Journal of Food Measurement and Characterization (2021) 15:2695–2704

https://doi.org/10.1007/s11694-021-00860-7

ORIGINAL PAPER

NiO nanostructures based functional none‑enzymatic electrochemical

sensor for ultrasensitive determination of endosulfan in vegetables
Hadi Bakhsh1 · Jamil A. Buledi1 · Nadir H. Khand1 · Bindia Junejo1 · Amber R. Solangi1 · Arfana Mallah2 ·
Syed Tufail H. Sherazi1

Received: 25 November 2020 / Accepted: 19 February 2021 / Published online: 4 March 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021

Abstract
In an effort to develop a rapid, sensitive and improved electrochemical sensing approach for the selective oxidation of endo-
sulfan, nickel oxide nanoparticles (NiO NPs) were anchored on glassy carbon electrode (GCE). The fabrication of NPs was
accomplished via aqueous chemical growth method and subjected to different analytical tools for the determination of surface
characteristics, crystallinity and elemental composition. The XRD and FESEM reveal a high crystallinity and nano seeds like
morphology for the synthesized NPs with the average size of 22 nm. Cyclic voltammetry (CV) and Electrochemical imped-
ance spectroscopy (EIS) approaches were exploited for the investigation of electrochemical behaviour of modified electrode
labelled as (NiO/GCE). A significantly enhanced response of NiO/GCE for the determination of endosulfan manifested the
salient role of the developed sensor in facilitating the charge transfer mechanism between the electrode’s surface and the
analyte. Differential pulse voltammetry (DPV) was utilized to quantify the amount of endosulfan. The certain parameters
were optimized for the fluent determination process of endosulfan such as phosphate buffer of pH 7, scan rate 80 mV/s and
potential range from − 0.6 to 0.8. The DPV (Ipa) response was linear over 0.05–25 µM range with the limit of detection
of 0.17 nM and limit of quantification 0.51 nM respectively. The applicability of proposed sensor was investigated in real
vegetable samples that showed acceptable percent recoveries for tomato and spinach samples which were calculated to be
94, 91, 87.3% and 98, 103, 100.2% respectively.

Keywords Nickel oxide nanoparticles · Nanoseeds · Endosulfan · Pesticides · Electrochemical sensor · Voltammetry · Food
preservatives

Introduction and it is well-known for its toxicity on non-target organ-

isms and has been responsible for severe-poisonings includ-
Endosulfan (hexachloro-hexahydro-methano benzodioxathi- ing several mortality cases [3]. It is also assumed to be a
epinoxid) is a broad spectrum organochlorine insecticide persistent-organic-pollutant (POP) and there is also a call
belonging to the class of cyclodien, which is being widely for ban on POPs around the globe because of their possible
used in agriculture for controlling the mites and insects [1, links to the dangerous diseases such as cancer and effects
2]. Endosulfan was firstly introduced in 1950s with its com- on reproduction, immune system and hormones. The con-
mon trade name Thiodan®. It is vastly employed to pro- centration of endosulfan is relatively high in different areas
tect the plants, vegetables and other agriculture products around the world because of its extensive use in agricultural
e.g. fruits, tea, grain, cotton and commonly utilized as food products, as compared to the other insecticides which are
preservatives. Endosulfan is considered as major pollutant dispersed worldwide [4]. It is considered as deadly pesticide
with high mortality rate in human when accidently ingested,
* Amber R. Solangi from contaminated water, food or in suicide case [5–10]. It
[email protected] also enhances the estrogen (a female hormone) that means
it might cause developmental and reproductive diseases in
1
National Centre of Excellence in Analytical Chemistry, both humans and animals. A research has found that the
University of Sindh, Jamshoro 76080, Pakistan
linked exposure to endosulfan delays the sexual matu-
2
M.A. Kazi Institute of Chemistry, University of Sindh, rity in boys as well [11, 12]. It can be absorbed through
Jamshoro 76080, Pakistan

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2696 H. Bakhsh et al.

