Green Synthesized Carbon Quantum Dots as Fluorescent

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Probes for Sensitive Detection of Metal Ions

Taliya Gunawansa1, Sangram K. Pradhan*1, Makhes K. Behera1, Jacob Strimaitis1, and Messaoud

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Bahoura1,2

1Center for Materials Research, Norfolk State University, Norfolk, VA, USA, 23504
2Dept. of Engineering, Norfolk State University, Norfolk, VA, USA, 23504

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Abstract:

We have demonstrated an easy, economical, one-step hydrothermal synthetic route to water-

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soluble fluorescent carbon quantum dots (CQDs) prepared from grapefruits for 2-, 4- and 8-hours

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reaction times at 180 oC through a Teflon-lined autoclave reactor. The surface morphology of the

CQDs, obtained by transmission electron microscopy, and structural characteristic by Fourier

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transform infrared spectroscopy predominantly confirmed that the synthesized CQDs contain

carbonyl and hydroxyl groups which can provide more adsorption sites. Spectroscopic properties

are characterized by ultraviolet absorption spectrum and photoluminescence spectrum. The size
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distribution of quantum dots is in the range of 10 ± 0.5 nm. The CQDs exhibit bluish-white
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fluorescence under UV light with an excitation wavelength of 285 nm. Furthermore, the

luminescence intensity of CQDs decreases gradually after the addition of various molar
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concentrations of heavy metal ions, such as Cu, Ni, and Sn. These optical and spectroscopic

findings reveal that CQDs prove to be effective nanoprobes for the fluorescence-based detection

of these heavy metal ions that have toxic and environmental impacts.
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Key words: Carbon Quantum Dots, PL quenching, Heavy metal ions detection, TEM
* [email protected]
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4191052
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1. Introduction

Uncontrolled and improper disposal of industrial waste introduced serious heavy metals

pollution in the water, soil, and plants [1]. Hence, it is important to monitor, detect, and control

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the toxicity levels of heavy metals to mitigate their impact on humans, animals, and the

environment. Consumption of iron [2, 3] mercury [4, 5], lead, [6] cobalt [7], palladium [8, 9],

bismuth [10], and chromium [11] in higher doses over a long period is detrimental to health and

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can be fatal. Ion sensing can be used to control these elements in water and soil samples by using

biocompatible green synthesized carbon quantum dots (CQDs). CQDs have shown good

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luminescence and optical properties that exhibit quenching in the presence of certain heavy metal

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ions, making them highly useful as optical probes for the detection of these harmful ions [12].

Nanomaterials containing carbon have been leading the research interest due to their non-
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toxicity, high conductivity, and excellent aqueous solubility [13-15]. Carbon exists in a wide

variety of forms: carbon nanotubes, fullerene, graphene, and diamonds [16]. Photoluminescence

CQDs were discovered in 2004 through the purification of single-walled carbon nanotubes [17].
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Typically, CQDs are zero-dimension quasi-spherical shape nanoparticles with ultra-small sizes
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ranging from a few nanometers to 10 nm that consist of sp2/sp3 hybridized carbon atoms as a core-

shell structure where a carbon core is surrounded by individual functional groups producing
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surface functionalization and passivation [18-20]. CQDs have preferable fluorescence and are

chemically stable, making them superior to traditional metal quantum dots [21-23]. CQDs also

possess the optical characteristic of bandgap tunability, which is an increasingly desirable

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characteristic for semiconductor materials [24].

Green synthesis of CQDs have gained much attention in recent years as an alternative to
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heavily toxic, energy-consuming, and costly metal-based quantum dot synthesis [25, 26]. This new

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 method utilizes abundant, less harmful, and natural resources, such as fruits, vegetables, plant

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leaves, and biowaste materials [27], that produce significantly cheaper and more plentiful

fluorescence CQDs [28, 29]. Research groups have successfully prepared carbon-based quantum

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dots from a variety of these natural precursors, including green tea [30], egg [31], potatoes [32],

lotus root [33], pepper [34], coriander leaves [35], and many other carbon-based sources [36-38].

Among these different natural precursors, grapefruit is an abundant carbon source rich in various

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acids, proteins, minerals, and vitamins [39], making it an excellent choice for this study.

