Sensors and Actuators B 252 (2017) 1169–1178

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Highly sensitive and selective detection of mercury ions using N,

S-codoped graphene quantum dots and its paper strip based sensing
application in wastewater
Nguyen Thi Ngoc Anh a , Ankan Dutta Chowdhury a , Ruey-an Doong a,b,∗
a
Institute of Environmental Engineering, National Chiao Tung University, 1001, University Road, Hsinchu, 30010, Taiwan
b
Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, 101, Sec. 2, Kuang Fu Road, Hsinchu, 30013, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: The development of robust and low-cost sensing materials with superior selectivity and sensitivity for
Received 25 May 2017 rapid detection of analytes in a wide variety of samples has attracted much attention. Herein, the N,
Received in revised form 24 July 2017 S-codoped graphene quantum dots (N, S-GQDs) with high quantum yield were fabricated by one-pot
Accepted 25 July 2017
hydrothermal method for highly sensitive and selective detection of nanomolar level of mercury ions
Available online 26 July 2017
(Hg2+ ) in water and wastewater. The as-prepared N, S-GQDs are uniform in size with mean particle size
of 3.5 ± 0.5 nm. The doping of nitrogen atoms increases the quantum yield to 41.9%, while the introduc-
Keywords:
tion of sulfur atoms enhances the selectivity of Hg2+ via strong coordination interaction. The fluorescence
N, S-graphene quantum dots (N, S-GQDs)
Heteroatom doping
intensity of N, S-GQDs is quenched proportionally after adding Hg2+ and a dynamic range of 4 orders of
Fluorescence quenching magnitude with limit of detection of 0.14 nM is obtained in deionized water. The N, S-GQDs nanosens-
Mercury ions ing probes can be successfully applied to the sewage and dye wastewater samples and a linear range
Wastewater of 0.1–15 ␮M with recovery of 96–116% is obtained. In addition, the coating of N, S-GQDs onto paper
strip provides an excellently rapid screening and highly selective technique for Hg2+ detection in real
wastewater. Results obtained in this study clearly indicate that the N, S-GQDs are promising nanoma-
terials which can open an new avenue to design the GQD based sensing probe for highly sensitive and
selective detection of metal ions and other analytes in environmental and biological fluid samples.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
The contamination of heavy metal ions such as Hg2+ , As2+ ,
Pb2+ and Cd2+ has been becoming one of the most serious prob-
lems in the environment because of the increasing industrial
and agricultural activities as well as the improper release of
metal ions from wastewaters and domestic effluents [1–4]. The
detection of metal ions in different media by simple and cost-
effective techniques is thus highly needed for environmental safety
and health diagnosis. Among the toxic metal ions, mercury ions
(Hg2+ ) are one of the most poisonous species to human beings
because of the strong interaction of Hg2+ with sulfhydryl groups
of proteins in a wide variety of organs including brain, kidneys,
central nervous system and immune system [5–7]. Although enor-
mous efforts have been carried out to develop a wide variety of
∗ Corresponding author at: Institute of Environmental Engineering, National Chiao
Tung University, Hsinchu, Taiwan.
E-mail address: radoong@mx.nthu.edu.tw (R.-a. Doong).
analytical techniques for Hg2+ detection, the most common method
is still dependent on the expensive, time consuming, and hectic
instruments like atomic absorption spectrometry, inductively cou-
pled plasma atomic emission spectrometry and high-performance
liquid chromatography–inductively coupled plasma mass spec-
trometry [8–11]. Therefore, there is still an unmet demand to
develop new materials for highly sensitive and selective detection
of Hg2+ in real water and wastewater samples.
The optical methods based on nanomaterials have recently been
evolved as one of the promising techniques for detection of metal
ions because of their potential advantages of simple preparation
and the sensitive recognition of some special metal ions [12].
Several studies have used various morphologies of Au-based nano-
materials for the detection of Hg2+ based on the changes in color
and absorption [2,13,14]. In addition, inorganic metal oxide quan-
tum dots such as CdSe and CdTe have been developed to detect
Hg2+ by fluorescence quenching methods [15–21]. Yao and Gou
have fabricated luminescent core-shell CdTe/CdS quantum dots for
Hg2+ detection and found that the dynamic range of Hg2+ was in
the range of 2–500 nM with the limit of detection (LOD) of 1.7 nM

http://dx.doi.org/10.1016/j.snb.2017.07.177
0925-4005/© 2017 Elsevier B.V. All rights reserved.
1170 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178
[15]. However, the highly toxic effect of inorganic quantum dots on
human beings and the environment has hampered the application
of this material to the real environmental application for metal ions
detection.
Zero-dimensional carbon-based nanomaterials including car-
bon dots (CDs) and graphene quantum dots (GQDs) have recently
been emerged as an excellent source of environmentally friendly
fluorescent nanoprobes because of their extra-ordinary proper-
ties such as excellent photoluminescence, tunable surface groups
for functionalization, good stability and easy preparation [22–26].
GQDs have recently ignited the increasing interest in detection
of metal ions and metabolites by fluorescence method using as-
prepared [27–30] and surface modified GQDs [31–33]. Although
several advantages can be accounted by using GQDs as the sensing
elements to detect metal ions, the relatively poor quantum yield
of GQDs has limited the detection sensitivity compared with those
standard methods. Doping of GQDs with heteroatoms such as nitro-
gen (N), boron (B) and sulfur (S) is an efficient method to improve
quantum yield to overcome this drawback [34–37]. Several studies
have depicted that the doping of N atoms on GQDs can enhance the
fluorescence property of GQDs and found that the sensing sensitiv-
ity is dependent on the coordination behavior of graphitic nitrogen
atoms [33,36,37]. In addition, the N, S-codoped GQDs have been
synthesized for the enhanced visible-light-driven photocatalytic
degradation of rhodamine B [35] or for cyanide detection [38].
However, the development of N, S-GQDs with high quantum yield
for sensitive and selective detection of nanomolar level of Hg2+
has received less attention. In addition, the development of sim-
ple and robust anlaytical technique for rapid screening of low level
of Hg2+ in real wastewater samples based on N, S-GQDs has not
been reported yet.