inhalation, ingestion, skin contact via transplacental routes. determination of residual pesticide and rest of the material
It is majorly known as bio-accumulate with several toxic had immunosensor based assembly which itself had certain
effects on main organs, observed with the first six hours drawbacks [28–30]. To overcome certain difficulties and
of exposure [7, 13–15]. The significant accumulation of drawbacks, the metal oxide NPs could be potential aspirant
endsulfan in patients may lead towards renal, hepatic and for the effective and sensitive determination of endosulfan
cardiac toxicities with common complications e.g. nausea, via chemically modified electrodes. Different metal oxide
renal failure, vomiting, tremors, hypotension, rhabdomyoly- nanostructures such as, ZnO, CuO, T ­ i2O, SnO2 [31–35]
sis and coma. Commonly the death of patients occurs with 4 are widely exploited in the electrochemical applications.
to 8 h due to biochemical instability and respiratory failure Amongst these metal oxide nanostructures, nickel oxide
resulting from widespread seizure activity [6, 16, 17]. For (NiO) possess attractive properties like magnetic, ferromag-
the assessment of possible occurrence and toxicity on the netic, optical, electrical and catalytic that make it suitable
human and the environment caused by long term exposure to candidate in the different fields including electrochemical
pesticides, extended analysis of different vegetables, fruits, sensors. The NiO nanoparticles are employed in chemically
surface, ground and drinking water with analytical tools with modified electrochemical sensors as conductive mediator to
sufficient low LODs are essential. Generally, endosulfan is enhance the selectivity and sensitivity of sensing probes.
analysed by different analytical methods, such as, high-per- NiO nanoparticles are also magnetic in nature thus these
formance liquid chromatography [18], gas chromatography nanoparticles are broadly used in chargeable batteries, catal-
and gas chromatography/ Mass spectrometry [19]. However, ysis, conductive colours and opto-electronics [36–39].
these traditional instrumental methods require high sample In present experimental work, we have developed a highly
pre-treatment, tedious clean-up and extraction procedures, selective, sensitive and efficient electroanalytical method
large amount of organic solvents and long analysis time. for the determination of endosulfan pesticide based on NiO
These certain requirements limit their practices in environ- NPs/modified glassy carbon electrode (NiO/GCE). The
mental studies [20]. Thus, there is a great need of devel- developed NiO based sensor provides multiple advantages
oping such an outstanding analytical method that must be such as fast response, low limit of detection, rapid analysis
simple, cost-effective, reliable, sensitive, selective and easy time and wide dynamic range with enhanced sensitivity and
to use and could provide low possible LOD for the detec- selectivity. For analytical applicability, the proposed sensor
tion of endosulfan. The electroanalytical tools and the sur- was exploited in different vegetable samples to monitor the
face modification of electrodes with metal oxide NPs can low concentration of endosulfan. Scheme 1 shows the pos-
effectively meet the above-mentioned criteria or conditions sible mechanism of endosulfan at NiO/GCE.
[21–25]. Endosulfan have also been determined through dif-
ferent electrochemical methods with modified materials. The
reported electrochemical sensors for the determination of Experimental
endosulfan are molecular imprinted polymer-based sensor
[26], C-18 modified carbon paste electrode [27], Wall-jet Reagents and solutions
electrode and immunosensor based vertically aligned carbon
nanotubes for direct determination of endosulfan pesticide Chemicals such as nickel chloride, sodium dodecyl sulphate,
[20]. These reported chemically modified electrodes have sodium hydroxide, endosulfan, methyl parathion, carbofuran,
determined endosulfan with acceptable percent recover- KCl, NaCl, glucose, were purchased from Sigma Aldrich
ies but most of them lacks low limit of detection for the (Switzerland) and used throughout the experiments without

Scheme 1  Proposed possible

mechanism of endosulfan at
NiO/GCE

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NiO nanostructures based functional none-enzymatic electrochemical sensor for ultrasensitive… 2697

further purifications. Glassware utilized in the experiments dried at room temperature. After the proper modification,
were carefully rinsed with tap water and then washed with a uniform layer of NiO NPs formed at electrode’s surface
deionized water thoroughly then dried in oven at 100 Ċ for and then the modified electrode was labelled as NiO/GCE
20 min. A 0.1 mM stock solution of endosulfan was prepared throughout the electrochemical measurements.
in deionized water and was further diluted before employing
in electrochemical measurements. 0.1 M solution of sup-
porting electrolytes such as borate buffer, sodium hydroxide Results and discussion
and phosphate buffer with different pH were prepared in
deionized water. Characterization of NiO nanoparticles

