ResearchGate wt Voltammetric Techniques at Chemically Modified Electrodes arto suraaatal Cres a15 8 46 ‘Som ofthe author he puieaton asso woking on there rete projects: + _synteesand chaacaston off Sensor Apples Vow oro ‘Acontenolowng spas was ponced Wy Riss ilswaran6T November 205{ISSN 101.988, Joma of nape henry, 2015, REVIEW Voltammetric Techniques at Ch Rakesh R. Chillawar, Kiran Kumar Department of Chemistry, Visvesvaraya National Insti e-mail: rkawadkan Received May 8, 2013; in fina Abstract—Voltammetric and amperometric techniques emically Modified Electrodes! Tadi, and Ramani V. Motghare* tute of Technology Nagpur 440010 (M.S), India srGichm.vnit.ae.in form, September 30, 2014 are powerful analytical tools that are widely used in. chemical analysis. This article reviews a summary of some important types of modifying agents and their application in voltammetric and amperomettic sensors for clinically and biologically important target species reported from the period 2003 to 2013. In this review, different modifiers such as molecularly imprinted poly- mers (MIPS), polymers, metal complexes, nanomaterials and composite films are discussed, Under the heading of each modifier, method of fabrication, propet trodes (CMEs) are given. Tables that give analyte, modi ties, and applications of chemically modified elec- fed electrode, measurement technique, measuring ‘meditim, linear detection range (LDR) and limit of detection (LOD) referenced from original work are also provided. Keywords: voltammetry, amperometry, chemically modi DOK: 10.1134/S1061934815040152 Electroanalytical chemistry is a branch of chemical analysis in which electroanalytical techniques are em- ployed to obtain information about chemical species with respect to their quantities, properties and envi- ronment. According to Izaak Maurits Kolthoff, elec- ‘troanalytical chemistry is the application of electro chemistry to analytical chemistry. It is appropriate to consider electroanalytical chemistry as an area of chemical analysis in which the electrode is involved as a probe to determine various chemical species directly or indirectly [1] Nowadays, the demand for improved analytical techniques is increasing, especially for pharmaceutical drugs and their metabolites, environment pollutants, food additives, ete which widely affect human health, So the development of simple, reliable, rapid, sensitive and accurate analytical methods is essential. Elec troanalytical chemistry provides such electrochemical methods like voltammetric techniques. These electro- chemical methods are characterized by simplicity, low cost instrument, high sensitivity, good stability, envi- ronmental friendliness and on-site monitoring [2] Voltammetry was discovered by Czech scientist Jaroslav Heyrovsky in the 1920s. It isa form of electro- chemistry, based on the measurement of current flow- ing through the working electrode immersed in a solu- tion containing electro-active sample to be analyzed by varying potential in some systematic manner. Hey- rovsky also discovered polarography for which he was awarded the Nobel Prize in chemistry in 1959 [3]. Vol- tammetric techniques are now becoming increasingly The article is published inthe original, 399 fled electrodes, voltammettic sensor important because of its simple, cost-effective and quick way of determining biologically and environ- mentally important species. In the last few decades, voltammetsic techniques have become a promising analytical tool in the study of electrochemical reac~ tions [4], model studies of enzymatic catalysis [5] and free radicals [6], co-ordination chemistry [7], envi- ronmental monitoring [8], industrial quality control [9], solar energy conversion [10] and determination of trace concentrations of biologically and clinically im- portant species [11, 12] Voltammetric techniques show excellent selectivity and sensitivity because the analyte can be readily iden- tified by its voltammetric peak potential. However, the major problem encountered in these techniques is the interference of concomitant compounds. Owing to their very similar oxidation peak potentials, over- lapped voltammetric responses are obtained. To over- come this problem, electrodes modified using various materials and techniques are employed [13, 14]. The voltammetric techniques involve reactions at different electrodes such as glassy carbon electrode (GCE), pencil graphite clectrode (PGE), carbon paste clec~ trode (CPE), gold and platinum electrodes, etc. How- ever, application of these electrodes is limited due to fouling of the electrode surface by several species, thereby decreasing sensitivity and accuracy of the methods. The performance characteristics of these electrodes can be increased by using CMEs. CMEs have attracted considerable interest in the study of the electro-catalytic reactions of various ana. Iytes such as pharmaceuticals, explosives, food cor taminants, metal ions, etc. According to TUPAC, a400 RAKESH R. Functional monomers “Template (analyte) CHILLAWAR et al. Cross-linker + Copolymerization Pre-polymerization complex Fig. 1.6 CME is defined as “an electrode made up of conduct- ing or semiconducting material and coated with a film ‘of chemical modifier, shows chemical, electrochemi- cal or optical properties of a film by means of faradaic reactions or interfacial potential differences.” CMEs offer various advantages over unmodified electrodes: they catalyze the oxidation or reduction of species that shows high overvoltages at unmodified electrodes, i.e. they lower the peak potentials. They also enhance sen- sitivity and improve selectivity in the application of pharmaceutical analysis [15—18} During past decades, a wide electrochemical re- search has been devoted to the development and appli- cation of different types of CMEs, Various materials such as carbon nanotubes (CNTs), gold nanoparticles (AUNPs), platinum nanoparticles (PtNPs), MIPs, molecularly imprinted conducting polymers, L-cys- teine (L-cys), Prussian blue, graphene (GR), metal complexes, zeolites, etc. were used for the modifica tion of electrode surface. Many reviews on the devel- ‘opment of modified electrodes and their applications in different fields of analysis have been reported. Blan- co-Lopez et al. [19] reviewed the electrochemical sen- sors based on non-covalent MIPS, giving details of dif- ferent recognition elements, electrochemical trans- duction and strategies for integration. A review on voltammetric techniques and their various applica tions to pharmaceutical analysis were reported by Vin- ‘od K. Gupta etal, [20], Eder Tadeu et al. [21] reviewed recent developments in the bioelectroanalysis of phar- maceuticals with respect to carbon-based materials, new potentiometric sensors and electrochemical bio- sensors, The objective of this review is to present a summary of some important types of modifying agents and their application in voltammetric and amperometric sen- sors for clinically and biologically important target species reported from the period 2003 to 2013. In this JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70, Tanto | | sesinine Qs Moleculary imprinted polymer jeneral principle involved in molecular imprinting. review, different modifiers such as MIPs, polymers, metal complexes, nanomaterials and composite films are discussed. Under the heading of each modifier, method of fabrication, properties, and applications of CMEs are given along with the table