It is known that all CQDs show a similar type of absorption and luminescence properties

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regardless of their various methods of synthesis [40]. The typical absorption spectrum of the CQDs

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in the UV region of the electromagnetic spectrum ranging from (230–320 nm) is related to 

transitions of the carbon core and the transition of n corresponding to the different passivation
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groups connected with various CQDs, for instance, C=O [41, 42]. The emission in CQDs is

currently an essential topic of discussion because the exact mechanism of this emission needs to

be more understood. Hence photoluminescence emission is an important property of the CQDs

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and responsible for its application in various fields. Fluorescence-based sensing method has

become an attractive area of interest in recent years due to its ability to easily recognize numerous
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target molecules or ions using versatile sensory materials with high sensitivity and excellent linear

response. Considering this feature, we focus on using CQD fluorescence properties, specifically
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in the applications of metal ions sensing [43]. A functional unit attached with the CQDs results in

certain fluorescence changes upon contacting the target species; the changes in fluorescence
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include changes in the intensity, emission peak position, total quenching, anisotropy, or lifetime

[44]. The quenching of the fluorescence spectrum is the most widely used principle for sensory
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applications. Some of the fluorescence quenching mechanisms are i) the photoinduced electron

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 transfer (PET); which happens through an internal deactivation process connecting the interaction

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electronic structure between the excited state of the recognition unit (fluorophore) and the target

molecule; ii) the photo-induced charge transfer (PCT); the fluorescence changes occur by the

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interruption of the electronic coupling between the donor and acceptor moieties; and iii) the Föster

resonance energy transfer (FRET); this is a process in which deactivation of an excited molecule

transfers the energy to another molecule to excite it.

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In search of a low-cost, non-toxic, green synthesis method for carbon quantum dots, grapefruit

juice was chosen for this study as a chemical precursor for synthesizing water-soluble CQDs via

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the hydrothermal method [39]. These prepared CQDs were used as optical probes for the detection

of toxic metal ions via luminescence quenching.

2. Experimental Set-Up
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2.1 Materials

The grapefruits were obtained from a local grocery store, Harris Teeter, USA. Distilled water

(DI) was used to suspend and collect the remnants of the quantum dots in an autoclave. Selected
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compounds used for ion introduction were tin (II) chloride (SnCl2), nickel (II) chloride (NiCl2),

and copper (II) chloride (CuCl2). All metal chlorides were purchased from Sigma Aldrich.
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2.2 Synthesis of Carbon Quantum Dots from Grapefruit

The CQDs were synthesized through a hydrothermal reaction process with high pressure and
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temperature. In the beginning, 20 mL of the grapefruit juice was collected from the raw fruits and

added to 20 mL of DI water. This solution was then mixed using a vortex and poured into a Teflon
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liner. The Teflon liner was inserted into a 100 mL hydrothermal synthesis autoclave reactor. The

Autoclave with the precursors was placed inside a furnace set at a temperature of 180 C for the
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preparation of three batches of samples for 2 hours, 4 hours, and 8 hours to initiate the chemical

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 reaction. All CQDs prepared at three different durations were cooled down to room temperature.

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The black solid remnants were extracted with a metal spatula and discarded, whereas the remaining

liquid containing the quantum dots was pipetted out.

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2.3 CQDs as Metal Ion Sensors

Various metal ions were introduced to the CQDs to observe their effect on luminescence

quenching. Solutions of CQDs with various molar concentrations of TiCl2, NiCl2, and CuCl2 were

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prepared by adding the respective metal ion powders to the suspended CQDs and subsequently

stirring the mixtures for 3 minutes. Molar concentrations of these solutions ranged from 5 μM to

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10 mM.

2.4 Characterization
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Fluorescence of the CQDs was observed under a 302 nm excitation wavelength ultraviolet
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lamp. The CQDs were diluted with DI water and transferred into a quartz cuvette for absorption

and photoluminescence data. Ultraviolet-visible spectroscopy (UV-VIS) was used to measure the

absorption in the visible region from 250 nm to 800 nm using a Perkin Elmer Lambda 1050
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spectrometer. Photoluminescence (PL) of the CQDs was measured with a Jobin Yvon Horiba

FluoroMax 3 Spectrometer at an excitation wavelength of 365 nm. The size and surface
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morphology of the quantum dots were determined using a Thermo Scientific Talos F200X

transmission electron microscope (TEM), after drying on copper mesh grids. Fourier transform
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infrared spectroscopy (FTIR) measurement was carried out using PerkinElmer ULTA to observe

the surface functional groups of the synthesized CQDs.

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 3. Results and discussions

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Figure 1. Potential formation mechanism of CQDs synthesized via hydrothermal reaction of grapefruit juice.

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The schematic representation of the formation of CQDs in the water medium during synthesis

is shown in Figure 1. Grapefruit juice, which contains carbohydrates and organic acids like
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glucose, fructose, sucrose, ascorbic acid, citric acid, etc. as carbon precursors are mixed with water.