Instruments To determine the phase purity and crystallinity, NiO NPs

were subjected to X-ray diffraction technique, which mani-
Different analytical tools were exploited for the characteri- fested that the prepared NPs exhibit remarkable crystal-
zation of prepared NiO NPs including X-ray Diffraction line nature and definite phase purity. The XRD patterns
(XRD-7000 Shimadzu-Scientific-instruments) and Field- shows that the fabricated NPs possess face-centred cubic
Emission Scanning Electron Microscopy (FESEM JSM- phase structure. The XRD patterns of NiO NPs are given in
7800F). For electrochemical determination of endosulfan, Fig. 1. The X-ray diffraction of patterns at 001, 002 and 022
electrochemical workstation (Auto-Lab CHI-760-USA) with confirm the successful synthesis of NiO, while the sharp-
three electrode system, Ag/AgCl, platinum wire, and glassy ness and high intensity of the peaks determines an excellent
carbon electrode were used as reference, counter and work- crystallinity and phase purity of NiO NPs. The average size
ing electrodes. of synthesized NiO NPs was also calculated as 22 nm by
using Debye–Sherer equation. The morphology of synthe-
Synthesis of NiO nanoparticles sized NPs was investigated by an advanced analytical tool
FESEM. As it has been discussed in a number of research
A simple, prolific and green synthesis of NiO NPs was car- articles by different scientists that NaOH is a strong base
ried out through aqueous chemical growth procedure. For and holds direct (OH) source to reduce the metal precur-
the effective preparation of NiO NPs, 0.1 M solution of sors. Thus, by utilizing NaOH as reducing agent to reduce
nickel chloride was carefully prepared in 100 mL beaker the nickel chloride precursor, a well-organized nano-seed
followed by the addition of 0.1 M solution of NaOH as like structure of NiO is obtained. Figure 2a shows low and
hydroxyl (OH) source. The solution was stirred for 20 min Fig. 2b manifested high resolution images of NiO NPs.
for complete homogenization, then carefully covered with Similarly, the elemental composition of prepared NPs was
aluminium foil and kept in an oven at 90 Ċ for 4 h. After- confirmed by Energy-Dispersive X-ray (EDX). The EDX
wards, the precipitates of nickel hydroxide Ni(OH)2 were spectra shows maximum percentage of nickel and oxygen
thoroughly washed several times with deionized water for noted to be 76.02 and 23.98 weight (%) correspondingly. No
the removal of remaining impurities and dried at room tem- additional element co-exists with the synthesized NPs as an
perature. To convert hydroxide phase into pure oxide phase, impurity. The EDX spectra of NiO nanoparticles is shown
Ni(OH)2 precipitates were kept in muffle furnace at 500 Ċ in Fig. 3. The overall characterization techniques evidenced
for 4 h. Finally, NiO NPs were fabricated and used for the
modification of electrode.

Deposition of NiO on glassy carbon electrode

The deposition of NiO NPs on GCE was carried out by fol-

lowing drop casting method. A 10 mg of synthesized NiO
NPs dissolved in 2.5 mL of deionized water and simultane-
ously 50 µL of nafion was added as binder between the NPs
and electrode surface then left for 20 min on sonication.
Before the deposition process, GCE was thoroughly polished
with 0.5 µm pore aluminium powder, washed with deion-
ized water and sonicated in ethanol for 20 min for complete
removal of any kind of dirt or impurities on electrode’s sur-
face. Afterwards, 5 µL of prepared solution of NiO NPs was
carefully deposited on the surface of GCE drop wise and Fig. 1  XRD spectra of NiO NPs

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2698 H. Bakhsh et al.

Fig. 2  FESEM a low and b high resolution images of NiO NPs

Fig. 3  EDX spectra of NiO

nanoparticles

the high crystallinity, uniform morphology and remarkable which manifests an excellent conductive nature of modified
phase purity of NiO NPs. electrode that could be suitable candidate for the electro-
chemical determination of endosulfan. Another, electro-
Electrochemical investigation of bare and modified chemical measurement for bare and modified electrode was
electrodes investigated via EIS. The impedance measurements deter-
mine Charge Transfer Resistance (Rct) for the analytes from
The electrochemical behaviour and conductive nature different electrochemical components. The EIS spectra as
of NiO modified and bare GCE was investigated through Nyquist-plot of modified and bare electrode with an equiva-
cyclic voltammetry (CV) and electrochemical impedance lent circuit are manifested in (Fig. 4b). The interfacial char-
spectroscopy (EIS) in 0.1 M KCl and [5 Mm ­K3Fe(CN)6 and acteristics of both modified and bare electrode were exam-
­K4Fe(CN)6] respectively. Figure 4a describes the CV redox ined via EIS under the following experimental condition;
peak current response of modified and bare electrodes in low frequency 1, high frequency up to 100,000 with initial
prepared electrolyte and it can be seen that redox response potential 1.5 V and quite time of 2 s. Rct from EIS mainly
of NiO/GCE is significantly enhanced than the bare one, rely upon the redox probe electron transfer kinetics at the