Herein, we have, for the first time, synthesized the N, S co-
doped GQDs with high quantum yield by one-pot hydrothermal
method for highly sensitive and selective detection of nanomolar
level of Hg2+ in wastewater samples. A simple and green fabrica-
tion method by hydrothermal treatment of citric acid and thiourea
was developed to synthesize N, S-GQDs. As shown in Scheme 1, the
N atoms in N, S-GQDs enhance the fluorescence quantum yield to
41.9%, while S atoms serve as the active sites for Hg2+ coordination
to increase the selectivity and sensitivity of Hg2+ . The interaction
of Hg2+ with N, S-GQDs quenches the fluorescence intensity and
a dynamic range of 4 orders of magnitude with LOD of 0.14 nM
is obtained. The N, S-GQDs are then applied for Hg2+ detection in
real sewage and dye wastewaters. The recovery of Hg2+ in differ-
ent wastewater matrices is in the range of 96–116%. In addition,
the N, S-GQD based paper strip is further prepared by coating N, S-
GQDs onto cellulose filter paper strips for rapid screening of Hg2+
in wastewater. Results obtained in this study clearly indicate the
superiority of as-prepared N, S-GQDs to detect nanomolar level of
Hg2+ in different matrices of water and wastewater.
2. Experimental
2.1. Synthesis of N, S-GQDs
The N, S-GQDs were prepared by a standard hydrothermal
method with minor modification by increasing the weight ratio
of thiourea to citric acid [35]. In brief, 0.23 g citric acid and 0.23 g
thiourea (Sigma-Aldrich) were dissolved into 5 mL of deionized
water (18.2 M cm) under stirring conditions to form a clear solu-
tion. The solution was then transferred into a 20-mL of Teflon
lined stainless steel autoclave tube and heated up to 160 ◦ C for 4 h.
The obtained brown suspension was added into ethanol solution
and centrifuged at 5000 rpm for 5 min. The final product was re-
dispersed into deionized water and stored at 4 ◦ C for further use.
The quantum yield of N, S-GQDs was determined according to our
previous study [28].
2.2. Surface characterization
The morphology as well as particle size of N, S-GQDs was iden-
tified by a JEOL JEM-ARM 200F transmission electron microscope
(TEM) and a JEOL JEM-2010 high-resolution TEM (HR-TEM) both
at 200 kV. Atomic force microscopy (AFM) images were obtained
by using an Agilent 5500 scanning probe microscope in tapping
mode to elucidate the topography of N, S-GQDs. The X-ray diffrac-
tometry (XRD) was performed by a Bruker D8 X-ray diffractometer
with Ni-filtered Cu K␣ radiation (␭ = 1.5406 Å). The change in chem-
ical species of N, S-GQDs was recorded by an ESCA Ulvac-PHI 1600
X-ray photoelectron spectrometer (XPS) from Physical Electronics
using Al K␣ radiation photon energy at 1486.6 ± 0.2 eV. The Fourier
transform infrared (FTIR) spectra of N, S-GQDs were determined
by using a Horiba FT720 spectrophotometer. The optical proper-
ties of N, S-GQDs including UV–vis and fluorescence spectra were
determined by Hitachi U-4100 UV–vis and F-7000 fluorescence
spectrophotometers, respectively. The fluorescence spectra of N,
S-GQDs were recorded by using various excitation wavelengths of
310–430 nm. Raman spectra of N, S-GQDs were recorded by Burker
Senterra micro-Raman spectrometer equipped with an Olympus
BX 51 microscope and an Andor DU420-OE CCD camera.
2.3. Detection of Hg2+ by N, S-GQDs
The detection of Hg2+ ions was performed at room tempera-
ture. The sensing solution was prepared by adding 0.16 mg mL−1 N,
S-GQD into 0.1 M PBS buffer at pH 7. The standard solution of Hg2+
was prepared by dissolving 30.75 mg HgCl2 ·2H2 O into 10 mL of
deionized water. For Hg2+ detection, appropriate volumes of stan-
dard Hg2+ solutions were added into the sensing solution to get the
final Hg2+ concentrations of 1 nM − 15 ␮M. The fluorescence inten-
sity of solution containing N, S-GQDs and Hg2+ was recorded from
350 to 700 nm at excitation wavelength of 340 nm after 2 min of
incubation. The calibration curve of Hg2+ was determined by mea-
suring the change in relative fluorescence intensity (I/I0 ) at various
Hg2+ concentrations ranging from 1 nM to 15 ␮M, where I0 and I
are the fluorescence intensities of sensing solutions in the absence
and presence of Hg2+ , respectively. Each experiment was repeated
for at least three times for quality control. The effect of pH on flu-
orescence intensity was examined by adding 15 ␮M Hg2+ into the
sensing solutions at pH 5–9. The initial pH was adjusted by 0.1 M
HCl or NaOH to reach the desired value.
2.4. Detection of Hg2+ ions in real wastewater samples
To evaluate the applicability of N, S-GQDs to the real wastewa-
ters, 2 effluent samples including sewage and dye wastewater were
collected from different wastewater treatment plants in Taoyuan
City, Taiwan. The physicochemical properties of wastewaters are
listed in Table S1 (see Supplementary data). The wastewater efflu-
ents were filtrated by 0.45 ␮m Millipore filter paper followed
by C-18 SPE column to remove suspended solids and impurities,
respectively. After filtration, wastewater samples were spiked with
50 nM–15 ␮M Hg2+ and then 0.16 mg mL−1 N, S-GQDs were added
to the solutions for fluorescence intensity measurement to evaluate
the matrix effect and recovery of Hg2+ in wastewaters.
2.5. Preparation of N, S-GQD-based paper strips for real
wastewater detection
The N, S-GQD based paper strips were prepared by cutting cellu-
lose filter paper (125 mm, Toyo Roshi Kaisha Ltd, Japan) with mean
 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178 1171

Scheme 1. Schematic diagram of Hg2+ detection using turn off fluorescence property of N, S-GQDs and paper based sensor images in real wastewater samples.

pore size of 25 ␮m into strips with dimension of 1 cm (W) × 3.5 cm
(L). The paper strips were then immersed into 0.16 mg mL−1 N,
S-GQDs solutions for 10 min and then dried in an oven at 60 ◦ C
for 30 min. For detection of Hg2+ in wastewaters, the N, S-GQD
based paper strips were immersed into the wastewaters contain-
ing 5–200 ␮M Hg2+ for 3 s and then dried in room temperature for
another 10 min. The paper strips were then irradiated with 340 nm
UV lamp and the change in fluorescence intensity was recorded by
Sony Digital camera for visual detection. In addition, the selectiv-
ity of N, S-GQD based paper filter toward 5 ␮M Hg2+ detection was
evaluated with other metal ions including 100 ␮M Fe2+ , Mn2+ , Cr3+ ,
Cd2+ , Co2+ , Pb2+ and Zn2+ .
