Sensors and Actuators B 252 (2017) 183–190

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Sensors and Actuators B: Chemical

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

One-step synthesis of water-soluble and highly fluorescent MoS2

quantum dots for detection of hydrogen peroxide and glucose
Xiaojie Wang a , Qian Wu a , Kaili Jiang a , Chuanxi Wang b,∗ , Chi Zhang a,c,∗∗
a
China-Australia Joint Research Centre for Functional Molecular Materials, School of Chemical & Material Engineering, Jiangnan University, Wuxi 214122,
PR China
b
Institute of New Energy Technology, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, Ningbo, 315201, PR China
c
School of Chemical Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, PR China

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

Article history: Transition metal chalcogenides, especially molybdenum disulfide, have recently got wide attention from
Received 16 March 2017 researchers because of their unique intrinsic characteristics. However, until now, few literatures have
Received in revised form 26 May 2017 reported the photoluminescent MoS2 materials and their applications. In this work, we reported a bottom-
Accepted 30 May 2017
up strategy to synthesize water-soluble molybdenum disulfide quantum dots (MoS2 QDs) through a facile
Available online 3 June 2017
hydrothermal route using sodium molybdate and glutathione as Mo and S sources. The obtained MoS2
QDs show blue emission with a high quantum yield (∼10.3%) and robust dispersibility and storage stability
Keywords:
optical property in aqueous solution. During the experiment, we found that in the presence of hydrogen
Molybdenum disulfide quantum dots
Water-soluble
peroxide (H2 O2) , the fluorescence of MoS2 QDs is quenched due to the interaction between H2 O2 and
Highly fluorescence MoS2 QDs. Simultaneously, glucose oxidase catalyzes the oxidation of glucose to produce gluconic acid
Hydrogen peroxide and H2 O2 , so we can use this probe to detect glucose. By reason of the high zymolyte specificity of glucose
Glucose oxidase, the detection of glucose has good selectivity and sensitivity with a detection limit of 5.16 ␮M.
Finally, the method is successfully applied for detection of glucose in fetal bovine serum samples.
© 2017 Published by Elsevier B.V.

1. Introduction which increase the difficulty of synthesizing PL MoS2 materials [8],

Layered two-dimensional (2D) nanomaterials have attracted
great attention because of their intrinsic characteristics, including
mechanical, electronic, and optical properties [1]. To date, various
layered 2D nanomaterials have been developed, such as graphene
[2], boron nitride [3] and transition metal dichalcogenides (TMDs)
[4]. Among them, molybdenum disulfide (MoS2 ) nanosheets, as a
typical kind of TMDs nanomaterials have 2D layered structures
and exhibit unique chemical, mechanical, and electronic proper-
ties, and have various applications in electronics, catalysis, sensing,
and energy storage [5–7]. However, these studies mainly focus on
the electrical and catalytic properties of MoS2 nanosheets. There
are few researches concerning their optical properties, especially
photoluminescence (PL). The reason may be MoS2 is an indirect
bandgap material and has highly thermal and chemical stability,
∗ Corresponding author.
∗∗ Corresponding author at: China-Australia Joint Research Centre for Functional
Molecular Materials, School of Chemical & Material Engineering, Jiangnan Univer-
sity, Wuxi 214122, PR China
E-mail addresses: 6150610018@vip.jiangnan.edu.cn (X. Wang),
18262283551@163.com (Q. Wu), 6140610003@vip.jiangnan.edu.cn (K. Jiang),
wangcx@nimte.ac.cn (C. Wang), chizhang@jiangnan.edu.cn (C. Zhang).
So the challenges remain in establishing easy synthesis methods for
PL MoS2 materials. Compared to the intrinsic 2D layers, when the
size of MoS2 decreased to less than 10 nm, leading to MoS2 quantum
dots (MoS2 QDs) with unique and extra electrical/optical properties
for the stronger quantum confinement and edge effects [9,10]. So
far, MoS2 QDs have shown predominant applications in catalyzing
and semiconductor industry for optoelectronics and energy har-
vesting, which spurring intense scientific interests in its physical
and chemical properties [11].
Now the strategies for synthesizing MoS2 QDs can be divided
into two types: top-down and bottom-up [12–19]. As the first
one, MoS2 QDs were prepared from bulk MoS2 nanomaterials
via a variety of methods including mechanical and chemical
exfoliation [13–15], electrochemically induced Fenton reaction
[16], and thermal ablation method [17]. For example, Stengl and
Henych prepared MoS2 QDs by refluxing the exfoliated single- or
few-layered MoS2 nanosheets in ethylene glycol [18]; Wu et al.
prepared MoS2 QDs through thermal ablation of MoS2 nanosheets
in N, N-dimethylformamide (DMF) [17]. Nevertheless, during these
“top-down” methods, hazardous reagent, organic solvent, or a long-
time pretreatment is typically demanded. For the later, MoS2 QDs
were synthesized by controlling the chemical reaction conditions
and using molybdate and sulf-containing small molecules as pre-

