Microchemical Journal 145 (2019) 756–761

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

High performance cypermethrin pesticide detection using anatase TiO2- T

carbon paste nanocomposites electrode
Muhammad Nurdina, , Maulidiyah Maulidiyaha, La Ode Agus Salima,
⁎

Muhammad Zakir Muzakkara, Akrajas Ali Umarb,

⁎

a
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Halu Oleo, Kendari 93232, Southeast Sulawesi, Indonesia
b
Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

ARTICLE INFO ABSTRACT

Keywords: The role of anatase TiO2 in the performance of carbon paste electrodes (CPE) electrochemical sensors for de-
Anatase TiO2 tection of cypermethrin pesticide has been investigated. It was found that the anatase TiO2-CPE nanocomposites
Carbon paste electrode exhibits excellent sensitivity towards the cypermethrin and its sensing sensitivity increases with the
Cypermethrin increasing of anatase TiO2 concentration and optimum at a concentration of 2 w/w (CPE is ~3 w/w). The
Voltammetric
detection limit of the nanoelectrode can be down to the level of ~ 0.1 ppm, which is below the maximum
Chemical sensor
residual limits of cypermethrin in the environment (~ 0.5 ppm) and is in the allowed limit for food products
(~0.05 to 0.2 ppm). The nanoelectrode is also excellent in the chemical stability with a performance decreasing
(%RSD) is only ~0.37% for 11 times repeated measurement. The enhancement of the electron transfer rate in the
present of anatase TiO2 in the CPE matrix as the result of excellent physico-chemical properties of anatase TiO2 is
considered as the key reason for the enhanced performance. The anatase TiO2-CPE system should find potential
application in cypermethrin pesticide monitoring in environment and agricultural products control.

1. Introduction
In the effort of eradicating pests in order to increasing the produc-
tion of agricultural crops, spraying pesticides onto the crops have long
been practiced by the farmers and even it is sadly reported that their
use continues to increase over the years [1,2]. This practice certainly
causes a bad impact on environment and creates pollution not only to
the agricultural product themselves but also to water resources [3,4].
Recently, it is reported that thousands of people each year suffered from
chronic diseases generated from consumption of food products that
have been contaminated by the pesticide [5,6]. Large cases of causal-
ities have also been reported as the result of long-time exposure to
pesticide-contaminated foods and drinks. Owing to the insufficient law-
enforcement by the authority in this issue, the use of pesticide in
agriculture is continuously increasing. Therefore, it is needed a con-
tinuous effort to develop a device that can detect the existence of
pesticide in the food products so that preventive measures can be taken
so that foods and drinks products with pesticide can be avoided. Thus,
health risk issues can be reduced or even eliminated.
Cypermethrin with IUPAC name of Cyano - (3-phenoxyphenyl) methyl
3- (using 2,2-dichloroethenyl) -2,2- dimethylcyclopropanecarboxylate is
amongst widely used pesticide in fruits and vegetables. This chemical is
a class of pyrethroid insecticides that has a molecular formula and
molecular weight of C22H19Cl2NO3 and 416.30, respectively [7,8].
Cypermethrin is a toxic chemical and has been recognized to attack
human's nervous system, suppress the immune system, inhibits the
formation of antibodies against the disease, and cause cancer [9,10].
About approximately 140 tons of cypermethrin per year are used on
fruits and vegetable and almost 110 tons per year are for indoor pest
control. Therefore, early detection of this toxic compound in foods and
drinks is highly demanded.
Generally, there have been a wide range of high-performance
methods that are employed in the detection of chemical substances or
pesticides in the liquid media, such as membrane sensor [11–15], sur-
face-enhanced Raman scattering [16], potentiometry [17], gas chro-
matography [18], high-performance liquid chromatography (HPLC)
[19] and fluorescent chemical sensor [20,21]. However, in the detec-
tion of cypermethrin trace in the environment, only some of them have
been applied, worked very well and have demonstrated a high sensi-
tivity and selectivity properties. They include particularly optical
spectroscopy [2], HPLC [22,23], gas chromatography/mass spectro-
scopy (GC/MS) [24,25], potentiometric or conductometric [15,26], and

⁎
Corresponding authors.
E-mail addresses: mnurdin06@yahoo.com (M. Nurdin), akrajas@ukm.edu.my (A.A. Umar).

