Full Paper
DOI: 10.1002/elan.201800893
Glassy Carbon Electrode Modified via Molybdenum
Disulfide Decorated Multiwalled Carbon Nanotubes for
Sensitive Voltammetric Detection of Aristolochic Acids
Ying Wang,[a, e] Xamxikamar Mamat,*[a] Yongtao Li,*[a] Xun Hu,[b] Ping Wang,[c] Yemin Dong,[d] and
Guangzhi Hu*[a, c]
Abstract: In this study, a molybdenum disulfide/multi-
walled carbon nanotubes (MoS2@MWCNTs) nanocompo-
site was synthesized by employing a simple hydrothermal
method. The flower-like structure of the
MoS2@MWCNTs was characterized via scanning electron
microscopy (SEM) and transmission electron microscopy
(TEM), and the load of crystalline MoS2 was verified via
X-ray diffraction (XRD) and energy-dispersive spectro-
scopy (EDS). The as-prepared MoS2@MWCNTs nano-
composite was used to modify glassy carbon electrode
(GCE) as an electrochemical sensor for detecting aristolo-
chic acids (AAs). With the optimized parameters, the
Keywords: Electrochemical sensor · MoS2@MWCNTs · aristolochic acids · linear sweeping voltammetry
1 Introduction
As a class of nitro-phenanthrene carboxylic acids, aristo-
lochic acids (AAs) containing AA-I and AA-II are
frequently found in aristolochia plants such as Aristolo-
chia debilis and Aristolochia fangchi [1–3]. These AAs are
used as a paregoric, anticarcinogen, antiphlogosis agent,
and diuretic in some traditional Chinese medicines [2–4].
During the past decades, a series of incidents of renal
failure related to herbal medicine and sliming pills
containing AA-I were reported [3]. It was confirmed that
AAs are associated with renal failure, renal tumors, and
urinary epithelial cancer [5]. The Food and Drug Admin-
istration (FDA) of United States banned the sale and
import of the plants containing AAs such as aristolochia-
fangchi, caulis aristolochiamanshuriensis, and aristolochia-
delilis [6]. Chinese government deleted a few Chinese
medicines containing high dosage of AAs from Chinese
pharmacopoeia in 2005 [7]. However, a few aristolochia
plants and Chinese patent medicine containing AAs are
still used for clinical treatment in China [4]. Therefore, it
is a necessary to establish a few sensitive and selective
quantification methods to detect AAs.
A few typical methods are reported to detect AA-I
and AA-II in aristolochia and related complex Chinese
patent medicines such as thin chromatography [7, 8], high-
performance liquid chromatography (HPLC) [8–13], and
capillary electrophoresis (CE) [7, 14, 15]. The HPLC
methods for AAs detection are mainly based on different
types of detectors such as a diode-array detector [10, 11],
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proposed electrochemical sensor exhibited good sensitiv-
ity and a broad linear concentration range for detecting
AAs from 0.2 to 10 μmol/L and 10 to 100 μmol/L, with the
sensitivity of 3.10 μA/(μmol/L) and 0.91 μA/(μmol/L),
respectively. The detection limit was also calculated as
0.06 μmol/L (S/N = 3) based on the low background signal.
Furthermore, the modified electrochemical sensor exhib-
ited good selectivity, repeatability, reproducibility, and
stability, thus showing potential application for detecting
AA in chinese herbs with good mean recovery and
accuracy. In other words, the MoS2@MWCNTs/GCE can
be used as an excellent platform to detect AAs.
ultraviolet spectrum (UV) [8, 11], mass spectrum (MS)
[8, 11], and fluorescence(FLD) [9, 13] detector due to the
complex composition in target objects. Wang. et al.
described the HPLC-FLD detection of AAs by applying a
cysteine-induced denitration reaction with detection limits
of 27.1 ng/g for AA-I and 25.4 ng/g for AA-II. Further-
more, different detector-coupling technologies are also
[a] Y. Wang, X. Mamat, Y. Li, G. Hu
Key Laboratory of Chemistry of Plant Resources in Arid
Regions, State Key Laboratory Basis of Xinjiang Indigenous
Medicinal Plants Resource Utilization, Xinjiang Technical
Institute of Physics and Chemistry, Chinese Academy of Sci-
ence, Urumqi 830011, China
E-mail: xamxikmr@ms.xjb.ac.cn
yongtao@ms.xjb.ac.cn
guangzhihu@ms.xjb.ac.cn
[b] X. Hu
School of Material Science and Engineering, University of Ji-
nan, Jinan 250022, China
[c] P. Wang, G. Hu
College of Environmental Science and Engineering, Central
South University of Forestry and Technology, Changsha
410004, China
[d] Y. Dong
State Key Laboratory of Functional Materials for Informatics,
Shanghai Institute of Microsystem and Information Technol-
ogy, Chinese Academy of Sciences, Shanghai 200050, China
[e] Y. Wang
University of Chinese Academy of Sciences, Beijing 100049,
China
Electroanalysis 2019, 31, 1390 – 1400 1390