http://dx.doi.org/10.1016/j.snb.2017.05.177
0925-4005/© 2017 Published by Elsevier B.V.
184 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190

cursors [19]. Wang and Ni synthesized MoS2 QDs using sodium

molybdate and cysteine as precursors, and resultant QDs can be
used as fluorescent probe for the detection of 2,4,6-trinitrophenol
[8]. But the PL quantum yield of this QDs was estimated to only be
2.6%. Very recently, Lin et al. prepared MoS2 QDs using ammonium
tetrathiomolybdate as a precursor and oleylamine as a reducing
agent [20]. However, the resultant MoS2 QDs is unstable in aqueous
solution. Therefore, it is of critical need to establish a simple method
for synthesizing water-soluble and highly fluorescent MoS2 QDs.
As previous reports, hydrothermal route is one of commonly well-
known means for synthesizing nanomaterials that has significant
economic and environmental advantages, and is also the most
common “bottom-up” method [21,22]. Thus, the development of
hydrothermal synthesis of PL MoS2 QDs is always attractive.
As the main component of animal and plant carbohydrates, glu-
cose plays a key role in living systems [23]. It performs not only as
an important energy source for living cells, but also as a metabolic
intermediate in the synthesis of other complex molecules. Blood
glucose levels are an important indicator of human health condi- Scheme 1. Schematic illustration of the oxidation of glucose by glucose oxidase and
tions. The deficiency of glucose may lead to diabetes, metabolic subsequently the fluorescence quenching of MoS2 QDs by H2 O2 .
syndrome, hypertension, and increased cardiovascular risk [24].
Thus, it is of great importance to be able to accurately monitor
the blood glucose levels in clinical diagnosis of diabetes. Some
analytical techniques, including chemiluminescence [25], electro- (GSH) was purchased from Sigma-Aldrich (USA). Glucose, fructose,
chemistry [26], enzyme-catalyzed analysis [27], and colorimetric sucrose, aspartic acid, and proline were obtained from Sinopharm
assays [28] have routinely been used for analysis of glucose with Chemical Reagent Co., Ltd. (Shanghai, China). Glucose oxidase
high sensitivity. Although these methods were quite powerful, (GOx) was gain from J&K Chemical Ltd (Shanghai, China). Fetal
most of these have some disadvantages, such as high cost, sophisti- bovine serum sample was purchased from Yuanchuang Biologi-
cated instruments, or requirement for testing staff owing to master cal Technology Co. Ltd (Shanghai, China). Phosphate buffer saline
professional skill or complex sample pretreatment. To deliver (PBS) buffer (10 mM, pH = 7.4) and HCl (0.1 M) were employed in
highly sensitive and specific detection of glucose, the glucose oxi- the experiment. Deionized water was used throughout the experi-
dase is the first choice on account of optical spectrum analysis of ments.
hydrogen peroxide produced from glucose oxidase (GOx) catal-
ysis of glucose [29–31]. But most of previous strategies usually
suffered from complicated modification or harsh detection envi-
ronment [32,33], so it remains a great challenge in designing a 2.2. The preparation of molybdenum disulfide quantum dots
simple, low-cost and sensitive biosensor to detect glucose.
In contrast to conventional methods, fluorescence assay have Molybdenum disulfide quantum dots (MoS2 QDs) were synthe-
obtained significant attention for their unique electrical, opti- sized through a hydrothermal process using Na2 MoO4 ·2H2 O and
cal properties, and low toxicity [34,35]. Herein, we account a GSH as Mo and S sources. In general, 0.121 g of Na2 MoO4 ·2H2 O
hydrothermal reaction to prepare high-quality and water-soluble was dissolved in 12.5 mL of water. After sonicated for 5 min, the
MoS2 QDs using sodium molybdate and glutathione as Mo and solution was adjusted to pH = 6.5 with 0.1 M HCl. Then, 0.615 g
S sources. Resultant QDs could be used as a sensor for detecting of GSH and 25 mL of water were added to the solution followed
glucose through fluorescence quenching process. The as-prepared by sonicated for 10 min. The mixture was then transferred into a
MoS2 QDs displayed narrow size distribution (2.7 ± 0.3 nm), blue 50 mL Teflon-lined stainless steel autoclave and reacted at 200 ◦ C