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NiO nanostructures based functional none-enzymatic electrochemical sensor for ultrasensitive… 2699

Fig. 4  a Redox peak current response of modified and bare electrodes. b EIS Nyquist-plot of bare and NiO/GCE under experimental conditions:
low frequency 1, high frequency up to 100,000 with initial potential 1.5 V and quite time of 2 s

surface of modified and bare electrodes, which is estimated

through the diameter of semicircle curve of EIS response
in Nyquist-plot. EIS study explains the conductive nature
and charge transfer resistance of electrodes with semicircle
harmonic curve. The EIS response in Nyquist-plot with nar-
rower semicircle curve faces low possible resistance, while
the broadness of curve explains the greater resistance faced
by electrode employed under EIS study. Herein, the broad-
ness of semicircle curve is monitored for bare electrode
which means bare electrode faces greater resistance with
the Rct value calculated as (8017 Ω) while the modified one
with narrower diameter exhibits excellent conductive nature
with low resistance and the Rct value was measured as (3678
Ω) respectively. From EIS results, the low possible resist-
Fig. 5  CV response of 15 µM of Endosulfan (a) NiO/GCE in analyte
ance and high conductivity of modified as compared to the
(b) bare electrode in analyte and c NiO/GCE in PBS electrolyte at pH
bare electrode is another evidence that the NiO NPs could 7 under the scan rate of 80 mV/s
be suitable aspirant for the electrochemical determination
of endosulfan.
AgCl. For better Ipa response, different supporting electro-
Electrochemical determination of endosulfan lytes were tested such as 0.1 M borate buffer (pH 8), phos-
phate buffer PBS (pH 7), Britton-Robinson buffer (pH 4) and
To investigate the electrocatalytic properties of NiO NPs sodium hydroxide (pH 12) respectively. Among all the men-
and anodic peak current (Ipa) response of bare and modi- tioned supporting electrolytes, a well resolved and enhanced
fied electrodes for endosulfan, CV response was monitored CV response for analyte was observed in PBS (pH 7), thus
for both modified and bare electrodes in 15 µM of endosul- PBS supporting electrolyte was optimized.
fan with 0.1 M phosphate buffer (pH 7) employed as sup-
porting electrolyte under the scan rate of 80 mV/s. Figure 5 Effect of pH
exhibited CV response of bare and modified electrodes, in
comparison of bare electrode, NiO/GCE showed improved To examine a better CV Ipa response, different pH of 0.1 M
response for endosulfan at very low concentration. The CV PBS supporting electrolyte was tested in 15 µM of endo-
response of analyte was examined at around 0.4 V vs Ag/ sulfan under the scan rate of 80 mV/s. For well resolved

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2700 H. Bakhsh et al.

and enhanced Ipa response, pH range was set from 5 to 9 electrode for analyte was examined at different scans from
with one-unit difference as shown in (Fig. 6). The current 10 to 100 mV/s and the enhanced Ipa response could be
response gradually increased from 5 to 6, while a maxi- seen by increasing the scans as shown in Fig. 7a. A linear
mum peak current response was observed at pH 7 then Ipa CV peak current response was observed that accounts for
response of analyte was seemed to be decreased as the pH uniform deposition of electrode with NiO NPs. The linear
raised to 9.0. A 0.1 M PBS pH 7 supporting electrolyte was regression equation with R ­ 2 0.99 represents the diffusion
optimized for the determination of endosulfan throughout control process for modified electrode which displayed in
the experiment. Fig. 7b. The diffusion-controlled behaviour can be well
defined by Randle-Sevcik equation and also confirmed
Effect of scan rate with reported literature [40–42]. According to the Ran-
dle-Sevcik, when the scan sweeps increase, the concentra-
In order to examine the smooth analysis of analyte via tion of ions from the electrolytic solutions rushes towards
electrochemical procedure, the effect of scan rate on NiO/ the electrode’s surface that usually cause pre-wave Ipa
GCE-Nafion for CV Ipa response of endosulfan was moni- response consequently decreases the peak current response
tored in 10 µM respectively. The CV response of modified of the analyte. Therefore, the good electrocatalyst restrain
this phenomenon and lead to increase the current linearly
as the scan rate is increased. In present study, the obtained
Ipa response is quite linear that exhibits that the process
is diffusion or adsorption controlled. The Randle-Sevcik
equation is described below.
√(
nFvD
)
ip = 0.4463 nFAC (1)
RT
where: ip is peak current response in amperes (A), “n” rep-
resents the electron transferred in redox reaction usually 1,
“F” is faraday constant C ­mol−1, “A” is electrode surface
area ­cm2, “C” is concentration in mol/cm3, “D” is diffusion
coefficient ­cm2/s, “ѵ” is scan rate V/s, “R” is the gas constant
in ­JK−1 ­mol−1, “T” is temperature in K.

