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Molecularly Imprinted Electrochemical Sensor Based on Modified Reduced

Graphene Oxide‐gold Nanoparticles‐polyaniline Nanocomposites Matrix for
Dapsone Determination

Article in Electroanalysis · March 2019

DOI: 10.1002/elan.201800818

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 Full Paper
1 DOI: 10.1002/elan.201800818
2
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4
Molecularly Imprinted Electrochemical Sensor Based on
5
6
Modified Reduced Graphene Oxide-gold
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8
Nanoparticles-polyaniline Nanocomposites Matrix for
9
10
Dapsone Determination
11
12 Houda Essousi+,[a] Houcine Barhoumi+,*[a] and Nicole Jaffrezic-Renault[b]
13
14
15 Abstract: This work was designed to develop an electro- dance spectroscopy (IS). Throughout this study several
16 chemical sensor based on molecular imprinted polyaniline analytical parameters, such as incubation time, pH value,
17 membranes onto reduced graphene oxide (RGO) and concentration of monomer/template molecules and elec-
18 gold nanoparticles (AuNPs) modified glassy carbon (GC) tro-polymerization cycles were investigated. Under the
19 electrode for dapsone (DDS) determination. The pre- optimized conditions, the experimental results showed
20 pared RGO/AuNPs/PANI-MIPs nanocomposite was char- best analytical performances for DDS detection with a
21 acterized by Ultra-Violet-Visible (UV-Vis), Fourier trans- sensitivity of 0.188 W/mol L 1, a linear range from 1.0 3
22 form infrared spectroscopy (FT-IR) and scanning 10 7 M to 1.0 3 10 3 M and a detection limit of 6.8 3
23 electronic microscopy (SEM) images. The feature of the 10 7 M. The bioanalytical sensor was applied to the
24 imprinted electrode was evaluated by cyclic voltammetry determination of dapsone in real samples with high
25 (CV), differential pulse voltammetry (DPV) and impe- selectivity and recovery.
26 Keywords: Dapsone · gold nanoparticles · molecular imprinted · polyaniline · reduced graphene oxide
27
28
29
1 Introduction
30 electrochemical sensor based on iron oxide nanoparticles
31 Dapsone, (4,4-diaminodiphenylsulfone, DDS), is amongst for dapsone detection using molecular imprinted polyani-
32 the most important sulfonamides [1, 2], and is widely used line [2]. Molecular imprint polymer (MIP) are synthesized
33 as an antibacterial and anti-inflammatory in the treatment by polymerization of functional monomers in the presence
34 of different array of diseases including methemoglobine- of template compounds, which results in a three-dimen-
35 mia [3], sarcoma [4], tuberculosis [5] and leprosy, caused sional matrix with specific recognition capability. After
36 by mycobacterium leprae [6]. Dapsone has been used to polymerization, the template molecule is leached out from
37 treat pneumocystis carinii pneumonia and treatment of the polymer matrix, leaving cavities, which are in
38 malaria [7]. Moreover, dapsone is extremely used in accordance with the size, positioning and shape selection
39 streptococcal coccidiosis and mastitis of cattle such as for to the template [18–20]. However, the MIPs modified
40 the oral treatment of bovine coccidiosis, for the intra- sensors can cause poor adhesion and low electrochemical
41 urine treatment of endometritis and for the inframam- signal [21]. To reduce these problems, nanomaterials are
42 mary treatment of bovine mastitis [8, 9]. For this reason, introduced to the surface of electrode for their unique
43 new indications for dapsone were successively identified, chemical, biological and mechanical properties [22–23].
44 and this drug gained widespread use. Dapsone can be Among these materials graphene, nanotubes [24], con-
45 successfully detected by several analytical methods, ducting polymers [25, 26], magnetic nanoparticles [27] and
46 including high-performance liquid chromatography metallic nanomaterials [28, 29] have been extensively used
47 (HPLC) [10], spectrophotometry [11, 12], flow injection as an excellent support to modify planar electrode
48 chemiluminescence [13] and electrochemical methods
49 [14]. However, these conventional methods have dis- [a] H. Essousi,+ H. Barhoumi+
50 played few disadvantages, such as time consuming and University of Monastir, Faculty of Sciences of Monastir, La-
51 poor chemical/mechanical stability. To address these boratory of Advanced Materials and Interfaces, Monastir,
52 issues, molecular imprinting technique as a recognition Tunisia
53 element for sensors, has aroused more attention in drugs + (216) 73 500 278
54 analysis thanks to their inherent advantages such as high + (216) 73 500 280
E-mail: Houcine.Barhoumi@fsm.rnu.tn
55 sensitivity, good accessibility to the target species, physi- [b] N. Jaffrezic-Renault
56 ochemical stability, time saving and excellent substrate University of Lyon, Institute of Analytical Sciences, Villeur-
57 selectivity which are encouraging for dapsone detection banne, Lyon, France.
