Article

pubs.acs.org/ac

Economical, Green Synthesis of Fluorescent Carbon Nanoparticles

and Their Use as Probes for Sensitive and Selective Detection of
Mercury(II) Ions
Wenbo Lu,† Xiaoyun Qin,† Sen Liu,† Guohui Chang,† Yingwei Zhang,† Yonglan Luo,†
Abdullah M. Asiri,§,∥ Abdulrahman O. Al-Youbi,§,∥ and Xuping Sun*,†,§,∥
†
State Key Lab of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, Jilin, P. R. China
§
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
∥
Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah 21589, Saudi Arabia
*
S Supporting Information

ABSTRACT: The present article reports on a simple, economical, and green

preparative strategy toward water-soluble, fluorescent carbon nanoparticles (CPs) with
a quantum yield of approximately 6.9% by hydrothermal process using low cost wastes
of pomelo peel as a carbon source for the first time. We further explore the use of such
CPs as probes for a fluorescent Hg2+ detection application, which is based on Hg2+-
induced fluorescence quenching of CPs. This sensing system exhibits excellent
sensitivity and selectivity toward Hg2+, and a detection limit as low as 0.23 nM is
achieved. The practical use of this system for Hg2+ determination in lake water samples
is also demonstrated successfully.

M ercury(II) ion (Hg2+) is one of the most dangerous and

ubiquitous pollutants, which raises serious environ-
mental and health concerns.1 It is demonstrated that Hg2+ can
easily pass through skin, respiratory, and gastrointestinal tissues,
leading to DNA damage, mitosis impairment, and permanent
damage to the central nervous system.2,3 Therefore, developing
effective analytical methods for the sensitive and selective
detection of trace amounts of Hg2+ is especially important.
Traditional techniques including atomic absorption/emission
spectroscopy, Auger-electron spectroscopy, inductively coupled
plasma mass spectrometry, and polarography require sophisti-
cated instrumentation and/or sample preparation, which limit
their practical applications.4−6 Fluorescence assays have several
advantages, such as high sensitivity, fast analysis, and being
nonsample-destructing or less cell-damaging, and have been
proven to be an alternative method for Hg2+ detection.7 So far,
many fluorescent probes including organic molecule, metal
nanoclusters, semiconductor quantum dots (QDs), etc. have
been developed for fluorescence detection of Hg2+. For
example, Gong et al. described a novel rhodamine thiospiro-
lactam derivative as an “off-on” fluorescent probe for the
detection of Hg2+ in aqueous samples;7 Lin et al. demonstrated
the use of lysozyme type VI-stabilized gold nanoclusters (Lys
VI-AuNCs) for the detection of Hg2+ based on fluorescence
quenching;8 Long et al. reported trace Hg2+ analysis via
quenching the fluorescence of a CdS-encapsulated DNA nano-
composite.9 However, the above fluorescent materials suffer
from complex synthesis routes or the involvement of toxic or
expensive regents. Accordingly, the development of a simple,
economical, and green preparative strategy toward fluorescent
materials is highly desired.
Fluorescent carbon nanoparticles (CPs) or nanodots (CDs)
constitute a fascinating class of recently discovered nano-
carbons with a size below 10 nm and have attracted
considerable research interest due to their excellent photo-
stability, favorable biocompatibility, low toxicity, and good
water solubility.10,11 As a consequence of their outstanding
properties, CPs or CDs form attractive applications. Sun and
co-workers reported the first study on CDs passivated with
poly(propionylethylenimine-co-ethylenimine) for two-photon
luminescence microscopy imaging of human breast cancer cells,
which was followed by a great deal of research.12−15 Li et al.
demonstrated the design of photocatalysts based on the
upconversion luminescence properties of CDs to utilize the
full spectrum of sunlight.16 The electron-donor capabilities of
photoexcited CDs have been demonstrated by Wang et al.
through photoreduction of Ag+ to Ag by photoirradiating
CDs in an aqueous solution of AgNO3 at a visible wavelength.17
Gonçalves et al. described an optical fiber sensor for Hg2+
Received: March 27, 2012
Accepted: May 31, 2012
Published: May 31, 2012

