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Analytica Chimica Acta 1030 (2018) 52e60

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Analytica Chimica Acta


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

Detection of Pesticide Residues (Fenitrothion) in Fruit Samples Based


On Niobium Carbide@Molybdenum Nanocomposite: An
Electrocatalytic Approach
Mani Govindasamy a, Umamaheswari Rajaji a, Shen-Ming Chen a, b, *,
Sakthivel Kumaravel a, Tse-Wei Chen a, Fahad M.A. Al-Hemaid b, M.Ajmal Ali b, **,
Mohamed Soliman Elshikh b
a
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei, 106, Taiwan
b
Department of Botany and Microbiology, College of Science, King Saud University, Riyadh, 11451, Saudi Arabia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Hydrothermal synthesis of NbC@Mo


nanocomposite.
 Electrocatalytic detection of
fenitrothion.
 Very low detection limit 0.15 nM.
 Practicality demonstration in fruit
samples.

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

Article history: We have reported an effective electrochemical sensor for assorted pesticide (i.e., Fenitrothion). Exact
Received 11 April 2018 tracking of these pesticides has become more important for protecting the environment and food re-
Received in revised form sources owing to their high toxicity. Hence, the development of compatible sensors for the real-time
14 May 2018
detection of pesticides is imperative to overcome practical limitations encountered in conventional
Accepted 15 May 2018
Available online 16 May 2018
methodologies. In this regard, the role of the novel, advanced functional materials such as niobium
carbide (NbC) supported on molybdenum nanoparticles (NbC@Mo) has drawn great consideration in
conventional sensory systems because of their numerous advantages over other nanomaterials. The
Keywords:
Hazardous pesticides
nanocomposite was characterized by XRD, XPS, HR-TEM, and EIS. Under optimized working conditions,
Nanomaterials the modified electrode NbC@Mo/SPCE responds linearly as 0.01e1889 mM concentration range and the
Hybrid materials detection limit is 0.15 nM. Most importantly, the method was successfully demonstrated in fruit samples.
Food safety © 2018 Elsevier B.V. All rights reserved.
Electrochemical sensor
Fenitrothion

1. Introduction
* Corresponding authors. Department of Chemical Engineering and Biotech-
nology, National Taipei University of Technology, Taipei, 106, Taiwan.
** Corresponding author. Department of Botany and Microbiology, College of Niobium based layered core-shell materials have received
Science, King Saud University, Riyadh, 11451, Saudi Arabia. considerable research and development attention recently due to
E-mail addresses: smchen1957@gmail.com (S.-M. Chen), ajmalpdrc@gmail.com their remarkable properties for numerous applications, such as
(M.Ajmal Ali).

https://doi.org/10.1016/j.aca.2018.05.044
0003-2670/© 2018 Elsevier B.V. All rights reserved.
M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60 53

