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DOI: 10.1002/elan.201900580

Highly Sensitive Electrochemical Sensor Based on Pt


doped NiO Nanoparticles/MWCNTs Nanocomposite
Modified Electrode for Simultaneous Sensing of Piroxicam
and Amlodipine
Aliyeh Dehdashti[a] and Ali Babaei*[a, b]

Abstract: In this paper, a high-sensitivity electrochemical were investigated using X-ray diffraction (XRD), energy
sensor based on platinum (Pt) doped nickel oxide (NiO) dispersive X-ray spectroscopy (EDX) and field emission
nanoparticles and multi-walled carbon nanotubes scanning electron microscopy (FESEM) techniques. DPV
(MWCNTs) modified glassy carbon electrode (Pt NiO/ responses of PIR and AML increased linearly with their
MWCNTs/GCE) has been developed to determine pirox- concentration in wide linear dynamic ranges of 0.6–
icam (PIR) and amlodipine (AML) simultaneously. The 320.0 μM and 1.0–250.0 μM, respectively. The limits of
electrochemical behavior of PIR and AML at the detection were 0.061 μM for PIR and 0.092 μM for AML.
proposed sensor has been investigated by cyclic voltam- The excellent analytical figure of merits of the proposed
metry (CV), differential pulse voltammetry (DPV) and modified electrode leads to application of it promising
chronoamperometry (CA) methods. Pt doped NiO nano- electrochemical sensor to determine PIR and AML in
particles were synthesized by the sol-gel procedure and human serum and urine with satisfactory results.
Keywords: Piroxicam · Amlodipine · Pt doped NiO nanoparticles · Modified glassy carbon electrode

1 Introduction
stability. therefore, they have been used favorably as a
Modification of electrodes with various modifiers is very modifier in electrochemical sensors [17, 18].
important for improving quality of sensors for drugs PIR is an analgesic drug of the oxicam class that has
analysis with low sensitivity [1–3]. In recent years, differ- been known as a nonsteroidal anti-inflammatory drug
ent types of nanomaterials such as metal oxide nano- (NSAID) [19, 20]. It has been generally used to treat
structures have been applied as modifiers in sensors [4–6]. rheumatoid arthritis spondylitis, osteoarthritis, ankylosing
Nanostructured NiO is one of the most remarkable p-type and other diseases accompanied by an inflammatory
semiconducting metal oxides with a constant wide band process or the pain syndrome [21]. In addition, this drug
gap for sensor applications due to excellent catalytic displays chemosuppressive activity and chemopreventive
activity, high surface to volume ratio, low toxicity, in various cancerous cell lines and animal models [22]. A
environmental friendliness and low cost [7, 8]. In partic- number of analytical analyses include high performance
ular, nanostructured NiO as an electrochemical modifier liquid chromatography (HPLC) [23, 24], capillary electro-
provides larger active areas and therewith lead to higher phoresis [25], spectrofluorometry [26], spectrophotometry
detection sensitivity of numerous important compounds [27] reported for the determination of PIR. These
such as; glucose [9], uric acid [10], and nitrite [11]. Doping techniques often have some disadvantages such as time-
modification is another effective method used to enhance consuming analysis, high cost and tedious sample pre-
sensing properties of the metal oxide semiconductor treatment steps. In contrast, electrochemical techniques
sensors. Doping with noble metals such as Ag, Au, Pd,
and Pt increases the surface area and improves the
electronic properties of the NiO nanostructures, which [a] A. Dehdashti, A. Babaei
can lead to higher sensor response than that of pure NiO Department of Chemistry, Faculty of Science, Arak Uni-
[12–15]. Among the noble metals, doping with platinum is versity, Arak, I.R. IRAN
believed to boost the electro-catalytic activity of the NiO Tel.: + 98 863 4173415
Fax: + 98 863 4173406
nanostructures [16].
E-mail: ali-babaei@araku.ac.ir
Carbon nanotubes (CNTs), including MWCNTs and [b] A. Babaei
single-walled CNTs (SWCNTs), have shown unique Institute of Nanosciences & Nanotechnology, Arak University,
attributes like small dimensions, high catalytic capability, 38156-8-8349, Arak, I.R. IRAN
large surface area, high conductance and great chemical Supporting information for this article is available on the
WWW under https://doi.org/10.1002/elan.201900580