Fig. 6  CV response of NiO/GCE for 15 µM endosulfan at different

pH values under the scan rate of 80 mV/s

Fig. 7  Effect of scan rate on NiO/GCE for 10 µM endosulfan a varied scans from 10 to 100 mV/s. b plot of scan rate with ­R2 = 0.993

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NiO nanostructures based functional none-enzymatic electrochemical sensor for ultrasensitive… 2701

Linear dynamic range and limit of detection However, we have developed a fluent determination process
for selective determination of endosulfan via NiO modified
Under the optimal conditions, endosulfan possess a strong GCE that enhanced the sensitivity of electrode by exhibiting
and well resolved oxidation peak current response, hence the lowest possible limit of detection for endosulfan and shown
linear range between the DPV Ipa response and the concen- exceptional stability and selectivity for long term use. The
tration of endosulfan was obtained over 0.05–25 µM. PDV comparison study of present work is shown in Table 1. All
Ipa response for NiO/GCE relative to the concentration the reported sensors have almost high LODs as compared to
of endosulfan are manifested in (Fig. 8a), while the linear the present work, only some have low LOD and those sen-
regression equation with ­(R2 = 0.9894) is shown in (Fig. 8b). sors are immunosensors which are very complex. Therefore,
The limit of detection of modified electrode for the deter- the present work manifests outstanding sensing capability
mination of endosulfan was found to be 0.17 nM, whereas, for the determination of endosulfan in vegetable samples.
the limit of quantification obtained as 0.51 nM respectively.
DPV response for the analyte linearly increased as the con- Interference study
centration raised up to 25 µM. Though, no signal fluctuation
or noise was examined during the sensitive determination The selectivity of the developed sensor was examined by the
of endosulfan at wide range of concentration. Our present addition of different interferants such as chlordane, eldrin,
work manifests an effective, sensitive and stable sensor for aldrin, methyl parathion and metal ions e.g. ­K+ and ­Na+
the selective determination of endosulfan. Nonetheless, dif- in 5 µM of endosulfan. The organic molecules, pesticides
ferent chemically modified electrodes have been reported and metal ions are added because of suspected possibility of
for the determination of endosulfan but faced certain bot- interference with analyte, that could lead toward the signal
tlenecks e.g. higher limit of detection and immunosensor fluctuation and can lessen the (Ipa) response of developed
based assembly, which limit their practises to some extent. sensor for the proposed analyte. The possible interference

Fig. 8  a Calibration plot of endosulfan. b plot of linear regression equation ­(R2 = 0.9894)

Table 1  Comparison of NiO/ Sensors Mode LOD (nM) Refs.

Nafion®/GCE with reported
electrochemical sensors for Molecular imprinted polymer-based sensor Potentiometric 200 [43]
determination of endosulfan
C-18 modified carbon paste electrode DPV 40 [27]
Wall-jet electrode and immunosensor based verti- SWV 0.02 ppb [20]
cally aligned CNT
CuO interface-based sensor DPV 8.30 [44]
NiO/GCE CV and DPV 0.17 Present work

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2702 H. Bakhsh et al.

