dimensions of the features of AuNSs and their LSPR peak positions as determined by TEM analysis; adapted with permission from ref. 41.
Copyright © 2018 American Chemical Society
Core diameter Tip–tip
AuCl4/mol Ag+/mol Quantity of seeds/particles LSPRmax (nm) (nm) distance (nm) Branch density
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Change in the amount of d ¼ 5 nm Au seeds in growth solution
2.5 106 1.02 107 2.5 1011 800 93 11 145 30 7–8
2.5 106 1.02 107 5.0 1011 738 70 9 105 28 8–10
6 7
2.5 10 1.02 10 1.0 1012 690 57 8 80 16 5–6
2.5 106 1.02 107 2.0 1012 658 46 7 67 15 5–6
6 7
2.5 10 1.02 10 3.0 1012 638 39 6 59 14 4–5
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Change in the amount of d ¼ 12 nm Au seeds in growth solution
2.5 106 1.02 107 1.5 109 800 105 13 148 23 9–10
6 7
2.5 10 1.02 10 3.0 109 750 89 11 130 18 9–10
2.5 106 1.02 107 4.5 109 696 86 27 114 36 6–7
6 7
2.5 10 1.02 10 7.5 109 650 64 10 89 17 5–6
2.5 106 1.02 107 1.0 108 630 67 17 50 12 4–5
Change the Au3+/Ag+ molar ratio with d ¼ 5 nm Au seeds in growth solution
2.5 106 2.50 108 1.0 1012 658 104 13 187 32 3
2.5 106 5.10 108 1.0 1012 742 90 13 134 30 5–6
2.5 106 2.04 107 1.0 1012 782 96 16 137 26 10
2.5 106 3.06 107 1.0 1012 822 68 9 136 31 15
Furthermore, not only can the Rseed value affect the resulting group in their seed-based, silver-mediated synthesis of gold
branch length : core ratio, but also the magnitude of the nanostars for in vivo tumor imaging.45 By simply adjusting the
morphological evolution of the particles during the growth precursor seed concentration at constant AgNO3, ascorbic acid,
process. As many branched nanoparticles are formed an inherent and HAuCl4 concentrations the group demonstrated synthesis
blue-shi in the LSPR can be observed as gold atoms located on of highly monodisperse gold nanostars at sizes of 30 or 60 nm.
high energy facets migrate in an effort to lower the overall particle The researchers examined the tumor accumulation rates of
surface energy.42 In the synthesis of seed-mediated gold nano- these nanoparticles and observed both a higher presence and
stars utilizing hydroquinone as both a capping and a reducing deeper tissue penetration of the 30 nm AuNSs when compared
agent it was discovered that such a blue-shi during particle to their 60 nm counterparts. This simple synthetic adjustment
evolution could be minimized relatively by lowering the relative allows for signicant changes to particle morphology without
seed concentration.43 The lower seed population may allow for modication or addition of reactants that may increase
more complete surface adsorption by the hydroquinone, biocompatibility or cytotoxicity of the nanomaterials.
arresting further possible evolution.44 As seed-mediated growth reactions are not one-pot, the
This facile method for morphological and size control of systematic order of seed addition to the synthesis must be
branched nanoparticles was demonstrated by the Vo-Dinh considered as well. Barbosa et al. identied that the addition of
Fig. 3 Comparison of the optical absorbance features and morphological characteristics of AuNSs with similar main LSPR peak positions (l1)
obtained by using Au seeds of different sizes. Normalized absorbance spectra (a and c) and the TEM micrographs (b and d) of AuNSs synthesized
using varying amounts of (a) d ¼ 5 nm and (b) d ¼ 12 nm Au seeds with l1 max at 650, 700, 750, and 800 nm. Scale bar 100 nm; reprinted with
permission from ref. 41. Copyright © 2018 American Chemical Society.
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Table 2 Qualitative comparison of the seed-mediated versus seed-less synthesis methods of branching gold nanoparticles
Seed-based syntheses Seed-less syntheses
Dened growth template from precursor seeds A more sensitive nucleation phase
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Greater control over particle size and morphology Lesser control over particle size and morphology
Relatively insensitive to reaction condition changes Highly sensitive to reaction condition changes
Not one-pot reactions One-pot reaction
Oen must utilize harsh reagents Can easily rely on “green” reagents
to be selectively red-shied to 750 nm making these ower-
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the seed precursor to the growth solution prior to full Au(III)–
Au(I) reduction resulted in higher polydispersity of the resulting like structures ideal candidates for imaging techniques such
branching products due to oxidation of the seeds themselves.46 as surface enhanced Raman scattering (SERS).
Conversely, if the addition of the seeds to the growth solution is The ability to control the morphology within seedless
delayed, nucleation of the Au salt can be observed.47 Identifying syntheses is paramount to their viability in application. While
optimal time-of-addition conditions can be accomplished by the tunability of seed-based syntheses of branching AuNPs is
observing the reduction of Au(III) to Au(I) by monitoring the UV- highly dependent on the Rseed value, Webb et al. demonstrated
Vis extinction spectrum of the growth solution; the reduction of the tunability of seedless 4-(2-hydroxyethyl)-1-
Au(III) witnesses the diminishment of the characteristic 314 nm piperazineethanesulfonic acid (HEPES)-reduced
absorption.
While the morphology-directing inuence of surfactants and
ions such as Ag(I) and halides cannot be ignored in seed-based
syntheses of branching AuNPs, the selection of the appropriate
gold nanoparticle precursor plays a signicant role and must be
approached with extreme scrutiny. While this review has
focused on isotropic gold nanoparticles, as they are the system
most oen used for seeded growth, the utilization of aniso-
tropic gold seeds is described periodically in later sections.
2.2 Seedless growth
The use of a gold seed precursor does offer some additional
controllability in the nal morphology of branching gold
nanosystems based on seed size and crystalline structure (Table
2). However, due to minor heterogeneities in the structures of
the seeds, this method of synthesis oen leads to polydispersity
in both size and shape of the resulting morphologies.48–50
Alternatively, the one-pot, seedless method is primarily depen-
dent on the choice of reducing agent and surfactant. Signicant
drawbacks do exist as such shape-directing agents (e.g. PVP and
CTAB) strongly adsorb onto the gold surface, limiting applica-
tion without additional “clean up” of the samples.51
It is of great interest then in a seedless approach to consider
more mild, water soluble, and biocompatible reducing/capping
agents to limit such barriers in the utilization of the nano-
systems in SERS, biolabeling and therapeutics.
A recent example of seedless-mediated AuNFs synthesized
under these considerations was demonstrated by Kariuki et al.52
Using a poly(pyromellitic dianhydride-p-phenylenediamine)
Fig. 4 Scanning electron microscopy images of AuNSs synthesized by
(PPDD) water soluble polymer as both a reducing and a capping (a) 160 mM HEPES buffer and (b) 300 mM HEPES buffer showing the
agent, the polycrystalline owers demonstrated well-resolved three-dimensional morphology of the MGNs. Transmission electron
peaks of (111), (200), (220), and (311) with preferential growth microscopy (TEM) images of AuNSs synthesized with varying HEPES
in the h111i direction, a deposition pattern in line with the face concentrations: (c) 30, (d) 100, (e) 160, and (f) 300 mM. High-resolu-
tion TEM images of AuNSs with d-spacing indicating (g) the {111} facet
centred-cubic structure of Au. Upon varying the polymer
in the AuNS core and crystal plane twinning and (h) growth along the
concentration it is likely that the rate of reduction of the free h111i direction for the AuNS protrusion. The scale bar is 2 nm in both (g)
gold ions increased, causing rapid deposition onto the and (h); reprinted with permission from ref. 48. Copyright © 2014
preferred facets. As such, the LSPR peak of the AuNFs was able American Chemical Society.
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multibranched gold nanoantennas by modifying the concen- proposed that an underpotential deposition (UPD) of up to
trations of the two reactants, HAuCl4 and HEPES, as well as the a monolayer of Ag(0) occurs on selective facets, stopping further
pH of the buffer (Fig. 4).48 As the HEPES : Au(III) ratio increased deposition or migration by gold ions.61,62 While there is exper-
(RHEPES) at a constant buffer pH of 7.4 from 1.5 to 18, the imental and theoretical support for the two proposed silver-
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resulting branches, protruding from the h111i direction, mediated methods, in both cases the presence of AgNO3
increased in length and thickness. As HEPES concentration appears to induce symmetry breaking at nucleation sites of
increases, the additional shape-directing ligands during the single crystalline gold seeds, leading to anisotropic growth.63
nucleation phase help shape the seeds in situ. The weakened The relative ratio of Ag(I) : Au(III) determines at which point of
adsorption of HEPES molecules onto the (111) plane allows seed growth the defects will form.
selective deposition of reduced gold atoms and growth in that As such, the two greatest parameters to consider when pre-
direction. This level of nucleation control may not be possible if forming a Ag(I)-mediated synthesis of seeded branching gold
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using prepared seeds as precursors. nanosystems are the concentration of Ag(I) and the crystalline
Many of the disadvantages of a non-seeded approach can be structure of the seed. Branching gold nanoparticles show
overcome by carefully tuning the synthetic parameters previ- distinct twin boundaries that match those of the seeds they are
ously mentioned (e.g. pH, reductant concentration/strength). grown from; however, at appropriate AgNO3 concentrations
One prominent remaining hurdle is matching the size-control additional defects can be introduced.36,62 During growth, the
demonstrated by seed-mediation. In an effort to do so, seed- shape and size of branches can be subsequently controlled by
less silver- and ascorbic acid (AA)-synthesized AuNSs were increasing the concentration of AgNO3 added. Atta et al.
created by carefully examining and altering the order of reactant recently showed that the role of AgNO3 in the synthesis of 6-
addition of the original seed-based method by Yuan et al.53,54 branched stars can move beyond morphological selectivity and
The seeded method procedure saw simultaneous addition of into tunability.38 As the Ag(I) concentration was increased in the
the reducing agent, AA, and shape directing agent, AgNO3, synthesis of the TritonX-100-capped six-branched species,
added to a solution containing colloidal seeds and HAuCl4. In branch length increased as well (Fig. 5).
the recent seedless method, Phiri et al. injected HAuCl4 into The spike growth was more drastic with relatively higher
a solution of AA at a low pH (RAA ¼ 2). Aer approximately 10 s silver concentration additions (8 nm per 10 mM addition from
of mixing AgNO3 was rapidly injected, leading to AuNS forma- 30 to 60 mM as opposed to 2–3 nm per 10 mM addition from 60 to
tion directed through the underpotential deposition (UPD) of 100 mM). Not only did the stars exhibit branch elongation, but
silver. The 10 s of mixing time before Ag(I) addition allowed for the branch sharpness (spike core width : tip width) increased as
creation of necessary nucleation sites by a seed-mediated well. At low AgNO3 concentrations, the stars will undergo
method. By adjusting the induction time allowed for the surface energy minimization by relocating atoms from the high
ascorbic acid and HAuCl4 before Ag(I) injection, Phiri et al. energy {111} facets on the sides of the tips to the low energy core
demonstrated non-seeded growth of AuNSs comparable in facets. However, reports have shown that as the amount of
terms of size control to that of the seeded-growth method. This
type of procedural discrimination demonstrates the necessity
for careful understanding of the experimental parameters
chosen during seedless synthesis of branching AuNPs, careful
control over the nucleation in particular. While seeded methods
hold the advantage as the nucleation phase occurs on
a template of known facet composition and crystallinity, one
much consider the initial reduction of Au(III) to Au(I) as a step of
heightened importance.