fluorescence with high quantum yield of 10.3%, storage stability, for 24 h. After the solution cooled naturally, the supernatant con-
non-toxicity, and excellent dispersibility in water. Furthermore, it taining MoS2 QDs was collected after being centrifuged for 5 min
is found that the MoS2 QDs exhibit high sensitivity to H2 O2 pro- at the speed of 9000 rpm. The resultant MoS2 QDs were stored in
duced in glucose oxidation-catalyzed by GOx. The course of the the dark for further use.
oxidation of glucose by glucose oxidase and the subsequent fluores-
cence quenching of MoS2 QDs by H2 O2 shown in Scheme 1. Glucose
was oxidized by dissolved oxygen (O2 ) in the presence of GOx 2.3. Photoluminescence quenching characteristic of MoS2 QDs
to produce glucose acid and H2 O2 through the electron-transfer toward H2 O2
mechanism. Consequently, the glucose concentration could be
determined indirectly by the amount of enzymatically produced To explore fluorescence quenching capacity of H2 O2 , we exam-
H2 O2 according to the fluorescence quenching. All that prove the ined the PL of MoS2 QDs with a series of compounds. The MoS2
as-prepared MoS2 QDs could be utilized as a biosensor reagent for QDs (0.2 mL, 0.013 M) was treated with various compounds (0.2 mL,
the detection of glucose. 10 mM), including ClO− , NO3 − , NO2 − , RCOO− , H2 O2 , Vitamin C, and
GSH, the final concentrations were 1 mM for all compounds. Then
the fluorescence intensity was investigated under the same condi-
2. Experimental section tions after kept for 10 min. To evaluate the sensitivity of the sensing
system, the fluorescent spectra of MoS2 QDs (0.2 mL, 0.013 M) con-
2.1. Materials taining different concentration of H2 O2 (0, 0.05, 0.1, 0.15, 0.2, 0.3,
0.8, 1.2, 1.5 mM) were kept at room temperature (RT) for 10 min and
Sodium molybdate (Na2 MoO4 ·2H2 O) was purchased from Hefei the fluorescence spectra collected with an excitation wavelength of
Kelong Fine Chemical Research Institute (China). Glutathione 340 nm.
 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190
2.4. Photoluminescence detection of MoS2 QDs toward glucose
In order to evaluate the specificity of developed sensor for
glucose, the effects of some other carbohydrates and metal ions
(0.5 mM) on the fluorescence response of MoS2 QDs were tested.
Typically, the MoS2 QDs (0.4 mL, 0.013 M) was treated with sucrose,
fructose, glucose, Na+ , K+ , Ca2+ , Mg2+ , proline, and aspartic (0.1 mL,
10 mM), then 30 ␮L of GOx (0.2 mg mL−1 ) added the mixed solu-
tion, diluted with PBS (pH 7.4) to 2 mL and kept for 10 min. The
fluorescence intensity was investigated under the same conditions.
Subsequently, to rule out other influencing factors, fluorescence
intensity of MoS2 QDs in the presence of 0.5 mM glucose (100 ␮L,
10 mM), 0.2 mg mL−1 GOx (30 ␮L), and MoS2 QDs containing
0.2 mg mL−1 GOx (30 ␮L) after the addition of 0.5 mM (100 ␮L,
10 mM) glucose were tested. All of the spectra were recorded after
mixing the components for 30 min at 45 ◦ C.
For the sensitivity of the sensing system, different concentration
of glucose in the range of 0–1500 ␮M were examined. Briefly, 30 ␮L
of GOx (0.2 mg mL−1 ) was mixed with 400 ␮L MoS2 QDs (0.013 M),
then the glucose solutions with different concentration of 0, 10,
50, 150, 300, 500, 1000, and 1500 ␮M were added into the MoS2
QDs/GOx mixture, then the mixed solution was diluted with PBS to
2000 ␮L. The mixture was incubated at 45 ◦ C for 30 min and then
the fluorescence spectra were investigated.
2.5. The procedure for glucose detection in fetal bovine serum
samples
The procedure for glucose detection in fetal bovine serum sam-
ples was as follows: firstly, the concentration of fetal bovine serum
samples was diluted to half with PBS buffer. Then 30 ␮L of GOx
(0.2 mg mL−1 ) was mixed with 200 ␮L MoS2 QDs (0.013 M), the
glucose solutions with different concentration of 0.1, 0.8, 1.5, 3.0,
and 5.0 mM were added into the MoS2 QDs/GOx mixture, next the
mixed solution was diluted with the dilute fetal bovine serum sam-
ples to 2000 ␮L, and the mixture was incubated for 30 min at 45 ◦ C.
Then all of the fluorescence detections were under the same con-
ditions.
2.6. Characterization methods
Transmission electron microscopy (TEM) images were per-