58 [15–17]. In previous work, we have already developed an [+] Corresponding author Houcine Barhoumi

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1 because it possesses a large surface area and further from Sigma Aldrich, Germany and used as received. A
2 increase the number of imprinting cavities from the 0.1 M phosphate buffer solution (PBS, pH 7.0) was
3 binding sites to the surface of the modified electrode [30]. prepared with KH2PO4, K2HPO4 solution and hexacyano-
4 In the last decades, the application of conductive polymers ferrate (II/III) were obtained from Fluka Chemika. The
5 such as polyaniline, polypyrrole and polythiophene have real samples (Urine and blood) were purchased from the
6 been extensively investigated as MIPs film to enhance the office of the state land in Enfidha.
7 sensitivity of the imprinted sensors [31–33]. Polyaniline
8 (PANI), one of monomer of the most outstanding
2.2 Apparatus
9 conduction polymers due to its excellent electrical,
10 chemical and electrochemical properties, unique redox Cyclic voltammetry and differential pulse voltammetry
11 behavior and facile synthesis [34, 35]. It has been em- were carried out using a potentiostat (DY200 POT Eco-
12 ployed to enhance the current response of the proposed chimie) and an Autolab PGSTAT 320 N potentiostat.
13 electrode in the experiment. Conductive polymers have Electrochemical impedance spectroscopy was controlled
14 been modified using nanoparticles and graphene oxide to by a computer using commercially available Nova version
15 enhance the selectivity and the sensitivity of imprinted 1.5 software. Impedance measurements of the MIP were
16 sensors [36, 37]. Recently, Graphene (GN), graphene performed in the frequency range from 0.1 to 100.000 Hz
17 oxide (GO), as a new form of carbon atom have enjoyed using an aqueous solution containing H2SO4 (pH = 3) as
18 widespread attention in several areas of research including supporting electrolyte. The pH of the solutions was
19 nanocomposite, cancer diagnosis, drug delivery and bio- measured with a pH meter (3505 pH meter JENWAY).
20 sensing owing to their unique properties such as large The Ultra-Violet-Visible measurements were carried out
21 specific surface area and good stability [38–40]. In fact, in 67 series spectrophotometers models 6705 UV/Vis
22 several MIP composites graphene or graphene oxide as JENWAY with an optical transparent working electrode,
23 supporter matrices for the recognition of antibiotics have indium-tin oxide (ITO) glass plate(10 W/mm) to study the
24 been successfully produced in recent years, which demon- UV-Visible absorption behavior. The samples were also
25 strated not only fast adsorption dynamics but also high characterized by FT-IR spectroscopy using Perkin Elmer
26 binding capacity toward the template [41]. Luo et al. 1600 FTIR spectrometer and scanned over the wave
27 reported a highly selective electrochemical sensor for number range between 400 and 4000 cm 1 after redissolu-
28 bovine hemoglobin based on graphene-MIP composite as tion of the deposited layers in chloroform. The morphol-
29 a recognition element [42]. On the other hand, another ogy of the nanocomposite deposited on the electrode
30 excellent material for sensor development is gold nano- surface was characterized using scanning electronic micro-
31 particles (Au-NPs). Au-NPs are widely applied in the scopy (MEB). Electrochemical data were carried out with
32 fabrication of various sensors due to their small dimen- three-electrodes system consisting of glassy carbon elec-
33 sional size, good stability, biocompatibility and excellent trode (GCE, diameter 3 mm) as the working electrode. A
34 conductivity compared to the bulk metal [43, 44]. Con- platinum wire electrode and Ag/AgCl (3 M KCl) elec-
35 ducting polymer and gold nanoparticles anchored on trode were used as auxiliary and reference electrodes,
36 reduced graphene oxide combined with the MIP for the respectively.