3. Synthetic techniques
3.1 Silver-mediated growth
The role of Ag(I) in the synthesis of anisotropic gold nano-
structures has been investigated since Chang et al. showed that
the aspect ratio of gold nanorods could be controlled by intro-
Fig. 5 (a–i) TEM micrographs of nanostars formed at different AgNO3
ducing AgNO3 into the growth solution.55,56 While the exact
concentrations: 30 mM (a), 40 mM (b), 50 mM (c), 60 mM (d), 70 mM (e), 80
mechanism of Ag(I) is debated, the addition of silver nitrate to mM (f), 90 mM (g), 100 mM (h), and 110 mM (i). The concentration of the
seed-mediated synthesis of branching gold nanoparticles allows other two chemical variables (ascorbic acid and Triton-X) was 1.6 mM
for control over spike length, even in the absence of surfactants and 0.15 M, respectively. Scale bars are 20 nm (inset). (j) UV-vis spectra
or templates.35,57,58 Initial investigations into Ag(I)-mediated (normalized) for each of the colloidal dispersions showing a gradual
red shift with increasing AgNO3 concentration as the spike length is
anisotropic growth suggested that a complexation between the
increased, and a blue shift after 100 mM AgNO3 as silver is deposited at
Ag(I) and the commonly used capping agent cetyl- the core. (k) Evolution of the average spike length as a function of
trimethylammonium bromide (CTAB) resulted in the blocking AgNO3 concentration. Reprinted from ref. 38 with permission from
of growth on specic seed faces.59,60 Alternatively, it has been The Royal Society of Chemistry.
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AgNO3 increases, reformation decreases and the spikes main- studies have examined the oxidation potential of aqueous
tain their sharpness; deposition of a monolayer or sub- HAuCl4, with recent work from Ayeni et al. proving through
monolayer of Ag atoms helps to stabilize the gold atoms cyclic voltammetry that, regardless of concentration, gold(III)
through Au–Ag–Cl interactions.37,64 Exploitation of this mecha- chloride solutions have oxidation potentials of 0.55 V and
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nism may allow for control over branch length that exceeds that reduction potentials of 1.23 V.66 As such, appropriate reducing
of nearly all the other common synthetic parameters. agents can be selected in order to reduce Au(III) salts to zero-
The Mirkin group has been instrumental in determining the valent multi-atom Au species. Moreover, the reducing agent
facet-selectivity of Ag(I) ions in such syntheses. Such a study by must be of signicant strength to guarantee that the reduction
Personick et al. demonstrated the synthesis of a variety of gold is an irreversible reaction. While the surface migration of gold
nanomorphologies mediated by AgNO3 at different Ag(I) : Au(III) atoms towards low energy facets and the use of etchants to
ratios.64 CTAC-capped 7 nm gold seeds were added to growth remove deposited gold are both common causes of nanoparticle
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solutions containing HAuCl4, and variable amounts of AgNO3, reshaping, instability due to reducing agent weakness may lead
HCl, AA, and CTAC. Four different Ag(I) : Au(III) ratios led to four to full degradation of the particle. Amongst previous literature
different morphologies: octahedral (1 : 500), rhombic dodeca- reports that does so, a recent, signicant study by Rodrigues
hedra (1 : 50), truncated ditetragonal prisms (1 : 12.5), and et al. describes in great detail the use of reductants on colloidal
concave cubes (1 : 5). The octahedral morphologies are bound metal nanosystems and their underlying mechanisms.67
by eight {111} facets which, as the most thermodynamically Accordingly, this section will briey describe common reducing
favourable of the gold fcc facets, are formed in the absence of agents used specically for branched AuNPs and the inu-
a signicant amount of Ag(I) ions for direct growth. Low encing parameters.
concentrations of silver ions are unable to completely cover Among the most common reductants in the synthesis of
large, high energy facets, leading to displacement by Au ions noble metal nanoparticles are hydrides, phenols, organic acids,
and Ag migration to lower energy facets where complete and nitrogen-containing compounds. As the nal morphology
coverage is possible. A higher concentration of Ag(I) will of the nanosystems is, at the very least, dependent on the initial
successfully deposit onto and fully cover open facets and avoid reduction rate of the metal salt, the choice of reductant strength
displacement, driving Au deposition and growth onto lower is vitally important.42 Extremely strong reducing agents such as
energy facets. Through careful control of the AgNO3 concen- sodium borohydride are rarely utilized in the synthesis of
tration in the synthesis, the growth phase of the nanoparticle anisotropic nanoparticles, as the extremely fast reduction
synthesis can be carefully controlled. instead oen yields small, isotropic particles.68,69 In seeded
This was additionally demonstrated by the Fabris group, who growth, such strong reductants will cause the reduction of free
in a seed-based nanostar synthesis demonstrated the tuning of Au(III) ions into new spherical particles rather than deposition
the particles' SPR into the shortwave infrared (SWIR) range.65 In onto pre-existing seeds.
a selective reduction of free Au(III) ions onto the precursor Alternatively, phenols such as ethylene glycol and hydro-
surface by ascorbic acid, facilitated by TritonX-100, the quinone are strong enough reducing agents to reduce Au(III) in
researchers demonstrate a range of the nanostars' primary the formation of gold nanomaterials, but are susceptible to
resonance peak from 600 to 2000 nm. This extreme, controlled oxidation to products capable of mild reduction, making
SPR red-shi is attributed to an increased concentration of branching morphologies possible. Lee et al. showed that
AgNO3 in the reaction mixture. The resulting monolayer of Ag is branched AuNPs could be synthesized using o- and p-hydrox-
hypothesized to increase the morphological stability of the yphenols without additional surfactants.70 The self-conversion
particles, in particular of the branch tips. It is thus suggested by of the hydroxyphenols into pyrocatechol (quinone) allowed for
this author that the increased silver concentration contributes initial electron donation and the propagation of gold seeds. The
to a full silver monolayer rather than a submonolayer as quinone species are less reactive than their hydroxyphenol
proposed at times in the literature, disallowing migration of predecessors and the mild reduction helps drive secondary
gold atoms from the peaks to low-energy core facets. The hyper- Au(III) reduction to Au(I), allowing deposition onto the seeds'
stability of the tips leads to increased branch length and the low energy facets, forming branches. Dopamine, an amine
resulting SWIR extinction. functionalized dihydroxylphenol, used extensively in the
However, a disadvantage to the use of silver in such synthesis formation of branching AuNPs, can generate secondary spikes
does exist. As the UPD of Ag is most efficient under acidic protruding from the primary branches.71,72 The terminal
conditions, attempts to manipulate the growth process through primary amine group introduces a tertiary reducing agent,
increases in the solution pH may be likely to cause a loss of leading to these thorns. Liu et al. found that at high concen-
tunability. As such some limitations will exist if attempting to trations of polyphenols such as pyrogallic acid, hydroxyl groups
alter the reduction or capping ability of certain reagents. are oxidized into carbonyl groups. Competition between
phenolic hydroxyl and carbonyl groups increases anisotropic
growth protection and can result in AuNFs.73 Phenolic synthesis
3.2 Reducing agent choice of branching AuNPs suggests that such anisotropic morphology
In the selective reduction of Au(III) salts in the synthesis of is dependent on competing and complementary reducing
nanoparticles, the choice of reducing agent is signicant in forces; however, the use of other mild reducing agents in the
determining the isotropic or anisotropic morphology. Extensive presence of other shape directing agents is widespread as well.
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donation of a singular electron resulting in radical formation.81
The oxidized products, whether amines, imines or nitriles, are
capable of coordinating with the resulting nanoparticles, and
drive facet-selective growth.67 Many biomolecules contain such
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nitrogen-groups and an understanding of their use as reduc-
tants is vital to the synthesis of green AuNPs.