optical-catalysis and photo-electrochemical applications [1,2]. For advantages such as simplicity and convenience, and high sensitivity
example, while metal nanoparticles (MNPs) supported niobium [22e24]. Therefore, we established the suitable electrode material
carbide have exploited in sensitive electrochemical sensors for the to improve the OPs sensing performance (see Scheme 1).
detection of hazardous substances [3]. However, these materials
are biodegradable; Niobium carbide has many moral properties 2. Experimental section
such as a good wearing resistance, excellent chemical stability, high
melting point, high hardness, stiffness magnetism, catalysis, bio- 2.1. Chemicals and apparatus
logical activity, etc., [2,4]. These properties make it is as an ideal
material for industrial applications such as cutting tools and thin Niobium pentaoxide (Nb2O5), molybdenum pentachloride
film coatings [5]. It is very suitable material for reinforcing in (MoCl5), Mg metal powder, fenitrothion (FTP), and all other re-
austenitic steel, martensitic steel, cast iron and cermet [6]. Mo- agents were purchased from Sigma-Aldrich. The phosphate buffer
lybdenum nanoparticles as many applications, such as high- (PB) solutions were prepared by using 0.1 M Na2HPO4 and NaH2PO4
temperature lubrication, hard alloys, cutting tools, nanowire, solutions, while adjusting their pH values with 0.1 M H2SO4 and
coatings, plastics, microelectronic films, nanofiber, high-power 1.0 M NaOH. The utilized chemicals used were of analytical grade,
vacuum valve and X-ray tube [11]. Nevertheless, there is no re- and deionized (DI) water is used.
ported literature on the toxic effects of molybdenum nanoparticles. As prepared NbC@Mo was analyzed by X-ray diffraction (XRD)
Therefore, NbC@Mo was prepared as an efficient electrode modi- on a XPERT-PRO diffractometer using Cu Ka radiation (k ¼ 1.54 Å).
fier. In order to reveal the electrocatalytic ability of material to- X-ray photoelectron spectra (XPS) studies were obtained by Per-
wards the detection of fenitrothion (FTN), voltammetric studies kinElmer PHI-5702. The morphology of NbC was observed from
were carried out. high resolution transmission electron microscope (HR-TEM) (H-
Detection of the organophosphate (OPs) pesticides and carba- 7600, Hitachi, Japan). Electrochemical impedance (EIS) was recor-
mate insecticides has become more important in recent years, ded on a EIM6ex Zahner (Kronach, Germany). Electrochemical
because of the widespread usage of these compounds. OPs pesti- studies (CVs) with a conventional three electrode system contain-
cides, which can disrupt the normal metabolic function in insects, ing a carbon as the counter electrode, a saturated Ag/AgCl electrode
humans, and animals [12,13]. It widely used in agriculture to pro- as the reference electrode and modified carbon as the working
tect crops from damages caused by insects to increase food pro- electrode (electrode surface area: 0.071 cm2). The Electrochemical
duction [14]. The increasing use of pesticides in agriculture has data were carried out on a CHI 1205a electrochemical workstation,
generated numerous concerns in food safety and water manage- and Differential pulse voltammetry (DPV) CHI900 (CH Instruments,
ment [15]. FTN, a derivative of (OPs), it introduced into the envi- Inc., U.S.A) at ambient temperature. Prior to each electrochemical
ronment from spraying on crops, soil, plants, and water [16e18]. experiment, the electrolyte solutions were deoxygenated with pre-
OPs can be absorbed by all routes, including ingestion, dermal ab- purified nitrogen for 15 min.
sorption, and inhalation. Due to its toxicity, OPs are potentially le-
thal to other living organisms, and need to be used carefully and 2.2. Synthesis of NbC@Mo nanocomposite
disposed properly. If these deformities continuous for a prolonged
time,it can damage our central nervous system (CNS) and also can Molybdenum pentachloride (MoCl5) (55 mg), ascorbic acid
cause environmental pollution and ecological problem, and their (35 mg), and 20 mL of ethanol were sonicated for 2 h. The black
presence in water and food imposes health risks to human [18,19]. precipitate, Mo nanoparticles (Mo NPs) were filtered, and purified
Determinations of these toxins are important for public health and through centrifugation with water and ethanol. The Mo NPs was
environmental security [20,21]. There are several methods for OPs collected and taken for the further synthesis of NbC@Mo NC. Then,
determinations have been proposed, among which electrochemical the nanocomposite was synthesized through the mixture of
technique, i.e., solid phase extraction of organophosphates com- niobium pentaoxide (Nb2O5) (1.0 g), acetone (10 mL) and Mg
bined with differential pulse voltammetric analysis, has the (1.51 g) metal powder, which were mixed together using agate-

Scheme 1. Schematic illustration of the synthesis procedure and practical application of the NbC@Mo NC.
54 M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60

the range between 0.4 V and 0.8 V (vs. Ag/AgCl), in pH 7.0


(0.1 M PB). Next, 8 mL NbC@Mo NC dispersion (1 mg mL1) in
ethanol was coated on SPCE and dried at ambient temperature.
Besides, Mo and NbC film modified SPCE were prepared as
controls.