formed using a JEM−2100 transmission electron microscope (JEOL,
Japan) with an accelerating voltage of 200 kV. Atomic force
microscopy (AFM) images were recorded with tapping mode in air
using a Dimension Icon and Multimode 8 atomic force microscope
(Bruker, Karlsruhe, Germany). X–ray diffraction (XRD) data were
collected on a Siemens D–5005 X–ray diffractometer with Cu K␣
radiation (␭ = 1.5418 Å) (Bruker, Karlsruhe, Germany). X–ray pho-
toelectron spectroscopy (XPS) study was carried out by using a VG
ES-CALAB MKII spectrometer with Mg K␣ excitation (1253.6 eV).
Fourier transform infrared spectra were recorded by using a Nico-
let 6700 FTIR spectrophotometer at wavenumbers ranging from
500 to 4000 cm−1 . UV–vis spectra were taken using a TU−1991
spectrophotometer (Shimadzu, Kyoto, Japan). Fluorescence spectra
and fluorescence lifetime were recorded on a Fluorescence Lifetime
Spectrometers (PTI, USA), which was equipped with a 500 W xenon
lamp and used for recording the fluorescence spectra with the slits
(Ex/Em) of 3.0/2.0 nm.
185
3. Results and discussion
3.1. Physicochemical characterization of molybdenum disulfide
quantum dots
Molybdenum disulfide quantum dots (MoS2 QDs) was prepared
by the one-pot hydrothermal method using sodium molybdate
(Na2 MoO4 ·2H2 O) and glutathione (GSH) as Mo and S sources. In the
hydrothermal process, Na2 MoO4 ·2H2 O could be reduced in pres-
ence of GSH due to its various functional groups, including carboxyl,
thiol and amino groups [36]. This reducing ability of GSH has been
proved in previously reported nanomaterials [37,38]. Moreover,
GSH worked as a surface passivation agent and provided amino
functional species for resultant MoS2 QDs, which made QDs have
high water-soluble and stability. The lateral size of MoS2 QDs could
be clearly revealed by transmission electron microscopy (TEM)
image. The typical TEM image of resultant MoS2 QDs (Fig. 1A)
showed good dispersion in aqueous without apparent aggregation
and highly uniform spherical morphology with the average size of
2.7 ± 0.3 nm (Fig. 1B). The atomic force microscopy (AFM) was per-
formed to further investigate the thickness of resultant MoS2 QDs
(Fig. 1C). The thickness of the MoS2 QDs was about 2 nm (Fig. 1D),
which is comparable with the theoretical interlayer space of few-
layer MoS2 nanosheets [39–41].
The X-ray photoelectron spectroscopy (XPS) spectrum was dis-
played to investigate the surface groups and compositions of
resultant MoS2 QDs. As shown in Fig. S1, the peaks appeared
at 162.8, 229.5 284.1, 401.3, 495.5, and 533.6 eV, which were
attributed to S 2p, Mo 3d, C 1s, N 1s, Mo 3s, and O 1s, respectively.
Mo and S, together with N, C, and O, can be detected, which came
from the chemicals involved in hydrothermal synthesis. Mo and
S were further confirmed with the high-resolution XPS spectrum,
respectively (Fig. 1E and F). The Mo 3d spectrum of as-prepared
MoS2 QDs showed three peaks at 227.1, 227.9, and 231.7 eV, corre-
sponded to S 2s, Mo 3d5/2 , and Mo 3d3/2 lines of MoS2 , respectively
(Fig. 1E) [42]. This suggests that the dominance of Mo is the 4+ oxi-
dation state [17,43,44]. The S 2p peak around 163.3 and 164.0 eV
were attributed to S 2p3/2 and S 2p1/2 orbitals of divalent sulfide ions
[16,17,39], is ascribed to the −2 oxidation state of S. And 167.7 eV
(2p3/2 ) and 168.8 eV (2p1/2 ), were very possibly attributed to the
S2 O3 2− group, which is possibly formed by oxidation due to local
high temperature in the experiment process (Fig. 1F) [43]. More-
over, the atomic ratio of Mo:S was calculated about to 1:2 (Table
S1), confirming the formation of MoS2 QDs.
The X-ray diffraction (XRD) pattern of MoS2 QDs was inves-
tigated to study the crystal structures with the bulk MoS2 as a
reference (Fig. S2). It shows a strong diffraction peak at 2␪ = 14.4◦
and three lower peaks at 2␪ = 32.7◦ , 39.5◦ , and 49.8◦ for bulk MoS2
(Fig. S2, red line), and these peaks were attributed to the (002),
(100), (103) and (105) planes of MoS2 , respectively [18,45]. For the
resultant MoS2 QDs, only two peaks can be detected at 2␪ = 14.4◦
(002) and 2␪ = 32.7◦ (100), and the peak intensity was weak, indi-
cating the formation of mono- or few-layered MoS2 QDs (Fig. S2,
black line). The results of TEM, XPS, and XRD can determine that