The use of two or more reducing agents has simultaneously
been employed in the creation of small, spherical nanoparticles
in fundamental gold seed production, such as the Turkevich
method. In these syntheses however, one strong reducing agent,
NaBH4, was used to reduce gold to its zero-valent state while the
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Fig. 6 (A–H) TEM images showing the morphology and branching
evolution of AuNPs formed in the presence of (A) 0.77, (B) 0.92, (C) second, citrate, acts as a stabilizing ligand. The use of two
1.07, (D) 1.34, (E) 1.97, (F) 2.63, (G) 3.49, and (H) 4.68 103 M ascorbic highly effective reducing agents without a stabilizing ligand can
acid while keeping the concentrations of TX-100, HAuCl4, and AgNO3 signicantly alter the mechanism for nanoparticle growth,
under standard conditions. Scale bars are 200 nm (main) and 70 nm leading to anisotropy. The reduction of HAuCl4 by both tannic
(inset). Reprinted with permission from ref. 78. Copyright © 2015 Wiley.
acid and NaBH4 saw tannic acid taking on the role of a stabi-
lizing ligand in the resulting spherical nanoparticles, as evi-
denced by similar results when tannic acid was replaced with
Organic acids such as ascorbic, citric, and formic acid are
the nonreducing stabilizing ligand PVP.82 When the tannic acid-
widely used in tandem with surfactants to achieve anisotropic
based dual reduction is undertaken with a more mild reducing
gold nanoparticles. The pH sensitivity of organic acids' redox
agent than NaBH4, ascorbic acid, the two reducing agents work
potentials allows for their use in seeded growth syntheses.
in tandem, conrmed by conformational changes as the
Arguably the most utilized reducing agent for branching AuNPs,
concentration of tannic acid increases, and yield both stars and
AA has been applied to form gold multipods,36 stars,74 urchins,19
urchin-like gold structures. The use of two reducing agents
dendrites,75 and more26,76,77 and can be examined as a model for
simultaneously can cause two-step reduction; rst a nucleation
organic acid reductants. Work from our group has shown the
event occurs directed by the more powerful reductant, followed
facile room-temperature non-seeded synthesis of quasi-
by growth of the remaining free Au(III) ions onto the newly
spherical gold particles by ascorbic acid as the sole reducing
formed structures by the secondary reductant.
and capping agent.69 However, by controlling the redox poten-
tial of AA through a pH decrease, the reducing agent is only able
to reduce free Au(III) ions to Au(I) in the absence of seed cata- 3.3 Surfactant choice
lysts. This allows for directed deposition of Au(I) atoms onto the
Upon reduction of a gold salt to a zero-valent species, surfac-
gold seeds as directed by additional capping ligands or ions
tants are oen needed to stabilize the colloid structures. While
such as Ag(I) or halides. The effect of ascorbic acid in these
some reducing agents will play roles as surfactants as well, in
syntheses is highly dependent on the surfactant and/or co-
many syntheses the choice of an additional reagent to adsorb to
reductant used. Increased AA concentration in the synthesis
the nucleation growth surface will be a dening factor in the
of TritonX-100 capped burr-like AuNPs increases branch length
nal morphology. This adsorption can change the relative
and is attributed to increased reduction ability while CTAB-
growth rates of crystal facets by altering their free energies.83
based syntheses show an inverse relationship between ascor-
Many surfactants will undergo adsorption on the gold crystal
bic acid and branch length/density (Fig. 6).78
surface through bilayer formation.84 As the hydrophobicity of
Small-branching trisoctahedral gold nanocrystals were ach-
the shape-directing agent increases, the micellar assemblies
ieved by Wu et al. by a synthesis that demonstrated signicant
become worm-like and preferentially form elongated morphol-
morphological control by adjusting the amount of AA in
ogies such as nanowires. As such head group modications,
a seeded CTAC-capped synthesis.79 Changes in reductant in the
such as ionic or zwitterionic groups, can loosen the micelle
growth solution demonstrated control over the rate of reduction
formation and help direct branching particles.
of gold atoms onto the seed, resulting in control over nal
Ionic surfactants such as the frequently utilized CTAB pref-
morphology.
erentially adsorb onto the {100} crystal planes of gold seeds and
Nitrogen-containing compounds are well established as both
are fundamental in the creation of gold nanorods by allowing
reducing agents and capping agents in the syntheses of gold
for {111} planar deposition.85 However the presence of signi-
nanomaterials.67 Regardless of structure, nitrogen–gold inter-
cant twin defects in the seed precursor will weaken the binding
actions are capable of shape-directing nal nanoparticle
of the surfactant and result in branch growth instead of
morphology, so protonation or deprotonation can play a signif-
symmetrical elongation.86 Greater CTAB concentration per seed
icant role.80 In HEPES-based syntheses of AuNSs and gold
subsequently causes a larger number of CTAB micelles leading
tetrapods, the tertiary amine of the piperazine ring must be
to increases in branch density and length as surfactant binding
a deprotonated free radical in order to cause the reduction of
directs the anisotropic growth.87
gold and formation of the branched AuNPs.48 Unlike other
The passivation of crystalline surfaces is better conducted by
common reductants, amines typically reduce gold through the
ionic surfactants than zwitterionic ones; zwitterionic
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surfactants will arrange in a zigzag-type fashion to limit repul- ions resulted in an LSPR blue-shi as not only did spike length
sive forces and lead to poor capping. These weakened interac- decrease but the width and the branch density as well (Fig. 7). I
tions can lead to controlled anisotropic growth. Pallavicini et al. ions, having the strongest affinity to adsorb onto gold surfaces
demonstrated such control by the zwitterionic laur- among the halides, understandably had the greatest morpho-
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ylsulfobetaine (LSB) in a silver-mediated, ascorbate-reduction of logical effect. Instead of yielding branching particles, the
HAuCl4.88 Oddly enough, LSB preferentially adsorbs onto the synthesis produced a mixture of spherical and triangular prism-
lower energy {111} facets, leading to Au deposition onto {220} shaped particles.
and {002} faces. This is unusual as most ligands prefer to
passivate high energy facets by adsorbing there, leaving lower 3.4 Surfactant-free synthesis
energy facets open for gold deposition. This adsorption is likely
The ability to synthesize and tune branching AuNPs sans
due to the cationic nature of the ligand, indicating that further
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surface adsorption is of great interest to many researchers.
control over the growth of such particles can be achieved
These “clean” nanosystems avoid the challenge of removing
through head-group alterations.
traditional capping agents such as CTAB, PVP, and DMF.
Another class of surfactants that demands scrutiny is halide
However, some stability issues tend to cause drastic morpho-
counteranions. These halides, specically Cl, Br, and I, are
logical changes in these nanosystems quite rapidly. Typically,
known to be able to adsorb onto preferred Au crystalline facets.
surfactant free-synthesized branching AuNPs are coated with
These effects were summarized by Kedia et al. as they examined
thiolated compounds aer synthesis to delay the aging
the introduction of halide ions into DMF–PVP synthesized gold
process.90
nanostars.89 The addition of Cl ions witnessed a red-shi of
AuNSs were synthesized by Yuan et al. via a seed based (12
the LSPR peak as the spikes widened in size while the core
nm) surfactant-free method by the AA (RAA ¼ 1.5–2) reduction of
maintained its morphology. Conversely, the addition of Br
HAuCl4 in the presence of AgNO3.53 The resulting AuNSs were
approximately 60 nm and demonstrated morphological control
by adjusting the concentration of AA and AgNO3, and pH in
a similar manner to nanostars synthesized with CTAB or PVP.
Poonthiyil et al. reported surfactant-free AuNUs through
a solvent-directed synthesis at a relatively mild temperature of
60 C.91 HAuCl4 (1 mM) was added to 50 mL of anisole solvent
and allowed reaction time resulting in AuNUs (1 min) or the
more thermally stable quasispherical AuNPs (15 min). Inter-
estingly, the reaction failed to result in any gold nanostructures
in the presence of thiol or amine capping agents. Finally,
seedless, surfactant-less, room temperature AuNFs were ob-
tained by a simple synthesis consisting of the reduction of
0.3 mM HAuCl4 at room temperature by 5-hydroxyindole-3-
acetic acid (0.075 mM).92 The AuNFs were shown by selected
area electron diffraction (SAED) to be single crystalline with
a (111) lattice plane. Not only were the nanosystems utilized for
SERS and electrocatalysis, but also demonstrated uorescent
emission at 585 nm.
The adoption of these “bare” branching AuNPs is especially
encouraged by the biomedical applications of surfactant-free
nanosystems. By eliminating possible toxicity from common
surfactants, the use of the nanoparticles as probes and sensors
becomes more attractive.92,93 Additionally, the free surface
allows for conjugation of application-specic biomolecules
such as immunostimulatory agents and photosensitizers.94
Nam et al. synthesized surfactant-free spiked AuNPs using these
very principles for the delivery of an adjuvant for immune
activation of bone marrow-derived dendritic cells (BMDCs).95
The AuNPs were synthesized through a seed-based method
utilizing ascorbic acid as a reducing agent.
Fig. 7 The increasing addition of (a) 0.20, (b) 0.40, (c) 0.60 and (d)
0.80 mM HBr to the precursor reaction mixture clearly influences the
formation as well as the self-organization of anisotropic gold nano- 3.5 Galvanic replacement
structures, as prominently revealed by the optical spectra and their
corresponding TEM images (scale bar 200 nm with inset scale bar 100 Galvanic replacement is a template-driven synthesis process in
nm). Reprinted with permission from ref. 89. Copyright © 2014 Royal which a noble metal salt such as HAuCl4 encounters nano-
Society of Chemistry. particles made of a metal with a lower reduction potential. In
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such a case, gold will be deposited while simultaneously systems must be completed through oxidative etching. Just as
corroding the nanoparticle template from the inside out.96 This with deposition-based growth, etching can be facet selective,
process is understandably most oen used for the creation of allowing for greater morphological control. The reshaping of
hollow nano-systems.6,97 As a consequence of the synthetic gold nanosystems through this method is dependent not only
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method, many of these hollow nanostructures are considered on the etching agent, but also on the surfactant and nano-
bimetallic structures, but in some the trace amounts of the particle surface curvature.36,101,102
templating metal are low enough to be considered Various etchants including cyanide,103 molecular oxygen,104
inconsequential.98,99 copper ions,105 and ferric ions106 have been used to selectively
Gold owers were produced through the galvanic replace- change the morphologies of anisotropic AuNPs. An additional
ment of resin immobilized Cu nanoparticles under surfactant- etching agent, hydrogen peroxide, has been used extensively
less conditions.100 As galvanic replacement causes the reduc- over the last decade as favourable interactions with halide ions
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tion of Au(III) to Au(0), the deposition of which is directed (atom help drive the reshaping of such particles.107,108 The effects of Cl,
on top of atom) by the negatively charged resin beads, petal-like Br, and I ions in this process have been investigated and all
branches form from the core due to the polarization effect. found to have profound etching ability which increases along
Adjusting the amount of resin bound-Cu(0) used under with redox potential of the ions and their Au-binding strength
constant (10 mM) HAuCl4 concentration produces structures (Cl < Br < I).109 It is believed that the halide ions promote
including nanoworms (30 mg resin immobilized Cu(0)), nano- gold etching by generating their diatomic species, whose
owers (100 mg resin immobilized Cu(0)), and nanocubes favourable redox potentials provide additional oxidation chan-
(300 mg resin immobilized Cu(0)). Copper was also used as nels alongside those of H2O2.110 The etching of non-seeded,
a templating metal in the synthesis of branching gold nano- silver-mediated, branched AuNPs capped with CTAB by H2O2
particles in oleylamine (OAm), an organic medium.99 The core in the presence of these three ions saw a continuous, time-
of these branching particles had a lattice spacing of 0.28 nm, dependent blue-shiing of the plasmon band of each nano-
a spacing that is absent in both cubic Au or Cu but that is system when exposed to each of the three halides, as well as
present in the (110) planes of the Au3Cu alloy (Fig. 8). a dampening in extinction intensity.