3. Results and discussions

3.1. Structural and physiochemical properties of NbC@Mo NC

Fig. 1 shows, the XRD patterns of NbC (a), Mo (b), and


NbC@Mo (c). For NbC, the reflections (2q) at 34.82⁰, 40.89⁰,
57.25⁰, 69.78⁰, 74.29⁰, and 88.46⁰ are ascribed to the characteristic
peaks (111), (200), (220), (311), (222), and (400), respectively,
which are consistent in agreement with (JCPDS no. 38e1364)
[25]. The patterns of Mo displayed significant reflections (2q) at
39.93⁰ (110), 60.12⁰ (200), which is accordance with the estab-
Fig. 1. X-ray diffraction pattern of (a) NbC, (b) Mo, and (c) NbC@Mo NC.
lished JCPDS no. 42e1120 [26]. As expected, the characteristic
patterns of NbC@Mo composite were confirmed from patterns of
mortar. The reaction mixture was then heated by means of hy- NbC and Mo.
drothermal treatment at 600  C for 7 h. After completion, the Fig. 2 (a) shows, the formation of NbC@Mo could be obtained
autoclave was allowed to cool. The black powder was collected and from the full range spectrum of the composite. Fig. 2 (b) shows
leached with HCl: H2O (1:1) solution to remove undesired content XPS spectrum of C1s peaks at 282.2eV could be attributed to the
in the powder mass. Subsequently, residue was washed with DI binding energy [27]. The XPS spectrum of Nb 3d core-level re-
water and ethanol, and then allowed to dried at 120  C in vacuum to gion. The peaks at 202.5 and 205.7 eV could be ascribe to the
obtain NbC@Mo NC. For control, Mo and NbC were individually binding energy of Nb 3d5/2 and Nb 3d3/2, Fig. 2 (c). which is
prepared. consistent with the previous reported value for NbC. The binding
energy of Mo 3d, XPS peaks at 230.9 and 236.5 eV could be
2.3. NbC@Mo film modified SPCE attributed to the energy of Mo 3d5/2 and Mo 3d3/2, respectively
Fig. 2 (d) [27].
The surface area of the SPCE was pre-cleaned by sweeping in Fig. 3aec, displays high-resolution TEM images of the Mo,

Fig. 2. (a) XPS survey spectrum of NbC@Mo nanocomposite, (b) C 1s, (c) Nb 3d, and (d) Mo 3d.
M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60 55

Fig. 3. HR-TEM images of Mo nanoparticles (a), NbC@Mo nanocomposite (b, c), and SAED pattern of NbC@Mo nanocomposite (d).

NbC@Mo nanoparticles, respectively. The Mo NPs encapsulated


with an ultrathin layer of NbC (Fig. 3bec). During hydrothermal
treatment, NbC layer with thickness of about 20e30 nm was
densely grown on the walls of the Mo NPs (Fig. 3c). We measured
the lattice space (0.24 nm) of NbC@Mo NC, which is correlated to
the plane of the cubic phase. The core-shell nature of NbC@Mo NC
is further proved by using selected area electron diffraction (SAED)
pattern (Fig. 3d). Finally, as-synthesized NbC@Mo NC morphology
was confirmed.
EIS analysis has been performed in order to examine the
electrical and interfacial properties. Fig. 4 displays the EIS ob-
tained at (a) NbC/SPCE, (b) Mo/SPCE, and (c) NbC@Mo/SPCE in
0.1 M KCl containing 5 mM Fe(CN)3/4- 6 as a model redox medi-
ator. Randles equivalent circuit model has been used to fit the
experimental data (inset to Fig. 4), in which, Rs, Rct Cdl and Zw
were representing electrolyte resistance, charge transfer resis-
tance, double layer capacitance and Warburg impedance,
respectively. EIS measurements were represented as Nyquist
plots, in which semicircles designates the parallel combination
Rct and Cdl at electrode surface resulting from electrode imped-
ance. The size of curves (diameter of the semicircle portion) Fig. 4. EIS curves of NbC/SPCE (a), Mo/SPCE (b), and NbC@Mo/SPCE (c) in 0.1 M KCl
obtained was in the order of NbC/SPCE > Mo/SPCE > NbC@Mo/ containing 5 mM Fe(CN)3/4-
6 as a model redox mediator. Randles equivalent circuit
model has been used to fit the experimental data (inset to Fig. 3a), in which, Rs, Rct Cdl
SPCE. Rct values of NbC/SPCE, Mo/SPCE and NbC@Mo/SPCE are
and Zw were representing electrolyte resistance, charge transfer resistance, double
1140.2 U, 650.81 U, and 210.66 U respectively. The Rct value of layer capacitance and Warburg impedance, respectively.
NbC@Mo/SPCE is lowest which indicating that the charge
transfer resistance at the interface of NbC@Mo/SPCE and elec-
trolyte is minimum compared with other electrodes. In other control electrodes and hence the nanocomposite is highly suit-
words, NbC@Mo/SPCE has high electrical conductivity over its able for electrochemical sensor applications (see Scheme 1).
56 M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60

Scheme 2. Schematic illustration of electro-reduction of FTN over the NbC@Mo film modified electrode.

