Article

pubs.acs.org/JAFC

Green Synthesis of Fluorescent Carbon Dots for Selective Detection

of Tartrazine in Food Samples
Hua Xu,† Xiupei Yang,*,† Gu Li,† Chuan Zhao,† and Xiangjun Liao*,§
†
College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637000, People’s Republic of China
§
Exposure and Biomonitoring Division, Health Canada, 50 Colombine Driveway, Ottawa K1A 0K9, Canada
*
S Supporting Information

ABSTRACT: A simple, economical, and green method for the preparation of water-soluble, high-fluorescent carbon quantum
dots (C-dots) has been developed via hydrothermal process using aloe as a carbon source. The synthesized C-dots were
characterized by atomic force microscope (AFM), transmission electron microscopy (TEM), fluorescence spectrophotometer,
UV−vis absorption spectra as well as Fourier transform infrared spectroscopy (FTIR). The results reveal that the as-prepared C-
dots were spherical shape with an average diameter of 5 nm and emit bright yellow photoluminescence (PL) with a quantum
yield of approximately 10.37%. The surface of the C-dots was rich in hydroxyl groups and presented various merits including high
fluorescent quantum yield, excellent photostability, low toxicity and satisfactory solubility. Additionally, we found that one of the
widely used synthetic food colorants, tartrazine, could result in a strong fluorescence quenching of the C-dots through a static
quenching process. The decrease of fluorescence intensity made it possible to determine tartrazine in the linear range extending
from 0.25 to 32.50 μM, This observation was further successfully applied for the determination of tartrazine in food samples
collected from local markets, suggesting its great potential toward food routine analysis. Results from our study may shed light on
the production of fluorescent and biocompatible nanocarbons due to our simple and environmental benign strategy to synthesize
C-dots in which aloe was used as a carbon source.
KEYWORDS: carbon quantum dots, tartrazine, aloe, fluorescence quench

■ INTRODUCTION
Tartrazine is a widely used synthetic food colorant that can be
found in certain food products such as candies, beverages,
bakery products, and dairy products.1,2 However, some studies
have revealed that tartrazine may cause adverse health effects
such as changes in hepatic and renal parameters and
reproductive toxicity, as well as neurobehavioral poisonousness
when it is excessively consumed.3,4 Therefore, the food industry
must strictly control and regulate the content of tartrazine in
foods, which necessitates an interest in the development of an
efficient measurement technique to determine tartrazine in
foods in terms of rapidity, simplicity, and sensitivity.
Until now, various instrumental techniques that analyzed
tartrazine in foodstuff products have been increasingly
employed, which include thin-layer chromatography (TLC)
method,5 electrochemical sensor,6 spectrophotometry,7 and
high-performance liquid chromatography (HPLC).8 Never-
theless, these methods may not be suitable for routine
monitoring because they require sophisticated equipment and
time-consuming sample preparation. As a result, the develop-
ment of a simple, economical, fast, and reliable assay of
tartrazine has been a challenge for analytical researchers.
Recently, carbon quantum dots (C-dots), which are a new
class of fluorescent nanomaterials with a size of <10 nm, have
received much attention owing to their good water solubility,
excellent photostability, low toxicity, and favorable biocompat-
ibility.9,10 The application of C-dots has been explored in
fluorescent biosensing and in vivo bioimaging and food
detection together with food-packaging domain.11−13 C-Dots
also served as reasonable candidates for future nanodevices,
cellular imaging, and biomedicine.14,15 Over the past years,
several methods have been developed for the synthesis of C-
dots, including arc discharge,16 laser ablation,17,18 electro-
chemical oxidation,19 and microwave irradiation.20 However,
hydrothermal carbonization has provided great advancement
over existing physical methods, which is due to its simplicity
and production of C-dots with good quantum yield. Recently,
hydrothermal carbonization of chitosan, orange peels, coffee
grounds, and grass has been successfully applied to synthesize
fluorescent C-dots, which could be probes for recognizing
various chemical species and cells in vitro and in vivo.21−24 All
of these proved that hydrothermal carbonization is an eco-
friendly, facile, and classical route for the synthesis of C-dots in
aqueous media. From the point of material preparation, there is
an urgent need to locate new carbon sources for simple,
economical, and green synthesis of C-dots.
In this work, a facile and green method for the preparation of
fluorescent C-dots by hydrothermal treatment of aloe and the
application has been proposed. On the basis of fluorescence
quenching, the prepared C-dots can serve as an effective sensor
for sensitive and selective determination of tartrazine. The use
of the synthesized C-dots for detection has been validated by
measuring the concentration of tartrazine in food samples
collected from a local supermarket.
Received: May 8, 2015
Revised: July 8, 2015
Accepted: July 8, 2015
Published: July 8, 2015

© 2015 American Chemical Society 6707 DOI: 10.1021/acs.jafc.5b02319

J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry Article

Figure 1. AFM images of the C-dots.