The observation that there was negligible copper content in I expectedly showed the most dramatic effect; in fact,
the nal branching gold particles suggests that aer initial alloy greater oxidation was observed in the presence of I at
seed formation, the remaining copper ions were replaced a concentration 1/10th that of the other halides. While there are
through further galvanic replacement and deposition of Au(0) to oen issues with controlling the size of non-seeded branched
the core and branches. These results suggest the further NPs, selective oxidative etching may provide a solution. The
possibility of forming monometallic branching particles with relatively lower surfactant density of the sharp arms of such
lattice spacing only seen in alloy cores. nanosystems should invite easy access for oxidizing species
leading to the ability to shorten branch length. Rodrı́guez-
3.6 Etching Lorenzo et al. demonstrated similar results in the etching of
PVP-capped AuNSs by CTAB into quasispherical structures.111
Once synthesized, it is understandably difficult to cause inten- While CTAB is most oen used as a stabilizing agent, the
tional and controlled morphological changes to branching authors believe that the reshaping occurs by an Ostwald
particles. While the particles can serve as seeds for further ripening process; the high binding constant of Au(I) to CTAB is
reactions, capping ligands can be exchanged and particles attributed to a facilitated migration of gold atoms from the
further functionalized, changes to the metal framework of the branch tips to the particle core. However, with this method of
size control, there is a signicant trade-off: loss of sharp,
pronounced branch-tips, the resulting “hot spots” and their
appeal in applications such as SERS.
3.7 Template-mediated growth
Of the synthetic efforts to directly control the size and shape of
anisotropic particles, growth from template-mediation allows
most for specic alterations. The arms of branching gold
nanoparticles synthesized within mesoporous silica shell-
templates can be tuned in size by altering the shell itself. The
silica structures are synthesized through adaptation of the
Stöber method, a surfactant-templated synthesis that allows for
Fig. 8 Top panel illustrates the nucleation and growth of AuNSs. (a) pore size control through surfactant choice.112 Gold nanostars
Analysis of an HRTEM image of nucleates from panel (b). The scale bar
were synthesized through an overgrowth reaction by CTAB-
is 2 nm. (b)–(g) TEM images of nanocrystals obtained at reaction times
of (b and c) 2 min, (d) 10 min, (e) 20 min, (f) 30 min, and (g) 40 min after based silica shell-coated gold seeds (Fig. 9).113
injection of the Au precursor. Reprinted from ref. 99 with permission The addition of free Au(III) ions in the presence of a mild
from The Royal Society of Chemistry. reducing agent, ascorbic acid, to these seeds led to branch
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nanosystems.114 In one such synthesis, an extreme excess of
HEPES reductant both reduces Au(III) and directs the formation
of the gold tetrapod morphologies.115 The buffer self-assembles
such that a bilayer of HEPES molecules forms on the gold
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surface, serving to direct and stabilize the branching
morphology. The Odom group has demonstrated the tunability
of HEPES-reduced gold nanostars; by increasing the relative
concentration of the reducing agent the resulting resonance
could be facilely red-shied within the NIR region from 700 to
860 nm.116 These stars were subsequently functionalized with
a DNA aptamer (AS1411). The attachment of the aptamer onto
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the AuNSs increased the stability of the anticancer agents
demonstrating the ability of branching AuNPs as drug delivery
agents.117
Considering that disadvantage, a different type of etching
has been utilized with branched particles, particularly with gold
nanostars. Rather than causing plasmonic shis through
alterations of the metallic frameworks themselves, this alter-
native approach achieves LSPR tunability by coating branching
AuNPs with a silica-based layer, followed by selective removal of
said coating. The coating of noble metal NPs by silica has
gained notable interest in recent years as a silica coating
enables biocompatibility and additional surface-function-
ality.112,118,119 Silica-coated gold nanostars are of particular
interest for their application in SERS, singlet-oxygen generation,
as photothermal agents, and more.120,121 The silica coating is
applied to already-formed gold nanostars by variations of the
Stöber method, an ammonia-catalysed sol–gel reaction
involving the hydrolysis of tetraethylorthosilicate (TEOS). Atta
et al. performed a reverse Stöber method to successfully coat
gold nanostars with a silica shell, replacing the CTAB surfactant
with TEOS (Scheme 1).122 By selectively etching away the silica
shells with NaBH4, the shell was removed isotropically, allowing
researchers to tune the optical properties of the nanoparticles
by changing the size of the quasispherical core while keeping
the tips of the branches, needed for the “lightning rod” effect,
intact.
4. Nonaqueous reaction conditions
Fig. 9 2D and 3D TEM characterization of hybrid nanostructures
containing different gold nanoparticles coated with mesoporous silica, 4.1 Organic solvents
after growing gold tips through the silica channels: AuNPs (a and e), While the majority of wet syntheses for branched AuNPs occur
single-crystal AuNRs (b and f), pentatwinned nanorods (c and g), and
in aqueous solutions, the use of organic solvents allows for
nanotriangles (d and h). All the images in the left panel were obtained
at the same magnification. In the right panel, a visualization of the 3D a higher maximum reaction temperature and a variety of
reconstructions for a representative nanoparticle of each type is dis- organic shape directing agents and surfactants.123 Additionally,
played, where the radial nature of both the channels and the gold
branches can be observed. Reprinted with permission from ref. 113.
Copyright © 2015 American Chemical Society.
growth along the silica pores. Upon selecting an alternate
surfactant-template for the silica shells, the pore size will
change, resulting in branch radius changes.
The reducing agent itself can play an additional role as a so-
template in the synthesis of branching gold nanostructures.
Scheme 1 Schematic illustration of the morphologies of silica coating
Good's buffers have been used extensively in the synthesis of and etching to expose only variable amounts of the spike's surface.
both seeded and seedless surfactant-free branching gold Reprinted with permission from ref. 122. Copyright © 2020 Wiley.
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solvent–particle interactions will differ under organic condi-
tions and can lead to anisotropic growth. Gold nanomaterials
synthesized in alcohols without excess surfactant can lead to an
asymmetric charge distribution on the particle surface.123 While
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this may lead to aggregation it can also help control the rate of
deposition and the targeted crystalline facets, leading to
branched growth. Stanishevsky et al. demonstrated that the
reduction of HAuCl4 by AA, followed by injection of additional
gold salt could be morphologically controlled by increasing
the methanol content of the water/methanol solvent.124 The
additional HAuCl4 added into samples of higher methanol
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composition yields branched particles without an additional
shape-directing agent as deposition is driven onto specic fac-
ets. The Senthil Kumar group showed that DMF, a polar aprotic
organic solvent, has shown the ability to produce branching
AuNPs with precise morphological control in the presence of
a shape-directing agent such as PVP.124,125 The complexation of
DMF and PVP facilitates a kinetically controlled growth that can
be controlled by the addition of HCl. Initially formed gold seeds
will compete with PVP molecules for DMF interactions,
reducing the growth rate of the particles enough to lead to
branched morphologies. Additional work performed by the Liz-
Marzán group has shown that, while PVP is typically unable to
reduce gold under ambient conditions without a photochemical
inuence, at high enough concentration in a DMF solvent
system, PVP is able to reduce Au(III) and result in multipods.126 Fig. 10 Top: SEM images of the snowflake-like AuNPs (a) and TEM
images of Au nanothorns (b). Bottom: HRTEM images of AuNPs
recorded along [110] (b–f) and the SAED pattern (a). Reprinted with
4.2 Ionic liquids and deep eutectic solvents permission from ref. 132. Copyright © 2008 Wiley.
New classes of solvents such as ionic liquids (ILs) and deep
eutectic solvents (DESs) have gained signicant attention in the
like structures occurred at higher DES percentages as the
production of noble metal nanoparticles. As green and designer
weakened protection of the growing gold structures by the
solvents, ILs demonstrate tuneable physicochemical properties
solvent rather than water allowed for branch formation along
that can assist in the tuning of anisotropic gold nanosystems.127
the (111), (200), (311) and (222) facets. As the DES percentage
Qin et al. demonstrated the synthesis of three-branched gold
increased above 10% multipod morphologies were observed
nanotips in a [BMIM][PF6] ionic liquid–formamide 1 : 1 solvent
instead. These morphological changes may be due to a rela-
ratio. The kinetically controlled synthesis was tuned by altering
tionship between the gold reduction rate and DES concentra-
the IL–formamide ratio, achieving monodisperse structures as
tion; as the amount of DES increases, so does the gold
the ratio decreased and a balance between diffusion rate and
deposition rate onto the branch tips, leading to the creation of
reaction rate was achieved. Anouti et al. demonstrated that the
energetically preferred 2D pod-like structures.
low mutual miscibility between a protic IL such as BEHAF and
Liao et al. utilized DES solvents to obtain branched AuNP
water led to the formation of multipod AuNPs while the same
structures by altering the water content in the DES.132 The
synthesis in water, DMF or a miscible IL yielded quasispherical
absence of water caused the formation of snowake-like AuNPs
AuNPs.128 The authors concluded that the anisotropic growth in
with branches along the (111) facets while increasing water
these particles is caused by the BEHAF preferential adsorption
content to 5000 ppm yielded AuNSs (Fig. 10). The higher water
onto the (111) surfaces allowing for selective growth onto higher
concentration is then proposed to increase the reaction rate
energy facets. While passivation of high energy facets to mini-
while also disrupting the liquid templating role that the DES
mize surface energy is the typical mechanism, the affinity to the
may be playing.