37 detection of specific molecules have proven to be effective
38 for great signal amplification and shorten binding time for
2.3 Preparation of Imprinted (MIP) and Non-imprinted
39 recognized target molecules. In this work, we report a new
(NIP) Electrodes
40 MIP based on conducting nanocomposites of RGO/
41 AuNPs/PANI modified GC electrode for DDS determi- Before modification, the glassy carbon electrode (GCE)
42 nation. The electrochemical behavior of MIP sensor was was carefully polished with aluminum oxide slurry
43 characterized by CV, DPVand EIS. The morphology and (0.3 mm) using a polishing cloth, rinsed with ultra-pure
44 structure of the MIP film has been characterized by SEM, water and then sonicated sequentially in absolute ethanol
45 UV-Visible and FTIR and its experimental parameters and double distilled water for five minutes to remove the
46 influencing the performance of the imprinted sensor were trace of alumina on the surface of the electrode. The
47 optimized. Moreover, the developed sensor provides an fabrication process of NIP-GCE/RGO/AuNPs/PANI and
48 efficient protocol for the detection of dapsone in serum MIP-GCE/RGO/AuNPs/PANI were shown in Scheme 1.
49 and urine samples. After passing nitrogen gas for 3 minutes, 15 ml of GO
50 were deposited on the clean GCE surface and then dried
51 for 24 h to obtain GCE/GO. The GCE/GO was electro-
52 2 Experimental chemically reduced in 0.1 M PBS buffer solution (pH = 7)
53 by performing 15 consecutive cyclic scans in the potential
2.1 Chemicals and Reagents
54 range of 0.6 and 1.4 V at a scan rate of 20 mV/s. Then,
55 Aniline was attained from Merck. Graphene oxide (GO), Au nanoparticles solution was dropped uniformly onto
56 gold nanoparticles (AuNPs), Dapsone (DDS), ethanol, the surface of GCE/RGO and dried at room temperature
57 sulfuric acid (H2SO4), uric acid (UA), ascorbic acid (AA), for 24 h. In order to prepare the MIPANI film, cyclic
58 sulfaguanydin, streptomycin and dopamine were obtained voltammetry was employed for the electropolymerization

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20 Scheme 1. Schematic illustration of the MIP sensor fabrication based on RGO/AuNPs/PANI obtained by electrodeposition method.
21
22
23 of aniline (0.2 M) in 0.5 M H2SO4 solution as supporting
24 electrolyte in presence of 5.0 mM of dapsone as template
25 molecules onto the RGO/AuNPs/GCE. The electro-poly-
26 merization was prepared by applying ten successive
27 polymerization cycles from 0.2 to 1.4 V with a scanning
28 rate of 100 mV/s. The recognition sites in the imprinted
29 matrix were formed after extracting the template from the
30 imprinted film. So, the selection of a suitable solution and
31 method to completely elute the template from the
32 imprinted film is very important. The template (DDS)
33 extraction was carried out by immersing the electrode in a
34 mixture of acetic acid and methanol (volume ratio = 1 : 9)
35 for 24 hours, leaving free surface imprinted sites corre-
36 sponding to the template shape. The resulting MIP-GCE/
37 RGO/AuNPs/PANI was thoroughly washed with distilled
38 water to remove unbound matter. For comparison the
Fig. 1. CV curve obtained on GO/GCE in 0.1 M PBS (pH = 7) at
39 NIP was prepared in a similar manner but without the a scan rate of 20 mV/s.
40 addition of dapsone.
41
42
43 3 Results and Discussion 3.2 SEM Characterization of the Modified Electrodes
44
3.1 Preparation of RGO/GC Modified Electrode
45 To investigate the morphology of the modified GCE
46 Figure 1 display the electrochemically reduction of GO on surface, SEM images were recorded. Figure 2 displays the
47 the GC electrode by cyclic voltammetry between 0.6 and SEM analysis of the GCE/GO (A), GCE/RGO (B), GCE/
48 1.4 V with the scan rate of 20 mV/sfor 15 cycles in 0.1 M RGO/AuNPs (C), GCE/RGO/AuNPs/PANI (D), NIP-
49 PBS buffer solution (pH = 7). As can be seen, a large GCE/RGO/AuNPs/PANI (E) and MIP- GCE/RGO/
50 reduction peak appears at approximately 0.58 V due to AuNPs/PANI (F), respectively. It can be clearly seen that
51 the reduction of oxygen functional groups, which increases the morphology of the prepared GO shows sheet-like
52 gradually after cycles, until the peaks disappeared com- shape with homogeneous, corrugated and relatively
53 pletely, ascribe to the complete reduction of the oxygen smooth surface (Figure 2A) evidently impede the current
54 functional groups present on the surface of GO [45]. response, while the surface of RGO/GCE (Figure 2B)
55 display a slight wrinkle, which provide a large electro-
56 active area on the electrode. Figure 2C display the
57 structure of wrinkles multilayer with many granular
58 AuNPs were distributed uniformly on the GCE/RGO film

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46 Fig. 2. SEM images of different modified electrodes: (A) GCE/GO, (B) GCE/RGO, (C) GCE/RGO/AuNPs, (D) GCE/RGO/AuNPs/