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exhibit many advantages to determine PIR in various 2.2 Apparatus
matrices, including, high sensitivity, simplicity, less time
consuming, fast and inexpensive [28–31]. Voltammetric measurements were done by applying an
AML is a calcium channel blocker of the dihydropyr- Autolab PGSTAT 30 Potentiostat/Galvanostat (EcoChe-
idine derivatives [32]. To enhance the supply of blood and mie, The Netherlands). For electrochemical investiga-
oxygen to the heart, AML relaxes the blood vessels. As a tions, a three electrodes system including the Pt NiO/
result, AML is used widely in the treatment of hyper- MWCNTs/GCE, saturated Ag/AgCl and platinum rod
tension and angina [33–35]. Further, AML is prescribed were applied as working, reference and counter electro-
for sick with diabetes, if they obtain heart related ailments des, respectively. The pH measurements of the CBS were
that necessitate use to calcium channel blocker drugs. accomplished at room temperature by using a Metrohm
Different methods have been employed to determine 744 pH meter. The XRD patterns were registered by X-
AML in biological samples such as HPLC [36, 37], gas ray diffraction instrument (PHILIPS, model PW1730). A
chromatography (GC) [38, 39], spectrophotometry [40, 41] field effect scanning electron microscope with an EDX
and capillary electrophoresis [42], several electrochemical detector. (FESEM, TESCAN, model MIRA III) was used
methods have been recently used to determine AML for morphological investigation.
because of their many mentioned advantages [43–46].
Chronic pain and hypertension can be frequent
2.3 Synthesis of Pt doped NiO Nanoparticles
comorbidities in the senile people and those with chronic
disease; thus, concomitant application of non-steroidal In a simple sol-gel synthesis procedure, the Pt doped NiO
anti-inflammatory drugs (NSAIDs) such as PIR and nanoparticles were prepared by dissolving 0.2 g starch in
antihypertensives such as AML is common. NSAIDs may 20 mL deionized water at 40 °C for 10 min. Then 50 mL
increase blood pressure and blunt the effects of many Ni(NO3)2.6H2O (0.5 M) solution and 0.03 g ammonium
antihypertensives. The results of study in 2008 showed hexachloroplatinate were added the previous solution and
that AML is suited for hypertensive patients taking the solution stirred for 45 min at room temperature.
concomitant NSAIDs like PIR [47]. Therefore, rapid and Afterward, sodium hydroxide (1.0 M) was added dropwise
simple simultaneous determination of PIR and AML in to the solution until the pH reached 9 and then solution
real samples is required due to the therapeutic impor- stirred for 3.0 h. Finally, the resulting light-green gel was
tance. Recently, the article has been published applying washed thoroughly with deionized water and ethanol to
liquid chromatographic method to determine captopril, remove any impurities; it was put to dry in a vacuum oven
piroxicam, and amlodipine simultaneously in real samples at 70 °C for 24 h and then calcinated at 500 °C for 3 h to
[48]. Electrochemical methods with previous mentioned obtain Pt doped NiO nanoparticles.
advantages are the powerful choice to determine electro-
active compounds. As far as we know, there has been no
2.4 Preparation of Pt NiO/MWCNTs/GCE
investigation on the application of the electrochemical
sensor for the simultaneous sensing of PIR and AML yet. Prior to Modification, the bare GCE was polished using
For these reasons, the main purpose of this work is to an aqueous slurry of 0.3 and 0.05 μm alumina and rinsed
develop a simple and sensitive electrochemical sensor for thoroughly with double-distilled water. Afterward, it was
rapid and reliable sensing of PIR and AML simultane- sonicated in a 1 : 1 mixture of water-ethanol for 5 min and
ously in aqueous solutions. then dried under a nitrogen gas flow. The amounts of Pt
doped NiO nanoparticles and MWCNTs in dimeth-
ylformamide (DMF) were altered to reach the highest
2 Experimental sensitivity of the sensor. According to the results, it was
possible to have the best sensitivity for the modified
2.1 Chemicals and Reagents
electrode through a suspension mixture of 10 % Pt doped
PIR, AML (as besylate, assay: � 98 %), nickel (II) nitrate NiO and 90 % MWCNTs in dimethylformamide (DMF).
hexahydrate (Ni(NO3)2.6H2O), (NH4)2[PtCl6] and sodium This suspension was dispersed by remain in ultrasonic
hydroxide were supplied from Sigma-Aldrich Co. bath for 30 min. In the final step, 20 μL of this suspension
MWCNTs (purity > 95 %) with the tube length of 1– was cast on the cleaned GCE surface. The electrode was
10 μm and number of walls of 3–15 were supplied from then dried at room temperature for achieve the Pt NiO/
Plasma Chem GmbH Co. Citrate buffer solution (CBS) MWCNTs/GCE.
was prepared from 0.1 M citric acid and 0.1 M sodium
citrate solutions. Electrochemical experiments were car-
ried out in solution of 0.1 M CBS (pH 5.0). All solutions 3 Results and Discussion
were prepared by double distilled water. About 10 mL of
3.1 Characterization of Pt Doped NiO/MWCNTs
the urine and blood serum samples were centrifuged;
Nanocomposite
then, after filtering, they were diluted 10-times with buffer
and used to determine spiked PIR and AML in the real The XRD analyses of the pure NiO and Pt doped NiO
sample without any further pretreatment. nanoparticles are shown in Figure 1. Figure 1(a) displays