low energy (111) surfaces may be due to the protic nature of the
IL, a preference demonstrated through recent work by Lin
et al.129 DESs, although closely resembling room-temperature 5. Reaction conditions
ionic liquids, are attractive alternatives due to their low cost,
nontoxicity, and biodegradability.130 Additionally, the extensive 5.1 Microwave-assisted reactions
hydrogen-bond network of DESs acts as a so template for Typically, nanostructure syntheses that require high tempera-
shape-control of noble metal nanosystems.131,132 AuNFs were tures are performed by heating reagents by conduction and
synthesized in DES for use in SERS.133 While reduction of convection in an oil-bath. Microwave dielectric heating has
HAuCl4 occurred at any signicant DES concentration, ower- been used less frequently but to great efficiency; MW
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irradiation's reactionary advantages include homogeneous nanosystems through uidic reactions has not been widely
nucleation due to uniform heating, enhancement of the investigated, spherical nanoparticles and nanorods have shown
metallic ion reduction rate, superheating of solvents, and great tunability by altering ow rates of one or more reaction
perhaps most importantly, selective formation of specic inputs.145,146 Silvestri et al. demonstrated milliuidic synthesis
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morphology.134 When utilized in tandem with PVP–SDS of gold nanostars through a seedless, silver-mediated
template-mediated growth, microwave-assisted ginger-like synthesis.143 The nal nanostar morphology was highly inu-
branching gold nanoparticles were synthesized, while ordi- enced by the ow rate; a slower ux rate caused inefficient
nary heating methods led to spherical nanoparticles.135,136 The mixing resulting in a polydisperse product while a higher ux
authors found that the so-template nature of PVP–SDS should rate yielded large nanocrystals and clusters. Another group
be further weakened by microwave irradiation, which, when obtained star-like gold nanosystem intermediates by adjusting
combined with the microwave-promoted rapid and abundant the pH of the reaction through an increased ow rate of an
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synthesis of gold seeds, led to anisotropy. Ngo et al. have alkaline growth solution.145 The robustness and accessibility of
recently shown that microwave-assisted, seed-based synthesis the microuidic systems, as well as easily tuned environmental
of monodisperse gold nanostars is not only possible, but also parameters associated with them, make them exciting new
tuneable.137 By altering the concentration of AA, CTAB, gold platforms for future study.
seed, and AgNO3, the researchers were able to take advantage of
the microwave irradiation to yield rapidly formed, highly
homogeneous nanostars. The use of both MW irradiation and 6. Towards common morphologies
ultrasound in the synthesis of template supported-metal
nanoparticles has shown that changes in the duration, inten- As previously mentioned, the creation of branching AuNPs is
sity, and any pulse-like ux rates of irradiation can alter the nal oen dependent on crystalline facet-driven adsorption of free
morphology of the nanosystem.138–140 Au(III) ions onto a nucleation site. However, as protruding arms
form during the growth phase the creation of additional facets
as well as changes to the free energy of pre-existing facets does
5.2 Microuidic synthesis occur. Consequently, the number of branching AuNP
When considering the tunability of nanosystems it is essential morphologies is considerable.
to promote controlled, consistent growth while limiting new Among the most common morphologies of branching
nucleation events.141 This separation can be achieved in tradi- AuNPs are stars, owers, urchins, dendrites and multipods. As
tional batch-reactor syntheses by temperature control or there is great overlap in the applications, and at times even the
through weakening of reduction agent strength.141,142 The use of synthetic methods of these nanosystems, the clearest distinc-
microuidic reactors allows for such separation while main- tion between them comes from shape.
taining otherwise suboptimal conditions by both timely and While both nanostars and multipods can be identied by
spatially separating nucleation and growth phases within the their arm-like protrusions, nanostars are traditionally dened
reaction (Scheme 2).143 by high numbers of narrow branches, sharp tips, and a small
Higher surface area-to-volume ratios, mixing rate control, particle core. Multipods however contain a few broad arms with
and readily available, accessible components make such reac- wide tips and typically smaller arm : core size ratios than their
tors intriguing.4,144 While synthesis of branching gold star counterparts. Nanourchins also contain sharp, narrow
branches; however, the protrusions exist in far greater numbers
and are signicantly shorter than those seen in nanostars,
much like their namesake of the sea urchin. Similarly, both
nanoowers and dendrites are appropriately named; the former
can be identied by petal-like nanosheet protuberances while
the latter resemble the branching extension of a nerve cell.
In the following sections the most common branched AuNP
morphologies will be examined with specic emphasis on
examples of tunability both during nucleation and growth
phases as well as aer.
6.1 Nanostars
Due to recent increased interest in the applications of noble
metal nanostars towards catalysis, optical imaging, and
biomedical uses, many pieces of signicant review literature
have explored arguably the most common branching nano-
Scheme 2 Schematic representation of the bench-top reactor
particle morphology.147–150 As such, this section will focus on the
designed for the synthesis of surface functionalized AuNSs. Reprinted most common strategies for synthesis and morphological
with permission from ref. 143. Copyright © 2017 Wiley. tuning of AuNSs.
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The seminal work of AuNS synthesis was conducted by induces a faster nucleation rate of the gold seeds, causing
a modied gold nanorod procedure involving the reduction of a broadening of the resulting branches.
free Au(III) ions onto gold seed precursors by ascorbic acid in the While synthetic control over nanostar size, branch number
shape-directing presence of cetrimonium bromide (CTAB).86 and branch length is vital, the full potential of these nano-
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Nehl et al. found in this work that the added presence of NaOH systems cannot be achieved without control over the morpho-
resulted in a kinetically controlled faster deposition of gold logical symmetry as well. The AuNSs obtained by Niu et al.
ions. Upon rapidly increasing the solution pH, it is likely that through an icosahedral seed-mediated approach highlights that
the chelating ability of ascorbic acid is altered as concentration highly symmetrical nanostars are obtainable through careful
of the less stable dianion increases, leading to branching consideration of precursor crystallinity combined with kinetic
anisotropic growth as the adsorption strength of the acid on the growth control through reductant concentration.152 For
nanoparticle surface weakens at lower energy facets.151 example, in the stars produced by Niu et al., dimethylamine
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By adjusting the concentration of NaOH in a seedless and (DMA) selectively adsorbs onto the {321} high-index facets of the
template-less synthesis of gold nanostars, Kedia et al. were able icosahedral seeds. Relatively high concentrations of DMA
to use pH adjustments prior to the nucleation phase to tune combined with relatively slow growth kinetics allow for the
AuNSs (Fig. 11).149 In this synthesis, the pH of an aqueous seeds to evolve into nanostars with {321}-faceted arms. These
solution of polyvinylpyrrolidone (PVP) in N,N-dimethyl form- results are consistent with a previous example of work by Kedia
amide (DMF) was adjusted through the increasing addition of et al. who observed that a faster nucleation rate caused by a pH
NaOH prior to addition of a HAuCl4 aqueous solution. As the pH adjustment caused a broadening of tips. Symmetrical control
of the DMF–PVP complex increases, the tips dull and become was exhibited by the Liz-Marzán group through ultrasonic
broader, transforming from star morphologies into multipods. irradiation of the growth solution of gold nanodecahedra.153
It is likely that the higher NaOH concentration, which results in This mechanism ensures a continuous supply of energy needed
an increased reduction capability of the DMF–PVP complex, to reduce Au(III) salt, ensuring simultaneous growth on each
face, leading to monodispersion of the nal product.
The role of the reducing and capping agents in the
morphological formation of star-like shapes has been demon-
strated as well. Early work by Sau and Murphy showed that
branching AuNPs could be synthesized, along with prisms,
rods, and cubes, by adjusting the synthetic parameters, mainly
concentrations of reagents, appropriately.154 Senthil Kumar
et al. demonstrated that PVP molecules, in DMF, could not only
reduce the gold in a gold halide solution, but also control the
rate at which AuCl4 ions were reduced on the surface of pre-
formed gold seeds.126 The resulting gold nanostar morphology
was dependent on the concentration of PVP, indicating that
capping ligands previously shown to yield isotropic particles
and non-branching anisotropic particles could be utilized in the
synthesis of more complex morphologies under careful
scrutiny.
In seed-based syntheses, a smaller seed diameter will yield
AuNSs of smaller core size and reduced branch density. Inter-
estingly, the ability to tune the LSPR of AuNSs by changing the
Rreductant value is not signicantly affected by precursor seed
size if the other reaction parameters are kept constant.46 These
results indicate a ruggedness of seed-based syntheses of AuNSs,
allowing for some exibility in achieving nal morphological
monodispersity regardless of initial seed size dispersity. By
varying seed size from 3 to 35 nm, Khlebtsov et al. were able to
tune the nal AuNS size from 45 to 150 nm, yielding LSPR red-
shis from 630 to 900 nm, respectively.155 The resulting increase
in core size resulted in an increased branch density as well.
AuNSs have also been tuned through careful consideration
of reducing agent concentration. In a seedless, one-step reac-
Fig. 11 Multiple Gaussian peak (dashed line) fitted optical absorption tion, AuNSs were synthesized by Good's buffer 4-(2-
spectra for the as-prepared anisotropic gold nanostructures, for
hydroxyethyl)-1-piperazinepropanesulfonic acid (EPPS).156 Upon
different NaOH concentrations (in mM) as mentioned. The corre-
sponding gold nanostructure morphology is shown in the inset. The increasing the concentration of EPPS at a constant pH of 7.4 in
scale bar in all the images is equal to 20 nm; reprinted from ref. 149 the presence of a constant HAuCl4 concentration the resulting
with permission from The Royal Society of Chemistry. morphologies transformed from quasispherical to short
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PVP molecules and high surface energy of side–face and face–
face alignments promote a side–side aggregation of the parti-
cles and the nal ower morphology. This work suggests an
advantage to the morphological control of AuNFs over their
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fellow branching nanoparticle counterparts; the ower-like
structures may benet from changes in the procedural steps
that can affect the degree of aggregation of building blocks such
as the aforementioned nanosheets.