© 2012 American Chemical Society 5351 dx.doi.org/10.1021/ac3007939 | Anal. Chem. 2012, 84, 5351−5357
Analytical Chemistry
Figure 1. (a) TEM images of the products thus formed. The inset shows the HRTEM image of one nanoparticle, (b) the corresponding particle size
distribution histogram.
in aqueous solution based on sol−gel immobilized CDs
functionalized with PEG200 and N-acetyl-L-cysteine.18 Until
now, a variety of preparative methods toward CPs have been
developed, including arc-discharge, laser ablation, electro-
chemical oxidation, combustion/thermal, supported synthesis,
and microwave heating.11 However, these approaches suffer
from disadvantages, such as involvement of complex or post-
treatment processes and the use of a large amount of strong
acid or expensive raw materials. More recently, carbonization of
chitosan, glucose, coffee grounds, ethylenediamine-tetraacetic
acid salts, and grass has been successfully employed to prepare
fluorescent CPs.19−25 From the point of view of material
synthesis, the exploration of new carbon source for simple,
economical, and green synthesis of such CPs is highly desirable.
In this article, we demonstrate the first use of low cost wastes of
pomelo peel as a carbon source for hydrothermal preparation
of water-soluble, fluorescent CPs with a quantum yield (QY) of
approximately 6.9%. We further demonstrate that such CPs can
serve as a very effective fluorescent probe for label-free,
sensitive, and selective detection of Hg2+ with a detection limit
as low as 0.23 nM, which is much lower than a previously
reported CPs-based sensing system.24 The sensing principle is
based on fluorescence quenching of CPs by Hg2+ presumably
due to facilitating nonradiative electron/hole recombination
annihilation through an effective electron or energy transfer
process.24,26 The fluorescence of CPs will recover when a
stronger Hg2+ chelator, cysteine (Cys), is added due to the
formation of a Hg−S bond with Cys that leads to the removal
of Hg2+ from CP.24 To demonstrate the practicality of this
fluorescence probe, it is further applied to the determination of
Hg2+ in lake water.
■ EXPERIMENTAL SECTION
Materials. AgNO3, CaCl2, CdCl2, CoCl2, CuCl2, FeCl3,
Hg(NO3)2, Mg(OAc)2, MnCl2, NiCl2, Pb(NO3)2, and Zn(OAc)2
were purchased from Beijing Chemical Corp. NaH2PO4 Na2HPO4
and Cys were purchased from Aladin Ltd. (Shanghai, China).
All chemicals were used as received without further purifi-
cation. The pomelo was purchased from local supermarket
and washed with water for further use. The water used
throughout all the experiments was purified through a Millipore
system.
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Article
Characterizations. UV−vis spectra were obtained on a
UV5800 spectrophotometer. X-ray photoelectron spectroscopy
(XPS) analysis was measured on an ESCALAB MK II X-ray
photoelectron spectrometer using Mg as the exciting source.
FT-IR spectrum was performed on an IFS 66 V/S (Bruker) IR
spectrometer in the range of 400−4000 cm−1. Transmission
electron microscopy (TEM) measurements were made on a
HITACHI H-8100 electron microscope (Hitachi, Tokyo,
Japan) with an accelerating voltage of 200 kV. The sample
for TEM characterization was prepared by placing a drop of
colloidal solution on carbon-coated copper grid and dried at
room temperature. Fluorescent emission spectra were recorded
on a RF-5301PC spectrofluorometer (Shimadzu, Japan). The ζ
potential measurement was performed on a Nano-ZS Zetzsozer
ZEN3600 (Malvern Instruments Ltd., U.K.). QY was measured
according to an established procedure.27 The optical densities
measured on UV−vis spectra were obtained on a UV5800
spectrophotometer. Quinine sulfate in 0.1 M H2SO4 (literature
quantum yield 0.54 at 360 nm) was chose as a standard.
Absolute values are calculated using the standard reference
sample that has a fixed and known fluorescence QY value.
In order to minimize reabsorption effects, absorbencies in the
10 mm fluorescence cuvette were kept under 0.1 at the excita-
tion wavelength (360 nm).
Preparation of Fluorescent CPs. CPs were prepared by
hydrothermal treatment of pomelo peel. In a typical synthesis,
1 g of pomelo peel was added into 15 mL of H2O. Then the
mixture was transferred into a 25-mL Teflon-lined autoclave
and heated at 200 °C for a period of 3 h. The CPs were
collected by removing the large dots through centrifugation at
12 000 rpm for 10 min and finally dried under vacuum for 48 h.
The CPs was dispersed in distilled water at a concentration of
0.5 mg/mL for further characterization and use.
Fluorescence Assay of Hg2+. The detection of Hg2+ was
performed at room temperature in PBS (0.2 M, pH 7.0) buffer
solution. In a typical run, 3 μL of CPs dispersion was added
into 1 mL of PBS buffer, followed by the addition of a
calculated amount of Hg2+ ions. The photoluminescence (PL)
emission spectra were recorded after reaction for 16 min at
room temperature. The sensitivity and selectivity measure-
ments were conducted in triplicate.
dx.doi.org/10.1021/ac3007939 | Anal. Chem. 2012, 84, 5351−5357
Analytical Chemistry Article