the MoS2 QDs have been synthesized, which show good dispersion,
small size and stable structure.
The optical behaviour of MoS2 QDs was also investigated. The
UV–vis spectrum of as-prepared MoS2 QDs showed a shoulder
peak at ∼280 nm (black line in Fig. 2), which could be attributed
to the blue-shifted convoluted Z, C, and D excitonic peaks [46].
Under the irradiation of 365 nm, the MoS2 QD solution displays
strong blue fluorescence (inset in Fig. 2). The fluorescence spec-
tra showed the obtained MoS2 QDs exhibited strong emission at
425 nm under the excitation of 340 nm (blue line in Fig. 2). And the
full width at half maximum of MoS2 QDs is about 77 nm, which
is relatively narrower than previously reported MoS2 QDs due to
186 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190
Fig. 1. (A) TEM and (C) AFM images of as-prepared MoS2 QDs; (B) the lateral size distribution and (D) the height distribution along the line overlaid on the image of Fig. 1C;
High-resolution XPS patterns of Mo 3d (E) and S 2p (F) electrons in synthetic MoS2 QDs.
uniform particle size distribution as shown in Fig. 1A. Since, MoS2
QDs showed high homogeneity, the excitation-independent fluo-
rescence of them were observed. As shown in Fig. S3, there were
no shifts of the fluorescent peaks with changing excitation wave-
length ranging from 300 to 380 nm. By using quinine sulfate (0.1 M
H2 SO4 as solvent; quantum yield = 0.54) as a fluorescent standard,
the photoluminescence (PL) quantum yield at 340 nm excitation
was estimated to be 10.3%, which was comparable to those reported
previously for carbon dots and graphene quantum dots [47,48]. In
particular, compared with the previously reported MoS2 QDs, the
quantum yield is also higher. We argued the presence of N/O on
the surface of MoS2 QDs could improve the quantum yield. Many
researches have confirmed doping N/O would be the effective way
to prepare high PL nanomaterials, such as carbon dots and graphene
quantum dots [49,50].
Besides, the stability of fluorophores is crucially important fac-
tors. Significantly, the MoS2 QDs display excellent photo-stability.
The MoS2 QDs retain almost the original fluorescence intensity after
irradiation for almost 100 min under a 500 W Xenon lamp excita-
tion source of 340 nm (Fig. 3A). Moreover, the effect of salt solution
on the performance of MoS2 QDs was further investigated. The as-
prepared MoS2 QDs exhibit stability under different concentrations
of NaCl solution (Fig. 3B). Those results show that the salt solution
hardly affects the fluorescence intensity of the MoS2 QDs, suggest-
ing that the MoS2 QDs was suitable for biological applications. The
high stability should be attributed to some functional groups on the
surface of MoS2 QDs, which was demonstrated by Fourier transform
infrared spectra (FTIR) and XPS spectra. As shown in Fig. S4A, the
weak peak around 609 cm−1 was ascribed to the Mo-S vibration [8].
The absorption peaks at 3443 cm−1 was correspond to the stretch-
ing vibrations of O H/N H, the peaks at 1728 cm−1 were assigned
to the bending vibration of C O, the peaks at 1638 and 1388 cm−1
were assigned to the N H and C N bending vibration, respectively
[22,51]. In addition, the XPS spectrum of C 1 s (Fig. S4B) revealed
some different unit moieties: C N (285.1 eV), C O (286.4 eV), and
C O (288.0 eV), respectively [52]. All these results demonstrated
that the amino groups and carboxyl were very likely located on the
surface of MoS2 QDs. These functional groups could improve quan-
 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190
Fig. 2. UV–vis (black), excitation (ex) and emission (em) spectra (red and blue) of
MoS2 QDs (inset: photographs of MoS2 QDs under room (left) and 365 nm irradiation
light (right)). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
tum yield, the solubility (inset of Fig. 2) and stability (Fig. 3) of MoS2
QDs in the aqueous system.
3.2. Evaluation the quenching effect of MoS2 QDs toward H2 O2
To prove the feasibility of the strategy, first we investigated the
PL emission of the MoS2 QDs under the H2 O2 . We can see the PL
intensity decreased after the addition of H2 O2 (curve b in Fig. S5).
The results indicated that H2 O2 could quench the fluorescence of