47 PANI, (E) NIP-GCE/RGO/AuNPs/PANI and (F) MIP-GCE/RGO/AuNPs/PANI.
48
49
50 with heterogenous diameter from 50 to 70 nm, confirming template (DDS) molecules, the surface of the MIP film
51 the presence of RGO/AuNPs nanocomposite on the displayed the recreation of rough morphology embedded
52 surface of GCE. It is obvious from Figure 2(D) that the in the SEM image of MIP-GCE/RGO/AuNPs/PANI (Fig-
53 electro-polymerized polyaniline film exhibited some ure 2F), which is comparatively similar to that of GCE/
54 bright spot and a rough film grown on the RGO/Au-NPs RGO/AuNPs/PANI.
55 modified electrode, while the SEM images of GCE/RGO/
56 AuNPs/PANI/DDS (Figure 2E) show disappearance of
57 porous structure after insertion of DDS molecules in
58 GCE/RGO/AuNPs/PANI film. After the removal of the

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1 3.3 Spectroscopic Characterization results affirm that DDS were completely extracted from
2 the imprinted structure. In addition, the FTIR spectra of
3 The successful synthesis of both NIP-RGO/AuNPs/PANI MIP and NIP possessed the same absorption bands,
4 and MIP-RGO/AuNPs/PANI matrix deposited on GCE differing only in intensity. A wide band in the range of
5 surface by electrochemical oxidation was confirmed using 3200–3450 cm 1 relative to the symmetric and asymmetric
6 FTIR spectroscopy method. The FTIR spectra of DDS N H stretching of the amine group overlapped with O H
7 powder, NIP-RGO/AuNPs/PANI and MIP-RGO/AuNPs/ stretching vibration observed. The symmetric and asym-
8 PANI matrix are shown in Figure 3A. The absorption metric stretching vibration CH2 were situated at 2870 and
9 peaks observed at 1632 and 1700 cm 1 for dapsone are 2920 cm 1, respectively. The broad peak at 1650 relate to
10 assigned to the bending vibration of primary NH2 in plan the stretching vibration of quinoid ( N=(C6H4) N ) ring.
11 [42]. On the other hand, the peaks at 1200 and 1400 cm 1, The UV-Vis spectra of DDS in 0.5 M H2SO4 and
12 which are related to S O and C N asymmetric stretching electrochemically deposited film of RGO/AuNPs, RGO/
13 modes in dapsone. Prior the removal of DDS, the AuNPs/PANI, NIP-RGO/AuNPs/PANI and MIP-RGO/
14 spectrum of the NIP-RGO/AuNPs/PANI displayed two AuNPs/PANI were further shown respectively in Fig-
15 weak absorption at 650 and 1190 nm, which are attributed ure 3B. The absorption band seen in the spectrum of DDS
16 to the substituted benzene ring and symmetric stretching are clearly visible at 290 nm, this peak may be due to the
17 mode of SO2. This suggested that the template DDS was benzene ring indicating the presence of an aromatic ring.
18 successfully interacted with RGO/AuNPs/PANI modified The spectrum of RGO/AuNPs shows an absorption band
19 GC electrode through hydrogen bands. The FTIR of MIP at 320 nm corresponding to the n-p* transitions of the C=
20 matrix after the removal of DDS molecules, the absorp- O band. Another strong characteristic absorption band
21 tion bands of template molecules disappeared. These appeared in the range of 500 and 730 nm can be assigned
22 to AuNPs [46, 47]. The spectrum for RGO/AuNPs/PANI
23 shows the characteristic band at 300 nm, attributed to
24 PANI benzenoid rings p-p* electronic transition [48, 49].
25 The broad band at 500–700 nm and the absorption peak at
26 800 nm, resulting from the polaron-p and polaron-p*
27 electron transition of benzenoid ring in the PANI chain,
28 indicates the presence of AuNPs in RGO/AuNPs/PANI
29 and their conjugation with PANI [50, 51]. After the
30 deposition of DDS on the RGO/AuNPs/ PANI surface, a
31 new peak with lmax around 290 nm is observed and a small
32 intensity peak with lmax around 385 nm as compared to
33 the peak obtained for RGO/AuNPs/PANI nanocomposite
34 [2]. This fact revealed the presence of higher number of
35 benzene ring in the last nanocomposite. After removal of
36 the DDS molecules, the band at lmax = 290 nm disappeared
37 and the spectrum changes to that of the NIP matrix, which
38 indicate the formation of artificial sites due to the ejection
39 of DDS molecules from the RGO/AuNPs/PANI matrix.