Figure 2. (a) XPS, (b) C1s, (c) O1s, and (d) N1s spectra of the nanoparticles thus obtained.

■ RESULTS AND DISCUSSION

Figure 1a shows a TEM image of the products thus formed,
revealing that they consist of nanoparticles well separated from
each other. The corresponding nanoparticle size distribution
histogram obtained by counting about 80 particles (Figure 1b)
indicates that these nanoparticles have diameters ranging from
2 to 4 nm. The high-resolution TEM (HRTEM) image taken
from one nanoparticle (inset in Figure 1a) shows a crystalline
structure with lattice spacing of 0.20 nm which may be
attributable to the (102) diffraction planes of graphitic (sp2)
carbon (in reference to JCPDS cards 26-1076), which is quite
similar with previously reported CDs.28,29
The surface composition and elemental analysis for the
resultant nanoparticles were characterized by the XPS
technique. The three peaks at 285.0, 400.0, and 532.6 eV
shown in the XPS spectrum of the these nanoparticles (Figure 2a) Figure 3. FT-IR spectrum of the nanoparticles thus formed.
can be attributed to C1s, N1s, and O1s, respectively.30 The
XPS results indicate that these nanoparticles are mainly
composed of C, O, as well as a limited amount of the N tively.35 The characteristic absorption band of C−OH stretch-
element (the atom ratio of C/O/N is 17.56:6.13:1). The C1s ing at 1272 cm−1 is also observed,36 and the peak at 2923 and
spectrum (Figure 2b) shows three peaks at 284.6, 286.0, and 815 cm−1 can be assigned to the C−H stretching mode and
288.0 eV, which are attributed to C−C, C−N, and CN/ C−H out-of-plane bending mode.24,36 The above observations
CO, respectively.31 The two peaks at 531.7 and 533.0 eV confirm that the synthesized nanoparticles function with
in O1s spectrum (Figure 2c) are attributed to CO and hydroxyl and carboxylic/carbonyl moieties which may originate
C−OH/C−O−C groups, respectively; 32 while the N 1s from carbohydrates in the pomelo peel.
spectrum (Figure 2d) shows four peaks at 399.5, 400.4, Figure 4 shows the UV−vis absorption and PL emission
401.5, and 406.4 eV, which are attributed to the C−N−C, N− spectra of the aqueous dispersion of the nanoparticles. It is seen
(C)3, N−H, and −NO3 bands, respectively.33,34 Figure 3 shows that the UV−vis spectrum shows a strong peak at 280 nm.
the FT-IR spectrum of these nanoparticles. The peaks at about Note that the dispersion shows a strong PL emission peak
3300 and 1050 cm−1 can be ascribed to the characteristic centered at 444 nm when excited at 365 nm, indicating the
absorption bands of the −OH stretching vibration mode. The nanoparticles are fluorescent. The photograph of the dispersion
peaks at 1600 and 1400 cm−1 can be attributed to the asym- under UV light (365 nm) exhibits a blue color (inset), further
metric and symmetric stretching vibration of COO−, respec- revealing that the resultant CPs exhibit blue fluorescence. The ζ
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Analytical Chemistry Article

Figure 4. UV−vis absorption (black line) and PL emission (blue line)

spectra of the aqueous dispersion of the nanoparticles. Inset: the
photograph of CPs dispersion under UV light (365 nm).

