Analytical

Methods
PAPER

The fabrication of an MoS2 QD–AuNP modified

Cite this: Anal. Methods, 2020, 12,
screen-printed electrode for the improved
3014 electrochemical detection of cefixime†
Pinky Sagar,‡a Monika Srivastava,‡b Rajiv Prakashb and S. K. Srivastava*a

Herein, we report a voltammetric method for the nanomolar detection of cefixime, a third-generation
antibiotic. The determination of cefixime is validated on a glassy carbon electrode (GCE) as well as on
a screen-printed carbon electrode (SPCE). In the present study, we have reported a facile "one step
simple hydrothermal synthesis" of MoS2 quantum dots and with the oxidation of aurochloric acid for the
further formation of an MoS2 QD–AuNP composite. The as-synthesized nanocomposite was
characterized via UV-Vis spectroscopy, FTIR spectroscopy, XRD, TEM and EDX techniques, and further
applied in the modification of working electrodes, showing excellent electroactivity. The sensing of
cefixime was done via cyclic and differential pulse voltammetry techniques. The presence of the only
anodic peak in the voltammogram reveals the irreversible oxidation of cefixime in the potential range of
about 1.3
0.1 V vs. Ag/AgCl. The study was also performed at different scan rates, which indicate
a diffusion-controlled mechanism. The proposed cefixime sensor showed a linear response in the
concentration range of 0.33–90.82 mM (at S/N ¼ 3) with a limit of detection (LOD) of 3.9–4.5 nm. The
electrochemical sensitivity is calculated as 8.63 mA mM1 cm2 and 7.07 mA mM1 cm2 in buffer and
Received 4th May 2020
Accepted 14th May 2020
pharmaceutical formulation (commercially available cefixime tablet), respectively. The effects of several
interferents were also investigated. The proposed sensor is effectively used for estimating cefixime in
DOI: 10.1039/d0ay00899k
phosphate buffer and the commercially available cefixime tablets with no cross-reactivity or matrix
rsc.li/methods effects and shows a promising prospect for real applications.

dosages for adults, children and infants according to their food

1. Introduction
Cexime is a third-generation cephalosporin antibiotic
prepared articially from the marine fungi by antibacterial
activity with Cephalosporium acremonium.1–4 The anti-bacterial
effect of cexime is the consequence of the hindrance of
mucopeptide fusion in the bacterial cell wall. It is used to kill
the bacteria as well as to prevent the further expansion and
growth of the bacteria.4,5 Cexime, a broad-spectrum antibiotic,
has been used for the treatment of ear, throat, lung, pneu-
monia, bronchitis infections caused by microorganisms.6
Beyond the positive effects of cexime, it has several side effects
too, such as stomach pain, gas, heartburn, and nausea, which
may cause diarrhea.4,7 There are some administered xed
a
Department of Physics, Institute of Science, Banaras Hindu University, Varanasi,
221005, India. E-mail: sanjay_itbhu@yahoo.com
b
School of Materials Science and Technology, IIT (BHU) Varanasi, 221005, India
† Electronic supplementary information (ESI) available: It comprises a schematic
representation of the synthesis of MoS2 QD–AuNP composite, data on UV-Vis
spectroscopy, FT-IR spectroscopy, X-ray Analysis, EDAX mapping of MoS2 QDs
and MoS2 QD–AuNP composite. It also includes the reproducibility study of the
MoS2 QD–AuNP composite-modied electrode towards the electro-oxidation of
cexime. See DOI: 10.1039/d0ay00899k
‡ Equally contributed authors.
intake and age.8 In this context, several methods have been
developed for the selective, sensitive and accurate detection of
cexime, such as liquid chromatography-mass spectrometry,9
spectrophotometry,10 uorometry,11,12 chemiluminescence,13,14
capillary electrophoresis,15 cyclic voltammetry,16,17 and square
wave voltammetry.18,19 However, most of the techniques are time
consuming, costly and less sensitive. Among these methods,
voltammetric techniques got considerable attention because of
a lesser quantity of sample consumption, high selectivity, fast
response and low detection limit, which can be used for the
detection of cexime.
Apart from the tremendous benets of graphene, transition
metal dichalcogenides (TMDCs) have been attracting consid-
erable attention due to their subtle properties.20–23 TMDCs have
a wide range of electronic, chemical, thermal, optical and
mechanical properties, which enable them to contribute in
nano-electronics, energy storage, sensing, photonics, non-
linear optics and numerous other applications.24–27 There is at
present a resurgence of scientic and engineering interest in
TMDCs28,29 because of their several exceptional properties. In
contrast to other materials, it is innocuous and environment-
friendly.30 The electrochemical behavior of MoS2 quantum dots
is much better than that of bulk MoS2, which may be benecial