https://doi.org/10.1016/j.microc.2018.11.050
Received 10 September 2018; Received in revised form 26 November 2018; Accepted 27 November 2018
Available online 28 November 2018
0026-265X/ © 2018 Published by Elsevier B.V.
M. Nurdin et al.
biosensor [27–31]. Notwithstanding, despites excellent performance
exhibited by the methods in this application, owing to the complexity of
the approaches and the issues related to the cost of the methods, the use
of some of them are not feasible. Nonetheless, amongst the above
methods, the voltammetry [17,32], particularly using mercury and
glassy carbon as the working electrode, has been reported to have a
better performance in detecting cypermethrin [33–35]. In addition, this
approach is assumed to be potential for a high sensitivity and se-
lectivity, fast response and low-cost cypermethrin detection. Further-
more, owing to its simple instrument design, this method provides a
high-flexibility for used in field measurements [36–40].
Carbon paste electrode has been widely used as potential working
electrode in pesticides detection that ranges from phenoxybenzyl [41]
to chlorpyrifos [42], tricholoro pyridinol [43], dicofol [44], diazinon
[45], etc. CPE is considered as a special group of heterogeneous carbon
electrode that has so far demonstrated a high-performance in most of
applications due to its high-conductivity and unique renewable surface
for electron exchange [46]. Due to the increasing demand of CPE per-
formance for sensitive detection of toxic compounds in environment
and foods and drinks [30,42,47–49], attempts to enhance the de-
tectivity of CPE electrode should be continuously demonstrated. In this
work, we report the investigation of the applicability of anatase TiO2-
CPE electrode and the effect of anatase TiO2 incorporation into the CPE
matrix in a voltammetric detection of cypermethrin. To our best
knowledge, no report on the use of anatase TiO2-carbon paste nano-
composites as an alternative electrode for cypermethrin detection is
available so far. Polymorph of anatase TiO2 has been well-known as
catalytically active materials due to its excellent surface physico-
chemistry properties and high-chemical stability [50–56]. In-
corporating the anatase TiO2 into the CPE matrix electrode is expected
to further augment the physico-chemistry of the electrode for a high-
sensitive detection of cypermethrin pesticide. Here, we discover that
the sensitivity of CPE electrode can be multiply enhanced, judging from
the cathodic current improvement, when the anatase TiO2 nanos-
tructure added into the CPE. In the typical procedure, the optimum
sample can detect the existence of cypermethrin in a solution sample as
low as 0.1 ppm, which is much lower compared to maximum residual
limit (approximately 0.5 ppm) of cypermethrin reported so far. Ac-
cording to the electroactive surface analysis infers that this dramatically
high improvement is assumed as the enhancement of the surface phy-
sico-chemistry of the electrode upon anatase TiO2 incorporation as the
result of highly active ligand to metal charge transfer in anatase TiO2
[57]. The mechanism for the performance enhancement of anatase
TiO2-CPE nanocomposites electrode will be discussed.
2. Experimental
2.1. Anatase TiO2-CPE nanocomposite electrode preparation and
characterizations
Prior to preparing the anatase TiO2-CPE nanocomposites, the CPE
was firstly prepared by mixing graphite powder with paraffin oil with
graphite to paraffin oil ratio of 7:3 (w/w). The mixture was then
blended using an electric mixer for 30 min at 80 °C to obtain a homo-
genous CPE system. Meanwhile, at the same time, the anatase TiO2 was
prepared by annealing approximately 1 g of Degussa P25 at 500 °C for
3 h in air. After that, the sample was kept under a controlled ambient
prior to the anatase TiO2-CPE nanocomposites preparation.
Finally, the anatase TiO2-CPE nanocomposite was prepared by simply
mixing the annealed Degussa P25 into the pre-prepared CPE, i.e. graphite
powder in paraffin oil (d = 0.88 g cm−3). In order to obtaining the effect
of anatase TiO2 addition to the CPE matrix, five concentrations of TiO2, i.e.
2 to 5 w/w, were used. All the chemicals were purchased from Aldrich
(USA) and used directly without any purification process.
The morphology of the nanocomposites was examined using a Field-
Emission Scanning Electron Microscopy JEOL-JSM-6510LV. The
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Microchemical Journal 145 (2019) 756–761
chemical structure of the nanocomposite was evaluated via a Fourier
Transform Infrared spectroscopy using a Shimadzu IR Affinity-1S
system. Meanwhile, the phase and crystallinity properties were char-
acterized via X-ray diffraction spectroscopy (XRD) using Philips X-ray
diffraction spectrometer with a CuKα irradiation (λ = 0.154 nm) and
scan rate as low as 2° min−1.
2.2. Cypermethrin detection
Prior to the detection of cypermethrin, anatase TiO2-CPE nano-
composite electrode was fabricated. In typical procedure, the nano-
composites electrode was prepared by simply inserting the paste into a
3 mm diameter glass-tube and then mechanically compressed for a
compact electrode structure [36,50]. A cooper wire was then used as
metallic contact for voltammetric applications.
Voltammetric detection of cypermethrin was carried out using a
DY2100B potentiostat with three electrode system where nanocompo-
sites function as the working electrode. Meanwhile, a platinum wire
and Ag/AgCl in 3.0 M KCl were used as the counter electrode and re-
ference electrode, respectively. For the measurement, the cypermethrin
was dissolved in supporting electrolyte of buffer citrate (pH 5) and so-
dium nitrate. Four solutions were prepared in this study starting from
0.1 to 0.3, 0.5 and 1.0 ppm to evaluate the sensitivity of the nano-
composite electrode system during the voltammetric detection of cy-
permethrin. Cypermethrin standard was used as test solution. Cyclic
voltammetry and differential pulse voltammetry modes were used in
this study. Voltammetric analysis in potassium ferricyanide (Sigma-
Aldrich 99%) was also performed for examining basic electrochemistry
properties of the nanocomposite electrode. All the solutions were pre-
pared using a doubly distilled water.
3. Results and discussion