potential of such CPs was measured to be −20.9 mV, which

further confirms that the nanoparticle surface functionalized
with hydroxyl and carboxylic/carbonyl moieties.24 It is
worthwhile mentioning that these CPs can be very stable for
several months without the observations of any floating or
precipitated nanoparticles, which can be attributed to their
small particle size and electrostatic repulsions between them.
It is of importance to mention that hydrothermal treatment of
another batch of pomelo peels or other fruit peels such as
apple, banana, orange, and pineapple, etc. also produces stable
fluorescent CPs, and thus the CPs preparation method Figure 5. The effect of (a) the solution pH value and (b) the NaCl
proposed herein is universal. concentration (0, 10, 50, 100, 200, 300 mM) on CPs fluorescence.
Figure 5a shows the fluorescence curves of CPs at different
pH values. It is seen that an increase of the pH value from
1.0 to 7.0 leads to increased PL intensity, but a further increase
to 13.0 results in a gradual decrease of fluorescence intensity,
indicating the fluorescence intensity of CPs strongly depends
on the pH value. It is found that such observations are similar
to those of CPs modified with hydroxyl and carboxylic/
carbonyl moieties.10,37 To confirm the stability of CPs under
high ionic strength environments, their PL intensities were
measured in a solution of 0.2 M PBS (pH 7.0) containing
different concentrations of NaCl. As shown in Figure 5b, only a
slight change in the PL intensity is observed, which reveals that
CPs are stable even under high ionic strength conditions. This
finding suggests that CPs have great potential for sensing
applications under physiological conditions.
We explored the feasibility of using such CPs for Hg2+
detection. It is seen that CPs solution in the absence of Hg2+
exhibits a strong PL peak at 444 nm (Figure 6, curve a) and its Figure 6. PL spectra of solutions of CPs (curve a), CPs-Hg2+ mixture
QY is determined to be 6.9%. In contrast, the presence of Hg2+ (curve b), and CPs-Hg2+-Cys mixture (curve c).
leads to an obvious decrease of fluorescence in intensity,
indicating that Hg2+ can effectively quench the fluorescence of
CPs (Figure 6, curve b). This observation can be attributed to fluorescence quenching data follows the Stern−Volmer
that Hg2+ can quench the fluorescence of CPs presumably via equation, via either a dynamic or a static mechanism:9,27
electron or energy transfer.24,26 Indeed, when adding a strong F0/F − 1 = K svc
Hg2+ chelator, Cys, Hg2+ is removed from the surface of CPs by
forming a Hg−S bond with Cys, which results in the fluorescence where Ksv is the Stern−Volmer quenching constant, c is the
recovery of CPs (Figure 6, curve c).24 For a sensitivity study, analyte (Hg2+) concentration, and F0, F are the PL intensities of
different concentrations of Hg2+ in the range of 0−4 × 104 nM CPs at 444 nm in the absence and presence of Hg2+. The
were investigated. Figure 7a shows a gradual decrease in PL in- Stern−Volmer plot shown in Figure 7b does not fit a linear
tensity at 444 nm with an increased Hg2+ concentration, revealing Stern−Volmer equation in the whole concentration range.
that the sensing system is sensitive to Hg2+ concentration. The The correlation coefficients (R2) are 0.9661 and 0.9876 for
5354 dx.doi.org/10.1021/ac3007939 | Anal. Chem. 2012, 84, 5351−5357
Analytical Chemistry Article

fluorescent probes for Hg2+ detection, suggesting our sensing

system exhibits superior sensitivity than previously reported
sensing systems.8,9,24,38−41 The time-dependent PL spectra of
CPs-Hg2+ solution shown in Figure S1in the Supporting
Information indicate that only 16 min is required to complete
the reaction between CPs and Hg2+.
Besides sensitivity, selectivity is another important parameter
to evaluate the performance of the sensing system. Therefore,
we examined the PL intensity changes in the presence of
representative metal ions under the same conditions, including
Ag+, Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Mg2+, Mn2+, Ni2+, Pb2+, and
Zn2+, as shown in Figure S2 in the Supporting Information. It is
seen that a much lower PL was observed for CPs upon addition
of Hg2+. In contrast, no tremendous decrease was observed by
adding other ions into the CPs dispersion. Furthermore, the selec-
tivity of this nanoprobe in the presence of all possible interference
ions was evaluated considering the cross reactivity. As demon-
strated in Figure 8, obviously, the present method can still detect