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Paper
for use in sensing applications as well as in energy storage
devices, optoelectronic devices, etc.23,31 Peculiar properties such
as high specic surface area, direct bandgap, quantum
connement and splendid electronic properties are rendering
its utility in numerous elds.31,32
However, the noble metal nanoparticles (MNPs) have various
formidable properties including catalytic activities and career
mobility. Among all the noble metal nanoparticles, gold nano-
particles (AuNPs) are the rigorously studied and synthesized to
a great extent due to their exceptional properties and are used in
numerous applications such as in biomedical applications for
diagnosis and sensing.32–37 The introduction of metal nano-
particles made a rapid enhancement in the charge carrier
mobility between the adjacent layers of the transition metal
dichalcogenides.
In the present study, we have reported a facile one hand
simple hydrothermal synthesis of MoS2 quantum dots and with
the addition of aurochloric acid for the further formation of an
MoS2 QD–AuNP composite. The as-synthesized products were
investigated via UV-Vis spectroscopy, FTIR spectroscopy, XRD,
TEM and EDAX techniques. The electrochemical investigations
of the as-synthesized materials were performed via GCE as well
as SPCE. As the surface of an electrode plays a key role in
deciding the sensitivity of any biosensor, a screen-printed
carbon electrode was chosen in the present study. Due to
their simplicity, miniature size and disposability, SPCEs are in
trend for electrochemical sensing. SPCEs have widespread use
in analytical chemistry, pharmaceutical drug sensing, clinical
and environmental studies owing to their remarkable
advancement over the past decades. The electrodes offer great
advantages over GCEs such as a small amount of sample
requirement, faster response time, enhanced repeatability and
reliability.38 The analytical performance of MoS2 QD–AuNP
modied SPCE for the determination of cexime was performed
via the differential pulse voltammetry (DPV) technique with
good reproducibility, sensitivity and selectivity.
2. Experimental
2.1 Chemicals and materials
Cexime was purchased from Sigma, Aldrich, USA. Sodium
molybdate and L-cysteine were procured from Merck, India.
Conc. HCl, absolute ethanol, ascorbic acid, urea, D-glucose, uric
acid were all purchased from Merck, India. Working solutions for
sensing experiments were prepared in deionized water. All the
other chemicals required in the method were of analytical grade
and used without additional purication. Cexime tablets were
purchased from a general medical store in Varanasi, India.
2.2 Instrumentation
The whole electrochemical measurements were performed using
Autolab (PGSTAT, 302, The Netherlands). For the electrochemical
analysis, a three-electrode assembly including GCE as the
working electrode (dia. ¼ 3 mm), a Pt foil as the counter electrode
and Ag/AgCl as the reference electrode were used. Also, SPCE
(Palm Sens, The Netherlands, Model no. IS-1) with a reference
This journal is © The Royal Society of Chemistry 2020
Analytical Methods
electrode (Ag/AgCl, area ¼ 1 mm2), a counter electrode (Pt disc,
area ¼ 3 mm2) and a working electrode (diameter ¼ 2 mm) were
used in several electrochemical measurements. For making
connections of the SPCE to Autolab, a specic connector was
used. Raman spectroscopy was performed using a Renishaw
Raman spectrophotometer (Germany) with a diode pump solid-
state laser with a constant power of 5 mW mm2. X-ray photo-
electron spectra (XPS) were recorded on an XPS spectrophotom-
eter, AMICUS, the U.K. All the measurements were taken at least
three times for each sample for the determination of the surface
elemental composition (at%). To record the UV-Vis spectra, an
Epoch 2 microplate reader, Biotech, USA with a spectrophotom-
eter using a quartz cuvette having 1 cm optical path length was
used. The structural morphology was investigated via trans-
mission electron microscopy using a TECHNAI G2 20 TWIN
(Czech Republic) instrument working at an accelerating voltage
of 200 keV on a carbon-coated copper grid. For the investigation
of functional groups present in the MoS2 QD–AuNP composite,
FT-IR measurements were performed on a Nicolet 380 FT-IR
spectrometer in the transmittance mode (Thermo Nicolet
Corporation, USA), with a DTGS KBr detector and a beam splitter.
The XRD patterns of MoS2 QDs and MoS2 QD–AuNP composite
were recorded on a Miniex 600 X-ray diffractometer (Cu-K
radiation, K ¼ 1.54056 Å, 3 min1 scan rate) at 2 theta ranging
from 5 to 70 .
2.3 Synthesis of MoS2 QDs
MoS2 QDs were synthesized via a simple and facile hydro-
thermal method in a single step. Sodium molybdate dihydrate
(Na2MoO4$2H2O) was used as the source of molybdenum and L-
cysteine (HO2CCHCH2SH) was the source of sulphur. Both the
chemicals were mixed in DI water separately and stirred for