■ EXPERIMENTAL PROCEDURES
Materials. Aloe was obtained from potted plants in our laboratory
of reabsorption within the sample on the observed emission spectrum,
the absorbance values (A) of all solutions in the 10 mm cuvette were
always controlled under 0.1.
and washed with water for further use. Dichloromethane (CH2Cl2,
Sample Pretreatment. Candy, steamed buns made of corn, and
99.5%) was purchased from Aladdin Industrial Corp. (Shanghai,
honey were selected as test samples because tartrazine may be added
China). Tartrazine (C 16 H 9 N 4 Na 3 O 9 S 2 , 87%), sunset yellow
as a colorant into them. All samples were obtained from a local
(C 1 6 H 1 0 N 2 N a 2 O 7 S 2 , 8 5 %) , e r i o g l a u c i n e dis od i u m s al t
supermarket in Nanchong, China. The candy or honey sample (10.0
(C37H34Na2N2O9S3, 85%), and amaranth (C20H11N2Na3O10S3, 85%)
g) was crushed and subsequently dissolved in hot water (∼60 °C).
were received from Aladdin Chemistry Co. Ltd. (Shanghai, China).
The resulting solution was transferred and diluted to a 50 mL
Sodium dihydrogen phosphate (NaH2PO4·H2O) and disodium
volumetric flask. The diluted solution was filtered through a 0.45 μm
hydrogen phosphate dodecahydrate (Na2HPO4·12H2O) were ob-
filter membrane for subsequent use. Ten grams of steamed buns and a
tained from Tianjin Fuchen Chemical Reagents Co., Ltd. (Tianjin,
certain amount of water were added into a 100 mL beaker, and then
China). All chemicals were of analytical reagent grade and used
the mixture was blended by electric mixer and extracted with ultrasonic
without further purification. The ultrapure water used throughout the
for 15 min, respectively. After extraction, the mixture was centrifuged
experiments was purified through an UPH-II-20T up water
at 12000 rpm for 10 min followed by transferring the supernatant and
purification system (Chengdu Ultrapure Technology Co. Ltd.,
diluting to 50 mL. The diluted solution was also filtered through a 0.45
Chengdu, China).
μm filter membrane for subsequent use. The above sample
Apparatus and Characterization. The AFM analysis was carried
pretreatment method is referenced to the literature with some
out on a Multimode/Nanoscope (Veeco Corp., USA) on a tapping
minor modifications.26
mode with a RTESP-Veeco cantilever on a platinum-coated mica
Detection of Tartrazine in Food Samples. The tartrazine
substrate. All absorption spectra were recorded on a Shimadzu UV-
detection procedure was carried out in phosphate buffer (PB) (30
2550 UV−vis absorption spectrophotometer (Kyoto, Japan). Fluo-
mM, pH 6.0) at 5 °C. In a typical run, 450 μL of C-dots solution was
rescence measurements were conducted with a Cary Eclipse
added into 500 μL of PB, followed by the addition of 1000 μL of
fluorescence spectrophotometer (Varian, Palo Alto, CA, USA). The
sample solution and thorough mixing. The resulting mixture was
infrared spectra were obtained on a Nicolet 6700 Fourier transform
reconstituted to 4 mL with water. After a reaction time of 5 min at 5
infrared (FTIR) spectrometer (Thermo Electron Corp., USA) with
°C, the spectra were recorded under excitation at 441 nm with slit
passed KBr pellet at room temperature.
widths setting at 10/10 nm. All of the recoveries were calculated
Synthesis of Fluorescent C-Dots. The C-dots were prepared by
according to the equation below:
hydrothermal treatment of fresh aloe in water. In a typical procedure, 5
g of aloe was added into 25 mL of water, and then the mixture was recovery = (Cmeasured − C initial)/Cadded

transferred into a 50 mL Teflon-lined autoclave and was heated at 180
°C for 11 h. After heating, the autoclaves were allowed to naturally
cool in a fume hood on a heat-resistant plate and the resulting yellow
solution was filtered with a 0.22 μm membrane followed by washing
with dichloromethane to remove the unreacted organic moieties.
Finally, the upper light yellow aqueous solution containing C-dots was
collected and stored at 4 °C for further characterization and use.
Quantum Yield Measurements. The quantum yield of the as-
synthesized C-dots was measured on the basis of a procedure
described previously.25 Rhodamine 6G aqueous solution was used as a
reference standard, for which the quantum yield was 0.95 at 488 nm
reported by the literature. Absolute values of the quantum yield were
calculated according to the equation
2 temperature rise. We finally chose 180 °C as the optimal
Ix A std ηx
Φx = Φstd 2
A x Istd ηstd
where Φ is the quantum yield of the as-prepared C-dots, A is the
absorbance, I is the corrected emission intensity at the excitation
wavelength, and η is the refractive index of the solvent. The subscripts
“std” and “x” refer to reference standard with known quantum yield
and the C-dots solution, respectively. For the sake of reducing effects
6708
■
RESULTS AND DISCUSSION
Optimization of the Synthesis Conditions. To ensure
excellent performance of the synthesized C-dots, we have
optimized the time and temperature of the synthesis simply,
and results are shown in Figures S1 and S2. From Figure S1 we
can see clearly that the fluorescence intensity gradually
increased with the reaction time up to 11 h but decreased
when the time exceeded 11 h. Therefore, 11 h was chosen as
the optimal reaction time. Simultaneously, as displayed in
Figure S2, the fluorescence intensity increased with the reaction
temperature because when the temperature exceeded 180 °C,
the fluorescence intensity increase was not obvious.
Characterization. Figure 1 shows the typical AFM image of
the as-synthesized C-dots solution. It reveals that the C-dots are
well dispersed in solution with spherical shape and have an
average size of 5 nm approximately. Similarly, Figure S3 shows
the typical TEM image of the C-dots. It can be seen that the C-
DOI: 10.1021/acs.jafc.5b02319
J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry Article

dots are in the monodispersion state and their size is consistent

with the results of AFM.
The absorption (black line) and emission spectra (green
line) of the as-synthesized C-dots are shown in Figure 2. A peak

Figure 3. Fluorescence emission spectra of C-dots obtained at

different excitation wavelengths progressively increasing from 370 to
480 nm in 10 nm increments.