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applied to enhance the sensitivity and selectivity of the
HPLC. Ioset et al. combined a UV detector in conjunction
with MS to detect the content of AAs in Chinese
medicines and weight loss drugs with high efficiency and
accuracy [11]. However, the CE exhibits a few advantages
including higher detection speed, efficiency, and lower
consumption of the solvent and sample when compared
with that of the HPLC. Furthermore, it was validated that
CE can offer good efficiency in various separation fields
including the analysis of medicinal plants [7, 14]. Li et al.
reported a CE method using β-cyclodextrin as a modifier
for fast analysis of AA-I and AA-II in medicinal plant
samples with high separation efficiency [14]. Nevertheless,
the above-mentioned methods suffer from certain dis-
advantages such as expensive equipment, high operating
costs, and complicated preparation procedures. Electro-
chemical technology exhibits the advantages of simple
instruments, low test cost and time consumption, high
sensitivity, linear range, and easy monitoring [16]. How-
ever, there are few electrochemical methods that analyze
AA-I and AA-II [16–18]. The electrochemical quantifica-
tion of AA-I and AA-II is conducted via cyclic voltamme-
try (CV) on conventional bulk electrodes with a low
detection limit and narrow linear range [16]. Additionally,
Kim et al. developed a square wave voltammetry (SWV)
to determine AA-I in a medicinal plant with the existence
of lead and cadmium [17]. However, the sensitivity and
selectivity of the electrochemical methods should be
improved for detecting AAs.
Typical two-dimensional transition metal disulfides,
such as molybdenum disulfide (MoS2) with a graphite-like
sandwich layer structure, attract increasing attention
[19, 20]. The Mo atomic layer is sandwiched between the
neighbored S atomic layers, which are covalently bonded
to Mo atom layer, and the layers are joined by the van der
Waals force [19, 21]. When the thickness of the MoS2 layer
is reduced to the nanometer scale, it exhibits good
photoelectric and thermodynamic properties, and this
plays an excellent role in the energy storage and catalysis
reactions of the electron device. It can also be used as a
good substrate to construct sensing devices to determine
glucose [22], trinitrotoluene (TNT) [23], dopamine (DA)
[24], uric acid (UA), ascorbic acid (AA) [25], 4-Nitro-
phenol [26], and heavy metals [27]. However, the surface
area and electron conduction rate of MoS2 are relatively
low when compared to that of carbon nanotubes (CNTs)
[20]. CNTs are promising materials that possess excellent
electron and thermal conductivity, high specific surface
area, good stability, high specific surface area, and easy
preparation, and thus it is widely applied in energy
storage, catalysis and detection sensors [20]. Joseph Wang
and co-authors fabricated a highly sensitive 2,4,6-TNT
sensor based on CNTs via adsorptive stripping voltam-
metric measurements with the detection limit correspond-
ing to the sub-μg/l level [28]. Generally, the reduction in
the current peak of the nitro group binding to phenyl ring
is easily electrochemically reduced and then used for the
quantification of nitrobenzene. Furthermore, AAs exhibit
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Fig. 1. Chemical structure of AA-I and AA-II.
structures similar to that of nitrobenzene (Figure 1).
Specifically, MoS2@MWCNT is easily synthesized via
hydrothermal method with different structures and prop-
erties by adjusting the synthesis parameter [29–33]. In the
present study, MoS2@MWCNTs were synthesized via a
simple solvent-thermal method [33], and then character-
ized via scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), energy-dispersive
spectroscopy (EDS), and X-ray diffraction (XRD). The
as-prepared nanocomposite was used to prepare a
modified glassy carbon electrode to construct an electro-
chemical sensor for detecting AAs. The electrochemical
response of AAs was explored on MoS2@MWCNTs
modified electrode via cyclic voltammetry (CV) and linear
sweeping voltammetry (LSV) [18]. The fabricated electro-
chemical sensor exhibited enhanced sensing properties
towards AAs when compared to pure MoS2 and
MWCNTs. Measurement parameters including solution
pH and accumulation time were investigated and opti-
mized. The proposed electrochemical sensor can be used
as a fast and economic quantification method for detect-
ing AA in chinese herbs with favorable sensitivity,
selectivity, repeatability, and reproducibility.
2 Experimental
2.1 Reagents and Instruments
AAs were purchased from Macklin Tech. Co. Ltd., China
(> 98 %). A stock solution of 1.0 mmol/L was prepared by
dissolving 8.53 mg of AAs in 25 ml of ethanol. Addition-
ally, 5 % Nafion solution was purchased from Sigma-
Aldrich and used as a binder to fix nanomaterials on the
electrode surface. Specifically, KH2PO4 and K2HPO4
(MACKLIN, 99.5 %) were used for preparing electrolyte
buffer solution. Glucose (99 %), uric acid (99 %), dop-
amine (98 %), and ascorbic acid (> 99 %) citric acid
(97 %), rutin (97 %), thiamphenicol (99.5 %), and luteolin
(98 %) were purchased from Macklin Tech. Co. Ltd.,
China. Oxytetracycline dihydrate (97 %) was purchased
from Aladdin Tech. Co. Ltd., China. All the other
chemical reagents were of analytical purity. Asarum
sieboldii was bought from the local drugstore.
Electroanalysis 2019, 31, 1390 – 1400 1391