45 min to get a homogeneous solution at 40  C. Further, the
solutions were mixed and again stirred for 20 min to get
a homogeneous mixture. Following this, concentrated HCl (12
N) was added to maintain the pH at 3.0.
Moreover, to start the process for the hydrothermal method,
the homogeneous mixture was transferred into a Teon auto-
clave of 100 ml capacity. The mixture was kept at 180  C for 48 h
for the reaction to occur and then the reaction mixture was le
to cool down at room temperature, a yellow-coloured solution
containing MoS2 QDs was collected. The resulting solution was
dialyzed using a dialysis bag (molecular weight 2000 Da) for 96 h
continuously (Fig. S1†).39
2.4 Synthesis of MoS2 QD–AuNP composite
For the synthesis of the MoS2 QD–AuNP composite, 100 mL of
the MoS2 QD solution was taken and added to 10 ml DI water.
Aer vigorous stirring, 200 mL of HAuCl4 was added dropwise to
the solution and heated near to boiling. The colour change was
the indication of the formation of AuNPs. Aer 10–12 min of the
reaction, the nanocomposite was collected and used for further
experimental procedures (Fig. S1†).39
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Analytical Methods
2.5 Preparation of the modied electrode
Initially, GCE was used for the electrochemical measurements.
MoS2 QD–AuNP-modied GCE with the surface area of 0.07 cm2
was polished with a 0.05 mm alumina slurry in the rst step.
Further, the surface cleaning of the electrode was done by
washing it 3–4 times with DI water and then sonication in DI
water and ethanol for a few minutes. Aerward, drop-casting
was done on GCE and dried carefully at ambient conditions
without touching the surface so that it can be used for all
electrochemical measurements and sensing.
Aer getting a good signature of the proposed cexime
sensor over GCE, it was worth switching to commercially
available SPCE for further measurements. The modication of
SPCE was done in the same way as that of GCE, except for its
cleaning and polishing as it was already ready to be used as an
electrode.37
3. Results and discussions
3.1 Characterization of nanomaterials via Raman, XPS, UV-
Vis and FT-IR spectroscopy techniques
The synthesis of MoS2 was veried rst via Raman character-
ization. Since Raman spectroscopy is used to a great extent for
the characterization of the vibrational properties of the transi-
tion metal dichalcogenides due to its manifested sensitivity and
non-reactivity with sample,40 we adopted the technique to
monitor the number of layers and modes present in the as-
synthesized MoS2 QDs. From Fig. 1, two prominent Raman
bands at 379.99 cm1 and 402.74 cm1 are observed that can be
attributed to the E12g in-plane vibrational mode and A1g out-of-
plane vibrational mode22,23,41 for the monolayer and bulk
MoS2, respectively, where E12g modes involve both types of atoms
Mo and S, and A1g modes involve only the S atoms.42 In our
measurement, we observed that the intensity of the Raman
signal is weaker in comparison to that of bulk. It can be due to
two factors (i) weaker van der Waals interactions and (ii)
Fig. 1 Raman spectra of MoS2 QDs.
3016 | Anal. Methods, 2020, 12, 3014–3024
Paper
absorbance of the residual solvents over the surface of quantum
dots.43
MoS2 is not suitable for electrochemical sensing due to its
semiconducting nature. Therefore, to overcome this problem,
the MoS2 QD–AuNP composite was synthesized and its presence
was further conrmed via XPS (Fig. 2).
The XPS measurements were performed to get quantitative
information about the surface elemental composition and
functionalization. Moreover, high-resolution XPS was per-
formed to study the bond formation between different types of
species during the synthesis. As shown in Fig. 2, multiple
spectra were found for Mo(3d), S(2p) for MoS2 QD and Mo(3d),
S(2p), Au(4f) for MoS2 QD–AuNP.
For MoS2 QDs, the Mo 3d spectrum (Fig. 2a) shows two peaks
at 228.05 and 232.20 eV, which can be assigned to 3d5/2 and 3d3/
4+
2 orbitals from Mo and Mo6+, respectively. When the peaks
were further deconvoluted, the binding energy peaks at 227.75
and 228.50 eV corresponded to 3d5/2 from Mo4+. Similarly, two
peaks at around 163.79 and 164.55 eV were assigned to the 2p3/2
and 2p1/2 orbitals from S2, respectively (Fig. 2b). These peaks
demonstrated the Mo4+ and S2 oxidation states in the as-
synthesized MoS2 QDs, as previously reported.44,45
For MoS2 QD–AuNPs, Fig. 2d shows two doublet peaks at
228.04 and 232.61 eV were representing 3d5/2 and 3d3/2 orbitals,
respectively, which were further deconvoluted to get more
information. Mo having four peaks at 227.34 and 232.38 eV
correspond to Mo4+, while 228.34 and 233.20 eV corresponded
to Mo6+. Similarly, two peaks were seen at 163.89 and 168.87 eV
for the S2 2p3/2 and S2 2p1/2 orbitals, respectively (Fig. 2e).46
Fig. 2f shows characteristic peaks for Au 4f representing 4f5/2
and 4f7/2 orbitals, conrming the reduction of AuHCl4 and the
formation of Au nanoparticles over the surface of MoS2 QDs,