3.2. Electrocatalysis of FTN NbC@Mo film modified electrode. In the presence of FTN, the CV of
NbC@Mo/SPCE feature with a cathodic peak at 0.58 V (vs. Ag/
The electrocatalytic ability of the NbC@Mo/SPCE towards FTN AgCl) in the forward scan and an anodic peak at 0.05 V (vs. Ag/AgCl)
has been investigated using cyclic voltammetry. Prior to each in the reverse scan. From the literature study, we elucidated that
electrochemical experiment, the electrolyte solutions were deox- the cathodic peak is due to the irreversible reduction of NO2 group
ygenated with pre-purified nitrogen for 15 min. The optimized to hydroxylamine. The oxidation peak in the reverse scan corre-
potential range was þ0.3 to e 0.8 V, the scan rate was 50 mVse1 and sponds to the oxidation of hydroxylamine to nitroso group, and
the supporting electrolyte was phosphate buffer (pH 7.0). Fig. 4 (a) additional reduction peak was observed at e 0.1 V, which corre-
compares the voltammograms of FTN (50 mM) on different elec- sponds to the reduction of nitroso group to hydroxylamine (Scheme
trodes and Scheme 2 displays the possible mechanism of FTN at 2) [23,28]. Because the cathodic peak of FTN (0.58 V) has shown

Fig. 5. (a) CVs obtained at unmodified (a’) SPCE, (b) Mo/SPCE, (c) NbC/SPCE, and (d) NbC@Mo/SPCE containing 50 mM FTN in phosphate buffer (pH 7) at 50 mV s1, (Inset) modified
electrode vs. response peak current. (b) CVs obtained at NbC@Mo film modified electrode in phosphate buffer (pH 7) containing FTN, (Inset) Corresponding calibration plot (a-f;
25e150 mM). (c) CVs obtained at NbC@Mo film modified electrode in different scan rate (50 mM). (c’) Square root of scan rate (Vs1)1/2 vs. peak current (mA).
M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60 57

Fig. 6. (a) long range DPV response of NbC@Mo film modified electrode with an addition of different FTN concentrations at 50 mVs-1. (a’) plots of [FTN]/mM) vs response peak
current (mA).

higher peak currents and hence we have chosen to study the FTN viability of the NbC@Mo modified SPCE for electrochemical detec-
reduction peak to develop sensitive FTN sensor. tion of FTN. Fig. 6a shows, the DPV curves obtained at NbC@Mo
In comparison with control electrodes, the NbC@Mo/SPCE nanocomposite film modified SPCE for sequential additions of FTN
exhibited significantly improved electrocatalytic ability over con- into phosphate buffer (pH 7.0). In this case, the DPV curves were
trol electrodes evident from the highly enhanced peak currents and recorded by varying the concentration of analyte. Thus, the
less over potential. The overpotential is considerably reduced NbC@Mo film showed fast and sensitive responses to each addition
to 0.58 V in NbC@Mo/SPCE, which is about 100 mV, 133 mV, and of FTN. Again, well-resolved reduction peaks arising were observed
157 mV lower than that of NbC/SPCE, Mo/SPCE and unmodified whose corresponding peaks currents were found to increase line-
SPCE, respectively. Similarly, the FTN reduction peak current is arly with increasing concentrations of respective analyte. The
greatly enhanced to 26.04 mA which is about 1.8, 2.5 and 6 orders concentration dependent linear plot displayed good linearity with
higher than that of NbC/SPCE, Mo/SPCE and unmodified SPCE. This slope of 0.0736 mA mM1 (Fig. 6a’). The working concentration range
could be ascribed to the largely exposed electrochemically active was linear from 0.01 to 1889 mM with sensitivity of
area due to the 3D network of NbC@Mo, excellent synergy between 0.355 mA mMe1 cme2. The limit of detection (LOD) was calculated as
NbC and Mo sheets (Fig. 5a). 0.15 nM. The LOD was calculated using the formula, LOD ¼ 3 sb/S
Fig. 5b displays the CVs obtained at NbC@Mo/SPCE in phosphate where, sb is the standard deviation of ten blank measurements and
buffer (pH 7.0) containing different concentrations of FTN. The S is the sensitivity. The important parameters of sensor, such as LOD
value cathodic peak current (Ipc) is increases linearly as the con- and linear range were compared with previously modified elec-
centration of FTN increases. A plot between Ipc and [FTN] exhibited trodes (Table 1). The analytical performance of the NbC@Mo film is
good linearly (inset to Fig. 5b). The linear concentration range was competitive to the previously reported sensors.
observed from 25 mM to 150 mM. Next, the influence of applied scan Selectivity of the NbC@Mo film modified electrode to detect FTN
rates to the electrochemical behavior of FTN at NbC@Mo/SPCE was in presence of possible interfering substances has been investi-
investigated from 10 to 100 mVs-1 (Fig. 5c). The reduction peak gated. The electrocatalytic response of the modified electrode to-
current is increased linearly as the scan rate increases and the plot wards (10 mM, 0.5 mM, and 5 mM) of FTN and interferents (Ascorbic
between reduction peak current and square root of the scan rate acid, Catechol, Glucose, Caffeic acid, Uric acid Hydroquinone,
exhibits linear relationship, a characteristic behavior expected for Dopamine, Ca2þ, Kþ, Zn2þ, Fe2þ, Ba2þ, Cu2þ, NO 2   
2 , SO4 , NO3 , I , Br ,