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Fig. 1. The XRD patterns of the pure NiO nanoparticles (a) and Pt doped NiO nanoparticles (b); EDX spectrums of the Pt doped NiO
nanoparticles (c) and Pt doped NiO/MWCNTs nanocomposite (d); FESEM images of the pure NiO nanoparticles (e); Pt doped NiO
nanoparticles (f) and Pt doped NiO/MWCNTs nanocomposite (g).

the XRD analysis of pure NiO nanoparticles that the fact that the amount of doped Pt in the synthesized
prominent peaks at 37.2°, 43.3°, 62.7°, 75.3° and 79.4° products is very small. However, upon adding up the
correspond to planes of (111), (200), (220), (311) and dopant, the decrease in the intensity of diffraction peaks,
(222), respectively, exhibits a NiO cubic structure accord- accompanied by a small broadening in the width has been
ing to JCPDS: 73–1523 [49]. Figure 1(b) displays the XRD observed. This can due to the decrease of nanoparticle
pattern of Pt doped NiO nanoparticles. size. This result corresponds with the FESEM results.
As can be seen, the rutile structure of NiO nano- Therefore, it is believed that the Pt + 4 ions could be
particles has not changed. In addition no corresponding substituted for the Ni + 2 ions in NiO nanostructures with
diffraction peaks from dopant was observed due to the no alteration in its rutile structure. In order to check