which are absent in Fig. 2c. To know more about the chemical
environment the peaks were deconvoluted. From this gure, Au
having 4 different peaks positioned at 84.43 eV and 87.96 eV
corresponded to Au0, and 85.60 and 89.0 eV corresponded to
Au3+.34,47 Interestingly, Fig. 2d and (e) indicated that the
hybridizations of MoS2 QDs did not affect the elemental envi-
ronment and crystal structure of the as-synthesized quantum
dots remarkably. However, a redshi towards a lower binding
energy was observed emphasizing the suppression of the Fermi
level towards the valence band in MoS2 due to p-type doping.48
In this case, AuCl4 is a withdrawer of the electrons from MoS2
QDs for the reduction of Au NPs from the HAuCl4; therefore,
AuNPs play a vital role as a p-type dopant.44,46,48
The UV absorption spectra of the MoS2 QDs (red) and MoS2
QD–AuNP composite (black) are shown in Fig. S2,† in which
characteristic absorption peaks at 230 nm and 273 nm are
observed due to the excitonic features49 of MoS2 differing from
those of the 2 dimensional MoS2 having peaks at 609 nm and
668 nm. In the optical absorption spectrum of MoS2 QDs there
exists a blueshi attributed to the quantum size effect.50
Moreover, for the MoS2 QD–AuNP composite, absorption peaks
at 215 nm, 247 nm and 547 nm are found. The absorption peak
at 547 nm can be assigned to the characteristic peak of AuNPs.39
For the investigation of the various functional groups and
chemical bond formation, FTIR spectroscopy over the surface of
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Paper
Fig. 2 High resolution core-level XPS spectra of MoS2 QDs (top) and MoS2 QD–AuNP composite (bottom) showing (a and d) for Mo 3d, (b and e)
for S 2p and (c and f) for Au 4f.
MoS2 QDs was performed. As shown in Fig. S3,† FTIR spectrum
of sodium molybdate, L-cysteine, as-synthesized MoS2 QDs and
MoS2 QD–AuNP composite show prominent peaks at
3490 cm1, 2922 cm1, 1629 cm1, 1400 cm1, which conrmed
the presence of –OH stretching vibration, –CH2 asymmetric
stretching, C]O vibration, C–NH–C or C]NC stretching
vibration, respectively. The smaller peaks at 1303 cm1,
1125 cm1, 821–985 cm1, 474 cm1 were assigned to the C–N
stretching vibration, C–NH–C or C–N stretching vibration of
aromatic and aliphatic amines, S–S bond, MoS2 formation,
respectively. The presence of hydroxyl and carboxyl groups
demonstrated the good solubility of the nanocomposite in the
water. However, the peaks at 898 cm1 and 465 cm1
showed that the MoS2 QDs got oxidized slightly.51 MoS2 QDs
and MoS2 QD–AuNP have shown similar absorption peaks,
which conrmed no change in the MoS2 even aer the forma-
tion of Au NPs over the QDs. Also, the absorption bands in the
MoS2 QDs and MoS2 QD–AuNP were observed the same way as
in their precursors, which is in good agreement as explained
previously.52
3.2 Structural characterization and elemental analysis by
XRD, TEM, EDAX and EDAX mapping
The crystalline phase of the as-synthesized MoS2 QDs and MoS2
QD–AuNP was analyzed via the XRD technique, as shown in
Fig. S4.† The XRD prole of the MoS2 QD–AuNP was well-
matched with the standard JCPDS les of MoS2 and Au (CAS
no. 77-1716 and 04-0784 respectively). From the XRD prole of
MoS2, we found eleven different peaks assigned to the reection
planes (002), (004), (100), (101), (111), (104), (106), (110), (112),
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Analytical Methods
and (108) respectively. Similarly, from the XRD prole of MoS2
QD–AuNP, we found three distinct peaks corresponding to
reection planes (200), (111) and (220). Fig. S4† indicates that
the peaks were shied toward a higher value when composite
was formed and deemed to be because of the contraction in the
interlayer spacing due to the formation of AuNPs over the MoS2
QDs. Moreover, a broad peak was assigned to a reection plane
(101) due to the glass substrate (CAS no. 89-8950). Inset shows
the magnied superimposed XRD prole of the MoS2 QDs,
MoS2 QD–AuNP composite and the glass substrate. These
results well conrmed the formation of the MoS2 QDs and MoS2
QD–AuNP composite.
The particle size was calculated by using Debye–Scherer's
formula:
0:9l
D¼
b cosðqÞ
where D is the particle size, l is the wavelength of the X-ray
(1.5414 Å), b is the FWHM of the peak, and q is the diffraction
angle.
Here, the most intense peaks are observed at 32.56 and
45.3 , corresponding to the (100) and (104) reection planes,
which were used to calculate the average particle size of the
MoS2 QDs. Aer calculation, the average particle size was found
to be 2.5 nm.53,54
Further TEM and EDAX mapping were performed for the
structural conrmation of the composite. Fig. 3a shows the
TEM image of MoS2 QDs at 100 nm resolution revealing its
uniform dispersion nature, and Fig. 3b is the histogram prole
done over a selected area for MoS2 QDs in Fig. 3c that depicts
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Analytical Methods Paper