Figure 2. UV−vis absorption (black line) and fluorescence emission

(green line) spectra of the C-dots. (Inset) Photographic images of C-
dots under (a) visible light, (b) ultraviolet light, and (c) ultraviolet
light with tartrazine (22.5 μM).

at 278 nm is exhibited in the UV−vis absorption spectrum,

which was attributed to n−π* transition of CO and π−π*
transition of CC.27 The photoluminescent (PL) spectrum
shows an optimal emission peak at about 503 nm when excited
at 441 nm. The inset photograph in Figure 2 indicates the C-
dots aqueous solution under visible (a) and UV illumination at
365 nm (b). The bright yellow PL of the C-dots under UV light
is strong enough to be seen with the naked eye, but when
tartrazine was added, the fluorescence was obviously quenched
(c). The full width at half-maximum (fwhm) is 100 nm,
suggesting a relatively small size distribution of C-dots, which
was consistent with AFM and TEM data and approximately
equal to that of most reported C-dots.28,29 The strong
fluorescence can be caused by the surface energy traps in the
C-dots that become emissive upon stabilization.17
To further investigate the optical properties, the PL emission
spectrum of the C-dots was recorded at progressively increasing
excitation wavelengths (Figure 3). It can be observed that a red
shift was attributed in the emission spectra of C-dots from 443
to 525 nm with increasing excitation wavelengths, accompanied
by a decrease of the fluorescence intensity, revealing that the
fluorescence of C-dots is strongly dependent on the excitation
wavelength. This finding is substantially in agreement with that
of Vaibhavkumar.30,31 To investigate the components, surface
groups, and structure of the as-synthesized C-dots, EDS and
FT-IR have been carried out. Figure S4 shows the as-prepared
C-dots are mainly composed of C, H, O, and N. As shown in
Figure 4, characteristic absorption bands of the −OH stretching
vibration mode at about 3400 and 1073 cm−1 could be
observed. The band at 2923 cm−1 corresponds to the C−H
stretching mode.32 In addition, the peaks appearing at 1590 and
1400 cm−1 may be caused by the asymmetric and symmetric
stretching vibration of COO−, respectively. These findings
provide evidence that both the hydroxyl and carboxylic groups
originated from carbohydrates in the aloe.
6709
Figure 4. FT-IR spectrum of C-dots.
It is well-known that the photostability of C-dots plays a key
role in sensitive fluorescence detection. In this connection, we
studied the emission behavior of the C-dots under continuous
UV light illumination at 365 nm for 120 min. It was also noted
that as shown in Figure S5 the photobleaching of C-dots is not
observed and the fluorescence intensity of C-dots remained
constant even after 120 min of continuous UV light
illumination, indicating the good photostability of C-dots.
Using rhodamine 6G as a reference, a PL quantum yield (QY)
of 10.37% was measured. Table S1 shows the comparison of
the optical properties and applications of the C-dots derived
from aloe with the reported methods. It can be seen that the
present method is green and simple and has a relatively high
quantum yield. At the same time, it is worth mentioning that
the as-prepared C-dots emit strong yellow fluorescence,
whereas most reported carbon dots are blue, and they can be
a sensitive fluorescent probe for colorant detention.
Design Principle of the Sensor. Under the same
experimental conditions, the fluorescence spectra of the C-
dots alone and the system of C-dots with tartrazine were
recorded, respectively. As shown in Figure S6, the C-dots
presented strong fluorescence at 503 nm when excited at 441
DOI: 10.1021/acs.jafc.5b02319
J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry Article

Scheme 1. Scheme of the Synthetic Strategy for C-Dots and the Principle of Tartrazine Sensing