containing ana- lytes, modified electrodes, measuring techniques, measuring media, LDR and LOD. It is our hope that this will help researchers to know the merits and de- merits of CMEs and facilitate them to plan their own strategies to develop selective, sensitive, reproducible, anti-fouling and cost-effective CMEs for voltammet~ ric detection of various types of clinically and biologi- cally important target species. MOLECULARLY IMPRINTED POLYMERS During the last decade, MIPs have become impor- tant recognition elements in the electrochemical sens- ing. These are synthetic polymers capable of mimick- ing natural systems like enzymes, antibodies, etc. In MIP synthesis, the template and functional mono- mers are mixed to allow self assembly between them. This is then followed by thermal or photo-polymeriza- tion in the presence ofa cross-linker. After completion of polymerization, the template is extracted from the polymeric matrix, leaving cavities which are exactly complementary in the size, shape and functionality to the original template molecule. Figure 1 shows the general principle involved in molecular imprinting MIPs are lower price materials than antibodies with higher thermal and chemical stability. Due to their sta- bility, MIP modified sensors are easy to store and op- erate and have a long shelf life [22-24]. Various poly- meric systems used in sensor fabrication are acrylic or vinylic type of polymers, electro polymerized films, self-assembled monolayers (SAMs), sol-gel poly- mers, pre-formed polymers, etc. [19] No.4 2015OLTAMMETRIC TECHNIQUES AT CHEMICALLY. When the electrode is modified with non-condue- tive polymers such as the highly cross-linked MIPs, detection of an analyte molecule in a polymeric layer is possible ifit contains an important concentration of well-connected recognition sites through a network of pores of appropriate size and density close enough to the electrode surface. The measurement is carried out in a medium which favours the release of the analyte. Ifthe thickness of polymeric layer is excessive, strong diffusion impediments would occur due to recognition, sites being far away from the electrode surface. There- fore, for successful MIP modified sensor, porosity of the ‘polymer should be controlled. This can be achieved by means of nature and volume of porogenic solvent used in the monomer mixture [25] Acrylic MIP modified GCE was suggested by Blanco-Lopez et al. for the voltammetric determina- tion of vanillyimandelic acid (VMA). A 1:8: 40 molar ratio of the template molecule (VMA), functional monomer methacrylic acid (MAA) and cross-linking agent divinylbenzene or ethylene glycol dimethacry- late (DVB or EGDMA) along with porogenic solvent acetonitrile (ACN) and initiator 2,2-dimethoxy- phenylacetophenone (DPP) were taken to prepare prepolymerization mixture. 10 1L of the mixture were Groped onto the electrode surface. Thin layers of MIPs were formed by spin coating (1000 1pm) fol- lowed by in-situ photopolymerization. The same pro- cedure was followed to prepare control electrode or non-imprinted polymer (NIP) electrode, but in the absence of VMA. A cyclic voltammogram of VMA was recorded in pH 3 citrate buffer solution (CBS), show- ing two oxidation peaks at 676 and 854 mV vs. ‘Ag/AgCl, which indicates two separate one-e~ oxida- tion steps mechanism for VMA. Under the conditions used, the MIP based voltammetric electrodes were able to successfully differentiate VMA and other struc- turally related compounds such as 3-methoxy-4-hy- droxyphenylethylene glycol, 3,4-dihydroxyphenilace- tic acids (DOPAC), 2,5-dihydroxyphenilacetic acids and homovanillic acid when compared to bare GCE [26]. The same group also reported on a similar modi- fied electrode for study of voltammetric response of di- clofenac (DCF). The best performance of the modified electrode was in 0.025 M CBS (pH 6) containing 10% ACN using differential pulse voltammetry (DPV). The ‘main disadvantage of the design of this electrode was the fouling of its surface by the oxidation products of DCF [271 Common MIPS often failed to produce selectivity for analyte in pure aqueous medium. The main reason is the non-specific hydrophobic interactions between the analyte and the surface of MIP materials [28, 29] Glycidylmethacrylate is a pro-hydrophilic co-mono- mer used in the synthesis of hydrophilic MIPs, im- parting water compatibility to them [28]. Peng Wang et al. proposed a novel hydrophilic MIP. prepared us- ing tetracycline (TC) as template, MAA as monomer and. glycidyimethacrylate as _pro-hydrophilic co- JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. 401 monomer by precipitation polymerization. Ten mi- croliters of the suspension of hydrophilic MIP was dropped on the GCE surface and dried at 40°C to pre pare modified working electrode. Glycidylmethacry- late was added in the polymerization feed after the complex formation between TC and MAA. As a result, epoxy groups were introduced onto the polymer with out disturbing hydrogen bonds formed between TC and MAA. Epoxy groups were then opened by using HCIO, to improve selectivity and rebinding capacity MIPs in aqueous media, Compared with common MIPs, the imprinting effect and adsorption amounts of proposed hydrophilic MIPs for TC were remarkably enhanced in aqueous media. The proposed method ‘was applied successfully to detect TC in foodstuff sam- ples using cyclic voltammetry (C¥) [30] Gholivand ct al. [31] used an acrylic MIP as a mod- iffer to fabricate a modified CPE for detection of piroxicam (PC) in real samples. A three-step proce- dure involving extraction, washing and electrochemi- cal determination in which MIPs acted as selective recognition elements and pre-concentrator agents was employed. The sensor is based on the oxidation of PC after its selective extraction into the electrode 3.9 mmol MAA, 0.8 mmol PC, 19.5 mmol EGDMA, 0.3 mmol 2,2-azobisisobutyronitrile (AIBN) and 8.5mL of N,N-dimethylformamide (DMFA) were ‘used to synthesize MIP for PC. The MIP modified CPE ‘was prepared by mixing graphite powder, n-eicosane and. MIP in ratio of 52.5: 31.5 : 16 (w/w/w, %). Electro chemical behaviour of PC at MIP—CPE was analyzed using CV while its determination in real samples was carried out by means of DPV. The proposed sensor has advantages such as simple preparation, cost effective extraction method consuming very low amounts of or- ganic and toxic solvents, a low limit of detection and a wide linear range as compared to previously reported PC sensors, The MIP—CPE was successfully applied to detect PC in Pharmaceutical as well as serum sam- ples [31]. Similarly, MIP—CPE was fabricated for de- termination of promethazine, metronidazole, sul- fasalazine, chloramphenicol and lamottigine [32-36] Kindschy et al. [37] designed a MIP biomimetic indium tin oxide (ITO) electrode for eyelic voltam- metric determination of a small drug theophylline (TP). The ITO electrode was silanized in 3-(tri- methoxysilyl)propyimethacrylate solution (10%, v/¥) at 80°C under N, atmosphere for 6 h, Silanization ac- tivated the electrode surface allowing covalent bond- ing of MIP with the surface. 