Fig. 3 (a) A TEM image of MoS2 QDs (inset showing their corresponding SAED pattern), (b) MoS2 QD particle size distribution profile. (c) An image
of MoS2 QDs at a higher resolution (inset showing HRTEM image of MoS2 QDs). (d) A TEM image of MoS2 QD–AuNP composite (inset showing
their corresponding SAED pattern). (e) A TEM image of MoS2 QD–AuNP composite at higher magnification. (f) An HRTEM image of MoS2 QD–
AuNP showing lattice spacings.

the average particle size of 1–5 nm, where particles having the
size of 2–3 nm were most abundant. Fig. 3c is the TEM image of
the MoS2 QDs at 20 nm resolution (inset showing an HR-TEM
image at 10 nm resolution), and Fig. 3d reveals the homoge-
neous dispersion of AuNPs over the MoS2 QDs that was also
conrmed by the EDAX mapping (Fig. S5f†). Insets in Fig. 3a
and d show the SAED pattern for the MoS2 QDs and MoS2 QD–
AuNP composite, respectively. A ring pattern was very distinct in
MoS2 QDs as well as in its composite, where it is more intense
for Fig. 3d directing the metallic nature of gold (Au). Further,
Fig. 3e shows the TEM image of MoS2 QD–AuNPs composite at
a higher resolution (20 nm), and its HR-TEM image in Fig. 3f
shows that these particles have beautiful lattice fringes at 10 nm
resolution. Lattice spacings of 0.238 nm and 0.27 nm corre-
sponding to AuNPs and MoS2 QDs are attributed to the
reection planes (111) and (100), respectively,28,55 and these
results well-matched the XRD results.
In order to authenticate the above results, EDAX mapping
and a spot prole of MoS2 QD–AuNP composite were done.
Fig. S5† shows the presence of Mo, Au and S elements and the
spot prole of the EDAX analysis conrmed the formation of the
as-synthesized composite.
3.3 Study of scan rate
As discussed in Section 2.5, the validity of the as-proposed
sensor was checked on GCE rst. For that purpose, electro-
oxidation depending upon the scan rates ranging from 50 mV
s1 to 200 mV s1 in 0.1 M phosphate buffer (pH ¼ 8) at bare
and MoS2 QD–AuNP-modied GCE (Fig. 4a and b) was
measured in the presence of 50 mM of cexime. The anodic peak