nm. Upon the addition of tartrazine, the fluorescence intensity

of the prepared C-dots decreased significantly. On the basis of
the fluorescence quenching, we speculated that a facile
fluorescence sensor for the determination of tartrazine could
be constructed. The synthetic strategy for C-dots and the
principle of tartrazine sensing are schematically presented in
Scheme 1.
Mechanism of Fluorescence Quenching. Broadly speak-
ing, various kinds of molecular interactions with the quencher
molecule can reduce the fluorescence quantum yield, such as
electron or energy transfer, collisional quenching, excited-state
reaction, and ground-state complex formation The quenching
mechanisms are usually divided into dynamic quenching, which
results from collision, and static quenching, resulting from the
formation of a ground-state complex between the fluorescence
material and quencher. On the other hand, they could be
distinguished by some additional formations such as the
relationship between the quenching and viscosity, temperature,
and lifetime measurements. 33 In general, the dynamic
fluorescence quenching constants will increase with the rise Figure 5. Stern−Volmer plots for the system of C-dots−tartrazine
of the system temperature due to the energy transfer efficiency, under temperatures of 278, 288, 298, and 308 K, respectively. F0 and F
are the fluorescence intensity of C-dots in the absence and presence of
and the effective collision times between molecules will also
tartrazine, respectively. Conditions: C-dots, 450 μL; PB, 30 mM, pH
increase. On the contrary, the values of the static fluorescence 6.0.
quenching constants will decrease with the rise of temperature.
Let us suppose that the mechanism is dynamic quenching; it Table 1. Stern−Volmer Quenching Constants for the
can be described by the Stern−Volmer equation34 Interaction of C-Dots and Tartrazine at Different
Temperatures
F0/F = 1 + KSV[Q] = 1 + Kqτ0[Q]
pH T (K) KSV (L mol−1) Kq (L mol−1 s−1) R SD
where F0 and F are the C-dots fluorescence intensities at 503 6.0 278 5.663 × 104
5.663 × 1012
0.9984 0.0278
nm in the absence and presence of tartrazine, respectively; KSV 6.0 288 5.213 × 104 5.213 × 1012 0.9960 0.0402
and Kq are the Stern−Volmer quenching constant and the 6.0 298 5.178 × 104 5.178 × 1012 0.9967 0.0361
bimolecular quenching constant, respectively; [Q] is the 6.0 308 4.734 × 104 4.734 × 1012 0.9939 0.0452
concentration of tartrazine; and τ0 is the average lifetime of
the C-dots without any other fluorescence quencher, with a dosage of C-dots, reaction temperature, and incubation time
general value of 10−8 s. Figure 5 shows the fluorescence were systematically optimized for the system.
intensities of the C-dots analyzed by plotting F0/F versus [Q] The effect of the solution pH on the fluorescence quenching
at 278, 288, 298, and 308 K. Table 1 summarizes the calculated of C-dots in the presence of tartrazine is shown in Figure 6a. An
KSV and Kq values for each temperature. As shown, the KSV is increase in pH from 4.0 to 6.0 results in the increased
inversely correlated with temperature, and the value of Kq is far fluorescence quenching efficiency (represented as F0/F, where
larger than 2.0 × 1010 L mol−1 s−1, which is the maximum F0 and F are the fluorescence intensities of the C-dots at 503
scatter collision quenching constant. These findings indicate nm before and after the addition of tartrazine, respectively.)
that the quenching process may be caused by static quenching. whereas a further increase in pH from 6 to 7.5 leads to a
Additionally, the UV−vis spectra of the prepared C-dots alone gradual decrease. Such an observation suggests that the
and the system of the C-dots with tartrazine are illustrated in fluorescence intensity of the C-dots strongly depends on the
Figure S7. As can be seen from this figure, with the addition of pH value of the system. Our results are consistent with those of
tartrazine, the absorbance intensity of the C-dots at 280 nm C-dots functioned with hydroxyl and carboxylic/carbonyl
increases, with a blue shift. This observation indicates that the moieties.10,19,32 Consequently, we selected 6.0 as the optimal
formation of ground-state complexes is generated due to the pH for our study.
interaction between tartrazine and C-dots. The effect of the dosage of C-dots on the fluorescence
Optimization of Experimental Conditions. With the quenching efficiency is presented in Figure 6b. The
purpose of investigating the sensitivity, precision, and selectivity fluorescence quenching efficiency gradually increased with the
of the analytical method, parameters including the medium pH, dosage of C-dots up to 450 μL. When the dosage of C-dots
6710 DOI: 10.1021/acs.jafc.5b02319
J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry
Figure 6. Effect of (a) pH of buffer solution, (b) dosage of C-dots, (c) reaction temperature, and (d) reaction time on fluorescence quenching
efficiency of the C-dots−tartrazine system. F0 and F are the fluorescence intensity of C-dots in the absence and presence of tartrazine, respectively.
Conditions: PB, 30 mM; tartrazine, 10 μM.
exceeded 450 μL, the fluorescence quenching efficiency
decreased. Therefore, 450 μL was used as the optimal dosage
for further performance
Figure 6c shows the fluorescence curves of the system at
different temperatures. As the temperature increased from 5 to
35 °C, the fluorescence quenching efficiency decreased
gradually. Among the temperatures studied, the maximum
fluorescence intensity efficiency was achived at 5 °C. Hence, 5
°C is selected as the optimum reaction temperature.
The effect of incubation time on the fluorescence intensity of
the system is shown in Figure 6d. No significant changes in F0/
F were observed after an incubation time of 1 min. To ensure
the consistency of the whole experiment, it is important to
record the stable fluorescence signal. Thus, 5 min is
conservatively chosen as the optimum incubation time.
Analytical Performance for Tartrazine Sensing.
Sensitivity. The dependence of F0/F on the different
concentrations of tartrazine under the identical conditions is
shown in Figure 7. As displayed, the fluorescence quenching
efficiency of C-dots gradually decreases with an increase in the
concentration of tartrazine. As shown in the upper right inset of
Figure 7, the decrease in fluorescence quenching efficiency
6711
Article
exhibited a linear response to the tartrazine concentration in
the range of 0.25−32.50 μM, which was consistent with the
photograph of the solutions under UV light. The calibration
curve can be depicted as F0/F = 0.9604 + 0.0577X (X is the
concentration of tartrazine, μM) with a correlation coefficient
of 0.9986. The relative standard deviation (RSD) was 0.25%
through five parallel determinations (n = 5) at a fixed tartrazine
concentration of 10.00 μM, indicating the excellent reliability of
this sensor. The detection limit is estimated to be 73 nM at a
signal-to-noise ratio of 3.
In Table 2, we compare the experimental results with those
for reported methods of tartrazine detection. As shown in Table
2, our developed assay exhibits a wider linear range and lower
RSD compared to some methods. Our method can be an
alternative to others for the determination of tartrazine in
samples, although the limit of detection (LOD) our method is
not the smallest in Table 2. It is worth mentioning that almost
all of the reported sensors need special equipment, a
sophisticated technique, or complicated operations. By contrast,
the sensor we developed here has its own features, including
low instrumentation cost, simplicity of operation, and fast
DOI: 10.1021/acs.jafc.5b02319
J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry Article