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Scheme 1. Synthetic routes of MoS2@MWCNT modified GCE.
Scanning electron microscope (SEM) equipped with
EDS (Zeiss, Germany) was used to observe the morphol-
ogy of the target material. Transmission electron micro-
scopy (TEM) was conducted on Titan G2 60-300 with an
image corrector. The XRD pattern of the as-prepared
nanocomposite was performed on SMART APEX II
instrument with Cu-K radiation. Additionally, LSV and
CV curves were recorded on the RST5200F electro-
chemical workstation with a three-electrode system.
2.2 Synthesis of MoS2@MWCNTs
The synthetic routes is presented on Scheme 1. First of
all, MWCNTs were activated by stirring them in concen-
trated HNO3 for 12 h and subsequently washing the same
via deionized (DI) water. They were dried at 80 °C for
12 h. In a simple synthesis of MoS2/MWCNTs, 10 mg
activated MWCNTs were dispersed in 100 mL N,N-
dimethylformamide (DMF) and sonicated for 2 h to form
a homogeneous suspension, and 0.046 g sodium molyb-
date and 0.048 g thiourea were added. After being stirred
for 30 min, the homogenous mixture was transferred into
a Teflon-lined autoclave and reacted at 200 °C for 12 h.
Finally, the dark suspension was collected, rinsed with
water and ethyl alcohol thrice, and dried at 80 °C in a
vacuum oven for 12 h.
2.3 Fabrication of MoS2@MWCNTs Modified Electrode
The synthesized material was dispersed in Nafion (0.1 %,
v/v) ultrapure (UP) water/isopropyl alcohol (4 : 1, v/v)
solution via ultrasonication to prepare a 2 mg/mL
MoS2@MWCNTs suspension. Next, 5 μL of ink suspen-
sion was placed on the surface of GCE, and this was
polished via 1-μm, 0.3-μm, and 0.05-μm aluminum oxide
powder. Subsequently, the MoS2@MWCNTs modified
GCE was dried under ambient conditions for 2–3 h.
2.4 Electrochemical Measurements
CV and SWV were performed on an RST-5200F electro-
chemical workstation with a three-electrode system. The
Ag/AgCl electrode, Pt wire electrode, and
MoS2@MWCNTs modified GCE (diameter = 3 mm) were
serviced as the reference electrode, counter electrode, and
the work electrode, respectively. Electrochemical impe-
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dance spectroscopy was carried out using PGSTAT 302N,
and the corresponding equivalent circuit was fitted via
Nova 2.1.4. The electrochemical measurement for detect-
ing AAs was conducted by using the LSV method with a
sweeping range from 0.2 to 1.0 V at 100 mV s 1 in the
phosphate buffer solution (pH = 5) after 100 s in the
accumulation step at 0 V under stirring (350 rpm). The
dissolved oxygen in the electrolyte was removed by high
purity nitrogen, and nitrogen was maintained as flowing
during the actual experiments.
3 Results and Discussion
3.1 Characterization of MoS2@MWCNTs
The morphology of MoS2, MWCNTs, and
MoS2@MWCNTs were characterized via SEM and TEM.
As shown in Figure 2a, MWCNTs exhibit individual
nanotubes with an average diameter of 20 nm and form
interwoven structures. This was convenient to the load of
MoS2. The agglomeration structure of stacked MoS2
flakes was observed on a pure MoS2 image (Figure 2b).
The structure is not conducive to electronic transmission.
However, with respect to MoS2@MWCNTs, as shown in
in Figure 2c–d, the outline of MoS2 flakes is visible and
ceases to stack up like pure MoS2 and is instead loaded on
MWCNTs like a flower structure, which coincides with
the structures of MoS2@MWCNTs reported by Min
Zheng. In order to observe the microscopic size of the
sample, it was characterized via high resolution trans-
mission electron microscopy. As shown in Figure 2e, the
lattice spacing of the sample is 1.45 nm and corresponds
to the distance between four layers of molybdenum
disulfide, and this explains the enhanced electrochemical
activity of MoS2@MWCNTs for AAs. In the high-angle
annular dark field (HAADF) mode (Figure 2f), the bright
outline of MoS2 flakes is observed. Separate and over-
lapped EELS mappings of carbon, molybdenum, and
sulfur are shown in Figures 2g–j. As shown in the figure,
Mo and S are homogeneously distributed over the carbon
skeleton, and this demonstrated that molybdenum disul-
fide forms on the surface of carbon nanotubes. XRD is
further employed to investigate the crystalline character-
istics of the samples. Figure 2k shows typical diffraction
peaks of MWCNTs and MoS2@MWCNTs. As shown in
the figure, MWCNTs exhibit graphitized carbon with 2θ
Electroanalysis 2019, 31, 1390 – 1400 1392
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Fig. 2. SEM images of (a) MWCNTs, (b) bulk MoS2, and (c) MoS2@MWCNTs; TEM images at (d) low and (e) high magnifications of
MoS2@MWCNTs; (f, j) high-angle annular dark-field scanning transmission electron microscopy (HAADF STEM) images and (g–i)
corresponding electronic emitter location system EELS maps of MoS2@MWCNTs. (k) XRD patterns of MoS2 (JCPDS No.86-2308),
MoS2/MWCNTs (red curve) and MWCNTs (black curve); (l) EDS of MoS2/MWCNTs.

