Accumulation and voltammetric determination of cobalt at zeolite-modified electrodes

Chemically modified electrodes based on zeolite-containing graphite pastes were constructed and evaluated as sensor electrodes for the voltammetric determination of trace cobalt in solution. Zeolite molecular sieves with pore sizes of 3, 4, and 5 Å were all suitable for chemical deposition and subsequent voltammetric quantitation of trace Co(II). In order to cover a large range of parameters, the investigations were carried out using three zeolites (A, X, and Y), selected for their different cation-exchange capacities and ion-sieving properties. The analytical scheme, “preconcentration/voltammetric detection” for the determination of cobalt(II) species using zeolite-modified carbon paste electrodes (ZMCPE) was chosen. Compared to the corresponding unmodified electrodes, improvements in sensitivity were observed when using ZMCPEs due to analyte accumulation at the electrode’s surface by ion exchange in zeolite particles. The detection limit obtained for Co(II) was 3 ppm following 15 min of chemical deposition. A good correlation was found between the results obtained by ion exchange voltammetry and conventional ion-exchange characterization.     

Characteristics of Voltammetric Determination and Speciation of Chromium – A Review

This article reviews the voltammetric methods of chromium determination, including adsorptive and catalytic adsorptive stripping voltammetry at liquid mercury, metallic films, and modified carbon paste electrodes. The principle applications of the catalytic adsorptive stripping voltammetric method of chromium(VI) determination in the presence of DTPA and nitrate, most useful in the analysis of chromium traces and its speciation, is presented in detail. Special emphasis is put on the presentation and characterization of the voltammetric procedures which make it possible to conduction speciation studies of chromium(VI) in the presence of a great excess of chromium(III) and surfactants. This survey is based on 173 articles.     

Factors affecting the analytical applications of zeolite-modified electrodes preconcentration of electroactive species

The influence of various experimental parameters on the electrochemical response of zeolite-modified electrodes (ZMEs) have been studied using ion-exchange voltammetry, with regard to their application as amperometric sensors. In order to cover a large range of parameters, the investigations were carried out using three zeolites (A, X and Y), selected for their different cation-exchange capacities and ion-sieving properties; four electroactive species (silver(I), copper(II), dopamine and methylviologen) chosen on the basis of their size, charge and inorganic or organic nature; and two kinds of ZMEs: the zeolite-modified carbon-paste electrode (ZMCPE) and the zeolite monograin layers coated on glassy carbon electrode (ZMGCE). Compared to the corresponding unmodified electrodes, improvements in sensitivity were observed when using ZMEs, due to analyte accumulation at the electrode's surface by ion exchange in zeolite particles. The concentration process, and the subsequent voltammetric response of ZMEs, were found to be strongly affected by the accessibility of the analytes to the ion-exchanging sites and their mobility within the zeolite framework. Good correlation was found between results obtained in ion-exchange voltammetry and conventional ion-exchange characterization. The advantage of these fundamental studies for electroanalytical purposes was exemplified for the determination of copper(II) ions, using both ZMCPE and ZMGCE, zeolites A, X and Y, and the following analytical scheme: “preconcentration/voltammetric detection”.     

A Multiple Evaluation Approach of Commercially Available Screen‐Printed Nanostructured Carbon Electrodes

Commercially available carbon‐based screen‐printed electrodes were studied by cyclic voltammetry and electrochemical impedance spectroscopy in their behavior towards electron transfer to the soluble fast redox probes hexacyanoferrate(III), hexaammineruthenium(III) and methyl‐viologen. Semi‐infinite linear diffusion was observed for hexacyanoferrate(III) probe, with heterogeneous electron transfer rate constants significantly favored on nanotubes‐modified surfaces. Finite diffusion was observed for methyl‐viologen on graphene electrodes, which was reflected in the enhancement of the faradic currents by 4‐folds. Hexaammineruthenium(III) showed mixed diffusion behavior. These characteristics are reflected in the voltammetric behavior of lead(II) and cadmium(II) stripping from in‐situ deposited bismuth layer.     