40 All this observation suggests the formation of MIP-RGO/
41 AuNPs/PANI.
42
43
3.4 Electropolymerization of Molecularly Imprinted
44
Polyaniline
45
46 Figure 4 presents the CVs of GCE/RGO/AuNPs/PANI
47 (NIP) and GCE/RGO/AuNPs/PANI/DDS matrices ob-
48 tained by electro-polymerization from 0 and 1.4 V in
49 0.5 M H2SO4. For NIP film it was clear that the currents
50 peaks due to the oxidation and reduction of the film was
51 gradually increased with increasing number of cycles
52 suggesting that the polyaniline film formed at the surface
53 of the RGO/AuNPs was compact, thicker and conductive.
54 For imprinted electro-polymerization, the effect of dap-
55 Fig. 3. (A ) FTIR spectroscopy behavior of both structures NIP sone template molecules can be easily distinguished. It
56 and MIP. (B ) UV-Vis absorption spectrum of ITO/RGO/AuNPs, was observed that oxidation and reduction peaks were
57 ITO/RGO/AuNPs/PANI, NIP-ITO/RGO/AuNPs/PANI and MIP- lower when DDS molecules were present in the electro-
58 ITO/RGO/AuNPs/PANI. deposition solution. During the electropolymerization the

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16 Fig. 4. Cyclic voltammograms of the electro-polymerization of
17 aniline (0.1 M) in the absence (black) and presence (red) of
18 (5 mM) DDS onto GCE/RGO/Au-NPs in 0.5 M H2SO4 solution
19 with a scan rate of 100 mV/s and Number scans of 10.
20
21
22 DDS molecules are trapped in the polymer matrix
23 through non-covalent interactions between -NH2 groups
24 of the polymer and the oxygen atoms of DDS.
25
26
3.5 Characterization of Electrochemical Behaviors of MIP
27
Films
28
29 The cyclic voltammetry (CV) measurement was inves-
30 tigated to monitor the electrochemical behavior of un-
31 modified and modified working electrodes with different
32 matrix. All measurement was performed in 1 mM
Fig. 5. Typical CVs (A) and EIS (B) spectra of bare GCE, GCE/
33 [Fe(CN)6] 3/ 4 containing 0.1 M KCl solution, at a scan GO, GCE/RGO, GCE/RGO/AuNPs, GCE/RGO/AuNPs/PANI,
34 rate of 100 mV/s with a potential ranging from 0.2 to NIP-GCE/RGO/AuNPs/PANI and IP-GCE/RGO/AuNPs/PANI
35 1.4 V. During this procedure [Fe(CN)6] 3/ 4 was served as matrix in 1 mM [Fe(CN)6]3 /4 and 0.1 M KCl at Scan rate of
36 an electroactive probe to characterize the recognition 100 mV/s.
37 performance of the molecularly imprinted membrane.
38 Figure 5 A showed a comparison of cyclic voltammograms
39 of the bare GCE, GCE/GO, GCE/RGO, GCE/RGO/ anodic peak around 0.792 mV and inverse cathodic peak
40 AuNPs, GCE/RGO/AuNPs/PANI, NIP-GCE/RGO/ around 0.614 mV. This pair redox peaks possibly due to
41 AuNPs/PANI, MIP-GCE/RGO/AuNPs/PANI in the probe the large effective area of RGO/AuNPs/PAN, which
42 solution. The bare GCE exhibits electrochemical charac- suggest the formation of a conductive and uniform film
43 teristics with a pair of redox peaks (curve (a)). The redox gradually covering the electrode surface. However, as
44 peaks of the [Fe(CN)6] 3/ 4 is not observed on the surface shown in curve (f) the CV obtained at NIP-RGO/AuNPs/
45 of GCE/GO which might be due to the coating of GO PANI modified electrode was decreased compared with
46 (curve (b)). In addition, an anodic peak appeared at a that of the RGO/AuNPs/PANI, it can be ascribed that this
47 potential of 0.151 mV. After reduction of GO, the surface template molecules have been embedded in RGO/
48 of GCE/RGO showed a pair of well-defined reversible AuNPs/PANI film. This may be explained by the inter-
49 redox peak and the current increased (curve (c)). This can action between DDS and RGO/AuNPs/PANI nanocom-
50 be attributed to the increase active electrode surface area. posite and their successful immobilization. After the
51 After dropping AuNPs, it was found that this material can template (DDS) was extracted from the MIP film, the
52 increase the conductivity and the adsorb-ability of the intensity of the current increased (curve (g)), this behavior
53 electrode (curve (d)), which might be due to the high is due to the increase of vacant recognition cavities
54 conductivity and favorable specific surface area of the produced in the imprinted membranes after the removal
55 nanocomposite. But, the peak current observed at the of DDS molecules could enhance the diffusion of the
56 nanocomposite is slightly shifted in the positive direction. redox probe [Fe(CN)6]3 /4 .