as-prepared MoS2 QDs. The fluorescence of MoS2 QDs with some
other guest molecules was studied to prove the unique for detecting
of H2 O2 . And the results showed the specificity of MoS2 QDs to H2 O2
(Fig. S6). To further evaluate the capability of the analytical system
for H2 O2 , quantitative detection process was carried out by chang-
ing the concentration of H2 O2 . As shown in Fig. 4A, we found that
the fluorescence intensity of the MoS2 QDs decreased with increas-
ing the concentration of H2 O2 from 50 ␮M to 1.5 mM. This change
also can be seen from photographs of the MoS2 QDs under 365 nm
irradiation with different concentration of H2 O2 (0, 0.1, 0.3, 0.8, and
1.5 mM) (Fig. S7). And the relationship between the concentration
and fluorescence intensity also was studied, and a good linear rela-
tionship was obtained in the concentration range from 50 ␮M to
1.2 mM (R2 = 0.99) (Fig. 4B). Moreover, it can be observed that when
H2 O2 was added to the solution of MoS2 QDs, the corresponding
absorption band of MoS2 QDs appeared red-shift (Fig. 4C). In order
to get insight into the quenching mechanism, the TEM of MoS2
QDs in the presence of 0.8 mM H2 O2 was obtained, and the aggre-
Fig. 3. (A) photo-stability of MoS2 QDs under a 500 W Xenon lamp excitation source for 100 min and (B) ion stability of MoS2 QDs with different concentrations of NaCl in
range of 50–200 mM.
187
gate was observed compared with the pure MoS2 QDs (Fig. 4D).
Therefore, upon adding H2 O2 , aggregation of the QDs occurred by
the partial oxidation process between H2 O2 and MoS2 QDs, which
caused the fluorescence quenching [53]. It could be proved by the
XPS of MoS2 QDs with H2 O2 (Fig. S8), the characteristic peaks at
233.35 eV corresponded to the Mo6+ , resulted from the oxidation
process of the MoS2 QDs treated by H2 O2 . This provides strong evi-
dence that H2 O2 leaded to aggregation of the QDs and fluorescence
quenching of MoS2 QDs.
To further check the applicability of the quenching effect of H2 O2
toward MoS2 QDs, we employed the PL sensor for detection of H2 O2
in the absorbent cotton. Specifically, 10 ␮L MoS2 QDs was added on
the absorbent cotton and dried in room temperature, then 10 ␮L
various concentration of H2 O2 (0, 1, 3, 5, 10 mM) was added on the
above absorbent cotton. After 10 min, the color change was col-
lected by a camera. From the photographs, we can clearly see that
fluorescence color of absorbent cotton with MoS2 QDs as a back-
ground changed gradually with the increasing the concentration of
H2 O2 under the 365 nm UV lamp (Fig. 5).
3.3. The fluorescence detection of glucose using MoS2 QDs
For glucose oxidase (GOx) can specifically catalyze the oxidation
of glucose to generate H2 O2 , the detection of glucose is possible
with the fluorescence quenching of MoS2 QDs by H2 O2 as the sig-
nal transducer. In order to confirm the PL quenching of MoS2 QDs
by H2 O2 , the PL spectra of MoS2 QDs in the presence of pure glu-
cose, GOx, and mixture of glucose and GOx were investigated. It
can be found that the fluorescence intensity of MoS2 QDs appeared
no change in the presence of GOx or glucose, but the PL intensity
decreased after the addition of glucose containing 0.2 mg mL−1 GOx
(Fig. 6A). These results demonstrate that the PL of MoS2 QDs was
quenched by H2 O2 produced from the GOx-catalyzed oxidation of
glucose.
The influence of the concentration of GOx on the fluorescence
quenching was also studied. The efficiency of fluorescence quench-
ing was calculated by F0 /F, where F0 and F were the fluorescence
intensity of MoS2 QDs in the absence and presence of glucose,
respectively. The efficiency of fluorescence quenching reached a
maximum value when the GOx concentration was 0.2 mg mL−1
(Fig. S9). Thus, 0.2 mg mL−1 glucose oxidase was selected as the
optimized concentration.
In order to prove the fluorescence quenching ability of the
GOx-catalyzed oxidation of glucose, the typical fluorescent assay
for glucose with a series of concentration were researched.
The fluorescent intensity decreased gradually with increasing
the concentration of glucose range from 10 to 1500 ␮M, which
suggested that the more H2 O2 was obtained with the higher
188 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190