diffraction peaks at 25.80°and 43.21° that are assigned to
lattice planes (002) and (100), respectively. Additionally,
the spectra of MoS2 (JCPDS No.86-2308) present 2θ
diffraction peaks at 14.49°, 29.21°, 33.07°, 34.16°, 38,27°,
41.13°, and 44.45°corresponding to the lattice planes
(003), (006), (101), (012), (104), (015), and (009),
respectively. When compared with MoS2 and MWCNTs,
MoS2@MWCNTs exhibit combined main characteristic
peaks of MoS2 and MWCNTs, and this indicates the
successful loading of crystalline MoS2 on MWCNTs. The
reduced intensity and broadened width of the peak is
interpreted as low concentration of reactant and forma-
tion of smaller crystallite sizes of MoS2. Additionally,
EDS was applied to calculate the content of the element
and determine the composition of the sample. A thicker
region on SEM was selected to obtain the EDS spectra.

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Fig. 3. (a) CV curves of GCE, MoS2/GCE, MWCNTs/GCE, MoS2@MWCNTs/GCE in 1.0 mmol/L K3 [Fe(CN)6]/K4 [Fe(CN)6]
containing 0.1 mol/L KCl (ν = 0.1 V/s), (b) Nyquist plots of GCE, MoS2/GCE, MWCNTs/GCE and MoS2@MWCNTs/GCE in
5.0 mmol/L K3 [Fe(CN)6]/K4 [Fe(CN)6] containing 0.1 mol/L KCl. (Frequency range from 10 1 to 10 5 Hz, open-circuit voltage,
0.311 V).
As shown in in Figure 2l, elements corresponding to C, O,
S, and Mo are detected and the overlapping of peaks
between Mo-L lines and S-K lines exists. The EDS also
provides information on element content. The ratio of Mo
and S is 2.2 and corresponds to the molecular structure of
MoS2.
3.2 Electrochemical Characterization of
MoS2@MWCNTs/GCE
Being a reversible diffusion system, the [Fe(CN)6]4 /[Fe
(CN)6]3 is used as the probe to characterize electrodes by
applying CV and EIS methods. Figure 3a. illustrates the
CV response of K3[Fe(CN)6] probe on GCE, MoS2/GCE,
MWCNTs/GCE, and MoS2@MWCNTs/GCE in 1.0 mmol/
L K3 [Fe(CN)6]/K4[Fe(CN)6] containing 0.1 mol/L KCl
solution (ν = 0.05 V/s). From the figure, a pair of signifi-
cant and reversible redox peaks of K3 [Fe(CN)6] was
observed on bare electrode and the ΔEp was calculated to
be 0.075 V. Furthermore, when modifying a certain
amount of MoS2, MWCNTs, and MoS2@MWCNTs, the
peak and charging current increase. Since the peak
current of MWCNTs/GCE is 1.5 times higher than that
compared to MoS2/GCE, we can concluded that
MWCNTs/GCE possesses better conductivity and larger
specific surface area than MoS2/GCE. Specifically, re-
markble increases of peak current occurs on
MoS2@MWCNTs/GCE, which is due to synergistic effect
of MoS2 and MWCNTs, and thus increased the peak and
charging current [34].
In order to study the properties of the material in
more detail, the electrochemical impedance spectroscopy
was applied to characterize the impedance changes on the
surface of the electrodes modified by materials. Figure 3b.
shows the Nyquist plots of GCE, MoS2/GCE, MWCNTs/
GCE and MoS2@MWCNTs/GCE in 5.0 mmol/L K3 [Fe
(CN)6]/K4 [Fe(CN)6] containing 0.1 mol/L KCl. The Ny-
quist plots consists of a semicircle part and a linear part.
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The semicircle part at higher frequencies corresponds to
the electron transfer limited process and the diameter is
equivalent to the electron transfer resistance (Rct). While,
the linear part at lower frequencies represents the
diffusion process [35]. From the figure, The EIS of the
bare GCE exhibits a larger semicircle that shows a much
higher interfacial electron transfer resistance. Whereas
the semicircle gets smaller on MoS2 modified electrode
and even turns to a line on MoS2@MWCNTs/GCE,
showing very low electron transfer resistance due to the
large surface area and excellent electrical conductivity.
The Rct obtained for GCE, MoS2/GCE, MWCNTs/GCE
and MoS2@MWCNTs/GCE are 716 Ω, 307 Ω, 74.3 Ω, and
35.7 Ω, respectively. This proves best electrochemical
performance of MoS2@MWCNTs/GCE among the elec-
trodes, consisting with the previous CV results.
3.3 CV of AA on MoS2@MWCNTs/GCE
Figure 4 exhibits the continuous CV responses of 5 μmol/
L AAs in 0.1 mol/L PBS solution of pH = 5.0. As shown
in the figure, AAs exhibit a reduction peak on the
cathode branch (a) and do not exhibit a peak on the
anode branch, thereby indicating that the electrochemical
reduction of AAs is irreversible, which is consistent with
the reaction mechanism of AAs on modified electrode.
(Figure 5) [36]. Furthermore, the reduction peak current
of AAs decreases rapidly when the scanning number
increases, and this indicates AAs exhibit adsorption
action on MoS2@MWCNTs/GCE.
3.4 LSV of AAs on MoS2@MWCNTs/GCE
The comparison experiment was conducted on bare GCE,
MoS2/GCE, MWCNTs/GCE, and MoS2@MWCNTs/GCE
via LSV to reveal the excellent electrochemical perform-
ance of the target sample. Figure 6 illustrates the LSV
responses obtained on different electrodes in 0.1 mol/L
Electroanalysis 2019, 31, 1390 – 1400 1394