Table 2  Effect of different interferants on (Ipa) response of Endosul- collected from Jamshoro, Sindh, Pakistan. The samples were
fan washed with deionized water for the removal of dust and
Added interferants Endo (5 µM) (n = 4) recov- RSD (%) other particulates. The washed samples were then ground in
ery (%) (n = 4) a blender in 20 mL of 0.1 M PBS buffer and centrifuged for
2 min for making homogenized suspension and left on con-
Chlordane 95.2 4.3
ventional filtration. Then the samples were subjected for the
Endrin 98.7 3.3
electrochemical measurements by adding 1 mL of filtered
Alderin 102.3 5.1
sample and 9 mL of 0.1 M PBS supporting electrolytes in
Methyl parathion 91.8 3.7
electrochemical cell of 10 mL capacity making the ratio of
Na+ 97.2 4.1
1/10. The accuracy of modified electrode was investigated
K+ 100.5 2.9
in water and vegetable samples followed by standard addi-
tion of prepared solution of endosulfan. The effect of matrix
and concentration was evaluated by spiking the real samples
with percent recoveries and relative standard deviation RSD with known concentration of endosulfan. The reproducibility
(%) were calculated and are shown in Table 2. The results of added concentration was monitored with three repetitive
show that the addition of certain foreign interferants in the cycles, which manifested satisfactory results with RSD less
given concentration of endosulfan didn’t show significant than 5%. While the percent recovery was observed as; lowest
effect on (Ipa) response for proposed sensor. The percent 87.3% and highest 103% for water and vegetables samples
recoveries were calculated in acceptable limits noted from which explains a well-defined efficiency/ applicability of
91.8 to 102.3% respectively. The selectivity of modified developed sensor for the proposed analyte. The %RSD and
electrode was investigated by calculating %RDS with (n = 4) percent recoveries of real samples are given in Table 3.
repetitive runs in given concentration of analytes and inter-
ferants. The RSD (%) was measured from lowest to high-
est relative standard deviation noted from 2.9 to 5.1, which Conclusion
implies that the given interferants didn’t show a significant
deviation from the analytes (Ipa) response, that witnessed In summary, we have developed a rapid, sensitive and selec-
the selectivity of developed sensor for endosulfan that could tive electrochemical sensor based on NiO NPs. The facile
be effectively used in different real samples. synthesis of NPs was carried out through aqueous chemi-
cal growth method and the prepared NPs were deposited on
Stability and reproducibility GCE to develop a rapid detection approach for the quantifi-
cation of endosulfan. Compared to the bare electrode, NiO/
The stability of NiO NPs based electrochemical sensor was GCE, revealed phenomenal electrocatalytic activity towards
examined by repeating the DPV (Ipa) response of 10 µM the oxidation of endosulfan due to the synergetic effect.
endosulfan solution at different times intervals over a time Under the optimized experimental conditions as, amplitude
period of 15 days. The RSD was found to be 3.1%, which 0.05 V, pulse width 0.045 s, and pH 7, the modified elec-
manifested an exceptional long-term stability of modified trode showed improved sensitivity for the determination of
electrode towards the proposed analyte. Whereas, for repro- endosulfan under the wide linear dynamic range from 0.05
ducibility measurements, the intra and inter day study was to 25 µM with the limit of detection 0.17 nM. The proposed
performed for the developed sensor. The DPV (Ipa) response promising modified electrode could be an effective sensing
of modified electrode was recorded repeatedly four times in probe for simple and sensitive determination of endosulfan
a day for three consecutive days at different concentrations in different vegetable samples and can be utilized in envi-
of endosulfan employed as 10, 15, and 20 µM respectively. ronmental monitoring.
The maximum variation in (Ipa) response of analyte men-
tioned in RSD (%), which was calculated to be 3.8%, that
explains an excellent reproducibility of NiO NPs based sen- Table 3  Detection of Endosulfan in vegetable samples
sor for the determination of endosulfan. Samples Added (µM) Found (µM) RSD (%) Recovery (%)

Tomato 0.5 0.47 2.83 94

Analytical applicability
1 0.91 3.51 91
1.5 1.31 3.22 87.3
To explore the selectivity and applicability of developed
Spinach 0.5 0.49 4.1 98
sensor for the determination of endosulfan in different real
1 1.03 2.98 103
samples, the developed sensor was exploited in vegetable
1.5 1.50 2.53 100.2
samples. The vegetable samples of spinach and tomato were

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NiO nanostructures based functional none-enzymatic electrochemical sensor for ultrasensitive… 2703

Acknowledgements The authors are highly thankful to the Higher substrates for direct detection of the pesticide endosulfan in
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