Fig. 4 CV responses of the (a) bare GCE (b) MoS2 QD–AuNP-modified GCE in the presence of 50 mM of cefixime in 0.1 M phosphate buffer (pH ¼
8) at different scan rates (c) corresponding to the calibration plot of the anodic peak current vs. the square root of scan rates.

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Paper Analytical Methods

Fig. 5 CV responses of the (a) (i) bare SPCE and (ii) bare SPCE with 50 mM cefixime, (b) (i) bare SPCE, (ii) modified SPCE and (iii) modified SPCE with
50 mM cefixime in 0.1 M phosphate buffer (pH ¼ 8) at a scan rate 50 mV s1 (inset showing CV responses of the commercial gold electrode in
a 0.1 M phosphate buffer with and without 50 mM cefixime).

currents of cexime were enhanced with increasing the scan
rates from 50 mV s1 to 200 mV s1 (Fig. 4a and b) in both cases.
The plot of the anodic peak current versus the square root of
the scan rate shows that the response is linear with R2 ¼ 0.996
for bare GCE and R2 ¼ 0.998 for MoS2 QD–AuNP-modied GCE
respectively following the Randles–Sevcik equation
ip ¼ (2.69  105)n3/2ACD1/2n1/2
where ip is the peak current, A is the electroactive area of the
electrode (cm2), n is the number of electrons changing, C is the
concentration of the cexime (mol cm3), D is the diffusion
coefficient of the cexime and n is the scan rate (V s1). From the
Randles–Sevcik equation (eqn (1)), the current is directly
proportional to the scan rate as well as the concentration.
Fig. 4a–c show the CV responses of the bare and modied GCE
at a constant concentration of cexime, where the anodic peak
current plotted against the square root of the scan rate. From
Fig. 4c, in both cases, straight lines were obtained unveiling the
electrochemical process as a diffusion-controlled process. The
addition of gold nanoparticles enhances the electron transfer as
revealed from the plot in the form of the shied anodic peak of
the as-modied GCE in comparison to that of the bare GCE.26
3.4 Comparative study of bare and modied SPCE towards
cexime detection
It was worth switching to SPCE aer getting encouraging results
discussed under Section 3.3. However, before that, we tested the
performance of a commercially-available gold electrode with
MoS2 QD–AuNP-modied SPCE for the electrochemical sensing
of cexime. It is clearly seen from the inset in Fig. 5b that the
(1)
standard gold electrode was not giving any signature with
cexime. Therefore, it was important enough to use MoS2 QD–
AuNP modied electrode instead of the standard gold electrode
for electrochemical detection of cexime antibiotics. Fig. 5
shows the electrochemical behavior of the bare and MoS2 QD–
AuNP modied SPCE in a 0.1 M phosphate buffer solution
(pH ¼ 8) at a scan rate of 50 mV s1 for 50 mM of cexime. We
observed from the graph that cexime oxidized in the potential
range 1.4–1.5 V in the case of bare SPCE, whereas oxidation
potential shied to a lower value (1.2–1.3 V) for the modied
SPCE. It might have occurred due to the composite formation of
AuNP with MoS2 QD, which amplied the electron transfer and
enhanced the anodic peak current signal.

