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Electrochemical behavior and analytical

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Article in Chinese Chemical Letters January 2016

DOI: 10.1016/j.cclet.2015.12.032

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Chinese Chemical Letters xxx (2016) xxxxxx

Contents lists available at ScienceDirect

Chinese Chemical Letters

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

1
2 Original article

3 Electrochemical behavior and analytical detection of Imidacloprid

4 insecticide on a BDD electrode using square-wave voltammetric
5 method
6 Q1 Mabrouk BenBrahim *, Hafedh Belhadj Ammar, Ridha Abdelhedi, Youssef Samet
7 Electrochemistry and Environmental Laboratory, Department of Materials Engineering, National Engineering School of Sfax, University of Sfax, B.P. 1173,
8 3038 Sfax, Tunisia

A R T I C L E I N F O A B S T R A C T

Article history: A sensitive square-wave voltammetric method for the determination of Imidacloprid (IMD) was
Received 27 May 2015 developed using electrochemically pretreated boron-doped diamond (BDD) electrode. Aqueous
Received in revised form 3 August 2015 solutions were prepared with Condor 200 SL as the commercial formulation of IMD. Sodium sulfate
Accepted 18 December 2015
(Na2SO4) was used as supporting electrolyte. The inuence of operating parameters, such as the pH of the
Available online xxx
medium, frequency, pulse amplitude, scan increment and the concentration of IMD was investigated. An
irreversible cathodic peak, corresponding to the reduction of IMD is observed at 1.21 V (vs. SCE) and the
Keywords:
electrode reaction was controlled by adsorption. Under optimized conditions, the square-wave
Imidacloprid
Square-wave volammetry
reduction peak current was linear over the concentration range of (30200 mmol L1) with a detection
Boron-doped diamond electrode and quantication limits of 8.60 mmol L1 and 28.67 mmol L1, respectively. The results were compared
Electrochemical detection with spectrophotometry and HPLC methods under some conditions and found to be in good agreement.
To investigate applicability to real samples, the proposed method was applied to the determination of
IMD in plum juice.
2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.

9
10 1. Introduction enzyme-linked immunosorbent assay (ELISA) [13]. However, these 26
methods suffer from some disadvantages such as high cost, long 27
11 Imidacloprid (E)-1-(6-chloro-3-pyridylmethyl)-N-nitroimida- analysis time and requirement for sample pretreatment when 28
12 zolidin-2-ylideneamine (Fig. 1) is one of the most used neonico- some procedures as derivatization, extraction and purication are 29
13 tinoid for the crop protection worldwide due to its low soil usually included. 30
14 persistence and high insecticidal activity at a very low application Electroanalytical processes have been successfully applied for 31
15 rate [1]. It acts as antagonist by binding to postsynaptic nicotinic the determination of inorganic and organic compounds, including 32
16 receptors in the insects central nervous system resulting in the pesticides, in many environmental matrices, due to their good 33
17 paralysis and death of insects [2]. IMD is the active substance of sensitivity, short time analysis, low-cost, and the possibility of 34
18 many commercial insecticides such as Condor, Gaucho, Prestige, sample analysis without extractions or pretreatments [1416]. 35
19 Admire, and Provado [3]. However, the intensive use of this Several electrode materials such as glassy carbon [17], modied 36
20 insecticide in agriculture and the improper storage is a source of glassy carbon electrode [18,19], carbon paste [20], modied carbon 37
21 contamination of the environment. For these reasons, a range paste electrode [21,22], carbon ceramic [23], bismuth modied 38
22 of methods have been utilized for the detection and quantication electrode [24], modied silver electrode [25], and dropping 39
23 of IMD, such as high performance liquid chromatography [47], mercury electrode [26,27], were used as cathodes for the detection 40
24 spectrophotometry [8], spectrouorimetry [9,10], capillary elec- and quantication of this insecticide. 41
25 trophoresis [11], micellar electrokinetic chromatography [12] and Differential pulse polarography and square-wave adsorptive 42
stripping voltammetry were used for the determination of IMD at 43
hanging mercury drop electrode [26,27]. Two reduction peaks 44
* Corresponding author.
were observed in large pH ranges in both methods. The rst peak 45
E-mail address: benbrahim.mabrouk@yahoo.com (M. BenBrahim). corresponds to a four-electron transfer to give the hydroxylamine 46