3.1. Characterization of anatase TiO2-CPE nanocomposites
The nanocomposites of anatase TiO2-CPE has been successfully
prepared in this study. In order to verifying the phase purity of anatase
TiO2 obtained from annealed Degussa P25, prior to preparing the na-
nocomposite, we carried out XRD analysis on the sample. The result is
shown in Fig. 1A. As the Fig. 1A reveals, there are at least 9 peaks
observed in the spectrum, namely at 2θ = 25°, 38°, 48°, 52°, 54°, 63°,
69°, 70°, and 76°. These diffraction peaks are in good agreement with
the standard diffraction peak for anatase TiO2 (JCPDS file no. 21-1272)
with peaks can be associated with (101), (004), (200), (105) (211),
(204) and (215) Bragg planes, respectively [53]. No peaks related to
rutile and brookite phases are observed in the spectrum, confirming the
phase purity of the anatase TiO2 sample.
We then prepared the nanocomposites of anatase TiO2-CPE and
evaluate its microscopic structure by field-emission electron micro-
scopy analysis. The result is shown in Fig. 1B. As can be seen from the
Fig. 1B, the anatase TiO2 nanoparticles seem to be effectively in-
corporated into the CPE matrix. This is indicated by the presence of
small particulates system that is homogenuously distributed in the CPE
matrix, shown as bright particle spots. The incorporation of the anatase
TiO2 into the CPE matrix also decreases the porosity of the sample,
which is in stark contrast to the microstructure of the pristine CPE that
is characterized with a large porous structure (see Fig. 1C). This com-
positing process certainly produces a compact matrix that may in turn
enhance the carrier mobility in the material for improved electrical and
electrochemical properties of the samples [58–62]. Thus, high vol-
tammetric performance is expected from the nancomposites sample.
In order to acquiring the nature of chemical process during the
nanocomposites formation, including the development of chemical
bonding or coordination, we carried a Fourier Transformed Infra-Red
(FTIR) spectroscopy on the sample. The result is presented in Fig. 2. On
the basis of the FTR results, it is understood that the addition of anatase
M. Nurdin et al.
Fig. 1. (A) XRD spectrum of anatase TiO2 obtained from annealed Degussa P25.
B and C are the FESEM image of CPE and anatase TiO2-CPE nanocomposites
matrices, respectively. Inset in B and C are their corresponding high-resolution
image.
Fig. 2. FTIR spectra of pristine CPE (lower curve) and anatase TiO2-CPE na-
nocomposites (upper curve).
TiO2 into the CE matrix does not involve the formation of bonds be-
tween carbon paste and TiO2 but they simply mixed forming a homo-
geneously and compact nanocomposites matrix. This is judged by the
absence of shift in the CPE's FTIR peaks upon being modified by the
anatase TiO2. For example, absorption band at wave number of
1458.18 cm−1, i.e. for CeC vibration, and 2850.79 cm−1 and
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Microchemical Journal 145 (2019) 756–761
Fig. 3. Cyclic Voltammogram of pristine CPE (a) and anatase TiO2-CPE nano-
composites with different anatase TiO2 concentration, i.e. 2 (b), 3 (c), 4 (d) and
5 w/w (e) in a 0.1 M K3[Fe(CN)6] solution. Scan rate is 0.1 V/s.
2920.09 cm−1, both for CeH vibration, are unchanged with the pre-
sence of anatase TiO2 in the CPE matrix. Nevertheless, the specific
absorption peaks for anatase TiO2 are observed at wave number of
1699.29 cm−1 and 669.30 cm−1, which are attributed to the TieO vi-
bration. Therefore, the absence of new chemical coordination during
the nanocompositing process may preserve the intrinsic properties of
individual element so that any performance modification from this
process could later be directly related to the extent effect of catalytic
properties of the anatase TiO2 in this nanocomposite, enhancing the
surface reaction or charge transfer as well as carrier mobility.
3.2. Voltammetric detection of cypermethrin
We then prepared the electrode system utilizing the anatase TiO2-
CPE nanocomposites and applied them in a voltammetric detection of
cypermethrin pesticide. Fig. 3 shows the typical cyclic voltammetry
spectra of nanocomposite with different anatase TiO2 concentration in
0.1 M K3[Fe(CN)6] solution with 0.1 M NaNO3 as a supporting electro-
lyte. The scan rate is 0.1 V/s. As the Fig. 3 reveals, the electron transfer
on pristine CPE is relative slow and quasi-reversible with current den-
sity as low as Ip = 1.78 × 10−5 A appeared at a potential of
Ep = 0.25 V (see Fig. 3). Interestingly, the electron transfer improves
significantly upon the addition of anatase TiO2 into the CPE matrix. The
performance increases with the increasing of anatase TiO2 concentra-
tion and optimum on the sample with anatase concentration of 2 w/w.
On this optimum condition, the sample demonstrates an excellent
electrochemical response with a high and sharp current peak. On the
basis of the voltammogram results, it can be remarked that the electron
transfer process is extremely fast as indicated by a remarkably small
difference in the reduction-oxidation potential, i.e. 0.06 V. Such dra-
matic increase in the rate of electron transfer could be attributed to the
excellent catalytic and electrical conductivity properties of anatase
TiO2. As judged from the FESEM image result as shown in Fig. 1B, high-
current density could also be related to the high compactness of the
nanocomposites, facilitating facile electron transport in the materials
[63]. Nevertheless, the electrochemical performance does not further
increase when the content of anatase TiO2 is continued to be aug-
mented in the nanocomposites. One main reason for this phenomenon
is the loss of nanocomposite matrix homogeneity with the increasing of
anatase TiO2 content above the optimum condition. This certainly
brings about the nanocomposite becomes less-compact and probably
contain high-trap density, limiting the charge transport in the nano-
composites. We calculate the electroactive surface area of the nano-
composite electrode by using Randles-Sevcik equation [64], namely
Ip = (2.69 × 105)n3/2AD1/2v1/2C where n, D, A, υ and C are number of
electrons, diffusion coefficient of electrolyte K3[Fe(CN)6]
M. Nurdin et al. Microchemical Journal 145 (2019) 756–761