0.119 mL MAA, 1.20 mL EGDMA, 0,036 g AIBN and 0.063 g TP were mixed in 3.31 mL of DMFA. The biomimetic MIP—ITO sensor was fabricated by immersing the silanized electrode in 2 mL of the above solution at 60°C under N, atmo- sphere for 12 h. The sensor so prepared was washed with a solution of methanol and acetic acid (9: 1, v/v) for I h to allow the extraction of template. Atomic force microscopy (AFM) was used to characterize the 4 201s402 MIP surface after template removal and rebinding. It ‘was found that the mean surface height and roughness of the MIP after rebinding of template were reduced due to the shrinking effect as compared to those after extraction of template. The proposed sensor exhibited no response to the structurally elated molecule like caf- feine. The further development of the proposed sensor could compete with other detection methods for TP. Amperometric detection of bilirubin from micro- sensing electrode modified with bilirubin-imprinted p(MAA-co-EGDMA) film was fabricated [38]. The author synthesized imprinted polymer film onto a thi- oltreated Au electrode by surface grafting polymeriza- tion, Au electrode was unable to detect specifically bi- lirubin in the presence of other matrix components if clinical samples were used. Therefore, the electrode ‘was modified with imprinted materials. A novel method was proposed by Bhim Bali Prasad et al, [39] for determination of ascorbic acid (AA) based on MIP modified hanging mercury dropping electrode (HMDE). The sensor was developed by the direct coating of AA imprinted polymer prepared from, melamine (mel) and chloranil (chl) on the surface of HMDE at +0.40 V. The use of a cross-linker in the MIP synthesis was avoided so that a better mass-trans- port was facilitated to the binding sites. The innovative polymer [mel-co-chl] was deliberately chosen to check its versatile nature, particularly in biomolecule recognition. The freshly’ renewed modified HMDE sensor was able to detect AA directly in aqueous, phar- maceutical as well as serum samples without any cross-reactivity and matrix effect. Moreover, it could bbe helpful for the diagnostics of hypovitaminosis C [39]. Similarly, creatinine and dopamine (DA) were determined in serum samples using MIP [mel-co-chl] modified HMDEs [40, 41] Dhana Lakshmi et al. [42] reported a differential pulse cathodic stripping voltammetric analysis of cre~ atine (crea) which was based on modification of HMDE surface with a typical water-insoluble MIP [poly(p-aminobenzoie. acid-co-1,2-dicholroethane)] film. The film casting was made on the electrode sur- face using drop coating method. The MIP used is a crea imprinted quaternary ammonium polyelectrolyte having pendant carboxylic groups, The molecular im- printing of crea was done via anion-exchange proper- ties of MIP modified electrode while the detection was done by surface attached voltammetric transduction principle. The proposed method was highly sensitive and selective for crea without any interference of ere- atinine in aqueous samples. Moreover, the freshly re- newed modified HMDE sensor is applicable for the sensitive and selective assay of crea in water, blood se- rum and pharmaceutical samples Bhim Bali Prasad ct al. 43] reported a MIP sol—gel modified PGE asa sensor for folic acid (FA). A hyper- branched MIP was prepared by stoichiometric imprint- ing process (template“monomer molar ratio 1 : 3) us- JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70, RAKESH R. CHILLAWAR et al ing 2,4,6-trisacrylamido-1,3,5-triazine as trifunctional monomer, creating multiple binding sites within the polymer. Acetonitrile—triethylamine (4 : 1, v/v) was used to extract the template. Dendrimer-like polymer was coated on PGE using sol—gel, prepared with tet~ zacthyl orthosilicate, and was examined by differential pulse cathodic stripping voltammetry (DPCSV). The proposed modified electrode was used successfully for the detection of FA at ultratrace level in human blood serum samples (RSD < 3.0%) without any cross-reac- tivities and real matrix complications, The same group used another “Grafting-to” ap- proach using sol—gel technique to modify a graphite electrode (GE) with a MIP [44]. Sol—gel (organosi- Jane) slurry mixed with carbon black powder was used to generate vinyl groups onto the polished surface of GE. The modified electrode underwent further sur face imprinting of AA using trifunctional monomer, 2,4,6-trisacrylamido-1,3,5-triazine and cross-linker, EGDMA. The proposed electrode oxidized AA at less positive potential (0.0 V) than the electrodes reported earlier. The diffusion coefficient (1.09 x 10-* cm*/s), rate constant (7.308 s~) and Gibbs free energy change (£12.59 kJ/mol) due to analyte absorption, were also examined to study kinetics of AA oxidation, The pro- posed electrode was applied successfully to detect AA at ultra trace level in hospitalized patients to diagnose hypovitaminosis C. Similarly, MIP—sol—gel-modified GEs were employed for voltammetric determination of uric acid (UA) in human serum and urine samples and crea in human serum samples [45, 46], Electro polymerization is a promising technique for the synthesis of MIP film in situ at the electrode surface. This technique has some remarkable advan- tages stich as simple, rapid, easy adherence of condi tive polymer film to a transducer of any size and shape and the ability of controlling film thickness under dif- ferent conditions of deposition [47]. Various types of electrosynthesized polymers using MIP technology have been reported such as polypyrrole (PPy) [48] poly(o-phenylenediamine) (poly-o- PD) [47], polyphe- ‘nol [49] and copolymer of aniline with o-phenylenedi- amine (o-PD) [50]. Figure 2 demonstrates the general procedure for molecularly imprinted conducted poly- ‘mers and its application in the electrochemical sensing. PPy has gained most attraction as a molecular rec- cognition system, since it can be conveniently synth sized on various electrode materials; its film is highly stable; it exhibits electrical conductivity as well as electrochemical redox acitivity even in a neutral pH region; it has wide range of applications [52, 53] The modification of PGE with a molecularly im- printed PPy film was reported by Ozcan et al. for the detection of AA [54]. The film was prepared clectro- chemically on the surface of PGE with potential scan between —0,60 and +0.80 V during seven cycles in aqueous solution of 0.1 M LiC1O,, 0.025 M pyrrole and 0.020 M AA. 0.05 M phosphate buffer solution No.4 2015OLTAMMETRIC TECHNIQUES AT CHEMICALLY. Template Fanetional Cross-linker strode Molecular cavity BAG Rereens OI ee Fig. 2. G: sensing. Adapted rom [51] (PBS) was used to extract AA, creating micro cavities in the polymeric film. The NIP electrode was prepared similarly, but in absence of AA. The effect of various parameters such as pH (optimal pH 8.5) monomer concentration (25 mM), template concentration (0 mM), number of electropolymerization cycles (7 cycles) and interferents (e.g. DA, D-glucose, UA, ec) were studied to evaluate the performance of MIP electrode. The proposed electrode shows a low re- sponse time, good mechanical stability. The modified electrode was found to be applicable in commercial sample analysis of AA (tablets, syrups, ete.) Nezhadali et al. [55] fabricated MIP-modified PGE with electro polymerization. The MIP was ob- tained by electrodeposition of pyzzole with template benzimidazole (BIZ) on the PGE surface using CV in the potential range between —1.0 and 1.9 Vin aqueous solution of 0.1 M NaClO,. The quantitative measure- ‘ments with the proposed electrode were done by DPV. ‘The template-monomer geometry and interaction en- ergy in the polymerization mixture were also exam- ined using density functional theory based computa- tional methods. The proposed electrode showed selec- tivity and sensitivity for the determination of BIZ in biological samples. Similarly, paracetamol, thiocarbo- hydrazide and DA were determined using electropoly- merized PPy modified electrodes [56-58] PPy undergoes an undesirable degradation owing to its overoxidation at positive potentials. This leads to the loss of conductivity and dedoping [59]. However, overoxidized of PPy has been employed in some elec- troanalytical applications as its film acts as a porous JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. 