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Fig. 4. CV curves of MoS2@MWCNTs/GCE in 0.1 mol/L PBS
(pH = 5) containing 20 μmol/L AAs; Scan rate: 0.05 V/s; cyclic
scanning number: 4.
Fig. 5. The reaction mechanism of electrode process of Aas.
Fig. 6. LSV of bare GCE, MoS2/GCE, MWCNTs/GCE, and
MoS2@MWCNTs/GCE in 0.1 mol/L PBS (pH = 5) containing
20 μmol/L AAs; Accumulation time: 100 s at 0.0 V; Scan rate:
0.05 V/s.
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Fig. 7. Optimization of accumulation time on MoS2@MWCNTs/
GCE for 10 μmol/L AAs in 0.1 mol/L PBS (error bar: standard
deviation for n = 3).
PBS solution (pH = 5) containing 20 μmol/L AAs after an
accumulation step (100 s) at 0 V. A well-defined reduction
peak appears on all electrodes at the potential ranging
from 0.549 to 0.569 V, and this is attributed to
reduction in the nitro group of the AAs molecule. The
obtained values of peak current at bare GCE, MoS2/GCE,
MWCNTs/GCE, and MoS2@MWCNTs/GCE correspond
to 7.94, 14.10, 24.94, and 41.65 μA, respectively.
When compared with bare GCE, the peak currents of
MoS2/GCE and MWCNTs/GCE increase due to the large
specific surface area and good electron conduction of
MoS2 and MWCNTs. Furthermore, MWCNTs possess
more electrochemical activity to detect AAs as opposed
to MoS2 as indicated by an increase of 1.77 times in
MWCNTs/GCE when compared to that in MoS2/GCE.
Interestingly, significant increases of peak currents
presents on MoS2@MWCNTs/GCE, and this is enhanced
by a factor of 2.95 and 1.67 with MoS2/GCE and
MWCNTs/GCE, respectively. The increasing sensitivity
of MoS2@MWCNTs/GCE is due to the excellent electro-
chemical activity of MoS2 and MWCNTs to AAs.
Furthermore, the most important factor corresponds to
the synergistic effect of MoS2 and MWCNTs, and thus
MoS2@MWCNTs is a feasible material for the detection
of AAs.
3.5 Optimization of Detection Conditions
Accumulation time influencing the sensitivity of AAs on
modified electrode was optimized. Specifically, the
MoS2@MWCNTs layer coated on the surface of the GCE
results in strong interfacial absorption of AAs and serves
as a preconcentration process for highly sensitive detec-
tion. Figure 7 illustrates the response of AAs for sensitive
LSV in the PBS solution (pH = 5) containing 10 μmol/L
AAs with an accumulation time ranging from 0–140 s.
First, a reduction peak current of approximately
4.20 μA is observed when LSV was directly performed
Electroanalysis 2019, 31, 1390 – 1400 1395

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without the accumulation step. The phenomenon is
potentially because the AAs undergo a rapid adsorption
process on the modified electrode within seconds. Sub-
sequently, peak currents increase linearly with accumu-