Potential shifts at electrodes coated with ion-exchange polymeric films

Voltammetry at electrodes modified with ion-exchange polymers, named "ion exchange voltammetry", has been recently developed for characterizing and determining quantitatively ionic electroactive analytes preconcentrated at the electrode surface. Like for other voltammetric techniques, characterization is based on the position of the response on the potential scale, but an appreciable difference is frequently observed between the formal half-wave potential for redox couples incorporated within ion-exchange polymeric films and those for the same redox couples in solution as measured at bare electrodes. Such a difference has been rationalized here by a generalized equation, inferred from a suitable elaboration of the Nernst equation, whose validity has been tested by a thorough investigation performed at glassy carbon electrodes modified with either cationic (Nafion) or anionic (Tosflex) polymeric films. With this purpose, the effect of both charge and concentration of the analyte and of the loading counterion, this last introduced as the cation or anion of the supporting electrolyte, of the ion-exchange selectivity coefficients of the redox partners and of their stoichiometric coefficients, as well as of the number of electrons involved in the charge transfer has been evaluated. The results obtained agree quite well with theoretical expectations and indicate that the potential shifts found are mainly conditioned by both charge and concentration of the counterion from the supporting electrolyte and by the ratio of the ion-exchange equilibrium constants for the two redox partners involved. Other parameters considered have no influence on the potential shift or lead to negligible effects, provided that the quantities of the redox partners incorporated within the ion-exchange coating represents less than 5% of the film capacity. Again in agreement with theoretical expectations, positive shifts are found for increasing supporting electrolyte concentrations when cationic redox species incorporated within cationic films are involved, while the opposite effect is found for anionic redox species incorporated within anionic films.     

Construction of an electrochemical sensor based on the electrodeposition of Au-Pt nanoparticles mixtures on multi-walled carbon nanotubes film for voltammetric determination of cefotaxime

Mixtures of gold-platinum nanoparticles (Au-PtNPs) are fabricated consecutively on a multi-walled carbon nanotubes (MWNT) coated glassy carbon electrode (GCE) by the electrodeposition method. The surface morphology and nature of the hybrid film (Au-PtNPs/MWCNT) deposited on glassy carbon electrodes is characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The modified electrode is used as a new and sensitive electrochemical sensor for the voltammetric determination of cefotaxime (CFX). The electrochemical behavior of CFX is investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results of voltammetric studies exhibited a considerable improvement in the oxidation peak current of CFX compared to glassy carbon electrodes individually coated with MWCNT or Au-PtNPs. Under the optimized conditions, the modified electrode showed a wide linear dynamic range of 0.004-10.0 μM with a detection limit of 1.0 nM for the voltammetric determination of CFX. The modified electrode was successfully applied for the accurate determination of trace amounts of CFX in pharmaceutical and clinical preparations.     

Anodic Stripping Voltammetric Detection of Arsenic(III) at Gold Nanoparticle‐Modified Glassy Carbon Electrodes Prepared by Electrodeposition in the Presence of Various Additives

The simple, fast and highly sensitive anodic stripping voltammetric detection of As(III) at a gold (Au) nanoparticle‐modified glassy carbon (GC) (nano‐Au/GC) electrode in HCl solution was extensively studied. The Au nanoparticles were electrodeposited onto GC electrode using chronocoulometric technique via a potential step from 1.1 to 0 V vs. Ag|AgCl|NaCl (sat.) in 0.5 M H₂SO₄ containing Na[AuCl₄] in the presence of KI, KBr, Na₂S and cysteine additives. Surfaces of the resulting nano‐Au/GC electrodes were characterized with cyclic voltammetry. The performances of the nano‐Au/GC electrodes, which were prepared using different concentrations of Na[AuCl₄] (0.05–0.5 mM) and KI additive (0.01–1.0 mM) at various deposition times (10–30 s), for the voltammetric detection of As(III) were examined. After the optimization, a high sensitivity of 0.32 mA cm^?2 μM^?1 and detection limit of 0.024 μM (1.8 ppb) were obtained using linear sweep voltammetry.     

Voltammetric determination of lead at chemically modified electrodes based on crown ethers.