Fig. 4. Cyclic voltammogram of 0.1 M K3[Fe(CN)6] solution in the presence of

pesticide cypermethrin solution 1 ppm on optimum nanocomposites (CPE to
anatase TiO2 ratio of 3:2) electrode (a) and nanocomposite sample with ratio of
3:3 samples for comparison. Scan rate is 0.1 V/s. Inset shows the mechanism of
cypermethrin reduction.

(7.6 × 10−6 cm2 s−1), electroactive surface area of the electrode, scan
rate, and electrolyte's concentration, respectively. By interpolating a
curve of peak current versus the scan rate, the electroactive surface area
can be determined, i.e. the slope of the curve. It was found that the
electroactive surface area of optimum nanocomposites electrode is high
as 0.26 cm2. Nevertheless, this value is lower than the pristine CPE
electroactive surface area, namely 0.39 cm2, which is consistent with
the porous nature of the pristine CPE matrix. However, it is greater than
the reported results, namely 0.15 cm2, enabling facile electron transfer
onto the nanocomposites surface for high electrochemical performance.
Fig. 4 shows voltammetric response of nanocomposites electrode of
optimum condition when cypermethrin of concentration as low as
1 ppm added into the supporting electrolyte. As the Fig. 4 demonstrates,
the cypermethrin has been effectively reduced on the surface of nano-
composites electrode with a reduction potential (Ep) value of 0.48 V.
For comparison, the reduction potential in supporting electrolytes only
is 0.23 V (see Fig. 3). Under this condition, the double bonded C atom
that contains 2 Cl atoms in the cypermethrin molecule will be reduced
on the surface of the nanocomposites electrode to a single bond C atom.
The mechanism for cypermethrin reduction is shown in inset of Fig. 4.
It also can be seen from the Fig. 4 that, although at a relatively low
cypermethrin concentration, the current density is relatively high, re-
flecting the reduction of cypermethrin is pretty facile involving active
electron transfer between the nanocomposites electrode and cypermethrin.
Therefore, we thought that the voltammetric detection limit of cyperme-
Fig. 5. (A) Plot of reduction current peak versus pH of citrate buffer solution
thrin should be much lower than 1 ppm. Thus, we proceed to evaluate the
containing 1 ppm cypermethrin. (B) Cyclic voltammetry of cypermethrin under
limit of the voltammetric detection of our nanocomposites electrode. a different scan rate and its corresponding plot of peak current versus scan rate.
Nevertheless, prior to continuing the detection limit evaluation, we
examine the role of reaction pH on the redox activity of nanocomposites
electrode in the presence of 1 ppm cypermethrin. For this purpose, ci- voltammetry analysis under a different scan rate is carried out. The
trate buffer was used as the supporting electrolytes and pH range be- result for cyclic voltammogram of cypermethrin recorded using dif-
tween 3 and 6 was applied. The results are shown in Fig. 5A. As can be ferent scan rate are shown in Fig. 5B and the plot of current peaks
seen from the Fig. 5A, at the reducing potential of cypermethrin, the versus scan rate are shown in Fig. 5C. As can be seen from both Fig. 5B
current increases following an exponential decay function with the in- and C, the reduction current increases with the increasing of the scan
creasing of the reaction pH. According the current growth function, it rate. Interpolating the graph peaks current against the scan rate reveals
can be predicted that the current seems not to effectively increase when that the adsorption of cypemethrin onto the nanocomposites electrode
the pH is increased above 6 [47]. Therefore, the voltammetric response follows a pseudo-second order kinetics where in this case the reaction is
at solution pH above 6 is not examined. Thus, for the rest of the ana- governed by the chemisorption process with a diffusion-controlled
lysis, we used the solution pH that facilitates a fast electron transfer process as high-current response on the increasing of the scan rate [65].
rate. On the basis of the current growth function plot, the solution pH of Finally, a differential pulse voltammetry (DPV) approach was used
5 should be the best condition to provide a rapid electron transfer. to investigate the voltammetric response of the nanocomposites elec-
Thus, the ultimate voltammetric detectivity limit on the presence of trode on the cypermethrin presence below 1 ppm, i.e. approximately
cypermethrin could be obtained. 0.1 to 1 ppm, to observe the electrode detection limit. The result is
Next, in order to gaining an understanding on the cypermethrin shown in Fig. 6A. As the figure shows, the current response change was
adsorption rate on the surface of nanocomposites electrode, cyclic found to be linear with the variation of cypermethrin concentration.