403 Self-assembly Hs (prepolymer complex) Electropolymerization Extraction of analyte (target) Analyte determination peat ob voltammetry, CA, potentiometry, EIS, etc.) eral procedure for obtaining molecularly imprinted condueted polymers and its application in the electrochemical electrode coating having cation exchange and molec ular sieve properties [60-66]. PPy on overoxidation, ejects dopant and carbonyl and carboxyl groups are in- troduced onto the pyrrole unit. As a result, it loses its electroconductivity. The accumulative properties of ‘overoxidized film for cationic species might be duc to the introduction of carboxylate onto the pyzrole nit [67] The modification of PGE using molecularly im- printed overoxidized PPy film was studied by Ozkoru- cucklu et al. [68]. CV and DPV were used to fabricate and evaluate the proposed electrode respectively, The modified electrode was applied successfully to the de- termination of sulfamethoxazole in commercial and pharmaceutical samples with satisfactory precision (RSD < 1%) and recoveries (>87%). Similarly, DA was ‘measured in rat striatum using overoxidized PPy mod- ified platinum microelectrode (PME) [69] 0-PDisalso a suitable functional monomer of elec~ tro-polymerization, asit can be easily electropolymer- ized on various electrode materials and its polymer- ized film has good chemical and mechanical stability (47, 70, 71]. Fabrication of MIP-modilied GCE by electropolymerizing o-PD on the electrode surface and its application in an amperometric sensor for tri- closan (TCS) was studied by Ying Liu ct al. [72]. Elec~ tropolymerization of 6 mM o-PD in presence of 0.1 mM TCS at pH 5.2 was carried out on GCE using CV (20 scans) in the range 0-08 V (scan rate 50 mV/s). The electrode was then dipped in 0.1 M NaOH solution for 10 min in order to remove the tem- plate. As both poly-o-PD film and TCS are electro active in acid medium in the potential window chosen, 4 201s404 RAKESH R. CHI Hexadecyl SG snercaptan/ ; | tectode = Cholesterol ILLAWAR et al, Fig. 3.Ascheme of molecular imprinting wsing SAM method. Adapted from: [76] an electroactive ferrocyanide was used as mediator be- ‘tween the modified electrode and substrate solution, CV was used to investigate the relation of current pro- duced by ferrocyanide with TCS concentration. The proposed method is able to avoid the fouling of the electrode surface by the oxidation products of TCS when compared with conventional direct clectro- chemical detection. Similarly, an electrochemical sen- sor based on poly-o-PD modified Au electrode was re- ported to determine 4-aminobutyric acid using mo- lecular imprinting method [73] ‘A square wave voltammetric determination of paracetamol based on poly(o-PD-co-aniline) film modified carbon fiber microelectrode (CFME) was studied successfully by Gomez-Caballero et al. [74]. CFMEs used in the proposed sensor are inexpensive and can be disposed after use. The proposed mi- crosensor exhibited a good stability and reproducibili- ty with RSD less than 5.6%. Italso has a good selectiv- ity against paracetamol with no interferences from structurally related compounds especially present in biological fluids like catecholamines. ‘Chen-Hsun Weng et al. {75] proposed a microflu- idic system using molecularly imprinted poly(3,4- ethylenedioxythiophene) (MIP-PEDOT) modified Pt electrode and amperometry as a measurement technique for the detection of morphine (MO). A. MIP film coating on a Pt electrode acted as highly se- lective recognition site in combination with electro chemical transducer, A MIP film, a polydimethylsi- Joxane-based microchannel, a peristaitic micropump, microvalves and sensing microelectrode were integrat- ed to produce a new microfluidic system for MO de- tection using micro-electro-mechanical-systems technologies. The developed microfluidic system showed low consumption of samples and required sample volume in microliters. It is compact in size and automatic. SAMs are the rigid nanostructures organized around the template molecule formed at the electrode surface. The technique can be considered as a two-di- ‘mensional imprinting. In the preparation of this sys- tem, simultaneous adsorption of template and mer captan molecules take place at the metallic electrode surface, usually an Au electrode. The recognition of JOURNAL 01 template is possible if the specific interactions are de- veloped between the template and alkyithiol chain to form a stable complex. This technique is illustrated in Fig. 3, The advantages of this technique are easy prep- aration and the possibility of the introduction of dif- ferent chemical functionalities. However, the main disadvantage is very low stability of the non- crosslinked film, due to which the recognition sites are collapsed by lateral diffusion of molecules, especially when template molecules have been removed [19, 76] PY. Chen et al, [77] developed an amperometric sensor for the determination of DA. The modified screen printed gold electrode was fabricated using thioglycolic acid (TGA), allyl mercaptan (AM), medi- ator, quercetin (Q) and MIP using SAM technique. TGA and AM were used as they consist of shorter car- bon chains, showing high electron transfer rate than those of longer ones, They were covalently bonded to Au electrode to control the TGA density. The covalent bonding between the mediator, Q and the carboxyl group of TGA was made possible using 1-ethyl-3-(- dimethylaminopropyl) carbodimide as carboxyl-acti- vating agent. The MIP-Au/TGA/Q electrode was pre- pared using methyl methacrylate as monomer. The modified electrode was more selective for isoproterenol than for methyldopa. The fabricated electrode showed the highest selectivity for the molar ratio of AM to TGA of 8 and sensitivity was 697.1 mA/(cm? M), A comprehensive list of clinically and biologically important target species investigated using MIP mod- ified electrodes is presented in Table 1 POLYMERS A differential pulse stripping voltammetric (DPSV) sensor was reported by Gopu et al. [78] which was based on nanosized PEDOT-immobilized GCE. The modified electrode was prepared by clectro-oxidation of 0.01 M 3,4-cthylenedioxythiophene (EDOT) in ACN containing 0.1 M tetrabutylammonium perchlo- rate (TBAP) using potentiodynamic method in the potential range between —0.2 and 1.2 Vat 50 mV/s us ing Ag/AgCl reference electrode. This modified elec trode was used for the study of cyclic voltammetric be- haviour of three analgesics: acetaminophen (AC), ace- )F ANALYTICAL CHEMISTRY Vol. 70, No.4 2015405 OLTAMMETRIC TECHNIQUES AT CHEMICALLY. ter w/a “Tw /H §1'0=L00°0, STA amor TOH-ON] —_Asoaa oa/P810F-a1H roe for aaWH tepl w/a LO w/a ge—11'0 VLG HON W,-01%s5] —_asoaa| /(@oa-e'1-0-vava)aIN unwary, Ww /B29-60 (trl “1a /8u S10. “T1/3 yS0'0-S000°0 (HORN W 100) LHe ASOdd ACIWH/(49-194) dT suturedocy tov! w/au st “Tw/8 y8-sc000 