Gold nanoowers have also been synthesized using biolog-
ical surfactants that, as insoluble in water, form vesicles as
opposed to the micelles seen in traditional surfactants such as
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CTAB.160 Cationic unilamellar vesicles formed by a bis(2-
ethylhexyl) sulfosuccinate sodium salt (AOT) and CTAB solu-
tion can reduce HAuCl4 without an additional reducing agent,
Fig. 12 The increased presence of a dual reducing and shape-
but neither can reduce it by itself.161 The resulting gold nano-
directing agent in EPPS promotes the elongated branching structure clusters are able to be used as pseudo-seeds; the fast addition of
by increasing the reduction rate of Au(III) while simultaneously allowing ascorbic acid and Ag(I) ions results in structured platelet
for additional ammine–Au shape-directing interactions. Reprinted aggregates with a ower-like inner structure.
with permission from ref. 156. Copyright © 2020 Wiley. Vesicle-based syntheses of these ower-like structures is
dependent on the “seed” solution undergoing formation at the
time that the reducing agent is added.162 The slow adsorption of
thorned particles to elongated-branched AuNSs (Fig. 12). EPPS, the vesicle surfactant is overcome by the reducing power of AA,
like many Good's buffers used in the synthesis of anisotropic leaving certain crystal planes of the “seed” uncapped, leading to
nanosystems, acts as both a reducing agent and shape-directing anisotropic growth and selective aggregation.
surfactant primarily through interactions between its pipera- Although much of the present literature of AuNFs consists of
zine ring and the gold nanocrystals.157 As these interactions the assembly of seed-like structures to form the resulting petal-
increase between the ligand and the higher energy facets as like morphologies, there is interest in less tedious, one-pot
EPPS concentration rises, the selective deposition of gold is syntheses. One such synthesis reduced HAuCl4 with AA and
more strictly directed towards lower energy facets resulting in utilized cetrimonium chloride (CTAC) as a capping ligand.163
the (111) directional branches. These results suggest that in the The AA causes a gradual reduction of the gold in a AuCl4–CTA
case of shape-directing reducing agents, rapid reduction and complex; the resulting gold nuclei aggregate until they reach
strong surface adsorption is a worthwhile strategy towards a critical size which allows for free surfactant to bind onto the
branching growth characteristic of stars. low energy (111) facets, a characteristic of ionic surfactants that
leads to anisotropic growth on higher energy facets usually
placated by capping ligands. As lower concentrations of Au are
6.2 Nanoowers subsequently able to adsorb onto the (111) facets, divots are
Nanoowers, having similar morphology characteristics to both formed leading to hydrangea-like structures. Rather than
nanostars and nanodendrites, can be distinguished by their varying seed-like precursors in order to tune the morphology of
pseudospherical cores and petal-like branches. AuNFs are of the nal ower-like structures, one can resort to more tradi-
particular interest for their applications in optoelectronic tional tuning techniques such as varying the concentrations of
devices, catalysis, and solar cells, but also for their distinct reagents, changing the solution pH, or temperature control.
synthetic production. The plasmonic properties of AuNFs are directly dependent
Unlike many of the other branching AuNPs described in this on the size and width of their petals; as the sheet-like structures
review, ower-like AuNPs are oen the result of self-assembled become thicker, the LSPR will tend to red-shi.164–167 As such,
parent morphologies such as rod- and sheet-like nano- researchers' attempts in tuning these nanosystems for specic
structures.158 For example, gold nanosheets were synthesized applications should focus on the size adjustment on the petals
through the UV-irradiation of HAuCl4 in the presence of etha- themselves rather than particle size.
nolic PVP and AgNO3.159 While PVP is typically considered
a nonreducing agent in the synthesis of gold nanostructures,
under the inuence of UV-light and Ag(I), reduction is possible. 6.3 Urchins
The strong interactions between PVP and the {100} facets of the Much like other multipod-esque gold nanostructures, urchin-
Au crystal led to preferential growth along the {111} facets, like gold nanoparticles are of considerable interest due to an
leading to sheet morphologies. Subsequent centrifugation of ability to tune the number, size, and length of spikes. Charac-
the nanosheets resulted in a self-assembled nanoower. The terized by an extreme number of short, sharp thorns and
repeated washing steps remove excess PVP and bring together subsequent numerous narrow voids, these features act as hot-
the nanosystems, increasing van der Waals attraction between spots for the lightning rod effect, as well as tuneable NIR plas-
the particles. The hydrophobic chains on the surface-adsorbed mon bands.168 As such, the formation and control of these, what
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could be considered unwieldly, hierarchical structures is vital to
their use. Wang et al. found that the rapid addition of excess
mild reducing agents such as AA to an aqueous Au(III) solution
caused a burst nucleation that can be further tailored to yield
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either spherical particles or branching urchins.169 The presence
of a capping agent such as bovine serum albumin (BSA) worked
in tandem with the dehydroascorbic acid (DHA) formed and
limited the initial gold seed growth to clusters, leading to the
formation of isometric particles. In the absence of the addi-
tional capping agent, the rapid injection of AA yielded 10 nm
particles which, due to high surface energy, aggregated quickly
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forming urchins with (111) facet nanogaps. Whereas slower
reduction is necessary in the syntheses of other branching
nanostructures, this work suggests that a morphological chaos
of gold nanourchins is formed through uninhibited growth. As
described previously in this review, methods towards kinetic
control in the synthesis of gold nanosystems can be achieved
through adjustments in the concentrations of seed precursors,
reducing/capping agents, and thermal control, leading to many
ways forward for the synthesis of similarly created urchin-like
morphologies.
This hypothesis is further supported by a seed-mediated
synthesis of gold urchins by the rapid reduction of Au(III) by
H2O2 in the absence of an additional reducing agent.57 Trace Fig. 13 Influence of hydroquinone amount on the morphologies of
the as-prepared gold NPs. The amount of hydroquinone was altered
Ag(I) ions were used to tune particle shape, size and thorn
from 50 (a), 100 (b), 120 (c), 150 (d), and 500 mL (e) to 1000 mL (f), while
length; as silver nitrate concentration increased the particles the amount of seeds, HAuCl4, and sodium citrate was fixed at 50, 25,
transformed from ower-like microspheres to urchins to and 22 mL, respectively. Reprinted with permission from ref. 42.
morphologies similar to that of a nanopopcorn. Researchers Copyright © 2011 American Chemical Society.
found that the urchin-like morphologies were formed from
small ower-like assemblies and that the thorns grew from the
petals on the owers: gold nanosheets with (111) basal planes. and observed that an increase in hydroquinone concentration
Further work undertaken by the Odom group has shown the resulted in urchin morphologies.42 The high hydroquinone
capabilities of various Good's buffers to facilitate the synthesis levels may directly have led to an increase in gold reactivity,
of Au urchins.170 Through a seed-based method AuNPs were promoting reduction of Au(I) to Au(0), fast nanoparticle growth,
synthesized using each of the biocompatible EEPS, HEPES, and and anisotropy (Fig. 13).
MOPS, respectively, as reducing and shape-directing agents. Increasing the amount of seed precursor at constant Au(III)
The authors found that the urchin morphology and the corre- and reducing agent concentrations led to a lower Au(0) : seed
sponding plasmonic properties could be manipulated through ratio and resulted in further anisotropy. The disallowance of
changes in Rseed, seed size, and pH. Interestingly, the group was isotropic growth is likely due to the increased reducing
able to conserve spike length and the corresponding LSPR agent : seed ratio; the excess of reducing agent is able to more
wavelength, while increasing the seed size and thus the overall efficiently saturate specic facets, inhibiting growth at those
seed side. This suggests that, as with other branching locations and promoting overgrowth at the facets that are less
morphologies synthesized through the use of Good's buffers, protected. This would be assumed to be a kinetically favourable
the anisotropic growth may be facilitated by a template-based process as the rapidly reduced Au(I) ions are selectively depos-
method in which the reducing agent acts as a shape-directing ited on open faces leading to the observed thorn-like
agent as well.171 protrusions.
Gold nanourchins have also been produced by dual reducing
agents. In a seed-mediated synthesis conducted by Cao et al.,
hydroquinone and citrate were used in tandem to create, at high 6.4 Dendrites
concentrations of hydroquinone, urchin morphologies with One great advantage exhibited by the morphology of branched
random spike growth on the {111}, {200}, {220} and {311} crys- gold nanoparticles is an increase in surface area caused by the
talline facets.71 The pseudospherical particles formed at low protruding appendages. Dendritic gold nanoparticles encap-
hydroquinone concentrations may suggest selective facet tar- sulate this quality perhaps better than any of the other
geting by reducing agents of different strengths, indicating branched morphologies as their shapes are dened by hyper-
dual-reduction options towards the tuneable synthesis of branching overgrowth; each branch protruding from the core
urchins. Li et al. also created gold nanourchins through the contains many secondary and even tertiary branches. Pine tree,
dual reduction of Au(III) by hydroquinone and sodium citrate fern and other complex shapes are oen observed and as such
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the use of biotemplates in the synthesis of dendritic AuNPs is a kinetically slower growth process in gold nanosystems
understandably appropriate. produced by HEPES has been demonstrated to yield gold
Seo et al. utilized the M13 virus' cationic carboxylate groups nanostars, the EPPS-reduced nanosystems retain the broad tips
for nucleation and growth of Au dendrites through electro- indicative of multipods.80,178 The resulting monodispersity
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chemical co-deposition.172 Interactions between the gold salt presents an advantage to this Good's buffer-based synthesis
precursor AuCl4 and the NH2 groups result in ammine- over its nanostar counterparts. While the broadened tips do
chloride complexes that, when a constant 0.2 V potential is decrease the intensity of electronic “hot spots” desired for use
applied, witness reduction of Au(III) to Au(0). Stabilization and in applications such as SERS the consistent structure leads to
growth of these zero-valent gold atoms is coordinated by the better control over the plasmon properties.
carboxylate groups of the M13 virus. The resulting anisotropic The morphological tuning of gold tetrapods from shuriken-
growth is dependent on the slow reduction of Au(III) as it is like structures has been described in a recent study by Zhang et
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released from the ammine-chloride, the rate of which may be al.179 Synthesized in DMF, the uniquely shaped structures were
able to be controlled by adjusting the electrical potential. This synthesized through the use of diethylamine, a capping agent
method of morphological control is unique to dendritic struc- that selectively adsorbed to the {110} facets, allowing preferen-
tures and is a relatively facile method towards tunability. tial growth in the [110] directions. As temperature increased,
This electrochemical behaviour was also observed by Rafat- the shape of the nanosystems changed from large core, sharp
mah et al. in the electrodeposition synthesis of Au dendrites tipped structures to tetrapods with broad, rounded branches
onto paper bres to be used as catalysts.173 As anisotropic (Fig. 14). The temperature dependence of the tetrapods may be
growth will oen occur under conditions far from equilibrium, due to competition between the rate at which gold is
sufficiently negative applied potentials will cause dendrite
formation. It is understandable to assume then that higher
deposition potential values would lead to denser gold nano-
structures. The authors demonstrated that increasing the
concentration of HAuCl4 led to signicantly higher branching
which may be a method utilized for size control.