The feasibility of fabricating lead-sensitive chemically modified electrodes (CMEs) for trace analysis in aqueous and 40% (v/v) ethanol-water media was investigated. Carbon paste electrodes modified with crown ethers were constructed by mixing the crown ethers into a graphite powder-paraffin oil matrix. The thus-formed electrodes were able to bind Pb(II) ions chemically, and gave better voltammetric responses than unmodified ones. The crown ethers studied and compared were 18-crown-6 and dibenzo-18-crown-6. With a 5% 18-crown-6 CME, Pb(II) could be quantified at sub-ppm levels by differential pulse voltammetry with a detection limit of 0.02 ppm. It was possible to selectively pick up Pb(II) from a solution of several other ions at an open circuit through complexation. A simultaneous analysis of Cu(II) and Pb(II) was also attempted. By differential pulse anodic stripping voltammetry Pb(II) could be quantified over the range of 1 to 100 ppb. Interference from metal ions like Ni(II), Co(II), Mn(II), Zn(II), Cd(II), Ag(I), Fe(III), Ca(II) and Mg(II) was also studied. The method was successfully applied to artificial as well as commercial samples of alcoholic beverages.     

Electrochemical behaviour of carbon paste electrodes enriched with tin oxide nanoparticles using voltammetry and electrochemical impedance spectroscopy

The effect of the SnO(2) nanoparticles (SNPs) on the behaviour of voltammetric carbon paste electrodes were studied for possible use of this material in biosensor development. The electrochemical behaviour of SNP modified carbon paste electrodes (CPE) was first investigated by using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques. The performance of the SNP modified electrodes were compared to those of unmodified ones and the parameters affecting the response of the modified electrode were optimized. The SNP modified electrodes were then tested for the electrochemical sensing of DNA purine base adenine to explore their further development in biosensor applications.     

Sequential-injection stripping analysis of nifuroxime using DNA-modified glassy carbon electrodes

The voltammetric behavior of nifuroxime was investigated comparing stationary voltammetric methods with the recently proposed sequential-injection stripping analysis (SISA), by using cyclic voltammetry (CV) and differential-pulse voltammetry at bare and DNA-modified glassy carbon (GC) electrodes. In cyclic voltammetry, reduction of nifuroxime at DNA-modified electrodes gives rise to a well-defined peak, and in contrast to bare GC surfaces, a re-oxidation peak could be observed. Optimization of the pre-concentration process at the DNA-modified surface led to a significant enhancement of the voltammetric current response, a better defined peak shape and an improved dynamic range. Based on this optimized voltammetric procedure, SISA has been evaluated for the determination of nifuroxime. The flow-system significantly facilitates the regeneration of the DNA-modified electrode surface, hence diminishing problems related to accumulation and memory effects. The linear detection range could be extended to 65 microM with a detection limit (3 s) of 0.68 microM, which corresponds to an absolute amount of 21 ng nifuroxime.     

Direct electrochemistry and electrocatalytic characteristic of heme proteins immobilized in a new sol-gel polymer film

Heme proteins were immobilized on glass carbon electrodes by poly (N-isopropylac-yamide-co-3-methacryloxy-propyl-trimethoxysilane) (PNM) and exhibited a pair of well-defined, quasi-reversible cyclic voltammetric peaks at about -0.35 V versus a saturated calomel electrode in pH 7.0 buffer solution, corresponding to hemeFe(III)+e-->hemeFe(II). Some electrochemical parameters were calculated by performing nonlinear regression analysis of square wave voltammetry (SWV) experimental data. The formal potential was linearly dependent on pH, indicating the electron transfer of Fe(III)/Fe(II) redox couple accompanied by the transfer of proton. Ultraviolet visible and Fourier transform infrared spectra suggested that the conformation of proteins in the PNM films retained the essential feature of its native secondary structure. Atomic force microscopy images demonstrated the existence of interaction between heme proteins and PNM. N,N-dimethylformamide (DMF) played an important role in immobilizing proteins and enhancing electron transfer between proteins and electrodes. Electrochemical catalytic reductions of hydrogen peroxide and trichloroacetic acid by proteins entrapped in PNM film were also discussed, showing the potential applicability of the film modified electrodes as a biosensor.     

Simplifying the evaluation of graphene modified electrode performance using rotating disk electrode voltammetry

Graphene modified electrodes have been fabricated by electrodeposition from an aqueous graphene oxide solution onto conducting Pt, Au, glassy carbon, and indium tin dioxide substrates. Detailed investigations of the electrochemistry of the [Ru(NH(3))(6)](3+/2+) and [Fe(CN)(6)](3-/4-) and hydroquinone and uric acid oxidation processes have been undertaken at glassy carbon and graphene modified glassy carbon electrodes using transient cyclic voltammetry at a stationary electrode and near steady-state voltammetry at a rotating disk electrode. Comparisons of the data with simulation suggest that the transient voltammetric characteristics at graphene modified electrodes contain a significant contribution from thin layer and surface confined processes. Consequently, interpretations based solely on mass transport by semi-infinite linear diffusion may result in incorrect conclusions on the activity of the graphene modified electrode. In contrast, steady-state voltammetry at a rotating disk electrode affords a much simpler method for the evaluation of the performance of graphene modified electrode since the relative importance of the thin layer and surface confined processes are substantially diminished and mass transport is dominated by convection. Application of the rotated electrode approach with carbon nanotube modified electrodes also should lead to simplification of data analysis in this environment.     