oun] asoaa) — aawH/tw-pmarW] ——aunmeaIy lee] Te/8u 970 “Teu/3nt 19-8°6 (HORN W 10°0) 04 H4| ASOdd ACINH/(9-19™) dN Pre s1qzoory tse] wu ot “pA o's—01 ssiea/t10x] Anewordiwy| — sponao my/aLn 269¥) ge Poxoeathy, lee! Were We pT Wes + ON WO AD] 909? OLI/ATIN HOV surTxydooy | toe! wero WWE 00P=Sz WU ST-8'0 SSH sav Ww sco'a ect qao/ann ociey | suratnoweT ise} WOrXe — | We 1 XOT,-01 x08 prov ououdsoud W Zr'0 Ader ad /aTW Kay |roorwouaareron (rel Wet xe W501 X01 01 X0'T STH se4Ma Ua W FOO Aaa Wad/aUN 269] surzeqesesing 1/8 01 x 6914-01 697 lee] yam ore — [1/801 x £92.01 x b9'g CHa sopn9 a ASOa Add/aIW MNAIey) — sTozeprTONOy ‘dd9/(Ad-A)dIN 20y laao/(anc-aaarW 205) W 01 IP-Z'T-09-pIs" sozuaqoun ‘qoute paxsprxo A) Kod —(ADEL-C'1-0>-VaVa)A “(OUDtK) BUI7IDAICTA— AA _ - (pas paypow) lush i sda] snoworsdury opens O/VOL/SVAIN| —_aururedog wir wizo-100 DAW TO+sda] Mworduy| aWa/Lodid-aiw suryioW anao/ Gumue lel wis We-01<07~y-01 x59 OLHA'saa WTO AMs| _-0%-da-0)siod-aIW) rouse it sponse pie teal wi 800 WOOO WS'0+PCNO)AT WHO'S Ada] _ev/(ad-0-s104) AI] suAngouny-p 'ONN, taal W501 08 W,-01x 0f= 01x07 | WIFPNOMATI NTO] Anaworduy| aD9/ad-0-s04) ATW) ues0P UL lol Wes WW" 001-01 TOFPLHE sda Wo] Anpwosduy| —awa/Gado) ann] euTedog WHOT-SLO ajo7x0 i391 waU-o1 xp IN SL, 01'S ous THE 13509 HE Aaa apa/Gaao) aw] —__-wemmms Iss] Wa0t x9 Wel 1-01 PERE saa W10 AMS aoo/Kdd) aN) suede, apr usl Wl xs ww 9—s'0 os Hd sya NE Ada Oa/(Kad) aI | -espsqoqresoryy WHS Hse DAW Tro+ ou HE los} W01 x8 WH OS O-WTS Sad W500 Aaa AOd/(Kaa) aw | _joweyaoereg Iss] WA01 XL Wel S501 OS HEINE ‘Aad BOd/Kad) aw] 1ozeprereueg saHd bs} Wool xt WeoL-stO Sad W S00+1ON WTO Aaa AOd/(Kaa) aI | _ prov s1qronsy (euus) Tw ge—ST (oxurey w/8H 7 “cunt “amiss pooja) Tu/an ¢1 | “28 PooIe) Tw/RH gs—H'T ‘(uantpat snoonibe) “(warypaut (orl Tuya TL snoanbe) “Tuy 901—¥'¢ rend Asad. aD /P2105- aN aunea19 (Guus) w/a SPI L oun) qwyrig —_fauas poora) THH/ x 901—F “amos pooys) T/A ¢ (coempatt Ispl_| Corpo snoanbe)-pw/3H4 yp) _suoonbe) 12/304 2.1L oune Asoaa AD /e8—105-aI pre aut9 vel “r/R 9 “w/a E6100 SEHO saa TO Asvad Dd/PRToraNW] Pree aIosy 3a aot xat umpayy anbruyoay, | aponsare pasrpoy suey pmo) “Taree, 201s No. 4 JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70,OLTAMMETRIC TECHNIQUES AT CHEMICALLY. + 1N—CH—cHy, Passat Coon “4 + HN—CH-CH,—CooH Ta boon HIN—CH—CH,—CO}NH-CH~ Coon coon], COON Sirota 407 luN-CH-CH,-coon coon : ° HIN-CH-CH,~COOKF coon xiecree dyn cH-cit,-coon coon], Coon Fig. 4. The mechanism of elecro-polymerization of L-aspartic acid on the GCE. Adapted from [$4] tylsalicylic acid (ASA) and dipyrone (DP), showing loss of 2 e~ in all pH media. From analytical point of view, pH 1.0 was found to be suitable for DPSV detec tion of all the three analgesics. The proposed method is more superior than available methods as they pro- vide lower detection limits for all the three analgesics. Similarly, niclosamide, N-acetyl-p-aminophenol and. p-aminophenol were’ determined using PEDOT- modified GCEs [79, 80]. ‘An ultrathin electropolymerized film of poly(S- amino-1,3,4-thiadazole-2-thiol) _ (p-AAT)-coated GCE was fabricated by Kalimuthu et al. [81] using po- tentiostatic technique in 0.20 M PBS. The modified electrode was able to resolve and separate the voltam- metric signals of AA, dihydroxyphenyl acetic acid (DOPAC) and UA with potential difference of 140 mV between AA and DOPAC and 130 mV. between DOPAC and UA when compared to bare GCE, Italso enhanced the oxidation currents of AA, DOPAC and UA as compared to bare GCE. The proposed elec~ trode shows anti-interference ability for the detection of DOPAC even in the presence of 2500-fold excess of common physiological iterferents. An electtopolymerized film of poly(actiflavin) (PAE) was prepared by Po-Chin Nien et al. [82]. A. compact thin film was deposited on GCE through electropolymerization using CV. When compared with the literature, the modified electrode provides the sec- ‘ond largest peak separation, 255 mV between AA and DA at pH 7 because of the positive nature of the PAF film. The rotating disc electrode analysis was carried ‘out to calculate the diffusion coefficient and the in- trinsic rate constant of AA, which were found to be 1.84 x 10-* cm?/s and 0.0032 cm/s, respectively. The effect of CNTs loading was also studied. With this elec trode, an amperometric detection of A was cartied ‘out in commercial samples like vitamin C tablet and fruit juices, showing less than 3% error as compared to standard value obtained by HPLC-EC. L-Aspartic acid (L-Asp) was electropolymerized on the GCE surface using CV in the potential range of 0.80—2.40 V (No. of scans 8, scan rate 100 mV/s) in PBS solution (pH 5.0) containing 2.0 x10-? M L-Asp JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. (Fig, 4). The E,, and E,, of norepinephrine (NE) on the modified electrode ‘were found to be 0.316 and 0.234 V respectively with £*, 0.275 V and the is./ie, approximately 1. The excellent electrocatalytic activi- ties of poly(L-aspartic acid) (PL-Asp) membrane for redox reaction of NE were attributed to its three di- mensional structure and its rich carboxyl group. The modified electrode was able to climinate interferents, such as AA and UA. The proposed electrode was em- ployed to determine NE in injections with good recov- eries. Moreover, the electrode was easy to prepare and regenerate [83]. Similarly, voltammetric analysis of DA and NE in commercially available injections was reported [84] Zeolite modified electrodes serve as best receptors in electrochemical sensors due to their intrinsic prop- erties such as molecular sieving and ion-exchange properties. The electrochemical behavior of atenolol at the surface of mordenite zeolite-modified CPE (MOR—MCPE) was reported by Arvand et al. [85] A comprehensive list of clinically and biologically important target species investigated using polymer ‘modified electrodes is presented in Table 2 METAL COMPLEXES Quintino et al. [86] developed a cobalt—tetraruthe- nated porphyrin (Co—TRP) film coated GCE for the determination of sodium metabisulphite, The Co— TRP solution was prepared by dissolving 1 mg of the complex in § mL of methanol, of which 1 j1L was transferred onto a freshly cleaned electrode surface and the solvent was allowed to evaporate to obtain the modified electrode. The modified electrode exhibited more favourable responses as compared to bare GCE. ‘The amperometric sensor associated with batch injec tion analysis technique had been applied to direct de- termination of sodium metabisulphite in commercial samples of injection formulations of Na and (or K) DCE showing well comparable results with those ob- tained by the polarographic method. An amperometric detection of DP based on apoly- meric nickel-salen (PNS)-modified Pt electrode was 4 201sRAKESH R. CHILLAWAR et al 408. “Ur MOY —VIA ‘togtes Assej8@—9H) ‘(omp-z-sjozerperm-p* stscqeue worsaf T-ourue-¢)4jod—pyy-d ‘jousydourue-d—ayq “jousydourure-d-4199e-N—IVaV Isal wire wios-po| oS HE 'saVIWTO AD Asvac AaW-IOW Toouny AN Wy-01 $1501 £911 WW c-01 X £9101 X 10°T ANWeATxO% | NOW,-01XZI--0TX 81) GN) oF HE ‘Sad ‘sunsydourdazou pue Lesh | va 01x01 WoO XE1-)-01 11] Ava) O'S HE Sa a soo /dsy-1d suturedog les WeOlX TE) We DIX SUE OT ET Ov Hd sad a9 goo /sy-1ad suuydourdaroy, (vin wt st (vid wt poet leak | reayy we ot “egg wy WH ozI=Sz OLHE'sda| AD Aneworsdiry| — sponsaye zva/20 funuedop puv proe axqroasy pre on lish Ind 0st W-01* 01-01 0 | O'S HE'Sdd WOr'O| Ada MnowoLedUy AOO/LWV-8| -onesuayd-cvoupsyia-'t