Figure 7. Fluorescence emission spectra of C-dots in the presence of
different concentrations of tartrazine in 30 mM PB (pH 6.0). From a
to l: 0.00, 0.25, 0.75, 2.50, 3.75, 5.00, 7.50, 12.50, 17.50, 22.50, 27.50,
32.50 μM, respectively. C-dots, 450 μL. (Inset) Photographic images
of the corresponding solutions under UV light and the relationship
curve between F0/F and concentration of tartrazine.
response, which makes it more applicable for routine analysis of
tartrazine in foods.
Selectivity. To evaluate the selectivity of this sensing system,
we examined the fluorescence response of the system to
tartrazine at a concentration of 5.0 μM with the presence of
coexisting foreign substances such as K+, Ca2+, Zn2+, Fe3+,
HCO3‑, NO2‑, glutamic acid, glutathione (GSH), citric acid,
phenylalanine, starch, tartaric acid, vitamin C, glucose, lactose,
sunset yellow, erioglaucine disodium salt, and amaranth under
the same conditions. As shown in Figure 8, for the present
study, various different substances were added in the test
solution at the amount of 100 times tartrazine initially, and the
ratio would be gradually reduced when the interference
presented. It was found that some of the materials, such as
Fe3+, sunset yellow, erioglaucine disodium salt, and amaranth,
could be only allowed at relatively lower levels. Nevertheless,
the concentrations of these substances were much lower than
the allowed levels in food samples. Meanwhile, most of the
common excipients in foods could be tolerated at high
Figure 8. Effects of potentially interfering substances: (0) non-
interference; (1) glucose, 500 μM; (2) lactose, 500 μM; (3) starch,
500 μM; (4) citric acid, 500 μM; (5) tartaric acid, 500 μM; (6)
ascorbic acid, 500 μM; (7) glutamic acid, 250 μM; (8) phenylalmine,
250 μM; (9) NO2−, 500 μM; (10) HCO3‑, 500 μM; (11) Ca2+, 500
μM; (12) Zn2+, 500 μM; (13) K+, 500 μM; (14) Fe3+, 25 μM; (15)
sunset yellow, 5.0 μM; (16) erioglaucine disodium salt, 25 μM; (17)
amaranth, 5.0 μM. Conditions: C-dots, 450 μL; PB, 30 mM, pH 6.0;
tartrazine, 5.0 μM.
concentrations up to 100 times. That is to say the established
strategy possesses a high selectivity toward tartrazine detection.
Application in Food Samples. The developed approach was
employed to detect the trace level of tartrazine in some food
samples. The results for the pretreated food samples spiked
with known amounts of standard tartrazine are shown in Table
3. The intraday and interday recoveries ranged from 88.6 to
103.4% and from 87.3 to 106.6%, respectively. All of these
results indicate that the accuracy and reliability of the proposed
method can be applied to the determination of tartrazine in
food samples.
In summary, C-dots based on aloe were synthesized via a
simple and green method. Without further chemical
modification, the synthesized C-dots have been applied to the
sensitive and selective detection of tartrazine in some food
samples. The new C-dots described here may extend their great
potential for cell imaging and drug delivery applications due to

Table 2. Comparison of the Proposed Method with Other Methods for Determination of Tartrazine

method linear range (μM) R2 LOD (nM) RSD% ref

graphene and mesoporous TiO2 electrochemical sensor 0.02−1.18 0.994 8 2.70 26
spectrophotometry method 0.00131−0.67 0.992 0.56 0.98 23
electrochemical detection 0.11−56 56 3.12 17
electrochemical detection 0.05−20 14.3 18
electrochemical sensor 0.00936−0.37 0.994 2.8 4.3 22
high-performance liquid chromatography 0.0934−9.34 0.999 18.5 4.3 35
alumina microfibers-based electrochemical sensor 0.005−0.14 0.998 2.0 4.7 36
gold nanoparticles carbon paste electrode 0.05−1.6 0.997 2 1.1 37
differential pulse polarography 0.19−19 0.999 30 38
multiwalled carbon nanotubes film-modified electrode 0.37−74.8 0.990 187 5.2 39
solid phase spectrophotometry 0.094−1.22 0.998 4.00 40
capillary zone electrophoresis 5.6−178 0.995 2430 41
thin-layer chromatography 74.9−356 0.992 0.03 5
reversed-phase high-performance liquid chromatography 0.011−39.3 0.999 3.5 42
fluorescence analysis 0.25−32.5 0.998 73 0.25 this work