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whether metallic ions Pt + 4 were successfully doped into and AML in 0.1 M CBS. Therefore, further electro-
the NiO nanoparticles, the EDX analyses were further chemical investigations were obtained in 0.1 M CBS.
conducted and presented in Figure 1(c,d). According to
Figure 1(c), the EDX investigation of the Pt doped NiO
3.3.2 Effect of pH of Supporting Electrolyte
nanoparticles displayed the existence of Ni, O, and Pt.
This result demonstrates that Pt is successfully doped into The solution pH as an important factor can affect on the
the NiO nanoparticles, although no XRD diffraction peak currents and potentials of AML and PIR at the
peaks were observed in Figure 1(b). According to Fig- Pt NiO/MWCNTs/GCE. The results of DPV studies are
ure 1(d), the EDX investigation of the Pt doped NiO/ shown in Figure 2. As shown in Figure 2(a), the highest
MWCNTs displayed the existence of C, Ni, O, and Pt. anodic peak currents (Ipa) toward PIR and AML was
The presence of Ni, O, and Pt peaks along with C peak observed at pH 5. Therefore the CBS with a pH of 5.0
verified that MWCNT was successfully modified with Pt was employed for subsequent experiments. Moreover, the
doped NiO nanoparticles. results indicated that variation the anodic peak potentials
FESEM images were used to investigate the surface (Epa) of PIR and AML with pH is linear (Figure 2b) as
morphology of the NiO nanoparticles, Pt doped NiO follows:
nanoparticles and Pt doped NiO/MWCNTs nanocompo-
site. According to Figure 1(e,f), Similar observations have PIR : Epa ¼ 0:028 pH þ 0:658 ðR2 ¼ 0:991Þ (2)
been seen on both the samples, except that the increase in
Pt doping leads to decrease in nanoparticle size. Accord- AML : Epa ¼ 0:024 pH þ 0:94 ðR2 ¼ 0:989Þ (3)
ing to Figure 1(g), the Pt doped NiO nanoparticles are
well located on the MWCNTs surface. As a result, the Pt From the plot of Epa vs. pH, slopes of 0.028 and
doped NiO/MWCNTs nanocomposite as a conductive 0.024 were determined for PIR and AML, respectively,
mediator could lead to the higher electrical conductivity which are close to the slope of 0.0296 V/pH at 25 °C.
of the modified electrode. These results suggest that the number of one proton and
two electrons are involved in the electro-oxidation process
of PIR and AML on the surface of the amplified electrode
3.2 Electrochemical Studies of Pt NiO/MWCNTs/GCE
as presented earlier [51, 52].
To investigate electrochemical performance of Pt NiO/
MWCNTs/GCE, CV experiments were carried out using
3.3.3 Effect of Accumulation Time
4 mM K3[Fe(CN)6] containing 0.1 M KCl as a redox probe
at the surface of GCE, MWCNTs/GCE, NiO/MWCNTs/ The accumulation time (tacc) as an effective factor in
GCE and Pt NiO/MWCNTs/GCE (Figure S1). The [Fe increasing the sensitivity of determination of PIR and
(CN)6]3 /4 redox system and the Randles-Sevcik equation AML were studied by DPV experiments (Figure S4).
for a reversible process were used to appraise the active According to the results indicated, the oxidation peak
surface areas of modified and unmodified electrodes [50]: current of PIR and AML increased with accumulation
time up to 80 s for PIR and up to 100 s for AML and then
I pa ¼ ð2:69 � 105 Þ An3=2 D1=2 C0 u1=2 (1) leveled off at higher accumulation times because of

Pursuant to the Randles-Sevcik equation and the


slopes of Ipa versus υ1/2 (Figure S2), the active surface
areas of MWCNTs /GCE, NiO/MWCNTs/GCE and
Pt NiO/MWCNTs/GCE were calculated about 10.01,
14.27, and 20.88 times more than the GCE electrode,
respectively. As a result, the Pt NiO/MWCNTs were able
to boost the effectiveness of the modifier on the GCE by
increasing active surface area and facilitating the electron
transfer.