http://dx.doi.org/10.1016/j.cclet.2015.12.032
1001-8417/ 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: M. BenBrahim, et al., Electrochemical behavior and analytical detection of Imidacloprid insecticide on
a BDD electrode using square-wave voltammetric method, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2015.12.032
 G Model
CCLET 3537 17

2 M. BenBrahim et al. / Chinese Chemical Letters xxx (2016) xxxxxx

NO
O2 O2
NO diamond (BDD) electrode. The development of a novel electro- 72
N HN
chemical technique using BDD electrode can furnish the priceless 73
services in the monitoring of the compounds that are important in 74
N N N
H
NH terms of human health defense, environment and food chemistry. 75
Cl N BDD electrodes have been excellently used as an alternative to 76
Cl N
other conventional electrodes (e.g., glassy-carbon or platinum 77
Fig. 1. Mesomeric form of imidacloprid. electrodes) and are particularly attractive in electroanalytical 78
applications for pesticides [2835]. It has several important 79
characteristics such as an inert surface with low adsorption 80
proprieties, remarkable corrosion stability, even in strong acidic 81
media, an extremely wide potential window in aqueous solutions 82
(up to 3.5 V) and high reproducibility of electrochemical responses 83
[3639]. 84
The aim of this work is to develop a simple, fast and sufciently 85
sensitive electroanalytical methodology for the detection and 86
quantication of IMD in the commercial formulation (Condor 87
200 SL) using square-wave voltammetry at a BDD electrode. The 88
results of the developed electroanalytical method were compared 89
with the UV spectrophotometric and HPLC methods. 90

Scheme 1. Proposed mechanism of IMD reduction at a mercury electrode [26,27]. 2. Experimental 91

Reagents: All solutions containing different amounts of IMD 92

47 derivative and the second correspond to a two electron-transfer to taken from an emulsiable concentrate (Condor 200 SL Bayer 93
48 give the corresponding amine (Scheme 1). The limits of detection Crop Science) containing 200 g L1 IMD were prepared with 94
49 (LOD) were 0.01 mmol L1 and 0.02 mmol L1, respectively. ultrapure water. These solutions were kept in the dark at 4 8C. The 95
50 Voltammetric determination of IMD at glassy carbon electrode supporting electrolyte was sodium sulfate (Na2SO4) 0.05 mol L1 96
51 has been reported [17]. The reduction peak is observed at high provided by Biochem. Sulfuric acid (H2SO4) and sodium hydroxide 97
52 scan rate of 500 mV s1. The reported detection limit was (NaOH) were supplied by Merck and added to the required pH 98
53 30.11 mmol L1, which is too high for carrying out trace analysis. values covering the pH range of 3.011.0. Before each experiment, 99
54 Differential pulse voltammetry (DPV) determination of IMD at the solution was purged with nitrogen for 5 min to remove oxygen 100
55 carbon paste electrode has been reported [20] with the LOD as and kept away from any agitation to achieve a balance between the 101
56 2.04 mmol L1. A copper(II) phthalocyanine modied carbon electrodes and the solution. 102
57 ceramic electrode fabricated by a solgel method [23], and a nano Apparatus: Square-wave voltammetry measurements were 103
58 silver-Naon/TiO2-Naon composite modied GCE [19], were used performed using a potentiostatgalvanostat (VoltaLab PST050), 104
59 for the detection of IMD by DPV technique, with the LOD and a conventional three-electrode cell at 25 8C. BDD was used as 105
60 0.28 mmol L1 and 0.25 mmol L1, respectively for both electrodes. working electrode for voltammetric experiments. A platinum 106
61 Recently, Lei et al. [18] describe a method for the determination of wire was used as a counter electrode and a saturated calomel 107
62 IMD on a GCE modied with poly(carbazole)/chemically reduced electrode (SCE) was used as reference electrode. The BDD electrode 108
63 graphene oxide. This modied electrode was used as a sensing (0.07 cm2) was provided by the Swiss Center for Electronics and 109
64 electrode for the detection of IMD. CV and DPV were used as Microtechnology (CSEM). It was synthesized by the hot lament 110
65 sensing techniques. The LOD and LOQ values of CV are chemical vapor deposition technique (HF-CVD) on single-crystal p- 111
66 0.22 mmol L1 and 0.74 mmol L1, respectively, while those values type Si h1 0 0i wafers (13 mV cm, Siltronix) [40]. The doping level 112
67 of DPV are 0.44 mmol L1 and 1.52 mmol L1, respectively. The LOD of boron in the diamond layer, expressed as B/C ratio, was about 113
68 and LOQ for the reduction of IMD on various electrodes are 3500 ppm. In order to obtain an active surface and reproducible 114
69 presented in Table 1. electrochemical response, the BDD electrode was subjected to 115
70 None of the previously conducted research works reports the potential cycling conditions in 0.05 mol L1 sodium sulfate 116
71 electrochemical determination of the IMD on boron-doped between 3.0 V and +3.0 V at a high scan rate of 5.0 V s1 for 117