diffusion controlled process (Fig. 5c’). Cl , Urea, 4-Nitrophenol, 4-Nitrobenzene, Fenamiphos, Carbofuran,

3.3. Effects of pH
Table 1
Comparison of analytical parameters for the determination of FTN at NbC@Mo
The influence of buffer pH on the electrochemical response of nanocomposite film modified electrode with reported works.
NbC@Mo/SPCE towards 50 mM FTN was investigated (Figure. S1a).
Electrode Linear range/mM LOD/nM Methods Ref.
As the pH of supporting electrolyte changes, the peak current and
potential of FTN reduction peak is also changed. The FTN reduction PANI/GCE 0.01e100 7.20 AdSV [29]
EC-pretreated GCE 0.40e50 70 SWV [23]
peak current increases as the pH increases from 1.0 to 13.0 and
RGO/DPA/PGE 0.1e1.91 3.48 SWV [30]
reached maxima at pH 7.0. From pH 7.0 to pH 13.0, the peak current SPCE-Ni(II) MIP 3.00e100 80.0 SWV [31]
progressively decreases. The reduction of FTN is more favorable at Au/GMIP-GR-IL/GCE 0.01e5.0 8.00 DPV [32]
neutral and acidic conditions than the basic pH conditions. Besides, Nano-TiO2/nafion/GCE 0.20e4.0 90.0 DPV [33]
MWCNTs/GCE 0.2e60 80.0 SWV [34]
the plot between different pH and peak potential exhibited a good
CeO2/RGO/GCE 0.025e2.0 3.0 DPV [35]
linearity with slope of 38.5 mVs-1 (Figure. S1b). SiO2/MWCNTs/RuPc 3e66 16.2 DPV [36]
NbC@Mo NC/SPCE 0.01e1889 0.15 DPV This work

3.4. Determination of FTN by DPV PANI¼ Polyaniline; EC ¼ Electrochemical; GCE ¼ glassy carbon electrode;
AdSV ¼ Adsorptive Stripping Voltammetry; SPCE-MIP¼ (screen-printed carbon-
based electrodes-poly Ni (II)-phthalocyanine); SWV ¼ square wave voltammetry;
Differential pulse voltammetry is a more sensitive analytical DPV ¼ differential pulse voltammetry; AuNPs ¼ gold nanoparticles; GMIP ¼ grafting
method to determine the level of FTN, a life-threatening hazardous molecular imprinted polymer; CeO2/RGO ¼ cerium oxide/reduced graphene oxide;
pesticide. This experiment was carried out to explore the practical MWCNTs ¼ multiwall carbon nanotubes; RuPc ¼ ruthenium phthalocyanine.
58 M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60

Fig. 7. Histogram of the selectivity to various interfering substances.

Azathioprine) were studied and the results were given as plot in 3.5. Real sample analysis
Fig. 7. As shown in the plot, the modified electrode delivered
excellent current response to FTN, however, negligible responses For the real sample analysis, the analyte solutions were made of
were observed for all the interferents. Thus, the selectivity study grapes and cranberry extract. The procedure of preparing the
clearly revealed that the NbC@Mo film has good anti-interference extract as follows, initially the skin of grapes and cranberry were
ability and it can be used for the selective determination of FTN peeled and crushed off. Finally, the liquid part from the crushed
in real samples. fruit sample was extracted. Then, defined amount of FTN was

Fig. 8. DPV response of FTN containing grapes (a), and cranberry (b) samples at NbC@Mo/SPCE in phosphate buffer (pH 7). [grapes-FTN]/mM vs. response current (mA) (a’), and
[cranberry-FTN]/mM vs. response current (mA) (b’).
M. Govindasamy et al. / Analytica Chimica Acta 1030 (2018) 52e60 59

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