IVAW -O1XTT | AVE WOT XT Ey-01 xO ousydourure-d pe lol |avavw,-01x0'y | avaVWN,-01x0T-,-0TX0T | OLA 'Saa WTO Aaa doO/Lodad | revsydourure-d-9399y-N, lou WyO1XTT wist-sivo| OLA saa Wo Asvac, g99/Lodad aprusopoIN aa“16/3H 200 dcr 1H F0-Sz0"0 ‘sv TWH /8 100 “vsv 16/31 p'o-st0'0 2uossdip pue proe 21160 sul | ‘ovTwy/st 100 ‘ov Twat po-S100 [oT HA *OstH IN TO ASAC) 199/LOdad-oweN | -Aes|s90" “uoyourutEreoy ane aor xt tampa, onbiuysay. | sponsor paurPoW ovteuy soponnate payrpour-soussjod Buen sarxpeue jo UONAMICL °Z AMR, 201s No. 4 JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70,OLTAMMETRIC TECHNIQUES AT CHEMICALLY. studied by Teixeira ct al. [87]. The proposed electrode ‘was fabricated by electropolymerization of nano struc- tured cellophane onto a Pt electrode using CV in the potential range of 01.4 V vs. saturated calomel elec trode (SCE) in ACN containing 0.1 M TBAP. The modified electrode offers remarkable advantages such. as thickness control, good membrane-forming prop- erties, easy preparation and allows amperometric ‘measurements in aqueous media. The developed sen- sor finds applications in quality control and routine determination of DP in pharmaceutical industry. Electrochemical oxidation of captopril (CAP) at CPE ‘modified with cobalt-5-nitrolsalophen (CoNSal) was reported by Kazimi et al. 2% w/w ratio of graphite powder in Nujol and CoNSal in dichloromethane was used in fabrication of CPE modified working elec- trode, Good recoveries were found from pharmaceuti- cal CAP tablets [88] ‘An amperometzic sensor for phenolic compounds using CPE modified with manganese phthalocyanine (Mn-PCy) and histidine (HD) was reported by Tanaka etal. [89]. Mn—PCy acts as catalytic mimicking centre for H,O, (Fig. 5). The phenol quantification was based con electrochemical reduction of quinine species on the electrode surface, recycling the substrate and con- sequently in signal amplification and reduction of de- {ection potential of the phenolic compound, Electo- catalytic oxidation of D-penicillamine at the surface of ferrocene modified carbon paste electrode (FCCPE) wwas proposed. The proposed method was successfully applied for pharmacextical samples containing DA (90 409 plecttode posed mechanism for oxidation of phenolic compounds at the CPE modified with Mn-PCy (Mn- PCYieg — manganese phthalocyanine, Ma-PCy, — ox dized Mn-PCy, Phgg — reduced phenol and Phy, — oxi dized pheno A comprehensive list of clinically and biologically important target species investigated using metal com- plexes modified electrodes is presented in Table 3. NANOMATERIALS, CNT (Fig. 6) continue to gain considerable atten tion in electrochemistry [91-97]. Iijima discovered ‘Table 3. Detection of analytes using metal complexes-modified electrodes Modified Refer- Analytc | Mould | technique | Medium LDR LoD Refer Sodium [Amperometry [0.2 MABS, soxtM | 86) metabisulite wv pHA7 404M NaNo, Dipyrone|PNSiilm/Pt | Amperometry [0.1 MKCL aparciaM fax | 18 electrode CA Captopat | ConsaycPE [DPV 0.1 MABS, oxi om fixie | Fal PHS Catechol | Mn- “Amperometry [0.1 M PBS, 20-130 4M LM 189) @henolie | PCy/D/CPE pH 7.0 + 250M compounds) H,0, Depenici [FCCPE,2.7- [evDPV oloMPBS, [6x 10210 M(Cy, [5x10 Mccy, | OO] lamine | BFEFMCPE pit7.00 7x 101.6 10M (DPY)] 6x 10-°M (DPV) FCCPE; FCCPE; 65% 101.110 M(CY),|6x 10° MCV), Tr 10-2 «10 M(DPY) | 75 19-6 ear 7M ore) 2,7-BFEFMCPE—2,7-bis(ferrocentyl ety) Muoren-9-one modified eatbon paste electrode, JOURNAL OF ANALYTICAL CHEMISTRY Val. 70 No. 4 201s410 a) RAKESH R. CHILLAWAR et al () Fig. 6, Schematic representations of SWCNT (a) and MWCNT (6). CNT using transmission electron microscopy (TEM) in 1991 [98]. Since their discovery, CNTs have been fone of the most important nanomaterials owing to their high chemical stability, high mechanical proper- ties, high surface area, unique electrical conductivity, mechanical strength and elasticity, unique metallic and structural characteristics, etc. [94, 99—101]. They fact as a metal or as a semiconductor electrically based on their atomic structure [102, 103]. The subtle elec- tronic properties suggest that’ CNTs can be used as electrode materials as they are able to promote charge transfer reactions [104-107], Multiwalled carbon nanotubes (MWCNIS) modified electrodes are widely used in electroanalytical chemistry in recent years due to their broad potential window, low background cur- rent, rich surface chemistry, chemical inertness, high sensitivities, resistance to surface fouling and low cost, [108-110] Suling Yang etal. [111] employed a nafion/ MWCNTS composite film modified GCE to study the electrochem- ical behaviour of TP. 5.0 mg of dried pretreated carbo. lic MWCNTs were sonicated in 10.0 mL 0.1% (w/w) nafion—methanol solution for about 30 min to make nafion/MWCNTs suspension. 10.0 iL of the suspension, was dropped on the electrode surface and nafion/MWCNTSs/GCE was achieved after evapora- tion of methanol at room temperature. CV was used to calculate the microscopic arcas of modified electrode and bare electrode using 1.0 mM K,Fe(CN), contain- ing 0.1 M KCI, It has been found that the microscopic area of modified GCE (0.8668 cm’) was around seven times higher than the bare GCE (0.1256 cm’), The scanning electron microscopy (SEM) study also con- firmed the enhancement of surface area of the modi- fied electrode which in turn, improved the capacitance at the electrode. With this modified electrode, a well defined oxidation peak was obtained at 1180 mV (vs SCE) in 0.01 M H,SO, medium (pH 1.8). The pi posed electrode greatly enhanced the anodic peak c rent and lowered the overpotential of TP oxidation, JOURNAL OF ANALYTICAL CHEMISTRY when compared to bare GCE and nafion/GCE. The reported electrode was useful for TP detection in real drug samples with good percentage recoveries. Simi- larly, the nafion/MWCNTs modified electrodes were employed for electrochemical determination of TC, DA, norfloxacin, nimesulide, tamsulosin hydrochlo— ride, amiloride, AA, UA and metoprolol in real sam- ples [112—120] Single-walled carbon nanotubes (SWCNTS) are made up of one single rolled up sheet of GR. Depend- ing on the fabricating methodology, they are having ci- ther open or closed ends. They have a very large sur- face area per unit mass, unique optical properties and outstanding mechanical strength [121]. SWCNTs modified electrodes are synthesized in three ways namely by casting SWCNTs suspension on various conventional electrode surfaces [122, 123], mixing SWCNTs with bonding agents to form SWCNTs paste electrode [124] and mixing SWCNTSs with other mate- rials to form composite film modified electrode [125] These electrodes are highly sensitive and reversible as they promote electron transfer reactions [126, 127] Goyal et al. [128] suggested SWCNTs modification at the GCE surface for investigating the electrochem- istry of bisoprolol fumarate (BF). 