3. Results and discussion
3.1. Characterization of N, S-GQDs
The surface morphology and particle size distribution of as-
prepared N, S-GQDs were first characterized by (HR)TEM and
AFM images. The TEM image of as-prepared N, S-GQDs shows the
homogenous distribution patterns (Fig. 1a) and the particle sizes
are in the range of 2–6 nm with an average diameter of 3.5 ± 0.5 nm
(Fig. 1b), indicating the formation of narrow size-distributed N,
S-GQDs for sensing applications. Fig. 1c deciphers the fringes of
carbon lattice spacing distances of 2.1 Å, which is similar to the
(100) plane of graphene [28]. In addition, the fast Fourier transform
(FFT) pattern (Fig. 1d) also corroborates that the N, S-GQDs are sin-
gle crystals with a spacing of 0.21 nm, which is in good agreement
with the result of HRTEM image (Fig. 1e). These results clearly indi-
cate that the N, S-GQDs are highly nanocrystalline in nature and
homogenously distributed. The AFM image shown in Fig. 1f also
shows the uniform distribution of N, S-GQDs. The height is around
0.5–3.0 nm with an average of 1.0 nm, which confirms that the N,
S-GQDs only contain 1–5 layers of graphene nanosheets (Fig. 1g).
Fig. 2 shows the XPS survey spectrum and deconvoluted peaks
of as-prepared N, S-GQDs. As illustrated in Fig. 2a, the XPS survey
spectrum shows two significant peaks at 284 and 531 eV, which
can be assigned as C 1s and O 1s, respectively [39,40]. Three small
peaks of N 1s (400 eV), S 1s (227 eV) and S 2p (164 eV) are also
noticed in the full survey scan of N, S-GQDs, which confirms the
successful co-doping of N and S atoms in GQDs. In addition, the
doped amounts of N and S atoms in N, S-GQDs can be estimated
from the XPS full survey spectrum by using CasaXPS software. As
shown in Table S2, the doped amounts of S and N in N, S-GQDs are
1.5 and 8.0 wt%, respectively. A previous study has used citric acid
and rubeanic acid to fabricate N, S-codoped CD and found that the
doped amounts of N and S were 4.0 and 4.7 wt% [39], respectively,
which are in a similar range with our results.
The deconvolution of C 1s region shows peaks of C C at 284.1 eV,
C-N/C-S at 284.3 eV, C O at 286.2 eV and C O at 288.3 eV (Fig. 2b).

Fig. 1. The characterization of N, S-GQDs. (a) TEM image, (b) particle size distribution (n = 50), (c) HRTEM image of single N, S-GQDs, (d) fast Fourier transform pattern, (e)
lattice spacing of as-prepared N,S-GQDs from HRTEM image, (f) AFM image and (g) topography of N, S-GQDs from AFM image.
1172 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178
Fig. 2. The XPS (a) survey scan and deconvoluted (b) C 1s, (c) N 1s and (d) S 2p peaks of as-prepared N, S-GQDs.
The high contribution of C C and C-N/C-S indicates the graphitic
structures with strong interaction with N and S atoms, while C O
and C O are mainly attributed from the carbonyl and carboxylate
groups [41]. Similarly, the deconvoluted peaks of N 1s spectrum
show pyrrolic N (C N C) and N H contributions at 399.7 and
402.1 eV, respectively (Fig. 2c) [42,43]. The strong pyrrolic contri-
bution in N 1 s peak means that the N atoms with ternary structure
are situated higher than its primary environment (N H), which is
the evidence on the successful N doping onto the graphitic surface.
Moreover, the deconvoluted spectrum of S 2p shows two peaks of
sulfur at 163.8 and 166.8 eV (Fig. 2d), which belong to the spin-
orbit coupling of thiophene 2p3/2 and 2p1/2 , respectively [44,45].
The additional peak located at 169.4 eV is the oxygenated sulfur. In
addition, the deconvolution of O 1s spectrum of N, S-GQDs (Fig. S1,
see Supplementary data) displays peaks of C O, O H and O–S at
531.1, 532.0 and 532.5 eV, respectively, confirming the successful
doping of S atoms into the graphene structures.
Fig. 3a shows the FTIR spectra of N, S-GQDs. A broad peak at
3458 cm−1 is the stretching vibration of O H and N H bonds,
which indicates the good hydrophilic nature of N, S-GQDs because
of the amino and hydroxyl groups on the surface. The strong peak
at 1639 cm−1 is the C O in the carboxylic group of graphitic plane.
Formation of graphitic layer is confirmed by the C H and C C
stretching at 1378 and 2096 cm−1 , respectively [28]. The C–S and
small peak of S–H stretching at 986 and 2340 cm−1 , respectively,
represent the sulfur doping [31]. In addition, the broad peak at
662 cm−1 is the weak stretching of C N bond, confirming the pres-
ence of nitrogen doping on GQDs surface. The Raman spectra shown
in Fig. 3b further confirm the quality of as-prepared N, S-GQDs.
The N, S-GQDs display two distinct D and G bands located at 1378
and 1583 cm−1 , respectively, which are ascribed to the character-
istic peaks of graphitic structure [36]. The disordered (D) band
at 1378 cm−1 is related to the presence of sp3 defects, while the
crystalline (G) band at 1583 cm−1 is attributed from the in-plane
vibration of sp2 carbon [28]. The ratio of intensities (ID /IG ) is found
to be 0.87 for N, S-GQDs, which means that N, S-GQDs are highly
graphitic materials. In addition, the broad peak at around 24.1◦ 2␪
shown in the XRD pattern (Fig. S2, see Supplementary data) is the
(002) plane of graphene, which is in good agreement with those
results obtained from Raman spectra and HRTEM images.
The optical property of as-prepared N, S- GQDs was identified
by UV–vis and fluorescence spectra. Fig. 4a shows the emission
fluorescence intensity of N, S-GQDs excited with various wave-
lengths ranging from 310 to 430 nm. The N, S-GQDs exhibit an
emission peak at 445 nm and the peak position is independent on
the excitation wavelength, which is perfectly matched with the
previously reported results [27,33,35]. The maintenance of emis-
sion peak position at 445 nm indicates the sequential absorption of
photons and then results in the emission of fluorescence light at a
constant wavelength. It is also noteworthy that the solution color
of as-prepared N, S-GQDs is almost transparent under visible light
irradiation. This means that the as-prepared N, S-GQDs have little
up-conversion and down-conversion properties in the visible light
region [39,46], which is in good agreement with the emission flu-
orescence spectra. Fig. 4b shows the UV–vis absorption spectrum
of N, S-GQDs where the strong absorption peak is found at 332 nm,
ascribing the n–␲* transition of C O. The absorption bands at 225
and 236 nm are contributed from the ␲–␲* transition [35]. In addi-
tion, the N, S-GQDs emit strong bright blue fluorescence after the
irradiation of UV light at 340 nm (Fig. 4c), indicating the excellent
photoluminescence property for optical sensing. The fluorescence
intensity at an excitation of 340 nm can be maintained for at least
2 months (Fig. S3, see Supplementary data), clearly depicting the
excellent stability of N, S-GQDs for sensing applications.