6712 DOI: 10.1021/acs.jafc.5b02319

J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry Article

Table 3. Recovery Test and Precision of the Analysis of Tartrazine in Food Samples
intraday interday
food sample detected (μM) spiked (μM) founda (μM) recovery (%) RSD (%) founda (μM) recovery (%) RSD (%)
steamed buns ND b
1.00 1.00 ± 0.07 99.9 2.8 1.06 ± 0.09 106.6 4.2
5.00 4.96 ± 0.07 99.2 0.6 4.99 ± 0.07 99.8 0.6
7.00 7.00 ± 0.05 100.0 0.3 7.02 ± 0.13 100.3 0.7

honey ND 1.00 1.04 ± 0.11 103.4 3.9 1.05 ± 0.15 105.4 5.8
5.00 4.96 ± 0.03 99.1 0.2 5.00 ± 0.07 99.9 0.6
7.00 7.04 ± 0.10 100.6 0.7 7.00 ± 0.18 100.0 1.0

candy 4.80 3.00 7.48 ± 0.15 88.6 0.8 7.44 ± 0.08 87.3 0.4
5.00 9.44 ± 0.06 92.3 0.2 9.51 ± 0.12 93.6 0.5
7.00 11.12 ± 0.12 90.0 0.5 11.16 ± 0.10 90.4 0.4
a
Value = mean ± SD (n = 5). bNot detectable.

the simplicity of their synthesis procedure and the use of simultaneous determination of sunset yellow and tartrazine. Electro-
affordable and environmentally friendly aloe as carbon source. chim. Acta 2012, 74, 151−157.

■
ASSOCIATED CONTENT
*
S Supporting Information
Experimental procedures for EDS, supplementary figures of
EDS, fluorescence spectra, and absorbance spectra of the C-
dots and the system of C-dots−tartrazine. The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/acs.jafc.5b02319.
(2) Ye, X. L.; Du, Y. L.; Lu, D. B.; Wang, C. M. Fabrication of beta-
cyclodextrin-coated poly (diallyldimethylammonium chloride)-func-
tionalized graphene composite film modified glassy carbon-rotating
disk electrode and its application for simultaneous electrochemical
determination colorants of sunset yellow and tartrazine. Anal. Chim.
Acta 2013, 779, 22−34.
(3) Amin, K. A.; Hameid, H. A.; Abd Elsttar, A. H. Effect of food azo
dyes tartrazine and carmoisine on biochemical parameters related to

■
renal, hepatic function and oxidative stress biomarkers in young male
rats. Food Chem. Toxicol. 2010, 48, 2994−2999.
AUTHOR INFORMATION (4) Tanaka, T. Reproductive and neurobehavioural toxicity study of
Corresponding Authors tartrazine administered to mice in the diet. Food Chem. Toxicol. 2006,
*(X.Y.) Phone/fax: +86-817-2568081. E-mail: xiupeiyang@ 44, 179−187.
(5) Soponar, F.; Moţ, A. C.; Sărbu, C. Quantitative determination of
163.com.
some food dyes using digital processing of images obtained by thin-
*(X.L.) Phone/fax: (613) 415-2098. E-mail: xiangjun.liao@
layer chromatography. J. Chromatogr. A 2008, 1188, 295−300.
mail.mcgill.ca. (6) Song, X. J.; Shi, Z.; Tan, X. H.; Zhang, S. H.; Liu, G. S.; Wu, K. B.
Funding One-step solvent exfoliation of graphite to produce a highly-sensitive
We thank the Natural Science Foundation of China electrochemical sensor for tartrazine. Sens. Actuators, B 2014, 197,
(21277109) and the Program for Young Scientific and 104−108.
Technological Innovative Research Team in Sichuan Province (7) Sahraei, R.; Farmany, A.; Mortazavi, S. S. A nanosilver-based
(2014TD0020) for research grants. spectrophotometry method for sensitive determination of tartrazine in
Notes food samples. Food Chem. 2013, 138, 1239−1242.
(8) Culzoni, M. J.; Schenone, A. V.; Llamas, N. E.; Garrido, M.; Di
The authors declare no competing financial interest.

■
ACKNOWLEDGMENTS
We thank Prof. Martin M. F. Choi of the Department of
Chemistry, Hong Kong Baptist University, for valuable
suggestions and fluorescence spectra study.
Nezio, M. S.; Fernández Band, B. S.; Goicoechea, H. C. Fast
chromatographic method for the determination of dyes in beverages
by using high performance liquid chromatographydiode array
detection data and second order algorithms. J. Chromatogr. A 2009,
1216, 7063−7070.
(9) Baker, S. N.; Baker, G. A. Luminescent carbon nanodots:

■ ABBREVIATIONS USED
C-dots, carbon quantum dots; TEM, transmission electron
microscopy; AFM, atomic force microscope; FTIR, Fourier
transform infrared spectroscopy; EDS, energy dispersive
spectrometry; TLC, thin-layer chromatography; HPLC, high
performance liquid chromatograph; fwhm, full width at half-
maximum; PB, phosphate buffer; PL, photoluminescent; QY,
quantum yield; LOD, limit of detection; RSD, relative standard
deviation; GSH, glutathione
emergent nanolights. Angew. Chem., Int. Ed. 2010, 49, 6726−6744.
(10) Liu, H. P.; Ye, T.; Mao, C. D. Fluorescent carbon nanoparticles
derived from candle soot. Angew. Chem., Int. Ed. 2007, 46, 6473−6475.
(11) Ding, C. Q.; Zhu, A. W.; Tian, Y. Functional surface engineering
of C-dots for fluorescent biosensing and in vivo bioimaging. Acc. Chem.
Res. 2014, 47, 20−30.
(12) Greenshields, M. W. C. C.; Mamo, M. A.; Coville, N. J.; Spina,
A. P.; Rosso, D. F.; Latocheski, E. C.; Destro, J. G.; Pimentel, I. C.;
Hümmelgen, I. A. Electronic detection of Drechslera sp. fungi in
charentais melon (Cucumis melo Naudin) using carbon-nanostructure-