0.05 mg SWCNTS was dispersed in 1.0 mL of DMFA by using ultrasonic agitation to produce 0.05 g/L suspension, 10.0 tL of this suspension were dropped on a clean and polished GCE surface followed by evaporation of DMFA under an IR lamp to form SWCNTS modified electrode. At the bare GCE, no anodic peak was observed for BF whereas the modified electrode produced a well de- fined oxidation peak at ~950 mV. A sharp anodic peak with an enhanced peak current clearly suggests that SWCNTS play a role as an efficient electron mediator in the electrocatalytic oxidation of BE The proposed electrode was successfully applied for the DPV deter- mination of BF in pharmaceutical formulations and biological samples such as human urine. Similarly, levodopa and capsaicin were determined using Vel. 70 No.4 2015OLTAMMETRIC TECHNIQUES AT CHEMICALLY. SWCNTS/GCE and SWCNTs/screen printed elec- trode (SPE), respectively |129, 130] GR is considered as a ‘rising star’ nanostructured carbon material. It is an intrinsic two-dimensional sheet of carbon atoms in which atoms are bonded by sp?ina hexagonal configuration [131]. GR has a much larger surface area of 2630 m?/g and very high electri- cal conductivity of 7200 $ mas compared to graphite and CNTs [132]. Ithas received remarkable attraction for potential application in electrochemical sensors because of its novel properties such as rapid electron transportation, huge specific surface area, exceptional thermal and mechanical properties, excellent electri- cal conductivity and perfect biocompatibility [133] ‘An amperometric sensor was developed for the deter- mination of AA by using GR doped CPE by Feng Li etal, [134] ‘A comprehensive list of clinically and biologically important target species investigated using nanomate- rials modified electrodes is presented in Table 4. COMPOSITE FILMS MWCNT:-alumina-coated silica (ACS) nanocom- posite modified GCE was proposed by Tar-Lung Lut etal. [135] for the determination of AC. 20 mg MWCNTs were dispersed in a 1 mL of ACS aqueous solution (1 wt %, pH 2) by means of ultrasonic agita- tion for 2 h. The pretreated GCE was immersed into the prepared MWCNTs—ACS solution for 1 h to achieve modified GCE after evaporating solvent at room temperature. MWCNTs—ACS nanocomposite was characterized by field emission scanning electron microscopy. It can been seen that the protruding MWCNT structure of nanocomposite behaves as high conductivity nanowires, which provides large electro- active surface and facilitates the rate of electron trans- fer reaction at the electrode surface. As a result, a pair of well defined redox peaks at 0.32 and 0.20 V (vs. Ag/AgCl), respectively, in 0.1 M Britton—Robinson (BR) buffer solution (pH 9.0) was observed with 100 times higher oxidation peak current than that of bare GCE and ACS modified GCE. Square wave vol- tammetric (SWV) determination of AC using the pro~ posed electrode revealed a sensitivity of 376.5 A/(M cm’). The proposed method could also be applied to determine other analgesic drugs such as DP. Ensafi et al. [136] reported simultancous voltam- metric determination of N-acetylcysteine and AC us- ing _N-G,4-dihydroxyphenethyl)-3,5-dinitrobenza- mide modified MWCNT paste electrodes. The sensors were successfully applied in pharmaceutical samples. Anovel modified CPE with vinylferrocene/MWCNTs (VE/MWCNTB) was fabricated for simultancous de- termination of MO and DCF [137]. The electrode ex- hibited good response to analytes by CV, chrono- amperometry and electrochemical impedance spec- JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. 4 troscopy (EIS). Moreover, the electrode could measure MO and DCF in one mixture by SWV. A selective and sensitive electrochemical sensor was designed by Yu-fang Hu et al. [138] for the mea~ surement of p-nitrophenol. The developed sensor was structed by coupling MIP/ZnO-nanoparticles (NP3)/MWCNTs—chitosan (CS) film modified ITO electrode with SWV technique. SEM, powder X-ray diffraction study, EIS, SWV and CV were used to study the morphologies and electrochemical behaviour of the proposed sensor. CV experiment using modified electrode showed that ZnO NPs effectively increase the electrode surface area and its active sites and MWCNTs enhanced the electrical conductivity of the composite materials. It also showed that CS adhered firmly to the electrode surface and increased the elec- tron transfer between redox centers and electrode sur- face. The proposed sensor was successfully applied to determine p-nitrophenol in various water samples. Santhiago et al. [139] designed a nanostructured platform (NSP) containing 5,5’-dithiobis-2-ni- trobenzoic acid (DTNB) modified GCE and applied it as an amperometric sensor for L-cys. The cleaned pre treated GCE was coated with MWCNTS suspension to obtain MWCNTS/GCE which was further immersed in_polyethylenimine (PEI) solution to achieve PEI/MWCNTS/GCE. This electrode was then kept in a negatively charged AUNPs solution for 1 h at 4°C and then in an ethanolic solution of DTNB for 15 h, The potential in the range between 0.1 and —0.7 Vvs. SCE_was applied at this electrode in 0.1 M PBS (pH 7.0) which lead to in-situ electro-generation of hydroxylamine species from DTNB. A two-level full factorial and a Doehlert design were employed to op- timize NSP and it was found that maximum current ‘was ensured with 20 tL of MWCNTIs, 2.2% of PEI and 30 mM DTNB solution. The proposed method of rap- id determination of L-cys at low overpotential is based on the redox couple R-NO/R-NHOH resulted after in-situ activation of DTNB. Electro-oxidation of ‘L-cys was found to occur at 0 mV vs. SCE, about 550 mV less positive than bare GCE, when the pro- posed electrode was employed. The’ modified elec trode was applied successfully to determine amino ac- ids in food supplement samples with sensitivity of 21 nA L/jmol, limit of quantification of 9.1 uM, and a response time of 0.12. Brucine (BO), known as an alkaloid and a drug, was determined in human serum using imprinted poly-o-PD/SWCNTs modified GCE by Ping Liu ct al [140]. The modified electrode was fabricated by dip- ping the SWCNTS/GCE in acetate buffer solution (ABS) (pH_5.2) containing 0.5 mM 0-PD and 0.25 mM BC followed by electrochemical polymer- ization by CV. AFM, SEM and CV were employed to characterize the proposed electrode. From these stud- ies, it can been seen that imprinted poly-o-PD was embedded in SWCNTs surface in which the former 4 201sRAKESH R. CHILLAWAR et al 412 soo fos asin yeruasayyp Surddins aandiorpe —agaspy AnsumuTeyos doaws se2u—AST vet oe] lez set loz) (ett uu for (sn) teu ler tan tu Dou aH9}9y Wy-01 XL wiz W-01 x W,-01*8. Wel wa) wi soo wir WoO XL W.-01X1 W,-01 x9 W-01 x5. we oe wero Wy-01 XZ dot W,-0X 901,01 x0 Wi ove—v't W-01 07-01 x0'§ Wwe Po-100 W 5-01 06-01 x01 WH 0S Lb00" W 01x S~ 5-01 %6 W.-01 XE ,-01 * 1 W501 XS 9-01 TE wr oot-r0. wr cor-1 Wr ooI-sz W5-01 X09 y-01 X08 wat ound ‘saa Wo rLHd’sdd o's Hd ‘saa Wo) TL ‘saa Wo) HA 'saa vLHd'sdd Lend ‘sav ro THe sna aE os Hd ‘sav ro) von ‘saa nzo yond sav so] vLHd ‘saa Wr) STH4 ‘sda W S00) ST Hd os W 100 ammpoyy, Anowrorodury Ao Aaa Aaa Adaspy | AMS Adaspy| AST AST a2 Axjourorsdury AD Ada onbreyoay, Aad padop ¥5 | ddS/ALNMS AOO/LNMS ADO/SLNMS ADD/ALNOMIN/HOURN, ADO/ALNOMIN/HORRN AOD/ALNOMW/HOURN, HOD/LNOMY/HOEN dD ALNOMWY/tOEN AOD /ALNOMIN/HONEN, AOD/SLNOMW/HORN 29pono9]9 OLT/SLNOMWAY/TOEN, TOD ALNOMW/HOREN, AOD/ALNOMIV/HOHRN, sponsope payTpOW, prov oiqioasy. urowsde9, edop-] ayeroumy jorordostgy Toroxdoroyy ioe aun pu pov oxqroose ‘surtuedoc, pioe orqioasy epuioqrary apoyyooupy wisojnstaey, ‘sprinsouyyy UIDEXOYION, uturedogt aumasoeney usydoouy, ouqeny ‘s9ponsaq9 payrpour-sjeusyewouru Fussn sov4qeue Jo UONISI°CI “FOR. 201s No. 4 JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70,OLTAMMETRIC TECHNIQUES AT CHEMICALLY. 