 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178
Fig. 3. The (a) Raman and (b) FTIR spectra of N, S-GQDs.
The emission fluorescence spectra of undoped GQDs was also
examined. As shown in Fig. S4a (see Supplementary data), the emis-
sion fluorescence wavelength at 450 nm is clearly observed when
excited at 340 nm. The blue shift in emission wavelength for N, S-
GQDs in comparison with the undoped GQDs is mainly attributed to
the doping of electron-rich N atoms on the surface [47–49], which
would result in the high quantum yield. The quantum yield of N,
S-GQDs, determined by using fluorescein ( = 0.79) as a reference
[27,28], is found to be 41.9%, which is significantly high among the
recently reported N-doped GQDs [27,30,33] and N, S-CDs [46]. Our
previous study has synthesized the as-prepared GQDs by the pyrol-
ysis of citric acid and the quantum yield of as-prepared GQDs was
11.9% [28], clearly showing that the N, S-GQDs have high quantum
yield than that of undoped GQDs. The doping of GQDs with N atoms
can provide more electron-enriched active sites, which facilitate
the high yield of radiative recombination as well as the decrease in
non-radiative recombination [42]. It is noteworthy that the doped
amount of N atoms in N, S-GQDs shows that the as-synthesized N,
S-GQDs contain higher amount of ternary N atoms than that of pri-
mary NH2 (Fig. 2c). Since the density of ternary N atoms strongly
affect the radiative path of GQDs, the doping of ternary N atoms can
make the N, S-GQDs more fluorescence active compares with the
pristine GQDs.
3.2. Detection of Hg2+ using N, S-GQDs
After the successful characterizations, the sensibility of N, S-
GQDs toward Hg2+ detection was evaluated by the change in
fluorescence intensity before and after the addition of Hg2+ . Fig. 5a
shows the change in fluorescence intensity of N, S-GQDs after the
addition of various concentrations of Hg2+ ranging from 1 nM to
1173
15 ␮M. The fluorescence intensity of N, S-GQDs decreases upon
increasing Hg2+ concentration and 90% of the original fluorescence
intensity is quenched at 15 ␮M Hg2+ . It is noteworthy that the
quenching of N, S-GQDs by Hg2+ can be attributed to both static and
dynamic quenching. After addition of Hg2+ into the N, S-GQD solu-
tions, the collision of Hg2+ with N, S-GQDs would produce dynamic
quenching first and then the successful binding of Hg2+ onto the
N, S-GQDs surface produces static quenching. In addition to the
carboxylic (−COOH) and hydroxyl ( OH) groups on the N, S-GQDs
surface which can serve as the effective coordination sites for Hg2+
binding [50], the main reaction mechanism for highly specific bind-
ing of Hg2+ is mainly attributed to the strong coordination reaction
between S atoms in the graphitic carbon structure of GQDs and
Hg2+ [39].
Fig. S4b (see Supplementary data) shows the change in fluo-
rescence intensity of undoped GQDs in the presence of various
Hg2+ concentrations ranging from 0 to 50 ␮M. It is clear that only
3–8% decrease in fluorescence intensity at 445 nm is observed when
1–50 ␮M Hg2+ are added into the undoped GQD solutions. This
sensing performance is much lower than that of N, S-doped GQDs,
clearly showing that doping of N and S atoms can significantly
enhance the sensitivity of GQD based nanomaterials.
Due to the well-known soft acid-soft base interaction between
Hg2+ and S atoms, Hg2+ can be easily attached onto the N, S-GQDs
via strong coordination chemistry. This would lead to the inter-
ruption of electronic ␲-␲ conjugation of N, S-GQDs to affect the
distribution of excitons obviously, and subsequently results in the
hindrance of electron transfer process as well as the quenching
effect of N, S-GQDs. In addition, the pH effect on the sensing effi-
ciency of Hg2+ was further investigated in the presence of 15 ␮M
Hg2+ . As illustrated in Fig. 5b, the fluorescence intensity of N, S-
GQDs before the addition of Hg2+ increases with the increase in pH
values from 5 to 9 because of the deprotonation of COOH group at
high pHs. However, the fluorescence intensity is quenched obvi-
ously at pH 6–9 after the addition of 15 ␮M Hg2+ , clearly showing
that the N, S-GQDs can serve as an efficient sensing probe for sen-
sitive detection of Hg2+ .
Fig. 5c shows the change in fluorescence intensity of N, S-GQDs
as a function of Hg2+ concentration. A two-stage linear relationship
between the change in fluorescence intensity and Hg2+ concentra-
tion is observed. It is clear that an excellent linearity in the Hg2+
concentration range of 0.05–15 ␮M with a correlation coefficient
of 0.995 is obtained. The sensing system also obey a linear rela-
tionship in the low Hg2+ concentration range of 1–50 nM with a
correlation coefficient of 0.96 (inset of Fig. 5c). The LOD of Hg2+ ,
which can be determined by the 3␦/S where ␦ is the standard devi-
ation of the lowest fluorescence signal and S is the slope of linear
calibration plot [28], is calculated to be 0.14 nM. The superior sen-
sitivity of N, S-GQDs is mainly attributed to the high quantum yield
obtained in this study. It is noteworthy that the addition of het-
eroatoms would increase the surface defects of GQDs, resulting in
the increase in isolated sp2 -conjugated carbon clusters to enhance
the fluorescence intensity as well as the quantum yield [44]. As
shown in Table S2 (see Supplementary data), the quantum yield
of 41.9% for N, S-GQDs is higher than those prepared by citric acid
with rubeanic acid [39] and biomass [46], which can provide a wide
and stable analytical range for sensing, and subsequently enhances
the sensitivity of N, S-GQD toward Hg2+ detection. In this study,
the doping of nitrogen widen the dynamic range and increase the
detection sensitivity of Hg2+ with ultra-low LOD.
Table 1 summarizes the analytical performance of Hg2+ detec-
tion by different inorganic and organic quantum dots. It is clear that
the LOD values for Hg2+ detection by inorganic quantum dots are
in the range of 0.47–750 nM [15–19,21,53]. In addition, the carbon
based materials including carbon dots (CDs) and as-prepared GQDs
have been developed for sensitive detection of Hg2+ and the LODs
1174 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178

Fig. 4. (a) The fluorescence spectra of N, S-GQDs excited with various wavelengths ranging from 310 to 430 nm, (b) UV–vis spectra of N,S-GQDs and (c) photographs of N,
S-GQDs under daylight (left) and UV light irradiation at 340 nm (right).