759
M. Nurdin et al.
Fig. 6. (A) Plot of peak current versus cypermethrin concentration. (B)
Electrochemistry stability profile showing a histogram of peak current density
during a repeated measurement.
Regression analysis on the result found that the current change upon
the variation of cypermethrin follow a relation of y = 8.5x − 0.02 with
correlation coefficient R2 as high as 0.98. From this relation, the de-
tection limit (LoD) value (given by the relation of LoD = 3σ/m, where σ
and m are residual standard deviation of measurement and the slope of
curve in the regression analysis, i.e. ca. 8.5, respectively) of this mea-
surement can be deduced to be as low as 0.0978 ppm. This value is
much lower than the reported maximum residue limits (MRLs) of cy-
permethrin in agricultural environment, which is at the level of 0.5 ppm
and is in the range of MRLs cypermethrin residue in foods products,
which is at 0.05–0.2 ppm [25].
Besides high-sensitivity property, nanocomposites electrode also
demonstrates high-chemical stability. In typical procedure, the elec-
trode shows invisible performance distortion upon being used in re-
peating measurement up to 11 times. Calculation on the voltammetric
response of the nanocomposites electrode found the change in the
performance (%RSD) up to 11 times is only as low as 0.37%. Judging
from the %RSD value for 11 times measurement, it can be worth to
predict that the nanocomposites should be still highly applicable for
used in 100 times with expected %RSD is only as low as approximately
3.5%. Differential pulse voltammetry was used during the stability
performance test. The result is shown in Fig. 6B. On the basis of this
result, it can be worth remarking that the nanocomposites electrode of
antase TiO2-CPE should find a potential use in cypermethrin pesticide
monitoring and control applications.
We understood that the differential pulse voltammetry (DPV) may
give information on specific different concentration of electroactive
species in the reaction. However, in our current study, we found that
the cyclic voltammetry is more sensitive and sufficient to predict the
concentration of cypermethrin, based on the redox current so that the
DPV analysis is not required.
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Microchemical Journal 145 (2019) 756–761
4. Conclusions
The performance of nanocomposites of anatase TiO2-carbon paste
(CPE) electrode in voltammetric detection of cypermethrin pesticide
has been investigated. It was found that the nanocomposite electrode
can effectively detect the presence of cypermethrin in the solution
voltammetric detection sensitivity increase with the increasing of ana-
tase TiO2 content and optimum at concentration of 2 w/w. Utilizing the
optimum condition, the nanocomposites electrode can detect the pre-
sence of as low as 0.1 ppm cypermethrin in the solution, which is much
lower than maximum residual limit (MRLs) of cypermethrin in en-
vironment, i.e. 0.5 ppm, and within the range of MRLs cypermethrin
residue in food products, i.e. 0.05 to 0.2 ppm. The nanocomposites
electrode system also demonstrates a high-chemical stability with per-
formance degradation in repeating measurement (%RSD) is only as low
as 0.37%. Based on this RSD value, the nanocomposites electrode
should be applicable for use up to 100 times with performance de-
creasing is only as low as 3.5%. The high performance in nanocompo-
site electrode is due to rapid electron transfer on the surface of elec-
trode due to the compact nature of structure and high-conductivity as
well as highly active physico-chemical process as the result of anatase
TiO2 incorporation into the CPE matrix in which the surface reaction is
governed by a pseudo-second order kinetic with a diffusion control.
FTIR analysis result reveals that the incorporation of anatase TiO2 into
the CPE matrix does not involve any chemical coordination, preserving
the highly active surface chemistry of the anatase TiO2 for high-per-
formance voltammetric detection of cypemethrin. The present system
should find a potential application in cypermethrin pesticide mon-
itoring and control in environment and agricultural products.
Acknowledgment
We acknowledge the financial support from the DRPM-Ministry of
Research, Technology and Higher Education of the Republic of
Indonesia under the research grant no 056/SP2H/LT/DRPM/2018 and
World Class Professor (WCP) visiting scientist program Skema B 2018
award no 123.47/D2.3/KP/2018.