3.3 Optimization of Experimental Variables


3.3.1 Effect of Supporting Electrolyte
Effect of the various electrolyte solutions, such as 0.1 M
of citrate buffer solution (CBS), phosphate buffer solution
(PBS) and acetate buffer solution (ABS) at pH 5.0 were Fig. 2. DPVs of Pt NiO/MWCNTs/GCE in 90 μM PIR and AML
studied on the DPV responses of Pt NiO/MWCNTs/GCE (0.1 M CBS, pH: 3, 3.5, 4, 4.5, 5, 5.5, 6); tacc = 100 s, scan rate
toward PIR and AML (Figure S3). The Pt NiO/ 0.01 V s–1. Insets: effect of pH on the peak currents (a) and peak
MWCNTs/GCE displayed the best sensitivity toward PIR potentials (b).

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saturation of the electrode surface with PIR and AML. comparison with NiO/MWCNTs and MWCNTs. In addi-
Thus, an accumulation time of 100 s was set as an optimal tion, the Pt NiO/MWCNTs/GCE shows the potential
time for further analyses. shift to lowest positive values that can be because of
highest electro-catalytic behavior of Pt doped NiO nano-
particles on oxidation of PIR and AML. Therefore, the
3.4 Electrochemical behavior of PIR and AML on
Pt NiO/MWCNTs/GCE was applied for a high-sensitivity
Pt NiO/MWCNTs/GCE
simultaneous determination of AML and PIR.
The electrochemical performance of a mixture of 90 μM
of PIR and AML were studied using DPV method at
3.5 Effect of Scanning Rate
GCE, MWCNTs/GCE, NiO/MWCNTs/GCE and
Pt NiO/MWCNTs/GCE (Figure 3). The effect of scan rate on the oxidation peak currents
The results display the highest oxidation peak currents (Ipa) and oxidation potentials (Epa) of PIR and AML at
for PIR and AML at Pt NiO/MWCNTs/GCE that can be the surface of the Pt NiO/MWCNTs/GCE was studied. In
due to largest surface area and the highest electrical order to study the mechanism of the corresponding redox
conductivity of Pt NiO/MWCNTs nanocomposite in reactions, the cyclic voltammograms of 90 μM of PIR and
AML were obtained in the range of 10 to 180 mVs 1
(Figure 4). As can be seen in the inset of Figure 4, the
oxidation peak currents of PIR and AML displayed a
linear relationship with the square root of scan rate (υ1/2)
in all scan rate ranges, corresponding to the following
equations:

PIR : I pa ðmAÞ ¼ 270:6 u1=2 ðV s 1 Þ1=2 19:01


2
(4)
R ¼ 0:997

AML : I pa ðmAÞ ¼ 242:4 u1=2 ðV s 1 Þ1=2 18:62


2
(5)
R ¼ 0:998

These results indicated electron-transfer reactions of


PIR and AML at the proposed sensor surface were
diffusion controlled processes.
Fig. 3. DPV voltammograms of GCE, MWCNTs/GCE, NiO/ For an irreversible anodic reaction, the electron trans-
MWCNTs/GCE and Pt NiO/MWCNTs/GCE for 90 μM PIR and fer rate constant (ks) and charge transfer coefficient (α)
AML in CBS (pH 5.0); tacc = 100 s, scan rate 0.01 V s–1. can be obtained by determining the difference of Ep
versus lnυ using Laviron’s theory, corresponding to the
following equations [53]:

Ep ¼ E0 ðRT=aa nFÞ ln ðRTKs =aa nFÞþ


(6)
ðRT=aa nFÞ lnu

It is possible to determine the formal potential (E°)


from the intercept of Ep versus υ curve by extrapolating to
the vertical axis at υ = 0 [54]. The values of αa for PIR and
AML were calculated to be 0.5 and 0.41, respectively, by
considering the slope of the straight line of Ep versus lnυ
(Figure S5). Using E° and αa values, the values of Ks for
PIR and AML were calculated to be 0.68 s 1 and
0.47 s 1respectively. The high value of Ks indicated the
significant capability of the Pt NiO/MWCNTs nanocom-
posite to elevate electron transfer between the analytes
and the proposed sensor surface.
Fig. 4. Cyclic voltammetry curves of Pt NiO/MWCNTs/GCE in
90 μM PIR and AML at different scan rates (10 180 mV s–1),
Insets: Plot of linear dependence of peak currents with square
root of scan rates (υ1/2).