6.5 Multipods
Branched gold nanoparticles consisting of multiple rounded
arms protruding from the core have been investigated as well.
These nanomultipods, consisting of three or more branching
structures, are differentiated from other morphologies such as
nanostars and urchins by thicker spikes and duller tips. Gold
tripods and tetrapods were among the rst branching AuNPs
synthesized through a CTAB and AA synthesis.9 Interestingly,
some of these multipods consist of quasispherical-like
branches attached to an anisotropic core rather than arm-like
protrusions and have been utilized for in vivo photoacoustic
imaging.174 Symmetrical-plane gold tripods are particularly
difficult to grow through traditional methods as they require
specic growth from every other h110i direction, but through
electroless plating methods gold nanospheres can undergo
morphological evolution to tripods using periodic double
gyroid nanoporous templates.175 This underexplored method of
multipod synthesis presents an interesting approach towards
the creation of branching gold nanoparticles; because control of
isotropic nanoparticle growth is oen signicantly higher than
their anisotropic counterparts greater nal morphological
control may be able to be achieved.
Nanotetrapods have been synthesized using a variety of
biological Good's buffers including HEPES, EPPS, and 3-(N- Fig. 14 (a–d) TEM images of the Au nanoshurikens with tips of
morpholino)propanesulfonic acid (MOPS).115,176,177 Morpholog- different lengths and sharpness obtained from a typical synthesis at
ical control differs between these buffers based on their carbon temperatures of 60, 80, 100 and 150 C, respectively. The reaction
times were 90, 40, 10 and 10 min, respectively. Inset: Au nano-
chain structures. For example, the additional methylene group
shurikens standing on their lateral sides. (e) Corresponding UV-vis-
between the piperazine ring and the sulfonic acid group in EPPS near infrared (NIR) spectra of the Au nanoshurikens. Right: Digital
compared to HEPES slows the reduction rate and increases photographs of the respective sols of the Au nanoshurikens. Reprinted
monodispersity, yielding tetrapods at a 75% rate.176 While from ref. 179 with permission from The Royal Society of Chemistry.
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preferentially deposited on the branch tips versus its migration enhancements due to the LSPRs of nanoparticles and is capable
to lower energy facets.180,181 At low temperature, a slight of providing complete vibrational blueprints of the analyte
advantage lies with deposition over migration, which leads to molecules.147 This enhancement is caused by the ability of
the observed sharp tips and broad core. As temperature AuNPs to act as nanolenses, channelling deep visible or NIR
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increases, the rate at which gold is deposited onto the tips of the wavelengths to subwavelength dimensions.188 The effect of
core must be signicantly higher than the rate at which it plasmonic nanoparticle structure on SERS depends on the
diffuses onto the lower energy facets, resulting in the broad chemical and electromagnetic effects.
tipped tetrapods observed in Fig. 14d. This work in particular The chemical enhancement is measured by the increased
shows the great control that temperature can have on tuning the Raman cross-section of an analyte adsorbed onto the nano-
morphologies of branching nanoparticles. particle versus that of the free analyte.189 The Raman cross-
Additional highly branched AuNPs with rounded tips have section of a AuNP-bound analyte can be preferentially
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been synthesized and morphologically controlled in a variety of increased if the excitation laser wavelength is resonant with the
procedures. Wang et al. found that gold nanorods could be used charge-transfer state of the nanoparticle–molecule complex,
as seeds to generate a variety of morphologies by altering both a property dependent on both the plasmon resonance of the
the aspect ratio of the rods and the reduction rate of AA by pH nanoparticle and the molecular resonance of the analyte.190 For
adjustments.177 Biomolecules such as dendritic peptides con- the nanoparticle, extinction intensity at the common SERS
taining NH2 termini such as L-glutamic acid derivatives were excitation wavelength of 785 nm can help enhance this state. As
able to form penta- and hexa-pods through kinetic control of the branched AuNPs oen demonstrate NIR absorption due to their
reaction by increasing reductant concentration or pH.182,183 core protrusions that are tuneable through branch elongation
or shortening, narrowing or thickening, they are excellent
6.6 Miscellaneous shapes candidates for SERS (Fig. 15).191
Branching AuNPs also lend themselves to SERS due to their
Many other branching gold nanoparticles exist that cannot be preferred electromagnetic effects. An increased number of tips,
strictly regulated to one of the previously described categories. valleys and edges give rise to the large EF areas, or “hot spots”
Gold nanocrosses were synthesized through reduction of necessary for successful use in SERS. As described previously,
HAuCl4 by various copper species in the presence of a shape tuning of branching AuNP morphologies can lead directly to an
directing agent, oleylamine.184 Morphological control was ob- increased number of protrusions and subsequent tips. The
tained by manipulating the reduction rate by copper species ability to introduce additional “hot spots” through synthetic
selection, either Cu(I), Cu nanowires, or their combination. adjustments in morphologies such as urchins and owers
Li et al. utilized hollow spiked gold nanoshells for chemo-
thermal antitumor therapy.185 The chitosan-functionalized-
liposome-based shells were synthesized by locking AuCl4
anions with charged ammonium species from chitosan, which
when reduced formed a branched gold coating. The overgrowth
of gold nanorods through kinetic control by CTAC and selective
surface blocking by Ag UPD was able to lead to gold nanoarrows
consisting of two pyramidal heads and a four-wing sha.30
Chitosan was also utilized as both a templating and
a capping agent to synthesize gold nanoraspberries for photo-
thermal therapy.186 Utilizing a silver-mediated ascorbic acid-
reduced synthesis, the templating role of chitosan was
employed to selectively alter the size of the resulting particles.
While many changes in reaction conditions that affect particle
size will result in signicant morphological changes as well,
decreasing the chitosan concentration resulted in a decreased
size of the particles while maintaining their berry-like shape.
The researchers attribute this scaled-down ability to the active
templating role exhibited by chitosan.
7. Applications
7.1 Surface-enhanced Raman spectroscopy Fig. 15 (A) SEM and TEM images of the HGNs prepared by using
While most photons readily experience elastic Rayleigh scat- different amounts of HAuCl4 (50 mM) at 60 C: (a and e) 0.1 mL, (b and
f) 0.2 mL, (c and g) 0.4 mL, and (d and h) 0.6 mL, while the amount of
tering during light scattering, only about 1 in 10 million
dopamine hydrochloride (53 mM) was fixed at 2.0 mL. (B) Vis-NIR
photons undergo Raman scattering, an inelastic exchange of absorbance spectra of the corresponding HGNs in part (A). (C) The
energy with the scattering material.187 Surface-enhanced Raman Raman spectra of 4-MBA labelled HGNs. Reprinted with permission
scattering (SERS) takes advantage of electromagnetic from ref. 191. Copyright © 2018 Xiaowei Cao.
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shows key advantages to the SERS capabilities of these determine such correlations in other branching gold particles
structures. as well.
To this end, branching AuNPs have been used extensively for Consideration of the morphological characteristics of
SERS applications.192,193 While top-down synthetic methods of branching AuNPs and the ability to tune them through careful
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SERS substrates, such as electron beam lithography and experimental consideration gives way to a direct pathway for
focused-ion beam lithography, are capable of producing highly greater SERS enhancement.
reproducible materials, the high cost and limited tunability, as
well as inability to synthesize anisotropic AuNPs make them less 7.2 Catalysis
attractive than bottom-up methods.194–196 However, the use of
Traditionally, when considering noble metal nanoparticles as
such AuNPs in SERS-based applications may require a “sand-
catalysts, small, <20 nm spherical particles with high surface-to-
wich architecture”; nanoparticles are positioned such that there
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volume ratios have been selected as they exhibit higher catalytic
is a narrow gap between them and a plasmonic lm allowing for
activity. As with other applications, branching AuNPs overcome
realization of the quantum connement effect.197,198 Indrasekara
the size limitation by increasing not only the exposed surface
et al. recognized and sought to improve on the disadvantages of
but also the number of activation sites.132 The abundant defects
the “sandwich architecture”, primarily a limit on the sensitivity
and high surface energies from the edges and tips of branches
of the application.192 Tuneable AuNSs and AuNPs were synthe-
increase the local electron density and, accordingly, reactivity in
sized through a seed-, AgNO3-, and AA-based method. The
morphologies such as stars, owers, and urchins. In order to
authors observed that the greater the plasmon peak maximum
examine morphological and size trends in the catalytic ability of
overlap with the 785 nm excitation wavelength, the greater the
gold nanomaterials to reduce 4-nitrophenol (4-NP) to 4-ami-
SERS enhancement. The species were able to detect analytes at
nophenol (4-AP) in excess NaBH4, Ma et al. recently synthesized
concentrations as low as 1 pM and boasted an enhancement
spherical and branching AuNPs of various sizes.201 Spherical
factor of 109, all without taking advantage of induced quantum
AuNPs of 4, 16, 40, and 80 nm diameter showed an expected
connement effects, but rather direct interactions between the
inverse relationship with size; the 4 nm particles completed the
nanoparticles and the analytes.