Fig. 4. (A) fluorescent spectra of MoS2 QDs with different concentration of H2 O2 . (B) the linear relationship between fluorescence intensity and H2 O2 concentration. (C)
UV–vis absorption spectra of MoS2 QDs in the presence of H2 O2 (0.8 mM, red) and absence of H2 O2 (black). (D) TEM image of MoS2 QDs in the presence of H2 O2 (0.8 mM).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

results clearly demonstrate that the MoS2 QDs can serve as a selec-
tive and reliable fluorescence probe for glucose monitoring.

3.4. Detection of glucose in fetal bovine serum samples

Glucose plays a key role in living systems, so blood glucose levels

Fig. 5. Photograph of the absorbent cotton with MoS2 QDs solution under different
concentration (0, 1, 3, 5, and 10 mM) of H2 O2 .
are an important indicator of human and animal health conditions.
In order to verify the feasibility of our approach for detection of
glucose in biological samples, we applied it to analyze glucose in
fetal bovine serum samples. The glucose solutions with different
concentration of 0.1, 0.8, 1.5, 3.0, and 5.0 mM were added into the
MoS2 QDs/GOx/fetal bovine serum mixture, then their fluorescence
spectra were investigated. The results showed that the fluorescent
intensity decreased gradually with increasing the concentration of
glucose (Fig. 7). It also can be found from photographs of the MoS2
QDs under 365 nm irradiation (inset of Fig. 7) with different con-
centration of glucose (0.1, 0.8, 1.5, 3.0, and 5.0 mM). The results
revealed that proposed method is viable for practical blood glucose
monitoring in real samples.