■
REFERENCES
(1) Gan, T.; Sun, J. Y.; Cao, S. Q.; Gao, F. X.; Zhang, Y. X.; Yang, Y.
Q. One-step electrochemical approach for the preparation of graphene
wrapped-phosphotungstic acid hybrid and its application for
based sensors. J. Agric. Food Chem. 2012, 60, 10420−10425.
(13) Purkayastha, M. D.; Manhar, A. K.; Das, V. K.; Borah, A.;
Mandal, M.; Thakur, A. J.; Mahanta, C. L. Antioxidative,
hemocompatible, fluorescent carbon nanodots from an “ end-of-
pipe” agricultural waste: exploring its new horizon in the food-
packaging domain. J. Agric. Food Chem. 2014, 62, 4509−4520.

6713 DOI: 10.1021/acs.jafc.5b02319

J. Agric. Food Chem. 2015, 63, 6707−6714
Journal of Agricultural and Food Chemistry
(14) Shen, J. H.; Zhu, Y. H.; Yang, X. L.; Li, C. Z. Graphene quantum
dots: emergent nanolights for bioimaging, sensors, catalysis and
photovoltaic devices. Chem. Commun. 2012, 48, 3686−3699.
(15) Hu, L. M.; Sun, Y.; Li, S. L.; Wang, X. L.; Hu, K. L.; Wang, L. R.;
Liang, X. J.; Wu, Y. Multifunctional carbon dots with high quantum
yield for imaging and gene delivery. Carbon 2014, 67, 508−513.
(16) Xu, X. Y.; Ray, R.; Gu, Y. L.; Ploehn, H. J.; Gearheart, L.; Raker,
K.; Scrivens, W. A. Electrophoretic analysis and purification of
fluorescent single-walled carbon nanotube fragments. J. Am. Chem. Soc.
2004, 126, 12736−12737.
(17) Sun, Y. P.; Zhou, B.; Lin, Y.; Wang, W.; Shiral Fernando, K. A.;
Pathak, P.; Mohammed, J. M.; Harruff, B. A.; Wang, X.; Wang, H. F.;
Luo, P. J. G.; Yang, H.; Kose, M. E.; Chen, B. L.; Veca, L. M.; Xie, S. Y.
Quantum-sized carbon dots for bright and colorful photolumines-
cence. J. Am. Chem. Soc. 2006, 128, 7756−7757.
(18) Wang, J.; Wang, C. F.; Chen, S. Amphiphilic egg-derived carbon
dots: rapid plasma fabrication, pyrolysis process, and multicolor
printing patterns. Angew. Chem., Int. Ed. 2012, 51, 9297−9301.
(19) Zhao, Q. L.; Zhang, Z. L.; Huang, B. H.; Peng, J.; Zhang, M.;
Pang, D. W. Facile preparation of low cytotoxicity fluorescent carbon
nanocrystals by electrooxidation of graphite. Chem. Commun. 2008,
5116−5118.
(20) Liu, J. M.; Lin, L. P.; Wang, X. X.; Lin, S. Q.; Cai, W. L.; Zhang,
L. H.; Zheng, Z. Y. Highly selective and sensitive detection of Cu2+
with lysine enhancing bovine serum albumin modified-carbon dots
fluorescent probe. Analyst 2012, 137, 2637−2642.
(21) Yang, Y. H.; Cui, J. H.; Zheng, M. T.; Hu, C. F.; Tan, S. Z.; Xiao,
Y.; Yang, Q.; Liu, Y. L. One-step synthesis of amino-functionalized
fluorescent carbon nanoparticles by hydrothermal carbonization of
chitosan. Chem. Commun. 2012, 48, 380−382.
(22) Prasannan, A.; Imae, T. One-pot synthesis of fluorescent carbon
dots from orange waste peels. Ind. Eng. Chem. Res. 2013, 52, 15673−
15678.
(23) Hsu, P. C.; Shih, Z. H.; Lee, C. H.; Chang, H. T. Synthesis and
analytical applications of photoluminescent carbon nanodots. Green
Chem. 2012, 14, 917−920.
(24) Liu, S.; Tian, J. Q.; Wang, L.; Zhang, Y. W.; Qin, X. Y.; Luo, Y.
L.; Asiri, A. M.; Al-Youbi, A. O.; Sun, X. P. Hydrothermal treatment of
grass: a low-cost, green route to nitrogen-doped, carbon-rich,
photoluminescent polymer nanodots as an effective fluorescent
sensing platform for label-free detection of Cu(II) ions. Adv. Mater.
2012, 24, 2037−2041.
(25) Dai, H. C.; Shi, Y.; Wang, Y. L.; Sun, Y. J.; Hu, J. T.; Ni, P. J.; Li,
Z. A carbon dot based biosensor for melamine detection by
fluorescence resonance energy transfer. Sens. Actuators, B 2014, 202,
201−208.
(26) Gan, T.; Sun, J. Y.; Meng, W.; Song, L.; Zhang, Y. X.
Electrochemical sensor based on graphene and mesoporous TiO2 for
the simultaneous determination of trace colourants in food. Food
Chem. 2013, 141, 3731−3737.