57 After the electrode was modified with PANI, the cyclic Consistent with CV study, impedance spectroscopy
58 voltammetry peak current (curve (e)) show clearly an (IS) is an effective method for probing the features of the

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1 modified electrode surface. Here in, EIS data were
2 typically used to follow the Rct changes occurring at the
3 interface after each stage of electrochemical modification.
4 In EIS studies, the semicircle part at high frequency
5 represents the charge transfer resistance (Rct) of the
6 electrode and the linear segment at lower frequencies
7 indicates the diffusion limited process [52, 53]. Figure 5B
8 depicts the Nyquist diagrams recorded at the frequency
9 range from 0.1 to 105 Hz with 100 mV amplitude using
10 bare and differently modified GC electrodes applying an
11 excitation potential of 0.238 V (vs. Ag/AgCl reference
12 electrode). All EIS measurements were carried out using
13 1.0 3 10 3 M [Fe(CN)6]3 /4 in 0.1 M KCl solution. The
14 characteristic EIS spectrum is a Nyquist plot, where Z’
15 and Z’’ are the real and imaginary part of impedance,
16 respectively [54, 55]. It was observed that the EIS results
17 were in good agreement with the CV results. As shown in
18 Figure 5B, the EIS of the bare GCE displays a small
19 semicircle and the charge transfer resistance (Rct) value is
20 95 W. Compared with bare GCE, GCE/RGO was associ-
21 ated by the increased in the Rct value to 244 W, which was
22 attributed to the poor electrical conductivity of the RGO.
23 The surface of GCE/RGO/AuNPs After the immobiliza-
24 tion of AuNPs, the surface of GCE/RGO/AuNPs showed
25 an increment in the charge transfer resistance (Rct =
26 60.4 W) which confirmed the presence of AuNPs on the
27 electrode surface, while the impedance curve of GCE/
28 RGO/AuNPs/PANI was almost a straight line and the Rct
29 value decreased to 22.8 W, which was attributed to the
30 higher electric conductivity of PANI which improves the
31 electron transfer process. Finally, when DDS was depos-
32 ited on the surface of GCE/RGO/AuNPs/PANI the Rct
33 value increased to 147 W, which may be attributed to the
34 nonconductive coating film on the electrode surface. This
35 result assures that dapsone had been attached to the
36 modified electrode surface. Once the template (DDS) was
37 removed from the MIP-GCE/RGO/AuNPs/PANI, the Rct
38 value decreased 49.7 W, produced large number of
39 cavities, which suggests that the conductivity of the
40 electrode surface has increased and makes the electron
41 transfer easy.
42
43
44 3.6 Effect of Several Significant Operational Parameters
45 on the Imprinted Sensor Response
46
3.6.1 Effect of Template and Monomer Concentrations
47
48 The performance of the imprinted sensor for DDS
49 detection can be affected by the ratio of aniline monomer
50 and DDS template during the electro-polymerization.
51 Therefore, to adjust the interaction between template and
52 monomer it will be necessary to optimize their concen-
53 trations. In Figure 6 we report the variation of the
54 imprinted MIP modified electrode sensitivity in presence
55 of dapsone for different concentration of monomer (Fig-
56 ure 6A) and template (Figure 6B). The analytical per-
57 formances for dapsone detection were obtained for a
58 template concentration of 5.10 3 M and 0.2 M of aniline
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monomer. Electrochemical measurements were investi-
gated using DPV (current variation) and EIS (Rct
variation) sensing methods.