Table 1 Zn2+ , Pb2+ and Ca2+ as the interference ions. As shown in Fig. 5d,
Analytical performance of Hg2+ by inorganic and organic quantum dot based sensors.
no obvious decrease in fluorescence intensity is observed after
Type Probea Dynamic LOD References the addition of interference metal ions. In contrast, the fluores-
range (nM) cence intensity decreases remarkably when Hg2+ is added to the
(mM)
sensing solutions. When mixing all the metal ions together with
CdTe@CdS 0.002–0.5 1.7 [15] Hg2+ , the sensor provides almost similar quenching effect in com-
CdSe@ZnS 36–600 1.6 [16] parison with the pure 15 ␮M Hg2+ solution. Several studies have
CdTe@SiO2 0.002–0.014 750 [17]
NAC-QDs 5–250 8.6 [18]
depicted that the N, S-codoped CDs can effectively detect Hg2+ and
Inorganic
CdS 0.04–13 1.7 [19] Fe3+ [39,46,51]. In this study, the N, S-GQDs show higher selec-
BSA- 0.001–1 tivity toward Hg2+ detection than that of Fe3+ , which is mainly
0.47 [21]
CdTe 0.00047–0.05 attributed to the well-known soft acid-soft base coordination inter-
CdTe/SiO2 /CDs 0.5–21 1 [53]
action between S atoms in the graphitic carbon structure and Hg2+ .
GQDs 0.001–0.050 0.439 [30]
N, S-CDs 0.1–20 180 [39] It is also noteworthy that N, S-GQDs prepared by citric acid and
N, S-CDs 0.01–1.2 10.3 [46] cysteine can effectively detect Au3+ in lake and river waters [27].
Organic
CDs 0.2–15 25 [51] In this study, however, the interference of Au3+ is not examined
CNPs 0.25–12 42 [52] because the Au concentration is insignificant in wastewater when
N, S-GQDs 0.001–15 0.14 This work
compares with that of Hg2+ .
a
NAC-QD: N-acetyl-l-cysteine functionalized quantum dots; GQDs: graphene
quantum dots; CDs: carbon dots; CNPs: carbon nanoparticles.
3.3. Real wastewater analysis

can be lowered to 0.44–180 nM [30,39,46,51,52]. Wang et al. have
recently developed N, S-codoped CDs for detection of Hg2+ and a
dynamic range of 0.1–20 ␮M with LOD of 0.18 ␮M was observed
[39]. In this study, the N, S-GQDs are highly sensitive toward Hg2+
detection and the dynamic range can be up to four orders of magni-
tude with LOD of 0.14 nM, which is better than those of the reported
data shown in Table 1.
The specificity as well as selectivity is one of the most impor-
tant parameters for sensing application. In this study, the selectivity
of N, S-GQDs was evaluated by adding 15 ␮M various metal ions
including Mn2+ , Cr3+ , Mg2+ , Fe3+ , Fe2+ , Al3+ , Co2+ , Cd2+ , Cu2+ , Ni2+ ,
After the demonstration of excellent analytical performances
of Hg2+ in deionized water, the applicability of N, S-GQDs to Hg2+
detection was further examined in the real wastewater collected
from the effluents of sewage treatment plants in Taoyuan city,
Taiwan. Fig. 6a shows the change in fluorescence intensity of N,
S-GQDs in sewage effluents in the presence of various concentra-
tions of Hg2+ . The addition of N, S-GQDs to wastewater sample in
the absence of Hg2+ (blank control) still shows good blue fluores-
cence intensity in sewage effluent. After spiking with 0.05, 0.5, 1, 10
and 15 ␮M of Hg2+ ions, however, the fluorescence intensities of N,
S-GQDs decrease dramatically (Fig. 6a). A good linear relationship
 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178 1175

Fig. 5. (a) Emission fluorescence spectra of N, S-GQDs in the presence of various concentrations of Hg2+ ranging from 0 to 15 ␮M, (b) the change in fluorescence intensity
as a function of Hg2+ concentration, (c) the pH effect on the fluorescence intensity of N, S-GQDs before and after the addition of 15 ␮M Hg2+ at various pHs of 5–9 and (d)
selectivity of N, S-GQDs in the presence of various metal ions.

Table 2 the range of 2.0–6.1% (n = 3), clearly indicating the excellent analyt-
Recovery of Hg2+ in real wastewater samples (n = 3).
ical performance of N, S-GQDs on Hg2+ detection in real wastewater
Sample Spiked con- Detected Recovery samples. It is noteworthy that the COD concentrations for sewage
centration concentration ± RSD(%) and dye wastewater effluents are 21.3 and 170 mg/L, respectively
Deionized Water 50 nM 53 nM 107 ± 2.0 (Table S1, see Supplementary data). However, the recovery of these
Sewage 50 nM 48 nM 96 ± 3.1 two wastewater samples has no obvious difference. In addition, the
Sewage 100 nM 105 nM 105 ± 3.9 recovery of Hg2+ between the deionized water and real wastewa-
Sewage 1 ␮M 1.15 ␮M 115 ± 5.1
ter are quite similar, clearly depicting that N, S-GQDs are promising
Sewage 15 ␮M 15.5 ␮M 103 ± 4.5
Dye wastewater 50 nM 58 nM 116 ± 3.8 nanosensing materials for detection of Hg2+ in different wastewater
Dye wastewater 100 nM 96 nM 96 ± 4.7 samples.
Dye wastewater 1 ␮M 1.05 ␮M 98 ± 5.7
Dye wastewater 15 ␮M 14.7 ␮M 98 ± 6.1
3.4. Rapid screening of Hg2+ by N, S-GQD-based paper strips

between Hg2+ concentration and change in fluorescence intensity
with a correlation coefficient of 0.995 is clearly observed (Fig. 6b),
indicating that the matrix effect of wastewater has less interference
on Hg2+ detection by N, S-GQDs.
The recovery of Hg2+ in real wastewater samples was also cal-
culated by spiking various concentrations of Hg2+ ranging from
50 nM and 15 ␮M into the wastewater samples collected from the
sewage treatment plant and dye wastewater treatment plant. As
shown in Table 2, the recovery of 107 ± 2% is observed when low
concentration of 50 nM Hg2+ is spiked into the deionized water.