lation time up to 100 s. When the accumulation time is
further extended, the value of peak current moves
towards a platform due to the saturation of AAs on the
modified electrode [37]. Therefore, the obtained peak
current versus time plot demonstrates that the optimal
enrichment time is 100 s.
The pH value, Which effects the sensitivity and
position of peak current of AAs on modified elelctrode,
was studied. Figure 8a. is the CV stacking graphics of
10 μmol/L AAs on MoS2@MWCNTs/GCE in solution pH
value from 4.0–6.5. As shown in Figure 8, in different pH
condition, the sensitivity and position of peak current of
AAs is different. Moreover, the peak potential of AAs
shifts negativly with increases of pH value, indicating that
proton is involved in this electrode reaction process [38].
The relationship of pH and peak potential (Epa) are fitted
as Epa (V) = 0.051 pH–0.34, R2 = 0.994. The value of
slope 0.051 V/pH is close to standard Nernst slope (at
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25 °C) 0.059 V/pH, implying that this is a process
involving an equal number of electrons and protons [39].
This is in accord with the reaction mechanism depicted in
Figure 5. In addition, the peak current of AAs signifi-
cantly increase with increases in pH ranging from 4.0 to
5.0 and then decrease at subsequent pH values. This
phenomenon is believed to be the results of two factors.
On the one hand, AAs are carboxylic acids with pKa of
3.3 and 3.2 for AAI and AAII [15]. Hence the existing
form of AAs is influenced by acidity of the solution,
which in turn affects the reduction process on the
electrode. For another, the electrochemical process of
AAs on modified electrode surface is a protons-partici-
pated process [39]. Based on the above, pH = 5.0 is
selected as the optimal pH for subsequent analytical
study.
The effect of scan rate to CV behaviour of AAs on
MoS2@MWCNTs/GCE was investigated. Figure 9a. is the
CV stacking graphics of 10 μmol/L AAs on
MoS2@MWCNTs/GCE at the scan rante value from 0.05–
0.5 V/s. From the figure, the peak response ip of AAs was
increased with increases of scan rate, and the reduction

Fig. 8. (a) The stacking graphics of CV of 10 μmol/L AAs on MoS2@MWCNTs/GCE in 0.1 mol/L PBS at pH value from 4.0–6.5
(accumulation time 100 s, scan rate 0.05 V/s) and (b) the corresponding peak current with respect to pH and (c) the linear relationship
between peak potential and pH.

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Fig. 9. (a) The stacking graphics of CV of 10 μmol/L AAs on MoS2@MWCNTs/GCE in 0.1 mol/L PBS (pH = 5) at scan rate value from
0.05–0.5 V/s (accumulation time 100 s) and (b) the linear relationship between peak current and scan rate.