3.6.2 Effect of the Electro-polymerization Cycles
It is well known that the thickness of the polymer
membrane is an important factor which can affect the
sensitivity and linearity of the imprinted sensors. Fig-
ure 6C shows the effect of the number of scan cycles on
the cyclic voltammograms recorded during the electro-
polymerization of aniline on the GCE/RGO/Au-NPs in
the presence of dapsone molecules. It can be seen that the
highest current intensity and charge transfer resistance
were established at 10 cycles, which indicate the successful
formation of MIP films with a suitable thickness. When
the number scan cycles were less than ten, the imprinted
polymer membrane became very thin and easy to break
when removing the template. If the number scan cycles
were more than ten, the imprinted polymer membranes
were too thick and the template molecules cannot be
completely removed from the film. Thus, the number of
scan cycles for the preparation of the MIP-GCE/RGO/
Au-NPs/PANI sensor was adjusted to 10 cycles in the
following investigation.
3.6.3 Effect of Incubation Time and pH
The incubation time and the pH medium of MIP film
habitually affect the sensitivity of imprinted sensors [56].
Thus, their influence was optimized. DPV and EIS
methods were further used to investigate the effect of pH
on the analytical performances of the developed MIP
modified electrode in the pH range from 1 to 7. As shown
in Figure 7A the current intensity of the imprinted sensor
increases when the pH increases from 1 to 3, then
decreased rapidly and reached a high peak at 3. For
impedance assay, we observe a decrease in the charge
transfer resistance when the pH increases from 1 to 3,
then increase, which was related to the role of proton in
the electrochemical reaction process. The highest current
intensity and charge transfer resistance were established
at pH = 3.0. This pH was used as optimal value for
subsequent experiments. The incubation process is an
important step for the sensitivity of the imprinted sensor
[57]. When the template was removed from the film, the
MIP sensor was incubated in H2SO4 solution (pH = 3)
containing 200 mL DDS under stirring. As shown in
Figure 7B the Rct values of the MIP for DDS concen-
tration increase gradually with increasing the incubation
time at the beginning of the experiments, but after 25 min
it kept almost stable, suggesting that the adsorption
reaction of DDS was saturated. Thus, 25 min has been
selected as the optimal incubation time.
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29 Fig. 6. Effect of monomer (A) and template (B) concentration on the Rct values and peak currents of the MIP sensor, (C) Effect of the
electro-polymerization cycles in 1 mM K3[Fe(CN)6]/K4[Fe(CN)6] containing 0.1 M KCl solution.
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Table 1. Comparison of different electrodes for the detection of DDS.
33
34 Electrode Method Linear range Detection limit Sensitivity Ref
35 6 4 1 6 1 1
CPE DPV 9.98 3 10 –4.99 3 10 mol L 3.86 3 10 mol L 36.8 mA L mmol [12]
36 GCE/OPPyox/MIP DPV 1.0 3 10 6–1.1 3 10 4 mol L 1 3 3 10 7 mol L 1 0.049 A L mol 1 [34]
37 SiO2/MIP CL 10 6–10 4 mol L 1 5.27 3 10 7 mol L 1 2.067 A L mol 1 [58]
38 Pt/Fe3O4NPs/PAN/MIP EIS 1.0 3 10 7–1.0 3 10 5 mol L 1 1.25 3 10 5 mol L 1 16.255 W L mol 1 [2]
39 GCE/RGO/AuNPs/PAN/MIP EIS 1.0 3 10 7–1.0 3 10 3 mol L 1 6.8 3 10 7 mol L 1 27.856 W L mol 1 This work
40 EIS: Electrochemical impedance spectroscopy, b DPV: Differential pulse voltammetry, CL: Chemiluminescence
41
42
43 3.7 Electrochemical Impedance Responses of the MIP by the variation of the charge transfer resistance (ob-
44 and NIP Decorated RGO/AuNPs/PANI Toward DDS tained through Nova analysis) versus the dapsone concen-
45 and Effect of Interferences tration as shown in Figure 8C. The linear response range
46 for DDS detection was obtained in the concentration
47 Based on above optimal experimental conditions, differ- range from 1.0 3 10 7 M to 1.0 3 10 3 M with a sensitivity
48 ent Rct values of the MIP and NIP modified electrodes of 0.188 W/mol L 1 for the MIP. A linear regression
49 were obtained by varying the DDS concentration in 0.1 M response was obtained (R2 = 0.987) with a low detection
50 H2SO4 solution (pH = 3). The impedance values are fitted limit of 6.8 3 10 7 M for MIP. Compared with other
51 by using the classical Randle’s equivalent circuit depicted methods, this sensor offered a good linear range and a
52 in Figure 8A. As seen in Figure 8B the charge transfer lowed detection limit for the MIP based electrochemical
53 resistance (Rct) of the electrode in the absence of DDS is sensor. The analytical performances of the dapsone sensor
54 relatively small (120 W). This value can be attributed to are listed in Table 1.