Table 1
Comparison of analytical parameters for the determination of IMD on various electrodes.

Method Electrode Linear range (mmol L1) LOD (mmol L1) LOQ (mmol L1) References

DPP HMDE 0.0390.782 0.01 [27]

SWASV 0.020.50 0.02 [26]
CV GCE 10.91956 30.1 101.6 [17]
DPV CPE 6.7117.4 2.04 6.8 [20]
CV 17 0.63 2.1
DPV nAgnf/nTiO2nf/GCE 0.53.5 0.25 0.83 [19]
Amperometry 15 0.93 3.1
SWV Hg(Ag) FE 3.55185.6 1.05 3.55 [25]
CV PCz/CRGO/GCE 310 0.22 0.74 [18]
DPV 310 0.44 1.52
DPV BiFE 9.5200 2.9 [24]
SWV BDD 30200 8.6 28.6 This work

HMDE, hanging mercury drop electrode; GCE, glassy carbon electrode; CPE, carbon-paste electrode; nAgnf/nTiO2nf/GCE, nanosilver Naon1/nanoTiO2 Naon1 modied
glassy carbon electrode; Hg(Ag) FE, Silver-amalgam lm electrode; PCz/CRGO/GCE, poly(carbazole)/chemically reduced graphene oxide modied glassy carbon electrode;
BiFE, Bismuth-lm electrode; BDD, Boron-Doped Diamond.

Please cite this article in press as: M. BenBrahim, et al., Electrochemical behavior and analytical detection of Imidacloprid insecticide on
a BDD electrode using square-wave voltammetric method, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2015.12.032
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M. BenBrahim et al. / Chinese Chemical Letters xxx (2016) xxxxxx 3

118 120 s. The electrode surface state was controlled by obtaining the of 200 mmol L1 IMD in a solution of 0.05 mol L1 Na2SO4 at the 160
119 same shape of the voltammogram recorded between 0.4 and BDD electrode. It is evident that, during the cathodic scan, a single 161
120 1.6 V at a scan rate of 100 mV s1. reduction peak was observed at a potential of 1.21 V vs. SCE. 162
121 UV spectrophotometric instrument: The spectrophotometric The optimization of the analytical method involved a system- 163
122 analysis was performed with UVvis spectro-photometer atic study of the experimental parameters that affect the SWV 164
123 (Shimadzu 1650 PC) with a Silicon photodiode detector for the response, namely, the pH of the medium, the frequency