413 ‘F Nib . WN, NH TNA S NTL, as 80°C, TBIIP, TMSPM, ) ote HN ANH, NE Det, B oC “Ny condensation Pe @tnman ‘nanoparticles wun} Nh HN uh, SMP “absorbing Hi, Chitosan Organositica®@chitosan 2 _ A od —- op HPC, CORP, Be absorbing redvcing Fig. 7, Ascheme of Pt-Au-OSI@CS composites modified GCE (the non-enzymatie sensor), TBHP—tert-butylbydroperoxide, TMSPM—3-(timethoxyslyD propyl methacrylate. Adapted from (144) acts as recognition element for BC and the latter plays a role in the amplification of current signals. The pre- pared electrode could find a great potential applica- tion in real sample analysis. A differential pulse voltammetric detection of DA based on PEDOT/CNTS/surfactants (SKS) modified PME was reported by Laubender et al. [141]. Poten- tiodynamic electropolymerization in aqueous solution with LiClO, as a supporting electrolyte was carried out to prepare thin PEDOT films and PEDOT with em- bedded CNTs. Adherent and stable films with a high content of CNTs were obtained with addition of the SF5 like sodium dodecyl sulphate and poly (sodium. styrenesulfonate), These SF's not only increased con- ductivity of PEDOT films but also improved permse- lectivity for cationic species like DA. SEM image of modified electrode showed morphology with spaghet- ti-like structures. The fabrication of AuNPs/poly-o-PD/GCE and its use in voltammetric sensor for TP was reported by Xianwen Kan ct al. [142]. The prepared poly-o- PD/GCE was immersed into 4 mM HAuCl, and 0.1M KNO, solution and potentiostatic deposition was carried by applying a potential of ~0.2 V for 180s to obtain AuNPs/poly-o-PD/GCE, The character- ization of the proposed electrode was done by SEM, CY, EIS, and DPV. Nyquist diagram obtained in EIS study for GCE, MIP/GCE and AuNPs/MIP/GCE shows that deposition of AUNPs on MIP/GCE reduces 3300 Q diameter of a semicircle for mere MIP/GCE to 120, indicating that the proposed electrode decreas- es electron transfer resistance and enhances the rate of electron transfer reaction significantly, The proposed JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70 No. method could find application in clinical determina tion of TP. Ke-Zhong Tang et al, [143] reported ITO/ PEDOT/IrO, composite electrode for MO electro- oxidation. An anodic clectropolymerization of 0.025 M EDOT aqueous solution containing 0.1 M LiClO, as the supporting electrolyte was carried out to make PEDOT modified ITO electrode which was fur- ther modified with IrO, layer by simply spreading a certain amount of IrO, colloid onto it, From SEM im- age, it was found that the active IrO, layer was dis- persed more uniformly at PEDOT intermediate layer than at bare ITO electrode. IrO, acts as an active clec- trocatalyst for oxygen evolution reaction and for re- yersible valence transition between lower and higher oxides. It enhanced electrochemical activity towards MO oxidation Assay of catechol (CO) and hydroquinone (HQ) using non-enzymatic amperomettic sensor have been reported based on platinum-gold organosilica@chito- san (Pt-Au-OSi@CS) composite modified GCE. (Fig. 7) by Dehua Yoan et al. [144]. The Pt-Au- OSi@CS NPs were prepared using OSi@CS NPs, Au colloid solution, I mL of 1% H,PtCl,, 2 mL of 1% ci- trate and 3 mL of 0.2 MAA. These NPs were dispersed. in 0.5% (wt) CS solution to prepare Pt-Au-OSi@CS, suspension, which was dropped on the pretreated sur- face of GCE to obtain the Pt-Au-OSi@CS/GCE. In this modified electrode, positively charged OSi@CS, NPs behave as templates to adsorb negatively charged 1-3 nm AuNPs seeds which, in subsequent step, act as, ucleation sites to reduce Pt, TEM, scanning trans- mission electron microscopy, energy dispersive x-ray 4 201sRAKESH R. CHILLAWAR et al 44 pmumezuagontinp ¢°¢-({auousydcxospsup-p'¢)-N—AdHa-N ispul WO1 Xb] WO x 0%yO1 OT TL sda WO ao a99/ao4@-vsava-4 edoponoy DH WT 10-0 OH Wi ELI-E0'°0 suoumbospsy pur [etl | ‘oo WH ZOO “20 WH 16-90°0 OL HE Sd WW 1'0 AD Snoworedury d90/so@Iso-AWd roysaieo, evr] - ~ OSHA TON WT) Anjoworodury| sponnoo9 “on1/Loaad/O1} yourgdioyy W 01x P'E7,01 XPT fer] | Worx oT] “Wel x S'I-j-01 xy OLHE sda WO Add go0/dIW/aNNV sumsydoau, tet] WE 007 wi op-z0 wore + pL Hd'sad Aaa AWd/S48/SLNO/LOCAA sureredog, [opt] | W.-O1x 1?) WO x e101 x79 *os‘HN V0 HOOALNMS/(dd-°- sarong, feet] wet wit ost-0'6 OL Hd ‘sad WO. auroysiiow 2pond9]9 OLT [ser] We0lX1| W-01x 07-01 x 0T OL sta W710 (/SO-SLNOMIN “SAN OUZ/aTIN yousydontn-d soa wn ¢ 4Od W" 009-0'S [ue] |ow Ww 600 “OW WM 0St-ZO. OL HE ‘sad WO AMS AA D/SLNOMW/A [ovuazoTOICT 7 ETOP ov o ov nt oLe—sT ound waydourmyaoe pue [ser] | OWN AH TO. ‘O¥N Wt 002-S°0] ‘sda W0. Add 9dO/SLNOMW/ddHC-N ‘SutoIsKo[A199Y-N (ams) (via) WH ooz—¢ sen Wisoe! — “Cre Wit ozi-sz jos Hd toMMaAA WTO AD AMS, AOD/SOW-LNOMIN aqdourmme soy oe v1 i wry ‘sposn9919 patnpo} austen DI aor xT MPO 3PONDAT® PAIH|POWN nareuy soponsoie paypour-wyy ausodwoo #ujsn saxsyeue Jo VONAMACL °S OME, 201s No. 4 JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70,\OLTAMMETRIC TECHNIQUI spectroscopy analysis were carried out to observe suc cessful preparation of Pt-Au-OSi@CS composite. Be- cause of efficient electro-catalysis, high conductivit high electron transfer ability and large active surface area, the proposed electrode offered a broad linear concentration range for HQ and very low LODs for CC and HQ. Moreover, the sensitivities of the pro- posed electrode for CC and HQ were 307 and 1714 pA/(mM cm), respectively: Thus non-enzymat- ic electrode reported here, shows good reproducibility, stability, selectivity, catalytic activity and fast response time for CC and HQ. The determination of levodopa using CV and a B-cyclodextrine (BCD) doped poly(2,5-diaminoben- zenesulfonic acid) (p-DABSA) coated GCE was de- scribed by Aslanoglu et al, [145]. The electrode was dipped in a solution of 10 mM 2,5-diaminobenzene- sulfonic acid (DABSA) and 10 mM BCD dissolved in 0.2 M KCl at pH 7.4, which was conditioned from =1,5 to +2.0 V for 10 scans and electroactivated from 0.6 to +0.8 Vat 50 mV/s in 0.1 M PBS at pH7.2.us- ing CV. The modified electrode offers a distinct shift of the oxidation potential of levodopa in cathodic diree- tion with a remarkable increment in the anodic cur- rent response when compared with bare GCE and p-DABSA/GCE, This modified electrode found to have excellent stability and reproducibility. A comprehensive list of clinically and biologically important target species investigated using composite film modified electrodes is presented in Table 5. Voltammetric and amperometric sensors provide a promising analytical tool as demand for rapid, selec tive and sensitive determination of samples. As com- pared to other analytical techniques, these techniques are inexpensive and capable of being incorporated into robust, portable or miniaturized devices, enabling tai- Joring for particular applications. The CMEs used ex- hibits several remarkable advantages such as selectivity and sensitivity, chemical and electrochemical stability, resistance to fouling, larger usable potential window, etc. However, the challenges remain in the successful construction of CMEs, particularly focussing on the Jong-term stability and reproducibility in order to use them commercially for real sample analysis. The CME used also suffer from drawback like adsorption problems or electrode surface changes or fouling of the electrode surface. These issues were partially solved. Hence, there is a tremendous scope in searching new material for electrode modification to obtain highly efficient sensor. Moreover, there is still much room for further development of cost-effective CMEs for their ‘commercial applications. 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