Similar to the deionized water, recoveries of 96–116% are observed
when low concentrations of 50–100 nM Hg2+ are spiked into the
wastewater samples. In addition, spiking with high concentration
of Hg2+ still can get excellent analytical performance and the recov-
eries are in the range of 98–115% and 98–103% when 1 and 15 ␮M
Hg2+ are added into different wastewater samples, respectively.
The relative standard deviations for all the spiking analysis are in
The development of potential and rapid screening techniques
for wastewater application is always challenging because of the
serious interference of matrix effect and suitable sensing elements.
After the successful detection of Hg2+ by N, S-GQDs in wastewater
effluents, we have also developed an N, S-GQD-based paper strip
for rapid sensing and screening of Hg2+ in wastewaters because
of its unique properties of high selectivity, low detection ability
and reliability toward Hg2+ detection. In this study, the low cost
and non-fluorescent cellulose filter papers were selected as the
supporting material. Fig. 7a illustrates the images of change in
fluorescence intensity of paper strip sensor after immersion into
wastewaters containing various concentrations of Hg2+ ranging
from 5 to 200 ␮M. It is clear that the paper strip has no fluores-
cence property under UV light irradiation. In contrast, the paper
strip coating with N, S-GQDs shows a bright blue fluorescence
under the irradiation of portable UV light and the fluorescence turns
into faint when wastewater contains 5–10 ␮M Hg2+ . Moreover, the
1176 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178

Fig. 6. The change in (a) emission fluorescence spectra and (b) fluorescence intensity ratio as a function of Hg2+ concentration.

Fig. 7. The N, S-GQDs based paper strips for detection of Hg2+ in wastewater effluent. (a) The change in fluorescence as a function of Hg2+ concentration and (b) interference
of 100 ␮M metal ions including Fe2+ , Mn2+ , Cr3+ , Cd2+ , Co2+ , Pb2+ and Zn2+ .
 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178
change in fluorescence intensity becomes distinct when the Hg2+
concentration increases from 10 to 200 ␮M, clearly showing that
the developed N, S-GQDs paper strips can serve as a platform for
rapid and robust detection of wide concentration range of Hg2+ in
wastewaters. In addition, the interference effect of high concen-
tration of 100 ␮M metal ions including Fe2+ , Mn2+ , Cr3+ , Cd2+ , Co2+ ,
Pb2+ and Zn2+ on N, S-GQD based paper strip was evaluated. As illus-
trated in Fig. 7b, the fluorescence intensity of paper strip decreases
at 5 ␮M Hg2+ in comparison with the as-prepared N, S-GQD based
paper strip. However, the fluorescence intensity of N, S-GQD based
paper strip remains almost unchanged when high concentration of
interference metal ions are spiked into the wastewater effluents,
clearly indicating the excellent selectivity and sensitivity of N, S-
GQD based paper strip for rapid and robust detection of mercury
ions in real wastewaters.
4. Conclusions
In this study, we have developed a highly selective and sensitive
N, S-GQD based sensing technique for rapid and robust detection of
nanomolar level of Hg2+ in water and wastewater. The 2–6 nm N,
S-GQDs with 1–5 layers of graphene nanosheets are successfully
fabricated by using one-pot hydrothermal method. The doping of
nitrogen atom can enhance the quantum yield up to 41.9%, resulting
in the high sensitivity and wide detection range. The introduction
of S atoms to N, S-GQDs can selectively detect Hg2+ via strong coor-
dination based on the soft acid and soft base interaction. The N,
S-GQDs exhibit excellent analytical performance on Hg2+ detection
and a dynamic range of 4 orders of magnitude with LOD of 0.14 nM
is obtained. In addition, the N, S-GQDs nanosensing probes can
be successfully applied for sewage and dye wastewater analyses
without obvious matrix interference. A linear range of 0.05–15 ␮M
with recovery of 96–116% is obtained for Hg2+ detection in dif-
ferent wastewater matrices. In addition, the coating of N, S-GQDs
onto paper strip provides an excellently rapid screening technique
for Hg2+ detection in wastewaters. Results obtained in this study
clearly indicate that the N, S-GQDs can selectively and sensitively
detect nanomolar Hg2+ in wastewaters, which can open an avenue
to provide a platform for fabrication of GQD based nanoprobe for
highly rapid and robust detection of metal ions in environmental
and biological fluid samples.
Acknowledgement
The authors thank the Ministry of Science and Technology
(MOST), Taiwan for financial support under grant No. 105-2113-
M-009-023-MY3.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2017.07.177.
References
[1] M.R. Saidur, A.R. Aziz, W.J. Basirun, Recent advances in DNA-based
electrochemical biosensors for heavy metal ion detection: a review, Biosens.
Bioelectron. 90 (2017) 125–139.
[2] G.-H. Chen, W.-Y. Chen, Y.-C. Yen, C.-W. Wang, H.-T. Chang, C.-F. Chen,
Detection of mercury (II) ions using colorimetric gold nanoparticles on
paper-based analytical devices, Anal. Chem. 86 (2014) 6843–6849.
[3] Y.V. Nancharaiah, S.V. Mohan, P.N.L. Lens, Metals removal and recovery in
bioelectrochemical systems: a review, Bioresour. Technol. 195 (2015)
102–114.
[4] S. Squadrone, A. Benedetto, P. Brizio, M. Prearo, M. Abete, Mercury and
selenium in European catfish (Silurus glanis) from Northern Italian Rivers:
can molar ratio be a predictive factor for mercury toxicity in a top predator?
Chemosphere 119 (2015) 24–30.
1177
[5] S.V. Rana, Perspectives in endocrine toxicity of heavy metals −a review, Biol.
Trace Elem. Res. 160 (2014) 1–14.
[6] E. Ha, N. Basu, S. Bose-O’Reilly, J.G. Dórea, E. McSorley, M. Sakamoto, et al.,
Current progress on understanding the impact of mercury on human health,
Environ. Res. 152 (2017) 419–433.
[7] P. Wang, L. Zhao, H. Shou, J. Wang, P. Zheng, K. Jia, et al., Dual-emitting
fluorescent chemosensor based on resonance energy transfer from poly
(arylene ether nitrile) to gold nanoclusters for mercury detection, Sens.
Actuators B Chem. 230 (2016) 337–344.
[8] J.R. Zhou, Y.F. Tian, X. Wu, X. Hou, Visible light photochemical vapor
generation using metal-free g-C3 N4 /CQDs composites as catalyst: selective
and ultrasensitive detection of mercury by ICP-MS, Microchim. J. 132 (2017)
319–326.
[9] D.S. Rajawat, S. Srivastava, S.P. Satsangee, Electrochemical determination of
mercury at trace levels using eichhornia crassipes modified carbon paste
electrode, Int. J. Electrochem. Sci. 7 (2012) 11456–11469.