(f), the 165
124 measurement of the complete ultra-violet to visible light pulse amplitude (DEa) and the scan increment DEi . The results of 166
125 spectrum. The UVvis spectra were recorded in a quartz cuvette these studies will be separately presented in the sequence. 167
126 of 1 cm path length. The spectrophotometer was connected to a
127 computer have the software UV-Prob version 2.21 that was used 3.1. Effect of pH 168
128 for all the spectrophotometric measurements and data processing.
129 The solutions were scanned from 200 to 400 nm. All measure- The pH of the supporting electrolyte has a signicant inuence 169
130 ments were performed at room temperature. on the determination of IMD by affecting the peak current and peak 170
131 High performance liquid chromatography instrument: HPLC potential. The effect of the pH value on the determination of IMD in 171
132 measurements (Fa. Knauer, Berlin, Germany) were carried out with the Na2SO4 solution at BDD electrode was carefully investigated in 172
133 HP 1081 series HPLC system with UV detection. A reverse phase a wide pH range of 3.0 to 11.0. Fig. 3 illustrates the dependency of 173
134 C18 (cartridge) column was used (150 mm length, 46 mm ID). The the IMD cathodic peak current and potential with pH. It could 174
135 mobile phase was a mixture of acetonitrile and ultrapure water in be seen that the cathodic peak current of IMD increases with the 175
136 ratio 8:2, v/v. The separation was performed in the isocratic regime increase of pH value until it reaches 7.0 at higher pH values, the 176
137 and the ow rate was 1 mL min1. IMD was detected at a electrode response becomes not stable and the results are not 177
138 wavelength of 270 nm with the retention time of 2.5 min. For the reproducible, especially above pH 9.0. The best sensitivity and 178
139 external calibration, at least three replications were performed for shape of the voltammograms were observed at pH 7.0. Therefore, 179
140 each standard concentration. The mean value was then used for pH 7.0 was chosen for the entire experiment. In addition, the peak 180
141 calibration curve. potential Ep is shifted to more negative values with the increase of 181
142 Preparation of plum red juice: Mature plum fruit was purchased the pH value. 182
143 from the local market of Sfax-Tunisia. Each fruit sample was
144 washed in ultrapure water and processed mechanically by braun 3.2. Effect of square-wave frequency 183
145 MP-80 multipress juice extractor. The suspension was ltered
146 through a 0.45 mm milli-pore lter (Watman lter paper), This parameter is important in SWV because it determines the 184
147 centrifuged for 20 min until a clear sample, then, the obtained intensity of the signal, which in turn, the sensitivity of the 185
148 juice was fortied by the IMD. The amount of IMD in the plum juice analytical method. Fig. 4 shows the square-wave voltammograms 186
149 was evaluated by the standard addition method. The IMD content obtained for different frequency values in the range of 20 Hz to 187
150 in the fruit juice was determined from the calibration curve of IMD 100 Hz. The cathodic peak current increases with the increase of 188
151 concentration vs. peak current. The pH of the juice extracted was the frequency value. A linear relationship was obtained between 189
152 modied to 7.0 with appropriate volumes of NaOH solution. the peak current (Ip) and the frequency (f) (inset of Fig. 4) according 190
153 Finally, 20 mL of the ltrate juice was added to the supporting to the accepted theory of SWV [41]. This behavior corresponds to a 191
154 electrolyte solution (0.05 mol L1) in the voltammetric cell for totally irreversible system controlled by the adsorption of species 192
155 measurement. All tests cited in this work were performed at 25 8C. on the electrode surface. 193
Moreover, the inset of Fig. 4 shows the dependence of Ep with 194
156 3. Results and discussion log f, the slope of this straight line was used to calculate an value 195
according to the following equation: 196
157 SWV technique was employed to understand the electrochem-
158 ical process of IMD occurring at BDD electrode. Fig. 2 shows the DEp 2:3RT
 (1)
159 square-wave voltammogram recorded in the absence and presence Dlogf anF
where a is the charge transfer coefcient, n the number of 198
197
electrons involved in the reaction. 199