Fig. 6 Differential pulse voltammetry responses of the (a) MoS2 QD–AuNP-modified SPCE in a 0.1 M phosphate buffer (pH ¼ 8) for the
successive addition of cefixime (a to p ¼ 0.33 mM to 90.82 mM) and (b) corresponding calibration plot of the anodic peak current vs.
concentration.

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Analytical Methods Paper

Fig. 7 Differential pulse voltammetry responses of the (a) MoS2 QD–AuNP modified SPCE in a 0.1 M phosphate buffer (pH ¼ 8) for successive
addition of commercially available cefixime tablet (a to k ¼ 0.55 mM to 90.82 mM) and (b) corresponding calibration plot of anodic peak current vs.
concentration.

3.5 Electrochemical sensing of cexime by differential pulse found maybe to due the faster charge transfer and enhanced
voltammetry surface area of the gold nanoparticles and quantum dot
composite through the as-modied SPCE.
The effect of the concentration of cexime antibiotic on the
Cexime antibiotic is a potent drug against treating bacterial
MoS2 QD–AuNP-modied SPCE via the DPV technique in
infections such as pneumonia, gonorrhea, and urinary tract
a 0.1 M phosphate buffer (pH) solution was studied. As the
infections. So, a sensing strategy cannot be concluded before its
concentration of the cexime increases, subsequently the
estimation for pharmaceutical formulations. To achieve this
anodic current peak value also enhanced, which is clearly
shown in the plot (Fig. 6a). The addition of a higher concen- rationale, cexime tablets were purchased from a general
tration of cexime and shiing of the peak towards a higher medical store and ground well using a mortar and a pestle. A
stock solution of the grounded powder was prepared under
potential in the curves depicted that the electrochemical
standard and optimised conditions. DPV on MoS2 QD–AuNP-
process was diffusion controlled. The sensing for the different
modied SPCE was then performed for the sensing of cex-
concentrations ranging from 0.33 mM to 90.82 mM of cexime
ime from its pharmaceutical formulations. Similar to the ideal
was performed with a regression coefficient of 0.99. The slope of
sensing in a buffer, electrochemical parameters were also
the line 0.61 mA mM1 demonstrates the consumption of the
analyzed for the cexime tablets. Fig. 7a shows the DPV
number of charge carriers in the electrochemical process. The
limit of detection and sensitivity were found to be 4.5 nM (ob- responses at modied SPCE with successive additions of the
tained by the back extrapolation of the calibration line on the X- concentrated cexime tablets, ranging from 0.55 mM to 90.82
mM. The calculated results showed a good LOD and sensitivity
axis) and 0.61 mA mM1, respectively, as shown in the Fig. 6b.
of 3.9 nM and 0.50 A M1, respectively (Fig. 7b).
The outstanding results towards the detection of cexime were

Fig. 9 Interference study with different biological compounds

Fig. 8 A schematic representation of the oxidation reaction mecha- towards cefixime in the 10 : 1 ratio in the presence of 0.1 M phosphate
nism of Cefixime on the MoS2 QD–AuNP-modified SPCE. buffer (pH ¼ 8).

3020 | Anal. Methods, 2020, 12, 3014–3024 This journal is © The Royal Society of Chemistry 2020
Paper Analytical Methods

Fig. 10 (a) Intra-day stability and (b) inter-day stability of MoS2 QD–AuNP-modified electrode by voltammetric detection in the presence of 50
mM of cefixime at pH ¼ 8 and in 0.1 M phosphate buffer.

Table 1 Comparison of the electrochemical sensor with the earlier reported work for the sensing of cefiximea

Technique Type of electrode LOD (mM) Linear range (mM) Matrix Ref.

CV AgD/MIP/cMWCNT/GCE 0.001 0.01–600 Pharmaceutical formulations and urine samples 16

CV NiFe2O4-MWCNT/GCE 0.020 0.1–600 Biological samples 17
SWV AuNP/SPGE — 10–1000 Biological samples 19
DPV MPTS/MWCNT/GCE 0.070 0.6–20 Human blood plasma sample 57
CV MIP/GNW/GO/GCE 7.1  103 (20–950)  103 Biological samples 4
DPV MoS2 QD–AuNP/SPCE 4.5  103 0.33–90.82 Buffer
Our work MoS2 QD–AuNP/SPCE 3.9  103 0.55–90.82 Pharmaceutical formulation
a
LOD ¼ lower detection limit, CV ¼ cyclic voltammetry, SWV ¼ square wave voltammetry, DPV ¼ differential pulse voltammetry.