Fig. 10. LSV curves of MoS2@MWCNTs/GCE at different concentrations of AAs (0.2, 0.4, 0.6, 0.8, 1, 3, 5, 7, and 10 μmol/L) and (10,
20, 30, 40, 50 and 100 μmol/L). Inset: the corresponding correlation plot.

peak potential Ep shifted to negative gradually. Moreover,
the linear equation between ip and ν was obtained
(Figure 9b), which is fitted as ip (μA) = 181.58 ν (V/s) +
9.07, with R2 = 0.992. This proves that the electrochemical
reduction of AAs on MoS2@MWCNTs/GCE is an elec-
trode reaction process controlled by adsorption step [40].
3.6 Analytical Performance of the MoS2@MWCNTs/GCE
Under optimal conditions, the favorable concentration
dependence with increments in AAs ranging from 0.2–
100 μmol/L was obtained. Figure 10 illustrates two linear
calibration curves ranging from 0.2–10 μmol/L and 10–
100 μmol/L and are fitted as y(current/μA) = 3.10 x(con-
centration/μmol/L) 0.10, R2 = 0.9988 and y (current/μA)
= 0.91 (concentration/μmol/L) + 20.39, R2 = 0.9989, respec-
tively. This is because the absorption of AAs on the
MoS2@MWCNTs/GCE approach the saturation point at a
concentration of 10 μmol/L. Hence, the electrochemical
process is mainly controlled by the adsorption process
when the concentration of AAs is below 10 μmol/L. The
diffusion process dominates although it exceeds 10 μmol/
L. Based on the low background signal (dash line), the
detection limit was calculated as 0.06 μmol/L (S/N = 3).
Furthermore, the MoS2@MWCNTs/GCE was compared
with other modified electrodes via electrochemical meas-
urements or other detection methods such as HPLC or
CE. As listed in Table 1, the fabricated MoS2@MWCNTs/
GCE offers the relative low detection limit. At the same
time, It meets the requirements of wide quantitative
detection.
3.7 Selectivity of AAs on the Sensor
The selectivity of AAs on MoS2@MWCNTs/GCE was
also examined. We selected a few interference ion and
compounds that potentially exist in the same environment
such as Zn2 +, Mg2 +, NO3 , Cl , SO42 , ascorbic acid,

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Table 1. Comparison of different methods for determination of AAs.

Methods Detection Linear References

limit range
(μmol/L) (μmol/L)
CE-DEa AA-I: 0.04 0.04–19 [7]
AA-II: 0.1 0.1–50
HPLC-FLDb AA-I: 7.94 × 10 4 0.28–14.07 [9]
AA-II: 8.16 × 10 4 0.28–14.07
c
PG Total AAs: 0.01 0.05–1.3 [16]
HMDEd – 0.0167–1.67 [17]
Co/GCf Total AA: 0.08 0.12–37 [18]
MoS2@MWCNTs/ Total AA: 0.06 0.2–10 and This study
GCE 10–100
a
electrochemical detection; b fluorescence detection; c pyrolytic
graphite; d static mercury drop electrode; f glass carbon.

Fig. 12. CV stack graphics of the analytical sample and four

successive addition of AAs standard solution on
MoS2@MWCNTs/GCE. (accumulation time 100 s, scan rate
0.1 V/s).