20 1.28

18 1.24
)

Ep (V)
IIpI (

1.20
16

1.16
14

2 4 6 8 10 122
pH

Fig. 2. Square wave voltammograms of the BDD electrode immersed in 0.05 mol L1 Fig. 3. Dependence of peak current and peak potential on pH for 200 mmol L1 IMD
Na2SO4 solution after bubbling with nitrogen for 5 min: without (dashed line) and in 0.05 mol L1 Na2SO4 solution at different pH (3.011.0). f = 100 Hz, DEa = 50 mV,
with (solid line) 200 mmol L1 IMD. f = 100 Hz, DEa = 50 mV, DEi 10 mV, pH 7.0. DEi 10 mV.

Please cite this article in press as: M. BenBrahim, et al., Electrochemical behavior and analytical detection of Imidacloprid insecticide on
a BDD electrode using square-wave voltammetric method, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2015.12.032
 G Model
CCLET 3537 17

4 M. BenBrahim et al. / Chinese Chemical Letters xxx (2016) xxxxxx

25
IIpI = 2.35 i 2.977
2
20 R = 0.993

15

IIpI ()
10

0
2 4 6 8 10

i (mV)

Fig. 6. Linear dependence of the peak current (Ip) with scan increment (210 mV).
f = 100 Hz, DEa = 50 mV, pH 7.0.

Fig. 4. Square wave voltammograms of the BDD electrode immersed in a solution

containing 0.05 mol L1 Na2SO4 + 200 mmol L1 IMD recorded at different coverage (G) by the adsorbed IMD molecules according to the 214
frequency values: (a) 20; (b) 40; (c) 60; (d) 80; (e) 100 Hz. DEa = 50 mV,
DEi 10 mV, pH 7.0. following equation [42]: 215

@I p
500Aa2 Ff DEi G (2)
200 an is equal to 1.73. From the literature [23], the number of @DEa
201 electrons exchanged by the IMD is assumed to be 4 leading to the where @Ip =@DEa is the slope of the graph Ip vs. DEa , A is the 216
217
202 formation of hydroxylamine derivative. Therefore, the charge electrode area and DEi is the scan increment. Thus, the quantity of 218
203 transfer coefcient a is about 0.43. IMD adsorbed on the electrode surface was estimated to be 219
6.881010 mol cm2. 220
204 3.3. Effect of pulse amplitude
3.4. Effect of scan increment 221
205 Another important parameter involved in SWV is the pulse
206 amplitude (DEa). The effect of square-wave pulse amplitude on the This parameter which allows the determination of the amount 222
207 reduction peak current of 200 mmol L1 IMD in 0.05 mol L1 of potential changes between two data points in the experiment 223


208 Na2SO4 was studied from 10 mV to 50 mV at a frequency of 100 Hz. was investigated. The effect of the scan increment DEj on the 224
209 The results have indicated that the peak current increased from electrochemical reduction of 200 mmol L 1
IMD by SWV was 225
210 3.33 mA to 20.3 mA when DEa increased from 10 mV to 50 mV studied in the range of 2 mV to 10 mV on the BDD electrode. Fig. 6 226
211 (Fig. 5). Therefore, at the pulse amplitude of 50 mV, the peak shows that the peak current enhanced with DEi . Therefore, a scan 227
212 current which was found to be much sharper than the others. On increment of 10 mV was selected in the present study. 228
213 the other hand, the inset of Fig. 5 allows to calculate the surface
3.5. Analytical determination of IMD 229