A schematic shown in Fig. 8 demonstrates the oxidation
reaction mechanism during the electrochemical sensing on the
MoS2 QD–AuNP-modied electrode surface. Fig. 8 shows the
electrooxidation of such a bigger molecule having functional
groups –COOH (carboxylic groups) and –NH2 (amino groups),
which probably gets oxidized in the presence of the as-
synthesized nanocomposite on the SPCE in the potential
range 1.2 V. It showed an irreversible electro-oxidation process
since there was no cathodic peak found.56
3.6 Interference study
In order to investigate the selectivity of the MoS2 QD–AuNP-
modied electrode for the sensing of cexime, possible
interference from numerous compounds was investigated in
a 0.1 M phosphate buffer solution (pH ¼ 8) in the presence of
50 mM cexime and 0.5 mM of other biological samples. It was
found that uric acid, urea, ascorbic acid, L-cysteine and D-
glucose did not interfere signicantly even at 10 times higher
concentrations than that of cexime. Results are represented
in the form of % interference in Fig. 9. Data plotted on the X-
axis was simply current obtained from cyclic voltammetry
measurement for only cexime taken as 100%; however, for
other biological samples along with cexime, the current ob-
tained was subtracted from that of cexime alone and the nal
subtracted values were converted to a percentage with respect
to 100% of cexime only. This suggests that the adopted
method was well suited for the sensing of cexime in the
biological samples.
3.7 Stability and reproducibility test
The stability of the modied electrode was investigated rst at
an interval of 2 hours on the same day (Fig. 10a) and further up
to 6 days at an interval of two days (Fig. 10b). The current was
measured at a particular concentration of cexime (50 mM) and
it was found that the anodic current peak responses reduced to
a maximum of only upto 5% aer 6 days. Hence the adopted
method and the prepared electrode shows rst-rate stability.
To check the reproducibility of the MoS2 QD–AuNP-modied
electrode, four electrodes were individually fabricated under
identical conditions. The relative standard deviation (RSD) of
the voltammetric signal was 0.68% (Fig. S6†). Thus the as-
synthesized modied electrode can be used safely up to 6
days with good stability and reproducibility (Table 1).
4. Conclusions
Here, we have developed a sensitive MoS2 QD–AuNP-modied
SPCE for the electrochemical detection of the cexime antibi-
otic. A facile one hand synthesis of MoS2 QDs and further MoS2
QD–AuNP composite was performed, which was aerward
characterized by UV-Vis spectroscopy, FTIR spectroscopy, XRD,
TEM and EDX techniques. The MoS2 QD–AuNP-modied elec-
trode shows a good electroactive response for the sensing of
cexime. The sensing was performed in phosphate buffer and
pharmaceutical formulation by DPV. The presence of an only
anodic peak in the voltammogram reveals the irreversible
oxidation of cexime at the potential about 1.3
0.1 V vs. Ag/

This journal is © The Royal Society of Chemistry 2020 Anal. Methods, 2020, 12, 3014–3024 | 3021
Analytical Methods
AgCl. The study is also performed at different scan rates, which
indicate the diffusion-controlled mechanism for the proposed
sensor. It shows a linear response of 0.33–90.82 mM (at S/N ¼ 3)
with a 3.9–4.5 nm LOD. The electrochemical sensitivity is
calculated as 8.63 mA mM1 cm2 and 7.07 mA mM1 cm2 in the
buffer and a pharmaceutical formulation, respectively. To study
the effect of several interferents, stability and reproducibility
tests were also performed. Our proposed sensor is highly
sensitive and reliable for developing electro-sensing devices
using screen-printed electrodes and shows potential prospects
for real applications in the arena of electro-sensing.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
Dr Monika Srivastava conveys her acknowledgement to DST,
New Delhi (SR/WOS-A/CS-52/2018) for the WOS fellowship. Ms.
Pinky Sagar is also thankful to DST INSPIRE fellowship (DST/
INSPIRE/03/2018/000041), New Delhi. The authors are also
thankful to Ashish Kumar, SMST, IIT(BHU) for discussion and
CIF, IIT (BHU) Varanasi for providing various characterization
facilities.
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