55 the free electron transfer from the surface of the electrode In order to check selectivity of the MIP sensor toward
56 to the solution. The increases of the DDS concentration dapsone, some possible interfering substances like sulfa-
57 induce the increases of the Rct values. The analytic guanidine, streptomycin, dopamine, glucose, uric acid and
58 response of the MIP and NIP sensors can be represented ascorbic acid were investigated under optimal experimen-

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30 Fig. 7. Imprinted GCE/RGO/AuNPs/PANI sensor performances.
31 (A) pH of the analysis medium and (B) the different incubation
32 times effects on the sensor performances.
33
34
35 tal conditions. The selective experiments were carried out
36 by detecting the Rct response of 1.0 mM DDS at MIP-
37 GCE/RGO/AuNPs/PANI in H2SO4 (pH = 3) solution
38 containing 100-fold concentration of interference species.
39 The results obtained by the electrochemical impedance
40 spectroscopy method were given in Figure 8D. EIS
41 measurements were performed in 0.1 M H2SO4 solution
42 (pH = 3) at a potential of 0.6 V over the frequency range
43 from 0.1 to 100.000 Hz, using a voltage amplitude of
44 100 mV. Only a slight change in the Rct values was
45 obtained in the presence of some potential interfering
46 species at various concentrations such as streptomycin and
47 sulfa-guanidine at the same operating potential in the Fig. 8. Standard Randles equivalent circuit used for modeling the
48 system. However, a high Rct response for glucose, uric EIS measurements(A), EIS responses of the MIP as a function of
49 acid, ascorbic acid and dopamine, the cavities formed in various concentration of dapsone in H2SO4 solution (pH = 3)(B)
50 the imprinting process could not bind them on the the corresponding calibration curve of Rct vs. logarithm of MIP
and NIP for DDS concentration (C) and (D) Calibration curves
51 electrode, which resulted in higher response. In addition
with interferent species such as sulfa-guanidine, streptomycin,
52 to that, the effect of different ions on the detection of dopamine, glucose, uric acid and ascorbic acid.
53 DDS was studied. The results showed that 100-fold of
54 Ca2 +, Pb2 +, Cu2 + and Mg2 + did not interfere with the
55 detection of DDS. These results might be ascribed to the
56 matched cavities on the surface of the MIP-based sensor
57 through their size, shape and functional groups of dapsone
58 molecules during the electro-polymerization.

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1 3.8 Reproducibility and Stability of the MIP Sensor template. Owing to the unique mechanical properties and
2 extremely large area of the Au-NPs, the resulting MIP-
3 The reproducibility of the imprinted sensor was evaluated GCE/RGO/Au-NPs/PANI nanocomposite matrix exhibits
4 by measuring the Rct response for four MIP-GCE/RGO/ high sensitivity, selectivity and lower limit detection
5 AuNPs/PANI replicated determinations at the same toward template molecules. The developed sensor can
6 electrode using the same procedure toward 10 4 M DDS specially recognize and determine DDS with a linear
7 in H2SO4 (pH = 3) by EIS. The sensor was stored at room range from 10 mM to 1 mM. The results of recovery,
8 temperature when not in use. The relative standard obtained during the detection of DDS molecules in urine
9 deviation (RSD) was 4.2 %, indicating that this sensor had and serum suggest that this method is suitable for the
10 good repeatability reproducibility for DDS determination. detection of DDS molecules in real samples. Besides, the
11 In order, to investigate the stability of the modified developed imprinted electrochemical sensor can be used
12 electrode, molecular imprinted film was stored for two in pharmaceutical and biological samples thanks to its
13 weeks in the refrigerator at 4 8C and used to detect 150 ml simplicity, selectivity and efficiency in target detection.
14 of DDS. Only little decrease of the original values was
15 observed. This reflected the relevant stability of the
Acknowledgements
16 imprinted sensor.
17 Authors would like to acknowledge PRF-2017-D4P1/
18 Tunisia project (No. 12Mag088), and the Ministry of
3.9 Real Analytical Application of MIP Sensor for the
19 Higher Education and Scientific Research of Tunisia
Determination of Dapsone
20 (LR11ES55).
21 As a newly developed method, the prepared electro-
22 chemical imprinted sensor was employed for the detection
23 of dapsone in cow urine and serum samples (purchased
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8 Molecularly Imprinted Electro-
9 chemical Sensor Based on Modified
10 Reduced Graphene Oxide-gold
11 Nanoparticles-polyaniline Nano-
12 composites Matrix for Dapsone De-
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