References
[1] Z. Arham, L.O. Asmin, M. Nurdin Rosmini, Heavy metal content of cocoa plantation
soil in East Kolaka, Indonesia, Orient. J. Chem. 33 (2017) 1164–1170.
[2] E. Janghel, J. Rai, M. Rai, V. Gupta, A new sensitive spectrophotometric determi-
nation of cypermethrin insecticide in environmental and biological samples, J. Braz.
Chem. Soc. 18 (2007) 590–594.
[3] M. Maulidiyah, D. Wibowo, H. Herlin, M. Andarini, R. Ruslan, M. Nurdin, Plasmon
enhanced by Ag-doped S-TiO2/Ti electrode as highly effective photoelectrocatalyst
for degradation of methylene blue, Asian J. Chem. 29 (2017) 2504–2508.
[4] M. Maulidiyah, T. Azis, A.T. Nurwahidah, D. Wibowo, M. Nurdin,
Photoelectrocatalyst of Fe co-doped N-TiO2/Ti nanotubes: pesticide degradation of
thiamethoxam under UV–visible lights, Environ. Nanotechnol. Monit. Manag. 8
(2017) 103–111.
[5] Z. Li, A. Jennings, Worldwide regulations of standard values of pesticides for human
health risk control: a review, Int. J. Environ. Res. Public Health 14 (2017) 826.
[6] R.P. Schwarzenbach, T. Egli, T.B. Hofstetter, U. Von Gunten, B. Wehrli, Global
water pollution and human health, Annu. Rev. Environ. Resour. 35 (2010)
109–136.
[7] Reregistration Eligibility Decision for Cypermethrin, Environmental Protection
Agency (EPA), 2006, pp. 1–117.
[8] S. Idris, S. Ambali, J. Ayo, Cytotoxicity of chlopyrifos and cypermethrin: the ame-
liorative effects of antioxidants, Afr. J. Biotechnol. 11 (2012) 16461–16467.
[9] H.C. Oudou, R.M. Alonso, R.M. Jiménez, Voltammetric study of the synthetic pyr-
ethroid insecticides cypermethrin and deltamethrin and their determination in
environmental samples, Electroanalysis 13 (2001) 72–77.
[10] H. Jin-xia, L. Yan-fang, L. Jing, P. Chen, H. Zhen, D. Hong-yan, X. Li-chun, Toxic
effects of cypermethrin on the male reproductive system: with emphasis on the
androgen receptor, J. Appl. Toxicol. 33 (2013) 576–585.
[11] V.K. Gupta, L. Singh, R. Singh, N. Upadhyay, S. Kaur, B. Sethi, A novel copper (II)
selective sensor based on dimethyl 4, 4′(o-phenylene) bis (3-thioallophanate) in
PVC matrix, J. Mol. Liq. 174 (2012) 11–16.
[12] S.K. Srivastava, V.K. Gupta, S. Jain, PVC-based 2, 2, 2-cryptand sensor for zinc ions,
Anal. Chem. 68 (1996) 1272–1275.
[13] S.K. Srivastava, V.K. Gupta, M.K. Dwivedi, S. Jain, Caesium PVC–crown (dibenzo-
M. Nurdin et al.
24-crown-8) based membrane sensor, Analytical Proceedings including Analytical
Communications, Royal Society of Chemistry, 1995, pp. 21–23.
[14] K. Vinod, Determination of lead using a poly (vinyl chloride)-based crown ether
membrane, Analyst 120 (1995) 495–498.
[15] V.K. Gupta, A. Nayak, S. Agarwal, B. Singhal, Recent advances on potentiometric
membrane sensors for pharmaceutical analysis, Comb. Chem. High Throughput
Screen. 14 (2011) 284–302.
[16] N.A. Bakar, M.M. Salleh, A.A. Umar, J.G. Shapter, Design and measurement tech-
nique of surface-enhanced Raman scattering for detection of bisphenol A, Adv. Nat.
Sci. Nanosci. Nanotechnol. 8 (2017) 025008.
[17] V.K. Gupta, B. Sethi, R. Sharma, S. Agarwal, A. Bharti, Mercury selective po-
tentiometric sensor based on low rim functionalized thiacalix [4]-arene as a ca-
tionic receptor, J. Mol. Liq. 177 (2013) 114–118.
[18] T.A. Albanis, D.G. Hela, Multi-residue pesticide analysis in environmental water
samples using solid-phase extraction discs and gas chromatography with flame
thermionic and mass-selective detection, J. Chromatogr. A 707 (1995) 283–292.
[19] E. Thurman, I. Ferrer, D. Barceló, Choosing between atmospheric pressure chemical
ionization and electrospray ionization interfaces for the HPLC/MS analysis of pes-
ticides, Anal. Chem. 73 (2001) 5441–5449.
[20] V.K. Gupta, A.K. Singh, L.K. Kumawat, Thiazole Schiff base turn-on fluorescent
chemosensor for Al3+ ion, Sensors Actuators B Chem. 195 (2014) 98–108.
[21] N. Abu Bakar, A. Ali Umar, M. Mat Salleh, M. Yahaya, B. Yeop Majlis, Highly red
luminescence properties from ternary ZnCdTe quantum dots, Proceedings of SPIE -
The International Society for Optical Engineering, 2009.
[22] S. Liu, K. Yao, D. Jia, N. Zhao, W. Lai, H. Yuan, A pretreatment method for HPLC
analysis of cypermethrin in microbial degradation systems, J. Chromatogr. Sci. 50
(2012) 469–476.
[23] J.-J. Zhang, L.-G. Zang, J.-E. Zhang, G.-W. Cui, B. Tang, X.-Y. Li, L. Zhou,
Determination of cypermethrin residues in Gingko biloba leaves by high perfor-
mance liquid chromatography, Bull. Chem. Soc. Ethiop. 23 (2009) 97–100.