glucose concentration (Fig. 6C). There is a good linear relation-
ship between the glucose concentration and fluorescence intensity
(Fig. 6D). This linear relationship can be fitted as a function is
(I0 − I)/I0 = 0.03016 + 1.8179 × 10−4 C with a correlation coefficient
of R2 = 0.99, where I0 and I were the fluorescence intensity of sens-
ing system in the absence and presence of glucose, respectively.
To investigate the unique of the strategy for detecting of glucose,
some other carbohydrates and metal ions were studied as the con-
trol experiment. These results showed that sucrose and fructose
exhibited little impact on glucose detection, suggesting the high
specificity of GOx (Fig. 6B). Typical metal ions and amino acids
also showed minimal interference in glucose determination. These
4. Conclusion
In summary, we have developed a water-soluble, selective and
sensitive fluorescent probe for glucose detection on the basis
of H2 O2 -mediated fluorescence quenching of molybdenum disul-
fide quantum dots (MoS2 QDs). The MoS2 QDs were synthesized
through an easy hydrothermal method and have water solubility,
high stability, bright blue fluorescence, and high quantum yields.
Significantly, the fluorescence of MoS2 QDs is found to be selec-
tively quenched by H2 O2 . Since, glucose can be oxidized by glucose
oxidase to produce H2 O2 , hence MoS2 QDs can be used as a con-
venient and selective sensor for quantitative detection of glucose.
The method was also applied to detect glucose in fetal bovine serum
 X. Wang et al. / Sensors and Actuators B 252 (2017) 183–190 189

Fig. 6. (A) The PL spectra of MoS2 QDs (black), MoS2 QDs in the presence of 0.5 mM glucose (red) and 0.2 mg mL−1 GOx (blue), the mixture of 0.2 mg mL−1 GOx and 0.5 mM
glucose (green). (B) Effects of the guest molecules (10−2 M) and 0.5 mM glucose on the PL quenching efficiency of MoS2 QDs containing 0.2 mg mL−1 GOx. (C) The PL spectra of
MoS2 QDs containing 0.2 mg·mL−1 GOx with different amount of glucose. (D) The linear response of the quenching efficiency and glucose concentration. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)

of supramolecular structure and materials (sklssm201724), Public

Health Research Center at Jiangnan University (No. JUPH201506),
the Programme of Introducing Talents of Discipline to Universities
(111 Project B13025).

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.2017.05.177.

References

Fig. 7. The PL spectra of MoS2 QDs containing 0.2 mg mL−1 GOx with different
amounts of glucose (0.1, 0.8, 1.5, 3.0, and 5.0 mM) in fetal bovine serum samples
and photographs of MoS2 QDs with different concentration of glucose (0.1, 0.8, 1.5,
3.0, and 5.0 mM) under 365 nm UV irradiation light (inset).
with satisfactory results, suggesting that our approach have great
potential application for diabetes mellitus research and clinical
diagnosis. In addition, the research provides an alternative plat-
form to further design novel nanosensors to detect other substrates
through oxidation by oxygen-dependent oxidase which could gen-
erate H2 O2 .
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 51503085), the Natural Science Foundation of
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Biographies
Dr. Chuanxi Wang associate professor of Materials Chemistry at Ningbo Institute
of Industrial Technology, Chinese Academy of Sciences. He received his Ph.D from
Jilin University in 2013. From 2013.7-2016.12 he worked as associate professor in
Jiangnan University. His research interests include the development of inorganic
semiconductor nanostructures and their applications in biomedical and optoelec-
tronic.
Prof. Chi Zhang PhD, FRSC, RACI, National Distinguished Professor Director, China-
Australia Jnt Res Ctr for Funct Mol Mater. Assistant to the President, Jiangnan
University Wuxi 214122, P.R. China. His research interests include the fluorescence
and magnetic chemical behaviour of low dimensional inorganic-organic hybrid
functional molecules, transition metal sulfur clusters and supramolecular aggre-
gation.