In the first step, dehydration of the precursor (grapefruit juice) occurs, leading to the accumulation

of decomposed products and gradually creating large-sized polymer particles. Furthermore, these
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polymer particles shrink in size because of continuous intramolecular dehydration as heating

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proceeds. At this point, carbonization began, and clusters are formed inside the polymers. Once

this so-formed cluster concentration reaches a critical supersaturation point, the nucleation of

CQDs takes place [45]. During this stage, nuclei are formed by the diffusion of the aromatic
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clusters toward the particle surface, and simultaneous passivation with various functional groups

(hydroxyl, carbonyl, carboxyl, etc.) follows. Subsequently, polymer nanoparticles tend to extinct
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and the formation of CQDs occurs.

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Figure 2. FTIR spectra of 2, 4, and 8-hour grapefruit CQDs.

Vibrational spectroscopy data were measured using FTIR spectroscopy. The functional groups
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of the grapefruit-based CQDs prepared for 2, 4, and 8-hours hydrothermal routes are shown in the

FTIR spectra in Figure 2. Interestingly, FTIR spectrum of the three samples looks similar with a
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clear overlap over each other. The spectra show a few distinct peaks with the observation of a very

strong peak at 3,343 cm-1 attributed to the presence of O-H stretching vibration mode. The strong
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absorption peak at 1,634 cm-1 is likely the generation of a C=O group being present in the sample.

The FTIR data provided the existence of important functional groups such as –OH, and C=O in
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our fruit-based carbon quantum dots [46].

Further investigation was carried out to study the photophysical properties of prepared CQDs.
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The CQDs are fully dispersed in water before taking the absorption spectra. The glass vial

containing water dispersed CQDs shows a light brown color under visible light and a very strong
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 blue light emission when exposed to a 285 nm UV lamp, as shown in the inset of Figure 3. The

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CQDs show a distinguished absorption peak around 264 nm which is ascribed to the π-π* transition

of C=C.

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Figure 3. UV-VIS spectra of 2, 4, and 8-hour grapefruit CQDs, inset shows the exposure of CQDs to UV light.
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The classic signature of CQDs is strongly related to their emission wavelength and particle

size-dependent luminescent behavior. From both fundamental and application points of view, PL
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exhibited by the CQDs is one of their most fascinating characteristics.

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Figure 4. Normalized PL spectra for 2, 4, and 8-hours of synthesized grapefruit CQDs.

Our water-soluble CQDs show bluish-white luminescence under 285 nm UV lamp light (inset
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of Figure 3). All samples are excited at the wavelength of 365 nm during PL measurements. PL

spectra for 2, 4, and 8 hours synthesized CQDs (Figure 4) clearly show a strong peak at 451 nm,
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and the intensity of PL emission depends on the synthesis time of the CQDs. The mechanism

associated with PL behavior of CQDs is very complicated and is yet to be reported. All the samples
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show a prominent PL peak and the peak position is shifted towards the shorter wavelengths of the

electromagnetic spectrum as the reaction time of the CQDs preparation increases from 2 hours to
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8 hours. This blue shifting of the fluorescence peaks indicates that the size of the CQDs decreases

with increasing duration of synthesis which is also confirmed by the TEM images.
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The size and morphology of the synthesized CQDs were analyzed by transmission electron

microscopy (TEM). TEM micrographs of CQDs with synthesis times of 2 and 8 hours are
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 presented in Figure 5. After 2 hours of the synthesis process, we do not see any significant amount

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of nanometer-sized particles formation and the particles seen here are bigger, Figure 5a. In the case

of 4 hours of synthesis time samples (not shown here), the particle sizes are not changed

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significantly but were smaller compared to the 2 hours sample. While there was a reduction in the

particle size, the change in the particle sizes was not significant. Figure 5b illustrates the sample

produced after 8 hours of hydrothermal treatment where a clear transition from micron to

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nanometer-sized spherical particles occurs. The particles are well connected with neighboring

particles forming a chain-like clustered structure with an average size of the spherical particles of

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a little over 10 ± 0.5 nm. These results confirm that an increase in hydrothermal reaction time plays

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an important role to produce nanometer-sized carbon dots.
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Figure 5. Transmission electron microscope images of (a) 2 hours, and (b) 8 hours of synthesized CQDs.
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CQDs in Cu ion sensing

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 The oxidized species of copper ions, which are highly studied and versatile catalytic systems

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[47], perform an important role in various biological processes that leads to neurodegenerative

diseases while cellular homeostasis is modified by the copper ions [48]. Hence, large amounts of

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Cu2+ ions, which could enter through contaminated water in the human body, can develop various

diseases including kidney damage or liver and gastrointestinal disturbance [49].