[24] G.C. Mattern, C.H. Liu, J.B. Louis, J.D. Rosen, GC/MS and LC/MS determination of
20 pesticides for which dietary oncogenic risk has been estimated, J. Agric. Food
Chem. 39 (1991) 700–704.
[25] A. Niewiadowska, T. Kiljanek, S. Semeniuk, J. Zmudzki, Determination of pyre-
throid residues in meat by gas chromatography with electron capture detection,
Bull. Vet. Inst. Pulawy 54 (2010) 595–599.
[26] A. Wong, T.A. Silva, F.R. Caetano, M.F. Bergamini, L.H. Marcolino-Junior,
O. Fatibello-Filho, B.C. Janegtiz, An overview of pesticide monitoring at environ-
mental samples using carbon nanotubes-based electrochemical sensors, J. Carbon
Res. 3 (2017) 8.
[27] T. McGrath, C. Elliott, T. Fodey, Biosensors for the analysis of microbiological and
chemical contaminants in food, Anal. Bioanal. Chem. 403 (2012) 75–92.
[28] A. Asfaram, M. Ghaedi, S. Agarwal, I. Tyagi, V.K. Gupta, Removal of basic dye
Auramine-O by ZnS:Cu nanoparticles loaded on activated carbon: optimization of
parameters using response surface methodology with central composite design, RSC
Adv. 5 (2015) 18438–18450.
[29] V.K. Gupta, M. Ganjali, P. Norouzi, H. Khani, A. Nayak, S. Agarwal, Electrochemical
analysis of some toxic metals by ion–selective electrodes, Crit. Rev. Anal. Chem. 41
(2011) 282–313.
[30] H. Karimi-Maleh, F. Tahernejad-Javazmi, N. Atar, M.L.t. Yola, V.K. Gupta,
A.A. Ensafi, A novel DNA biosensor based on a pencil graphite electrode modified
with polypyrrole/functionalized multiwalled carbon nanotubes for determination
of 6-mercaptopurine anticancer drug, Ind. Eng. Chem. Res. 54 (2015) 3634–3639.
[31] M.L. Yola, V.K. Gupta, T. Eren, A.E. Şen, N. Atar, A novel electro analytical nano-
sensor based on graphene oxide/silver nanoparticles for simultaneous determina-
tion of quercetin and morin, Electrochim. Acta 120 (2014) 204–211.
[32] V.K. Gupta, H. Karimi-Maleh, R. Sadegh, Simultaneous determination of hydro-
xylamine, phenol and sulfite in water and waste water samples using a voltam-
metric nanosensor, Int. J. Electrochem. Sci. 10 (2015) 303–316.
[33] M. Maulidiyah, D.S. Tribawono, D. Wibowo, M. Nurdin, Electrochemical profile
degradation of amino acid by flow system using TiO2/Ti nanotubes electrode, Anal.
Bioanal. Electrochem. 8 (2016) 761–776.
[34] N. Dali, A.W. Wahab, M. Firdaus, M. Nurdin, Synthesis of Hexa (p-tert-butyl) hexa
(carboxylic acid) calix[6]arene from Hexa (p-tert-butyl) hexa (ethyl ester) calix[6]
arene, Int. J. ChemTech Res. 9 (2016) 486–490.
[35] T. Zhang, Q. Lang, L. Zeng, T. Li, M. Wei, A. Liu, Substituent effect on the oxidation
peak potentials of phenol derivatives at ordered mesoporous carbons modified
electrode and its application in determination of acidity coefficients (pKa),
Electrochim. Acta 115 (2014) 283–289.
[36] M. Nurdin, A. Zaeni, E.T. Rammang, M. Maulidiyah, D. Wibowo, Reactor design
development of chemical oxygen demand flow system and its application, Anal.
Bioanal. Electrochem. 9 (2017).
[37] R. Ruslan, M. M, M. Nurdin, A. Wahab, Characterization and photocurrent response
of Mn–N–TiO2/Ti electrode: approach for chemical oxygen demand (COD) sensor,
Int. J. Appl. Chem. 12 (2016) 399–409.
[38] M. Maulidiyah, N. M, E. Widianingsih, T. Azis, D. Wibowo, Preparation of visible
photocatalyst N-TiO2 and its activity on congo red degradation, J. Eng. Appl. Sci. 10
(2015) 6250–6256.
[39] A.A. Ensafi, E. Heydari-Bafrooei, B. Rezaei, Simultaneous detection of hydro-
xylamine and phenol using p-aminophenol-modified carbon nanotube paste
761
Microchemical Journal 145 (2019) 756–761
electrode, Chin. J. Catal. 34 (2013) 1768–1775.
[40] M. Maulidiyah, R. H, R. Salamba, D. Wibowo, M. Nurdin, Organic compound
rhodamine B degradation by TiO2/Ti electrode in a new portable reactor, Int. J.
ChemTech Res. 8 (2015) 645–653.
[41] P. Manisankar, P. Sundari, R. Sasikumar, D.J. Roy, Voltammetric determination of
phenoxybenzyl-type insecticides at chemically modified conducting polymer-
carbon nanotubes coated electrodes, Electroanalysis 20 (2008) 2076–2083.
[42] A. Kumaravel, M. Chandrasekaran, Electrochemical determination of chlorpyrifos
on a nano-TiO2/cellulose acetate composite modified glassy carbon electrode, J.
Agric. Food Chem. 63 (2015) 6150–6156.
[43] I. Švancara, K. Vytřas, J. Barek, J. Zima, Carbon paste electrodes in modern elec-
troanalysis, Crit. Rev. Anal. Chem. 31 (2001) 311–345.
[44] P. Manisankar, P.A. Sundari, R. Sasikumar, S. Palaniappan, Electroanalysis of some