[10] Y. Du, R. Liu, B. Liu, S. Wang, M.-Y. Han, Z. Zhang, Surface-enhanced Raman
scattering chip for femtomolar detection of mercuric ion(II) by ligand
exchange, Anal. Chem. 85 (2013) 3160–3165.
[11] H. Wang, B. Chen, S. Zhu, X. Yu, M. He, B. Hu, Chip-based magnetic solid-phase
microextraction online coupled with microHPLC–ICPMS for the
determination of mercury species in cells, Anal. Chem. 88 (2015) 796–802.
[12] S.M. Xu, Y. Liu, H. Yang, K. Zhao, J. Li, A. Deng, Fluorescent nitrogen and sulfur
co-doped carbon dots from casein and their applications for sensitive
detection of Hg2+ and biothiols and cellular imaging, Anal. Chim. Acta 964
(2017) 150–160.
[13] L.Y. Chen, C.M. Ou, W.Y. Chen, C.C. Huang, H.T. Chang, Synthesis of
photoluminescent Au ND–PNIPAM hybrid microgel for the detection of Hg2+ ,
ACS Appl. Mater. Interfaces 5 (2013) 4383–4388.
[14] S. Bothra, Y. Upadhyay, R. Kumar, S.A. Kumar, S.K. Sahoo, Chemically modified
cellulose strips with pyridoxal conjugated red fluorescent gold nanoclusters
for nanomolar detection of mercuric ions, Biosen. Bioelectron. 90 (2017)
329–335.
[15] J. Yao, X. Gou, An investigation of preparation properties, characterization and
the mechanism of zinc blende CdTe/CdS core/shell quantum dots for sensitive
and selective detection of trace mercury, J. Mater. Chem. C 4 (2016)
9856–9863.
[16] H. Li, Y. Zhang, X. Wang, Z. Gao, A luminescent nanosensor for Hg (II) based on
functionalized CdSe/ZnS quantum dots, Microchim. Acta 160 (2008) 119–123.
[17] T. Li, Y. Zhou, J. Sun, D. Tang, S. Guo, X. Ding, Ultrasensitive detection of
mercury (II) ion using CdTe quantum dots in sol-gel-derived silica spheres
coated with calix [6] arene as fluorescent probes, Microchim. Acta 175 (2011)
113–119.
[18] B. Hu, L.L. Hu, M.L. Chen, J.H. Wang, A FRET ratiometric fluorescence sensing
system for mercury detection and intracellular colorimetric imaging in live
Hela cells, Biosen. Bioelectron. 49 (2013) 499–505.
[19] Y. Long, D. Jiang, X. Zhu, J. Wang, F. Zhou, Trace Hg2+ analysis via quenching of
the fluorescence of a CdS-encapsulated DNA nanocomposite, Anal. Chem. 81
(2009) 2652–2657.
[20] H.Y. Xu, K.N. Zhang, Q.S. Liu, Y. Liu, M. Xie, Visual and fluorescent detection of
mercury ions by using a dually emissive ratiometric nanohybrid containing
carbon dots and CdTe quantum dots, Microchim. Acta 184 (2017) 1199–1206.
[21] J. Zhu, Z.-J. Zhao, J.-J. Li, J.-W. Zhao, CdTe quantum dot-based fluorescent
probes for selective detection of Hg(II): The effect of particle size,
Spectrochim. Acta A Mol. Biomol. Spectrosc. 177 (2017) 140–146.
[22] J. Ju, W. Chen, Synthesis of highly fluorescent nitrogen-doped graphene
quantum dots for sensitive, label-free detection of Fe(III) in aqueous media,
Biosens. Bioelectron. 58 (2014) 219–225.
[23] F. Wang, Z. Gu, W. Lei, W. Wang, X. Xia, Q. Hao, Graphene quantum dots as a
fluorescent sensing platform for highly efficient detection of copper (II) ions,
Sens. Actuators B Chem. 190 (2014) 516–522.
[24] L.L. Li, G.H. Wu, T. Hong, Z.Y. Yin, D. Sun, E. Abdel-Halim, J.F. Zhu, Graphene
quantum dots as fluorescence probes for turn-off sensing of melamine in the
presence of Hg2+ , ACS Appl. Mater. Interfaces 6 (2014) 2858–2864.
[25] X. Gao, C. Du, Z. Zhuang, W. Chen, Carbon quantum dot-based nanoprobes for
metal ion detection, J. Mater. Chem. C 4 (2016) 6927–6945.
[26] X. Gao, Y. Lu, R. Zhang, S. He, J. Ju, M. Liu, et al., One-pot synthesis of carbon
nanodots for fluorescence turn-on detection of Ag+ based on the Ag+ induced
enhancement of fluorescence, J. Mater. Chem. C 3 (2015) 2302–2309.
[27] T. Yang, F. Cai, X. Zhang, Y. Huang, Nitrogen and sulfur codoped graphene
quantum dots as a new fluorescent probe for Au3+ ions in aqueous media, RSC
Adv. 5 (2015) 107340–107347.
[28] A. Dutta Chowdhury, R.A. Doong, Highly sensitive and selective detection of
nanomolar ferric ions using dopamine functionalized graphene quantum
dots, ACS Appl. Mater. Interfaces 8 (2016) 21002–21010.
[29] J. Ju, W. Chen, In situ growth of surfactant-free gold nanoparticles on
nitrogen-doped graphene quantum dots for electrochemical detection of
hydrogen peroxide in biological environments, Anal. Chem. 87 (2015)
1903–1910.
[30] Z. Li, Y. Wang, Y. Ni, S. Kokot, A rapid and label-free dual detection of Hg (II)
and cysteine with the use of fluorescence switching of graphene quantum
dots, Sens. Actuators B Chem. 207 (2015) 490–497.
[31] B.-X. Zhang, H. Gao, X.-L. Li, Synthesis and optical properties of nitrogen and
sulfur co-doped graphene quantum dots, New J. Chem. 38 (2014) 4615–4621.
1178 N.T.N. Anh et al. / Sensors and Actuators B 252 (2017) 1169–1178
[32] R. Zhang, W. Chen, Nitrogen-doped carbon quantum dots: facile synthesis and
application as a turn-off fluorescent probe for detection of Hg2+ ions, Biosens.
Bioelectron. 55 (2014) 83–90.
[33] Z. Yan, X. Qu, Q. Niu, C. Tian, C. Fan, B. Ye, A green synthesis of highly
fluorescent nitrogen-doped graphene quantum dots for the highly sensitive
and selective detection of mercury (II) ions and biothiols, Anal. Methods 8
(2016) 1565–1571.