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Figure 6. Normalized PL spectra for different concentrations (5 µM to 10 mM) of metal chloride immersed into
8 hours of synthesized CQDs for the detection of metal ions (a) CuCl2, (b) SnCl2, and (c) NiCl2.
We further evaluated the sensitivity of CQDs for various concentrations of Cu2+ ions. Figure

6a shows the normalized PL spectra of the 8 hours of synthesized pristine CQDs and various
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concentrations of the CuCl2 starting from 5 µM to 10 mM added to the CQDs at room temperature.

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 We noticed that the pristine quantum dots show the highest PL intensity. However, quenching of

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fluorescence intensity is apparent with increasing the molar concentration of the Cu ions without

shifting the emission peak. The sharp quenching of the PL spectra results from the photo-induced

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charge transfer mechanism: upon coordination of Cu2+ to the functional groups. A charge transfer

between CQDs and Cu2+ ions was possible, showing non-radiative recombination, and, therefore,

the fluorescence quenching effect [50].

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CQDs in Sn ion sensing

The neurotoxicity of tin hydride by inhalation in humans has been confirmed. High-level

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intakes of inorganic tin compounds can cause nausea, vomiting, diarrhea, stomach complaints,

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skin rashes, palpitations, and headaches [51]. The effect of environmental relevant Sn metal ions

on the fluorescence intensity of the 8 hours synthesized CQDs was investigated and shown in
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Figure 6b. A significant quenching effect of PL spectra was observed with the incorporation of Sn

ions, which indicated that CQDs could potentially be used for the detection of Sn (II) ions with

high sensitivity. All three types of CQD samples show a similar trend in their PL spectra at various
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concentrations of Sn ion.

CQDs in Ni ion sensing

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Nickel is a harmful pollutant that poses environmental and health concerns. Specifically, it is

known to contaminate industrial wastewater which can then affect the environment. Diverse
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diseases are associated with the accumulation of Ni ions in the human body, such as Minamata

disease, which is related to severe neurological pathologies including motion disorders, ataxia, and
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paroxysmal convulsion [52]. Therefore, the detection of Ni ions is very important to mitigate its

impact on the environment. Figure 5c shows the quenched PL spectra of the Ni ion added to the
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CQDs compared to the pristine CQDs. When the Ni ion concentration was 5 M, the fluorescence

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 intensity reached 80%. However, with further addition of the Ni ion by adjusting the concentration

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to 500 mM, a significant reduction in the fluorescence peak intensity is observed and the value

reached 55%.

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Figure 7. Representative plot of quenching of CQDs emission with respect to different metal ions added (5 µM to
10 mM) into 8 hours of synthesized carbon quantum dots.

The Stern-Volmer plots of the PL quenching for the three different metal ions added in
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concentration from 5 µM to 10 mM into the 8 hours synthesized CQDs are shown in Figure 7. The
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CQDs exhibited PL quenching for the three types of metal ions. The strongest PL quenching was

observed by Sn metal ions, where the PL was quenched to about 40% over the metal ion
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concentration range. Cu metal ions quenched PL to about 60%, and lastly, the relatively weak PL

quenching was observed for Ni metal ions, where the PL was quenched to about 70%. Compared

with other detection methods in terms of detection limit and detection range, the limit of detection
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of this method is higher. In addition, in this sensing system, the synthesis of CQDs is simpler, the

raw materials are cheaper and more environmentally friendly, and the operation is simpler.
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 4. Conclusion

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We have demonstrated an easy, economic, one-step successful hydrothermal synthetic route to

water-soluble fluorescent CQDs prepared from grapefruits for various reaction times at 180 oC

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through a Teflon-lined autoclave reactor. Fourier transform infrared spectroscopy (FT-IR)

predominantly confirmed that synthesized CQDs contain carbonyl and hydroxyl groups, which

can provide more adsorption sites. Spectroscopic properties were then characterized by ultraviolet

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absorption spectrum and photoluminescence spectrum. The average size of the spherical particles

is a little over 10 ± 0.5 nm and they are connected well with neighboring particles forming a ribbon-

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like structure. The CQDs exhibit a good range of photoluminescence emission with bluish-white

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fluorescence under a UV lamp at 285 nm. Furthermore, the luminescence intensity of CQDs

decreases gradually after the addition of various molar concentrations of heavy metal ions. These
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optical and spectroscopic findings reveal that CQDs can be used as effective nanoprobes for heavy

metals sensing applications from the environment, such as Cu, Ni, and Sn ions, that have biological

and negative environmental impacts.

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Acknowledgments

This work is supported by NSF-CREST Grant number HRD 1547771. Appreciation to Dr. Sam
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Sun for his input and for providing the quartz cuvettes, Dr. Amar Kumbhar for his assistance with

the TEM measurements, and Dr. Carl Bonner for fruitful discussion.
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