common pesticides using conducting polymer/multiwalled carbon nanotubes
modified glassy carbon electrode, Talanta 76 (2008) 1022–1028.
[45] M. Rani, U. Shanker, Degradation of traditional and new emerging pesticides in
water by nanomaterials: recent trends and future recommendations, Int. J. Environ.
Sci. Technol. (2017) 1–34.
[46] M. Lutz, E. Burestedt, J. Emnéus, H. Lidén, S. Gobhadi, L. Gorton, G. Marko-Varga,
Effects of different additives on a tyrosinase based carbon paste electrode, Anal.
Chim. Acta 305 (1995) 8–17.
[47] M.H. Mashhadizadeh, E. Afshar, Electrochemical investigation of clozapine at TiO2
nanoparticles modified carbon paste electrode and simultaneous adsorptive vol-
tammetric determination of two antipsychotic drugs, Electrochim. Acta 87 (2013)
816–823.
[48] R. Liu, Y.-C. Hao, T.-F. Kang, Determination of organophosphorus pesticides using
biosensors based on carbon nanotubes modified electrodes, Chin. J. Anal. Lab. 26
(2007) 9.
[49] J.-B. Raoof, R. Ojani, M. Baghayeri, Simultaneous electrochemical determination of
glutathione and tryptophan on a nano-TiO2/ferrocene carboxylic acid modified
carbon paste electrode, Sensors Actuators B Chem. 143 (2009) 261–269.
[50] M. Maulidiyah, N. M, D. Wibowo, A. Sani, Nanotube titanium dioxide/titanium
electrode fabrication with nitrogen and silver metal doped anodizing method:
performance test of organic compound rhodamine B degradation, Int J Pharm
Pharm Sci 7 (2015) 141–146.
[51] S.K.M. Saad, A.A. Umar, H.Q. Nguyen, C.F. Dee, M.M. Salleh, M. Oyama, Porous
(001)-faceted Zn-doped anatase TiO2 nanowalls and their heterogeneous photo-
catalytic characterization, RSC Adv. 4 (2014) 57054–57063.
[52] A.A. Shah, A.A. Umar, M.M. Salleh, Porous (001)-faceted anatase TiO2 nanorice
thin film for efficient dye-sensitized solar cell, EPJ Photovoltaics 7 (2016) 70501.
[53] A.A. Umar, S. Nafisah, S.K.M. Saad, S.T. Tan, A. Balouch, M.M. Salleh, M. Oyama,
Poriferous microtablet of anatase TiO2 growth on an ITO surface for high-efficiency
dye-sensitized solar cells, Sol. Energy Mater. Sol. Cells 122 (2014) 174–182.
[54] A.A. Shah, A.A. Umar, M.M. Salleh, Efficient quantum capacitance enhancement in
DSSC by gold nanoparticles plasmonic effect, Electrochim. Acta 195 (2016)
134–142.
[55] A.A. Umar, M.Y.A. Rahman, S.K.M. Saad, M.M. Salleh, M. Oyama, Preparation of
grass-like TiO2 nanostructure thin films: effect of growth temperature, Appl. Surf.
Sci. 270 (2013) 109–114.
[56] A.A. Umar, M.Y.A. Rahman, S.K.M. Saad, M.M. Salleh, Effect of NH3 concentration
on the performance of nitrogen doped TiO2 photoelectrochemical cell, Int. J.
Electrochem. Sci. 7 (2012) 7855–7865.
[57] Y. Tachibana, J.E. Moser, M. Grätzel, D.R. Klug, J.R. Durrant, Subpicosecond in-
terfacial charge separation in dye-sensitized nanocrystalline titanium dioxide films,
J. Phys. Chem. 100 (1996) 20056–20062.
[58] D. Dahlan, S.K.M. Saad, A.U. Berli, A. Bajili, A.A. Umar, Synthesis of two-dimen-
sional nanowall of Cu-doped TiO2 and its application as photoanode in DSSCs, Phys.
E. 91 (2017) 185–189.
[59] S.K. Md Saad, A. Ali Umar, M.I. Ali Umar, M. Tomitori, M.Y. Abd Rahman, M. Mat
Salleh, M. Oyama, Two-dimensional, hierarchical Ag-doped TiO2 nanocatalysts:
effect of the metal oxidation state on the photocatalytic properties, ACS Omega 3
(2018) 2579–2587.
[60] S.K.M. Saad, A.A. Umar, M.Y.A. Rahman, M.M. Salleh, Porous Zn-doped TiO2 na-
nowall photoanode: effect of Zn2+ concentration on the dye-sensitized solar cell
performance, Appl. Surf. Sci. 353 (2015) 835–842.
[61] A.A. Umar, E. Rahmi, A. Balouch, M.Y.A. Rahman, M.M. Salleh, M. Oyama, Highly-
reactive AgPt nanofern composed of {001}-faceted nanopyramidal spikes for en-
hanced heterogeneous photocatalysis application, J. Mater. Chem. A 2 (2014)
17655–17665.
[62] A.A. Umar, S.K.M. Saad, M.I.A. Umar, M.Y.A. Rahman, M. Oyama, Advances in
porous and high-energy (001)-faceted anatase TiO2 nanostructures, Opt. Mater. 75
(2018) 390–430.
[63] S.K. Hassaninejad-Darzi, M. Rahimnejad, S.N. Mirzababaei, Electrocatalytic oxida-
tion of glucose onto carbon paste electrode modified with nickel hydroxide deco-
rated NaA nanozeolite, Microchem. J. 128 (2016) 7–17.
[64] P. Deng, Z. Xu, J. Li, Simultaneous voltammetric determination of 2-nitrophenol
and 4-nitrophenol based on an acetylene black paste electrode modified with a
graphene-chitosan composite, Microchim. Acta 181 (2014) 1077–1084.
[65] B.R. Eggins, N.H. Smith, Diffusion control in linear sweep voltammetry, Anal.
Chem. 51 (1979) 2282–2283.