reduction of 4-NP in within 2 min while the 16 nm and 40 nm
The surface characteristics of the branching AuNPs used in
AuNPs took 12 and 15 min, respectively. Alternatively, as the
SERS applications may play as signicant a role as their surface
size of the branching AuNPs increased from 40 nm to 117 nm
plasmon resonances. By synthesizing a series of increasingly
the larger core size and branch lengths cause reduction time to
branching gold nanoparticles through a thiol-driven arrested
decrease from 1.5 min to 0.6 min. The higher catalytic activity
growth method, Meng et al. were able to quantify the effect that
can be attributed to the highly energetic surfaces of the sharp
the sharp protrusions in their nanostar morphologies had on
tips.26 As control over branch length, density, and sharpness
the resulting SERS effectiveness.199 SERS spectra were measured
becomes more facile through greater understanding of the
directly from the various 4-mercapto-benzoic-acid-capped AuNP
driving forces behind morphological changes, catalytic capa-
samples, including rough, spherical AuNPs and highly
bilities should increase as well.
branching AuNSs. The authors found the SERS intensity from
A recent comprehensive review by Priecel et al. has described
the AuNS solution to be three times that of the AuNP solution.
the advantages of branched AuNPs for electrocatalytic reac-
This preferential increase in the SERS activity can understand-
tions.202 The authors attribute the effectiveness to the struc-
ably be attributed to the increased surface area due to long
ture's ability to utilize the observed enhanced electric elds
branching protrusions as well as the “lightning rod” effect of
produced at edges and tips. The anisotropic gold nanoparticle-
the sharp tips.
catalysed oxidation of methanol by nanoprisms, nano-
It is the complexity of branched gold nanoparticle
periwinkles, and nanoowers immobilized on porous silicate
morphologies that allows for such a wide breadth of applica-
networks was compared to that of spherical nanoparticles.203
tions. However, it is these intricate particle shapes that intro-
Catalytic activity was observed to increase not with an increase
duce a degree of difficulty in identifying appropriate surface
in surface area but rather as more high-index facets were
functionalization. The Fabris group has identied an approach
observed. Understandably, the periwinkle and ower shapes
to determine optimal conditions for an anisotropic
were signicantly more efficient than prisms and spherical
nanoparticle-based SERS system.200 By coating gold nanostars
particles. This trend was observed in dendrite-supported elec-
with a silica layer in tandem with ATP as a Raman reporter
trodes as well; the greater the high-index facets the stronger the
molecule the researchers were able to measure the SERS
electric eld enhancement and the more efficient the catalytic
response as the silica encasing was selectively etched away. This
ability. The directed synthesis of branched gold nanoparticles
process allows for identication of the most efficient combi-
with the intention of propagating high-index facets amongst
nation of surface functionalization and morphological struc-
numerous edges and tips should drive the future of metal
ture. In the case of the surfactant-free gold nanostars
nanoparticle-based catalysis.
synthesized in this experiment for example, the group was able
to determine a correlation between the intensity of the stars'
morphology and the SERS signal enhancement. Their work 7.3 Photothermal and photodynamic therapy
suggests that such a process could be used to experimentally The desire for non-invasive, collateral-free treatment of
cancerous cells has directed research of nanoparticle-mediated
3998 | Nanoscale Adv., 2021, 3, 3980–4004 © 2021 The Author(s). Published by the Royal Society of Chemistry
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photothermal therapy (PTT). The photothermal heating process
of gold nanomaterials was described in detail by Link et al.204
Absorption of NIR light by gold nanosystems causes an excita-
tion of plasmon band free electrons. The resulting hot electron
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
pulse undergoes rapid cooling through collisions with the gold
framework and instantly heats the nanosystems to tempera-
tures in the thousands of degrees. That heat is then transferred
to the surrounding cells and can induce hyperthermia, leading
to cell death.
Understandably, the absorption of NIR light is a key
parameter in choosing an appropriate nanomaterial. Gold
Open Access Article. Published on 21 April 2021. Downloaded on 7/28/2024 8:14:07 PM.
nanostars in particular are intriguing materials for PTT as their
LSPR can be selectively red-shied into the NIR as the core size,
number of branches, length of branches, and sharpness
increase, morphological changes that can be selectively
Fig. 16 Characterization and optical properties of AuNEs. (a and b)
changed through procedural alterations.205 Pallavicini et al.
Scanning electron microscope (SEM) and transmission electron
synthesized seed and silver-mediated gold nanostars reduced microscope (TEM) images of the as-synthesized AuNEs. (c) UV/Vis/NIR
by ascorbic acid that showed two intense, photothermally active absorption spectrum (black solid line) and excitation spectrum (black
LSPRs.206 250 mL of 4 mM AgNO3 and 5 mL of 1 mM HAuCl4 were dashed line) for singlet oxygen phosphorescence of lipid-coated
added to 5 mL of a 0.2 M solution of TritonX-100. 140–400 mL AuNEs (lem ¼ 1267 nm). The NIR I and II biological windows are
indicated by the pale pink and green bars. The inset shows the SEM
ascorbic acid was subsequently added and reduction was
image of a single AuNE. (d) Singlet oxygen phosphorescence emission
observed by a colour change in solution from yellow to clear, spectra sensitized by lipid-coated AuNEs at 550, 808, 915, and
followed by an addition of a TritonX-100-capped gold seed 1064 nm excitation wavelengths. Reprinted with permission from ref.
solution. At least one branch from the resulting stars is formed 208. Copyright © 2014 Wiley.
at an angle to the others, leading to the two distinct NIR peaks,
tuneable based on the concentration of ascorbic acid, at 670
and 1170 nm, 795 and 1450 nm, or 960 and 1590 nm. Upon as its biomedical applications could serve to elevate the use of
irradiation of the stars in water with a suitable laser, a change in noble metal nanoparticles in therapeutic settings to practical
the environmental temperature of 7 and 12 K was observed at heights.
laser powers of 50 and 100 mW, respectively. While morphology and application are undeniably linked,
Photodynamic therapy (PDT), an alternative treatment that a nal impressive feat of branching AuNPs is their multi-
has proven effective for numerous cancers, is a promising functionality. The Vo-Dinh group exemplied this by their
landscape for the eld of nanotheranostics to expand. In brief, creation of quintuple-modality AuNSs.209 By creating a nano-
PDT involves the delivery of photosensitizers (PSs) to a tumour material with an SPR within the NIR tissue optical window and
site, followed by activation by illumination with NIR or visible functionalizing the surface with a traditional magnetic reso-
light.207 The photochemical reaction generates singlet oxygen, nance imaging (MRI) contrast agent (Gd-DOTA) and SERS
which induced apoptosis and necrosis in the tumour cells, by reporter (para-mercaptobenzoic acid), the researchers were able
transferring the absorbed energy to normal tissue oxygen. to create a singular platform for ve different applications:
Treatment of deep-tissue tumours with PDT is normally chal- SERS, MRI, computed tomography, two-photo-luminescence
lenging; penetration of such tissue depth is exclusive to NIR imaging and PTT. The absolute exibility of such nanoparticle
light, but very few PSs are activated by such low energy. platforms should lend to their continued exploration.
As such, multi-branched gold nanoechinuses (AuNEs) were
synthesized through a seed- and silver-mediated method,
utilizing a double chain CTAB (DC14TAB) surfactant and 7.4 Biosensing
ascorbic acid as a reducing agent. The DC14TAB surfactant was Colorimetric-based assays for biosensing rooted in gold nano-
removed through a water and methanol wash, allowing for materials have gained traction due to the nanomaterials' ability
coating with PS Lipofectamine 2000 (LP-2000) which formed to act as a colorimetric assay upon aggregation and etching. As
surface-coated bilayers.208 The AuNEs showed extinction inten- nanomaterials aggregate, LSPR wavelengths will shi, allowing
sity well into the NIR, up to 1700 nm, molar extinction coeffi- for robust point of care (POC) uses, which can be further
cients 7–9 times higher than those of conventional organic dyes conrmed if necessary by TEM or surface plasmon resonance
and photosensitizers and 3–4 orders high than those of other imaging.210,211 By utilizing the tunability of branching AuNPs,
gold nanoparticles (Fig. 16). The tunability of other branching the LSPR maxima can be red- or blue-shied such that the
AuNPs into the second biological window has been demon- colour change upon aggregation is drastic enough to be dis-
strated, indicating that their use as upconversion nanoparticles cerned by the naked eye. Additionally, the easy functionaliza-
(UCNPs) is a promising eld. tion of gold nanoparticle surfaces allows a wide array of
Further work into the tunability of a second NIR plasmon detection techniques. For example, aggregation between CTAB-
band should be of great interest to researchers moving forward capped gold nanostars, which is usually prevented by the
© 2021 The Author(s). Published by the Royal Society of Chemistry Nanoscale Adv., 2021, 3, 3980–4004 | 3999
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positive charge on the ligand, can be induced by interactions connected to their morphologies this advantages does not
with negatively charged cell walls of target bacteria such as simply stop at changing the size and shape of nanoparticles but
Staphylococcus aureus. Verma et al. observed that such stars in at advancing the practical elds in which they are applied as
the presence of S. aureus, DMPC, DMPE, and DMPG will selec- well.
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
tively aggregate in the presence of only the negatively charged The published literature has shown that the tunability of
biochemicals: S. aureus DMPG liposome.87 These nanostars in branching gold nanoparticles is not only possible but also
a water or saline solution display a deep blue colour and a cor- facile. However, the parameters that can lead to careful modi-
responding 580 nm LSPR maximum with little extinction cation of the metallic frameworks of gold nanoparticles are
intensity in the NIR. Upon injection of the negatively charged not yet completely discovered nor understood. It is believed that
bacteria the AuNSs aggregate, causing the loss of the distinctive a constant pursuit of this knowledge will not only open addi-
580 nm LSPR caused by Mie scattering and displaying absor- tional synthetic pathways for modications of gold nano-
Open Access Article. Published on 21 April 2021. Downloaded on 7/28/2024 8:14:07 PM.
bance in the NIR instead. The colour of solution shis from materials but will help expand the understanding of the
a deep blue to gray or colourless depending on bacteria fundamental nanoparticle nucleation and growth processes as
concentration and is evidence of a robust POC device for S. well.
aureus detection.
Conflicts of interest
7.5 Drug delivery
There are no conicts to declare.
The high biocompatibility and surface functionalization of
AuNPs make them intriguing platforms for drug delivery. Along
with PDT/PTT functionality, the increased surface area of References
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