The validation of an analytical method aims at demonstrating 230

that the analytical procedure is suitable for the intended use. It 231
involves determination of accuracy, precision, repeatability, 232
intermediate precision, reproducibility, specicity, limit of detec- 233
tion (LOD), limit of quantication (LOQ) and linearity range [43]. 234
Fig. 7 shows the square-wave voltammograms obtained for the 235
reduction of IMD at different concentrations (30200 mmol L1) 236
under optimum experimental parameters. The inset in Fig. 7 shows 237
the linear dependence of jIpj vs. IMD concentration. The LOD and 238
LOQ were calculated using the following equations [43]. 239
3s
LOD (3)
m

10s 241
240
LOQ (4)
m
where s is the standard deviation of the peak currents and m is the 242
243
slope of the calibration curve. 244
The calculated values of LOD and LOQ were, respectively, 245
8.60 mmol L1 and 28.67 mmol L1. Table 1 compares the perfor- 246
Fig. 5. Square wave voltammograms of the BDD electrode immersed in a solution
mance of the proposed SWV approach with several electrochemi- 247
containing 0.05 mol L1 Na2SO4 + 200 mmol L1 IMD recorded at different values of
DEa: (a) 10; (b) 20; (c) 30; (d) 40; (e) 50 mV. Inset: linear dependence of the peak cal methods reported in the literature for IMD determination. 248
current with DEa. f = 100 Hz, DEi 10 mV, pH 7.0. Despite their general satisfactory sensitivities, several methods 249

Please cite this article in press as: M. BenBrahim, et al., Electrochemical behavior and analytical detection of Imidacloprid insecticide on
a BDD electrode using square-wave voltammetric method, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2015.12.032
 G Model
CCLET 3537 17

M. BenBrahim et al. / Chinese Chemical Letters xxx (2016) xxxxxx 5

Table 2
Determination of IMD by SWV, UV spectrophotometry and HPLC.

Parameters Methods

SWV Spectrophotometry HPLC

Linearity range (mmol L1) 30200

Intercept (mA) 0.390 0.0106 4.407
SD of intercept (mA) 0.367 0.014 4.216
Slope (mA m(mol L1)1) 0.128 0.005 1.665
SD of slop (mA m(mol L1)1) 0.360 0.007 0.048
Regression coefcient, R2 0.999 0.997 0.995
LOD (mmol L1) 8.6 8.42 7.61
LOQ (mmol L1) 28.6 28.03 25.36
Accuracy (%) 99.1  1.60 98.9  1.69 99.5  1.29