3.8 Repeatability and Reproducibility of

MoS2@MWCNTs/GCE

Repeatability and reproducibility were also examined. In

Fig. 11. LSV response of 10 μmol/L AAs in 0.1 mol/L PBS
solution of pH = 5 at MoS2@MWCNTs/GCE for different inter-
ference compounds (1-blank, 2-Zn2 +, 3-Mg2 +, 4-NO3 , 5-Cl , 6-
SO42 , 7-ascorbic acid, 8 -dopamine, 9-glucose, 10 -uric acid, 11-
citric acid, 12-luteolin, 13-oxytetracycline, 14-rutin, 15-thiamphe-
nicol).
dopamine, glucose, uric acid, citric acid and some active
components in chinese traditional herbs such as luteolin,
oxytetracycline, rutin, thiamphenicol, which may interfere
with the determination of aristolochic acid. As shown in
Figure 11, when the concertration of AAs in the 0.1 mol/L
PBS (pH = 5) is fixed at 10 μmol/L, 100-fold Zn2 +, Mg2 +,
NO3 , Cl , SO42 , 20-fold ascorbic acid, dopamine,
glucose, uric acid, citric acid, 10-fold luteolin, oxytetracy-
cline, rutin, thiamphenicol effect slightly the LSV peak
current of AAs on MoS2@MWCNTs/GCE. This confirms
that MoS2@MWCNTs/GCE displays good selectivity
towards AAs. However, the modified electrode has no
selectivity to nitro containing compounds, since they have
the same electrode reaction mechanisms.
order to investigate the repeatability, we calculated the
peak current of 20 μmol/L AAs on a modified electrode
for five successive measurements. The relative standard
deviation (R.S.D) of five responses corresponded to
7.9 %. Furthermore, the reproducibility was determined
by calculating the five responses of 20 μmol/L AAs as
shown in the five modified electrodes at the same batch
with an R.S.D of 4.6 %. The results indicate that
MoS2@MWCNTs/GCE exhibits good reproducibility and
repeatability.
3.9 Analysis of a Real Sample
In order to investigate the application for real samples,
the MoS2@MWCNTs/GCE was performed to determine
AAs in chinese herbal Asarum sieboldii via the standard
addition method [17]. To make the analytical sample, 5 g
of dried root of Asarum sieboldii was extracted three
times with 300 mL ethanol by ultrasonic methods, fol-
lowed by filtration and vacuum drying at 80 °C. After-
wards, the obtained extract was dissolved in 10 mL
methanol and transferred to 100-mL volumetric flask, and
then diluted with 0.1 mol/L PBS (pH = 5) to volume.
After that, 20 mL of this analytical sample was measured
by CV after a accumulation step (100 s), and then 40 μL
of 1 mmol/L AAs standard solution was successively
added four times followed by CV measurement every
time. Figure 12. is the CV curves of the analytical sample
and four successive addition of AAs standard solution.
The concertration of AAs in analytical sample was
1.16 μmol/L via extrapolation method (Table 2.). Then
the content of AAs in Asarum sieboldii could calculated

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Table 2. Determination of AAs in Asarum sieboldii (Error bar:
standard deviation for n = 3).
Samples Analytical sample Dried herb Recoveries (%)
(μmol/L) (μg/g)
Sample 1 1.17 7.99 97.5
Sample 2 1.2 8.19 101.6
Sample 3 1.12 7.64 93.3
Ave. 1.16 7.94 – 2010, 24, 1350–1355.
RSD (%) 3.5 3.5 – [5] X. Ji, G. Feng, G. Chen, T. Shi, Sci. China. Life Sci. 2018, 61,
to be 7.94 μg/g, with good recovery and precision.
Accroding chinese pharmacopoeia (2015 edition), the
content of AAs in Asarum sieboldii should be less than
0.001 % by using HPLC. Therefore, the Asarum sieboldii
we tested was conform to standard. This comfirmed that
MoS2@MWCNTs/GCE is practical and accurate in terms
of detecting AAs.
4 Conclusions
In the study, we fabricated an AAs sensor based on GCE
coated by MoS2@MWCNTs for sensitive determination.
Experimental parameters including pH, accumulation
time, and scan rate were investigated and optimized.
Under optimal conditions, the analytical performance of a
modified electrode was obtained with good sensitivity.
The linear range corresponded to 0.2–10 μmol/L and 10–
100 μmol/L with the sensitivity of 3.10 μA/(μmol/L) and
0.91 μA/(μmol/L), respectively. The detection limit cor-
responded to 0.06 μmol/L based on the low background
signal. We also compared the MoS2@MWCNTs/GCE
with GCE, MoS2/GCE, and MWCNTs/GCE, and the
highest peak current of MoS2@MWCNTs/GCE was
observed in the modified electrodes. This indicated the
synergistic effect of MoS2 and MWCNTs. The application
test was also examined on MoS2@MWCNTs/GCE and
was associated with good recovery and accuracy. There-
fore, MoS2@MWCNTs/GCE constitutes an excellent plat-
form to detect AAs. However, the exploration conditions
of AAs in the experiment were excessively simple for
their suitability in applications in a more complex analytic
environment, such as body fluids, soil. and river water
containing thousands of compounds, which can affect the
detection of AAs [41]. Hence, it is necessary to consider
the pretreatment process with respect to complex samples
before electrochemical detection.
Acknowledgements
This work was supported by West Light Foundation of
Chinese Academy of Sciences (2016-YJRC-1), Xinjiang
International Science and Technology Cooperation Pro-
gram (20166010), the National Natural Science Founda-
tion of China (21677171).
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Received: December 29, 2018
Accepted: April 1, 2019
Published online on April 25, 2019
Electroanalysis 2019, 31, 1390 – 1400 1400