[34] S. Dey, A. Govindaraj, K. Biswas, C. Rao, Luminescence properties of boron and
nitrogen doped graphene quantum dots prepared from
arc-discharge-generated doped graphene samples, Chem. Phys. Lett. 595
(2014) 203–208.
[35] D. Qu, M. Zheng, P. Du, Y. Zhou, L. Zhang, D. Li, H. Tan, Z. Zhao, Z. Xie, X. Sun,
Highly luminescent S, N co-doped graphene quantum dots with broad visible
absorption bands for visible light photocatalysts, Nanoscale 5 (2013)
12272–12277.
[36] T.V. Tam, N.B. Trung, H.R. Kim, J.S. Chung, W.M. Choi, One-pot synthesis of
N-doped graphene quantum dots as a fluorescent sensing platform for Fe3+
ions detection, Sens. Actuators B Chem. 202 (2014) 568–573.
[37] J. Ju, R. Zhang, S. He, W. Chen, Nitrogen-doped graphene quantum dots-based
fluorescent probe for the sensitive turn-on detection of glutathione and its
cellular imaging, RSC Adv. 4 (2014) 52583–52589.
[38] C.X. Chen, D. Zhao, T. Hu, J.A. Sun, X.R. Yang, Highly fluorescent nitrogen and
sulfur co-doped graphene quantum dots for an inner filter effect-based
cyanide sensor, Sens. Actuators B Chem. 241 (2017) 779–788.
[39] Y. Wang, S.-H. Kim, L. Feng, Highly luminescent N, S-co-doped carbon dots and
their direct use as mercury (II) sensor, Anal. Chim. Acta 890 (2015) 134–142.
[40] R.S. Sahu, K. Bindumadhavan, R.A. Doong, Boron-doped reduced graphene
oxide-based bimetallic Ni/Fe nanohybrids for the rapid dechlorination of
trichloroethylene, Environ. Sci. Nano 4 (2017) 565–576.
[41] S. Sahu, B. Behera, T.K. Maiti, S. Mohapatra, Simple one-step synthesis of
highly luminescent carbon dots from orange juice: application as excellent
bio-imaging agents, Chem. Commun. 48 (2012) 8835–8837.
[42] D. Qu, M. Zheng, L. Zhang, H. Zhao, Z. Xie, X. Jing, et al., Formation mechanism
and optimization of highly luminescent N-doped graphene quantum dots, Sci.
Rep. 4 (2014) 5294.
[43] R.A. Doong, C.Y. Liao, Enhanced visible-light-responsive photodegradation of
bisphenol A by Cu, N-codoped titanate nanotubes prepared by
microwave-assisted hydrothermal method, J. Hazard. Mater. 322 (2017)
254–262.
[44] X. Li, S.P. Lau, L. Tang, R. Ji, P. Yang, Sulphur doping: a facile approach to tune
the electronic structure and optical properties of graphene quantum dots,
Nanoscale 6 (2014) 5323–5328.
[45] L.J. Zhang, Z.H. Li, Y.L. Yang, Y.B. Zhou, J.H. Li, L.L. Si, B. Kong, Research on the
composition and distribution of organic sulfur in coal, Molecules 21 (2016)
630.
[46] Q.H. Ye, F.Y. Yan, Y.M. Luo, Y.Y. Wang, X.G. Zhou, L. Chen, Formation of N,
S-codoped fluorescent carbon dots from biomass and their application for the
selective detection of mercury and iron ion, Spectrochim. Acta A 173 (2017)
854–862.
[47] J. Gu, X. Zhang, A. Pang, J. Yang, Facile synthesis and photoluminescence
characteristics of blue-emitting nitrogen-doped graphene quantum dots,
Nanotechnology 27 (2016) 165704.
[48] X. Niu, Y. Li, H. Shu, J. Wang, Revealing the underlying absorption and
emission mechanism of nitrogen doped graphene quantum dots, Nanoscale 8
(2016) 19376–19382.
[49] J. Ju, W. Chen, Synthesis of highly fluorescent nitrogen-doped graphene
quantum dots for sensitive, label-free detection of Fe(III) in aqueous media,
Biosens. Bioelectron. 58 (2014) 219–225.
[50] Z. Wu, W. Li, J. Chen, C. Yu, A graphene quantum dot-based method for the
highly sensitive and selective fluorescence turn on detection of biothiols,
Talanta 119 (2014) 538–543.
[51] Y.H. Ma, Z. Zhang, Y.L. Xu, M. Ma, B. Chen, L. Wei, L.H. Xiao, A bright
carbon-dot-based fluorescent probe for selective and sensitive detection of
mercury ions, Talanta 161 (2016) 476–481.
[52] M. Lan, J. Zhang, Y.-S. Chui, P. Wang, X. Chen, C.-S. Lee, H.-L. Kwong, W. Zhang,
Carbon nanoparticle-based ratiometric fluorescent sensor for detecting
mercury ions in aqueous media and living cells, ACS Appl. Mater. Interfaces 6
(2014) 21270–21278.
[53] H. Xu, K. Zhang, Q. Liu, Y. Liu, M. Xie, Visual and fluorescent detection of
mercury ions by using a dually emissive ratiometric nanohybrid containing
carbon dots and CdTe quantum dots, Microchim. Acta 4 (2017) 1199–1206.
Biographies
Nguyen Thi Ngoc Anh received her BS from Can Tho University, Vietnam in 2010. She
is now a PhD candidate majoring in Environmental Engineering under the super-
vision of Professor Ruey-an Doong at the Institute of Environmental Engineering,
National Chiao Tung University, Taiwan. Her research interest mainly focused on
the fabrication of smart materials for sensing and biosensor applications.
Ankan Dutta Chowdhury received his B.S. degree in 2006 from the Calcutta Univer-
sity, Kolkata, India and M.S. from G.G.U., Bilaspur, India in Chemistry. He received
his PhD degree in Chemical Sciences Division at Saha Institute of Nuclear Physics,
India in the field of Chemistry. He is currently continuing his research as a post-
doctoral research fellow at National Chiao Tung University, Taiwan on biosensing,
drug delivery and capacitative study using functional nanomaterials. His research
interests lie in the area of biosensors and different nano materials for biosenssing
applications.
Ruey-an Doong is currently a distinguished professor in the Institute of Envi-
ronmental Engineering, National Chiao Tung University, Taiwan. His current
research interest includes the fabrication of nanomaterials with novel optical
and electrochemical properties for biosensing of analytes, environmentally benign
nanotechnology for treatment of contaminants, and porous materials for energy
storage and conversion.