electrode. The analytical curve in ultrapure water solutions was 267

also obtained by the standard addition under the same interval for 268
the SWV (30200 mmol L1). Fig. 8 shows the obtained chromato- 269
gram of IMD in aqueous solution containing 0.05 mol L1 Na2SO4 270
at pH 7.0 and temperature 25 8C. The peak area increased with the 271
Fig. 7. Square wave voltammograms of the BDD electrode immersed in a solution increase in concentration. The inset in Fig. 8 corresponds to the 272
containing 0.05 mol L1 Na2SO4 + IMD at different concentrations: (a) 30; (b); 40 (c) analytical curve, i.e., the linear dependence of the peak area with 273
50; (d) 60; (e) 70; (f) 100; (g) 200 mmol L1. Inset: linear dependence of the peak IMD concentration for the studied concentration interval. The 274
current with the IMD concentrations. f = 100 Hz, DEa = 50 mV, DEi 10 mV, pH 7.0.
calculated value of LOD was 7.61 mmol L1 and the LOQ was 275
25.36 mmol L1 (Table 2). 276
250 listed in Table 1 used modied electrodes, and complex biosensors The UV spectrophotometry method was also developed with 277
251 whose preparation is laborious and expensive. It also requires the objective to obtain comparative results for the validation of the 278
252 skilled labor and involves several steps. However, the BDD electroanalytical method. The absorption spectra obtained for IMD 279
253 electrode does not need everytime of pretreatment and it surface exhibits one band at 270 nm (Fig. 9). The result shows a linear 280
254 state remains stable after several tests. This electrode shows a relationship between absorbance and IMD concentration in the 281
255 better electrocatalytic activity towards the reduction of IMD. The same range of SWV. The LOD and LOQ were 8.42 mmol L1 and 282
256 repeatability and reproducibility of results are excellent. In fact, to 28.03 mmol L1, respectively. The main results obtained with the 283
257 evaluate these properties, two IMD solutions (50 mmol L1 and three techniques are summarized in Table 2. 284
258 75 mmol L1) were tested four times by SWV. The repeatability of
259 the current measurement was 1.17% RSD for 50 mmol L1 and 3.6. Determining of IMD in plum fruit juice 285
260 1.05% RSD for 75 mmol L1. The reproducibility of the current
261 measurement was also calculated 0.97% RSD for 50 mmol L1 and The possibility of applying the voltammetry technique to the 286
262 0.88% RSD for 75 mmol L1. Low values of RSD showed the good determination of IMD in plum juice was also successfully tested 287
263 precision of the proposed SWV method for the determination of by standard additions of IMD in the experimental section. 288
264 IMD. Voltammograms of IMD in plum juice are given in Fig. 10. As can 289
265 Various IMD concentrations were analyzed by HPLC in order to be seen from this gure, the juice of plum extracted from the 290
266 validate and compare the results obtained with SWV using the BDD unfortied plum sample by IMD (dashed line) did not block the 291
BDD electrode surface and did not contain other voltamme- 292
trically active compounds, which are favorable facts for the IMD 293
determination. All voltammograms recorded after addition of 294
IMD show a single irreversible cathodic peak. The current of this 295
peak allows the determination of IMD concentration using the 296
calibration curve in Fig. 7. The result of this analysis is 297
summarized in Table 3. 298

Fig. 9. Evolution of the UVvis spectra of IMD at different concentrations: (a) 30; (b)
Fig. 8. HPLC-UV chromatogram of 30 mmol L1 IMD in 0.05 mol L1 Na2SO4 solution 40; (c) 50; (d) 60; (e) 70; (f) 100 and (g) 200 mmol L1 in 0.05 mol L1 Na2SO4
at pH 7.0. Inset: linear dependence of the area with IMD concentration. Mobile solution at pH 7.0. Inset: linear dependence of the absorbance with IMD
phase: 80% acetonitrile, 20% ultrapure water (vol%), l = 270 nm. concentration at l = 270 nm.

Please cite this article in press as: M. BenBrahim, et al., Electrochemical behavior and analytical detection of Imidacloprid insecticide on
a BDD electrode using square-wave voltammetric method, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2015.12.032
 G Model
CCLET 3537 17

6 M. BenBrahim et al. / Chinese Chemical Letters xxx (2016) xxxxxx

Table 3
Analytical parameters obtained at a BDD electrode for determination of IMD in Plum juice using SWV technique.

Sample Number of experiments IMD added (mmol L1) IMD found (mmol L1) Bias (%) Recovery (%) RSD (%)

Plum juice 4 50 48.4 4.4 96.6 1.02

4 75 75.7 3.7 100.9 1.08
4 100 98.2 3.9 98.2 1.11

the limit of detection LOD and the limit of quantication LOQ of 326
IMD were found to be 8.6 and 28.6 mmol L1, respectively. A Good 327
recoveries and low relative standard deviation reect the high 328
accuracy and precision of the proposed method. It can be 329
concluded also that, the proposed voltammetry method can 330
undoubtedly be considered as an effective to detect and quantify 331
IMD in real samples such as, plum fruit. 332

Uncited reference Q2 333

[44]. 334

Acknowledgment 335

This work was nancially supported by the Tunisian Higher Q3 336

Education and Scientic Research Ministry. Q4 337

References 338

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