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3.6 Chronoamperometric Study of PIR and AML PIR and AML in 0.1 M CBS (pH 5.0) (Figure 6). Figur-
es 6a and 6b display the calibration plot of the mixture of
To obtain the diffusion coefficient (D) of PIR and AML PIR and AML, respectively.
at Pt NiO/MWCNTs/GCE, the CA method was used As shown, the peak currents were proportional to PIR
(Figure 5). and AML concentrations in the range of 0.6–320.0 μM
The CA data were analyzed using Cottrell equa- and 1.0–250.0 μM, respectively. When the signal to noise
tion [55]: ratio (S/N) is 3, the detection limits were calculated to be
0.061 μM and 0.092 μM for PIR and AML, respectively.
I ¼ n F D1=2 A C0 p 1=2
t 1=2
(7) The corresponding calibration equations for PIR and
AML are as follows:
Under the diffusion control condition, the plot of I
versus t 1/2 is linear, and the value of D can be calculated PIR : I pa ðmAÞ ¼ 1:208 C ðmMÞ þ 1:596
from its slope. The plots of I versus t 1/2 for PIR and AML (8)
ðR2 ¼ 0:998Þ
are shown in the insets. The values of D were estimated
to be 9.1 × 10 5 cm2 s 1 and 2.8 × 10 5 cm2 s 1 for PIR and AML : I pa ðmAÞ ¼ 0:640 C ðmMÞ þ 3:485
(9)
AML, respectively. ðR2 ¼ 0:998Þ

These results showed that Pt NiO/MWCNTs/GCE is


3.7 Calibration Curve and Limits of Detection
capable of providing excellent sensitivity and wide linear
To investigate the analytical performance of the proposed dynamic range with low detection limit.
sensor and quantitative determination of PIR and AML,
DPV technique was applied using Pt NiO/MWCNTs/
GCE with simultaneously changing the concentrations of

Fig. 6. DPVs of Pt NiO/MWCNTs/GCE in various concentra-


tions of PIR and AML as 0.6 + 1.0 (a), 2.0 + 2.0 (b), 6.0 + 12.0 (c),
25.0 + 30.0 (d), 50.0 + 60.0 (e), 90.0 + 90.0 (f), 130.0 + 120.0 (g),
180 + 150 (h), 250 + 200 (i) and 320 + 250 (j) in μM under
optimum conditions, respectively. Insets: Plot of linear relation-
ship of peak current with PIR concentrations (a). Plot of linear
relationship of peak current with AML concentrations (b).

Table 1. Maximum tolerable concentrations for usual interfering


species.

AML PIR Interference


Cint/(μM) Cint/(μM)
1000 1000 K +, Na +, Ca + 2,Mg + 2 Cl , Br , NO3
900 800 Ascorbic acid
Fig. 5. Chronoamperograms curves of Pt NiO/MWCNTs/GCE in 700 550 Uric acid
0.1 M CBS (pH 5.0) in the presence of 0.1, 0.2, 0.3 and 0.4 mM of 800 600 Aspartic acide
PIR (a) and in the presence of 0.1, 0.2, 0.3 and 0.4 mM of AML 650 700 L-alanine
(b). Insets: Plots of I vs. t 1/2 obtained from chronoamperograms 500 450 Dopamine
for PIR and AML. Cint refers to interfering species concentration.

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Table 2. Results for PIR and AML determination in human serum and urine.