Figure 7. (a) PL spectra of CPs dispersion in the presence of different

Hg2+ concentrations (from top to bottom: 0, 0.5, 1, 5, 10, 50, 100, 500,
1 × 103, 5 × 103, 1 × 104, 2 × 104, 3 × 104, and 4 × 104 nM). (b) Plots
of the values of (F0/F) − 1 at 444 nm versus the concentrations of
Figure 8. The difference in PL intensity of CPs dispersion under
Hg2+ (excitation at 360 nm; incubation time was 16 min. The error
various conditions in PBS (pH 7.0; excitation at 360 nm; mixed metal
bars represent standard deviations based on three independent
ions including Ag+, Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Hg2+, Mg2+, Mn2+,
measurements.).
Ni2+, Pb2+, and Zn2+; [Mn+] = 5 × 104 nM. The error bars represent
standard deviations based on three independent measurements.).
determining Hg2+ over the two linear concentration ranges of
0.5−10 and 500−4 × 104 nM, respectively. The detection limit
is estimated to be 0.23 nM at a signal-to-noise ratio of 3, which Hg2+ in the presence of all possible interference ions (the
is much lower than other previously reported values and lower concentration of each metal ion in the mixture was
than the maximum level (10 nM, 2 ppb) for mercury in 5 × 104 nM). The outstanding selectivity and specificity can
drinking water permitted by the United States Environmental be probably attributed to that Hg2+ has a stronger affinity toward
Protection Agency.7 Table 1 shows the comparison of different the carboxylic group on the CPs surface than other metal ions.42,43
The feasibility of CPs for detecting Hg2+ in real water
samples was explored by lake water samples obtained from the
Table 1. Comparison of different fluorescent probes for Hg2+ South Lake of Changchun, Jilin province, China. The lake water
detection samples were filtered through a 0.22 μm membrane and then
performance
centrifuged at 12 000 rpm for 20 min. The resultant water samples
were spiked with standard solutions containing different
detection limit linear range concentrations of Hg2+. It is seen that the PL intensity decreases
fluorescent probes (nM) (nM) ref
with increased concentration of Hg2+ from 5 to 50 nM, as shown
Lys VI-AuNCs 0.003 0.01−5 8
in Figure 9a. The calibration curve for determining Hg2+ in lake
CdS-encapsulated DNA 4.3 10−110 9
water was obtained by plotting the values of (F0/F) − 1 versus the
CDs 4.2 0−3 × 103 24
concentrations of Hg2+ (Figure 9b). In spite of the interference
fluorescent gold 5 10−1 × 104 38
nanoparticles from numerous minerals and organics existing in lake water, this
fluorescent Ag clusters 10 10−5 × 103 39 sensing system can still distinguish between fresh lake water and
Au@Ag core−shell 9 10−450 40 that spiked with 5 nM Hg2+, satisfying the practical Hg2+ detection
nanoparticles in real samples. These results imply that the Hg2+ probe is likely
CdTe quantum dots 1.55 2−14 41 to be capable of practically useful Hg2+ detection upon further
CPs 0.23 0.5−10 this work development.
5355 dx.doi.org/10.1021/ac3007939 | Anal. Chem. 2012, 84, 5351−5357
Analytical Chemistry
Figure 9. (a) PL spectra of CPs dispersion in the presence of different
Hg2+ concentrations (from top to bottom: 0, 5, 10, 20, 30, 40, and
50 nM) in lake water. (b) The dependence of (F0/F) − 1 on the
concentrations of Hg2+ within the range of 0−50 nM.
■
CONCLUSIONS
In summary, hydrothermal treatment of pomelo peel has been
proven to be an effective strategy for producing fluorescent CPs
for the first time. Furthermore, no further chemical modification
of CPs is required, which offers the advantages of simplicity and
cost efficiency. Such CPs have been further used as a novel
sensing probe for label-free, sensitive detection of Hg2+ ions with
a detection limit as low as 0.23 nM. This sensing system also
possesses high selectivity toward Hg2+ analysis and has been
successfully used for the analysis of a lake water sample. Our
present study allows upward scalability in terms of the green
production of fluorescent and biocompatible nanocarbons which
could be applied in bioimaging and other applications.11−18
■
ASSOCIATED CONTENT
*
S Supporting Information
Time-dependent PL spectra and the difference in PL intensity
of CPs dispersion between the blank and solutions containing
different metal ions. This material is available free of charge via
the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*Phone/Fax: 0086-431-85262065. E-mail: sunxp@ciac.jl.cn.
Notes
The authors declare no competing financial interest.
5356
■
Article
ACKNOWLEDGMENTS
W. Lu and X. Qin contributed equally to this work. This work
was supported by the National Natural Science Foundation of
China (Grant No. 21175129), the National Basic Research
Program of China (Grant No. 2011CB935800), and the
Scientific and Technological Development Plan Project of Jilin
Province (Grant Nos. 20100534 and 20110448).
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