(27) Yang, X. M.; Zhuo, Y.; Zhu, S. S.; Luo, Y. W.; Feng, Y. J.; Dou,
Y. Novel and green synthesis of high-fluorescent carbon dots
originated from honey for sensing and imaging. Biosens. Bioelectron.
2014, 60, 292−298.
(28) Wang, X.; Cao, L.; Yang, S. T.; Lu, F. S.; Meziani, M. J.; Tian, L.
L.; Sun, K. W.; Bloodgood, M. A.; Sun, Y. P. Bandgap-like strong
fluorescence in functionalized carbon nanoparticles. Angew. Chem., Int.
Ed. 2010, 49, 5310−5314.
(29) Fan, R. J.; Sun, Q.; Zhang, L.; Zhang, Y.; Lu, A. H.
Photoluminescent carbon dots directly derived from polyethylene
glycol and their application for cellular imaging. Carbon 2014, 71, 87−
93.
(30) Vaibhavkumar, N. M.; Sanjay, J.; Hirakendu, B.; Rakesh, K. S.;
Suresh, K. K. One-step hydrothermal approach to fabricate carbon
dots from apple juice for imaging of mycobacterium and fungal cells.
Sens. Actuators, B 2015, 213, 434−443.
(31) Vaibhavkumar, N. M.; Sanjay, J.; Rakesh, K. S.; Suresh, K. K.
Preparation of multicolor emitting carbon dots for HeLa cell imaging.
New J. Chem. 2014, 38, 6152−6160.
6714
Article
(32) Lu, W. B.; Qin, X. Y.; Liu, S.; Chang, G. H.; Zhang, Y. W.; Luo,
Y. L.; Asiri, A. M.; Al-Youbi, A. O.; Sun, X. P. Economical, green
synthesis of fluorescent carbon nanoparticles and their use as probes
for sensitive and selective detection of mercury(II) ions. Anal. Chem.
2012, 84, 5351−5357.
(33) Paramaguru, G.; Kathiravan, A.; Selvaraj, S.; Venuvanalingam,
P.; Renganathan, R. Interaction of anthraquinone dyes with lysozyme:
evidences from spectroscopic and docking studies. J. Hazard. Mater.
2010, 175, 985−991.
(34) Papadopoulou, A.; Green, R. J.; Frazier, R. A. Interaction of
flavonoids with bovine serum albumin: a fluorescence quenching
study. J. Agric. Food Chem. 2005, 53, 158−163.
(35) Li, W. J.; Zhou, X.; Tong, S. S.; Jia, Q. Poly(N-
isopropylacrylamide-co-N,N′-methylene bisacrylamide) monolithic
column embedded with g-alumina nanoparticles microextraction
coupled with high-performance liquid chromatography for the
determination of synthetic food dyes in soft drink samples. Talanta
2013, 105, 386−392.
(36) Zhang, Y. Y.; Hu, L. T.; Liu, X.; Liu, B. F.; Wu, K. B. Highly-
sensitive and rapid detection of ponceau 4R and tartrazine in drinks
using alumina microfibers-based electrochemical sensor. Food Chem.
2015, 166, 352−357.
(37) Ghoreishi, S. M.; Behpour, M.; Golestaneh, M. Simultaneous
determination of Sunset yellow and tartrazine in soft drinks using gold
nanoparticles carbon paste electrode. Food Chem. 2012, 132, 637−641.
(38) Dominguez, F. B.; Diego, F. G.; Mendez, J. H. Determination of
sunset yellow and tartrazine by differential pulse polarography. Talanta
1990, 37, 655−658.
(39) Zhang, W. K.; Liu, T.; Zheng, X. J.; Huang, W. S.; Chidan Wan,
C. D. Surface-enhanced oxidation and detection of Sunset Yellow and
tartrazine using multi-walled carbon nanotubes film-modified elec-
trode. Colloids Surf., B 2009, 74, 28−31.
(40) Capitan-Vallvey, L. F.; Fernandez, M. D.; Orbe, I. D.; Avidad, R.
Simultaneous determination of the colorants tartrazine, ponceau 4R
and sunset yellow FCF in foodstuffs by solid phase spectrophotometry
using partial least squares multivariate calibration. Talanta 1998, 47,
861−868.
(41) Pérez-Urquiza, M.; Beltrán, J. L. Determination of dyes in
foodstuffs by capillary zone electrophoresis. J. Chromatogr. A 2000,
898, 271−275.
(42) Minioti, K. S.; Sakellariou, C. F.; Thomaidis, N. S.
Determination of 13 synthetic food colorants in water-soluble foods
by reversed-phase high-performance liquid chromatography coupled
with diode-array detector. Anal. Chim. Acta 2007, 583, 103−110.
DOI: 10.1021/acs.jafc.5b02319
J. Agric. Food Chem. 2015, 63, 6707−6714