Spiked (μM) Added (μM) Proposed method Proposed method Reference method F-testb (%) t-testb (%)
Founda (μM) Recovery (%) Founda (μM)
PIR AML PIR AML PIR AML PIR AML PIR AML PIR AML
Human serum – – < DL < DL – – < DL < DL – – – –
10.0 10.0 10.21 � 0.22 9.84 � 0.34 102.1 98.4 10.47 � 0.25 10.61 � 0.38 0.77 0.80 1.35 2.62
20.0 20.0 19.74 � 0.53 19.58 � 0.76 98.7 97.9 19.68 � 0.57 20.39 � 0.61 0.86 1.55 2.45 1.44
Human urine – – < DL < DL – – < DL < DL – – – –
10.0 10.0 9.83 � 0.24 9.71 � 0.36 98.3 97.1 10.32 � 0.29 9.47 � 0.32 0.68 1.27 2.31 2.53
20.0 20.0 19.48 � 0.57 20.18 � 0.83 97.4 100.9 19.75 � 0.49 19.21 � 0.86 1.35 0.93 1.17 1.67
a
Average of three determinations at optimum conditions. c The theoretical values of F and t at p = 0.05 are 39and 2.78, respectively.

3.8 Repeatability and Stability of the photometric results as a refrence method. Statistical
Pt NiO/MWCNTs/GCE calculations were indicated that both methods are in good
agreement with no significant difference for the 95 %
The repeatability of the proposed sensor was studied by confidence level. The results are listed in Table 2. The
successive determinations (n = 10) of 90 μM of PIR and good recoveries corroborate that the Pt NiO/MWCNTs/
AML solution using DPV method. The relative standard GCE could be efficiently used as a voltammetric sensor to
deviations (RSDs) were obtained 2.86 % and 4.12 % for determine PIR and AML simultaneously in biological
PIR and AML, respectively. According to the results, the samples without need any special pretreatments and using
Pt NiO/MWCNTs/GCE was not subjected to surface time-consuming analysis time.
contaminate during the voltammetric analysis that makes
the sensor excellent in terms of repeatability. To inves-
4 Conclusion
tigate the stability of the Pt NiO/MWCNTs/GCE, DPV
experiments of PIR and AML were performed after In this work, a sensing platform based on Pt doped NiO/
keeping the modified electrode in 0.1 M CBS (pH 5.0) or MWCNTs nanocomposite modified glassy carbon elec-
air for a certain time. At wet condition, it was found that trode was introduced as a high-sensitivity electrochemical
the Pt NiO/MWCNTs/GCE was subjected to six experi- sensor to determine of PIR and AML simultaneously.
ments during 12 h leading to a less than 5.1 % and 6.5 % The voltammetric responses of the Pt NiO/MWCNTs/
reduction in the peak currents for PIR and AML, GCE were significantly improved toward PIR and AML
respectively. At dry condition, retaining 89.6 % and due to the synergistic electro-catalytic properties. The
87.3 % of the initial oxidation peak currents of PIR and proposed sensor presented numerous advantages such as
AML, respectively after 10 days corroborated the high superior electro-catalytic performance, simple preparation
stability of the Pt NiO/MWCNTs/GCE. process, low response time, high sensitivity and stability,
wide linear dynamic range, very low detection limits,
excellent repeatability, high tolerance limit for common
3.9 Interference Studies
interfering agents and satisfactory recovery to determine
The influences of some the usual interfering species on of analytes in real samples which can recommend
the sensing of 90 μM of PIR and AML at the proposed Pt NiO/MWCNTs/GCE as a excellent and marvelous
sensor were studied under optimum conditions by DPV candidate for feasible applications.
technique. The tolerance limit for each interfering species
is shown in Table 1; it was taken as the concentration of
Acknowledgment
the interferent that gives an error less than 10 % in peak
current of target analytes. The results confirmed that the The authors would like to thank the research council of
usual interfering species did not influence the sensing of Arak University for the financial support (No: 98.662).
PIR and AML in biological samples at the Pt NiO/
MWCNTs/GCE significantly.

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Chem. 2018, 823, 1–8. Published online on ■■■, ■■■■

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Highly Sensitive Electrochemical
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