Voltammetric Determination of Thiourea at Conductive Diamond Electrodes

The oxidation of thiourea (TU) at boron‐doped diamond (BDD) electrodes was investigated by the use of anodic voltammetry. The results indicated that the overall TU oxidation reaction is rather complicated and takes place via two steps: a slow electron‐transfer yielding the corresponding free radical, followed by a fast oxidation of this radical, prior to its dimerization. It was found that in acidic media the voltammetric response is suitable for analytical applications, and unlike glassy carbon (GC), BDD electrodes exhibit very low susceptibility to adsorption. The same conclusion was supported by the results of AC voltammetric measurements. Based upon the voltammetric peak for the first step of TU oxidation, a method is proposed for the determination of this compound in the micromolar concentration range. The analytical performance characteristics of the method are comparable to those reported for TU determination by the use of platinum electrodes or enzyme‐modified platinum electrodes.     

Ion-exchange properties and electrochemical characterization of quaternary ammonium-functionalized silica microspheres obtained by the surfactant template route

Porous silica spheres functionalized with quaternary ammonium groups have been prepared by co-condensation of N-((trimethoxysilyl)propyl)-N,N,N-trimethylammonium chloride (TMTMAC) and tetraethoxysilane (TEOS) in the presence of cetyltrimethylammonium as a template and ammonia as a catalyst. The physicochemical characteristics of the resulting ion exchangers have been analyzed by various techniques and discussed with respect to the amount of organofunctional groups in the materials. For comparison purposes, both an ordered MCM-41 type mesoporous silica and two silica gels of different pore size have been grafted with TMTMAC. The ion-exchange capabilities were first evaluated from batch experiments (determination of anion-exchange capacities) and then by ion-exchange voltammetry at carbon paste electrodes modified with these hybrid materials. Effective concentration of Fe(CN)(6)(3)(-) species in the anion exchangers was pointed out, while no significant accumulation of Ru(NH(3))(6)(3+) was observed. The preconcentration efficiency was discussed on the basis of the organic group content in the materials as well as their structure and porosity. A second series of materials displaying zwitterionic surfaces was finally prepared and characterized with respect to their physicochemical properties and ion-exchange voltammetric behavior. They consisted of sulfonic acid-functionalized mesoporous silica samples resulting from the oxidation of thiol-functionalized silica spheres obtained by co-condensation of mercaptopropyl-trimethoxysilane (MPTMS) and TEOS, which were then grafted with TMTMAC at various functionalization levels. Possible interactions between the ammonium and sulfonate moieties in the confined medium were pointed out from X-ray photoelectron spectroscopy. The competitive accumulation-rejection of Fe(CN)(6)(3)(-) and Ru(NH(3))(6)(3+) redox probes was finally studied by cyclic voltammetry.     

Gold Nanoparticle Modified Electrodes Show a Reduced Interference by Cu(II) in the Detection of As(III) Using Anodic Stripping Voltammetry

Interference by Cu(II) causes serious problems in the detection of As(III) using anodic stripping voltammetry at gold electrodes. The behavior of Cu(II) and As(III) were examined at both a gold macro electrode and two kinds of gold nanoparticle modified electrodes, one where gold particles are deposited on glassy carbon (GC) and the other where basal plane pyrolytic graphite (BPPG) is the substrate. The sensitivity of As(III) detection was higher on gold nanoparticle modified electrodes than those on a macro gold electrode by up to an order of magnitude. In addition, the stripping peak of As(III) was narrower and more symmetric on a gold nanoparticle‐modified GC electrode, leading to analytical data with a lower limit of detection. At a macro gold electrode, the peak currents of Cu(II) were higher than those on gold nanoparticle modified electrodes. Accordingly, through the use of gold nanoparticle modified electrodes, the effect of copper interference to the arsenic detection can be reduced.     

Voltammetric determination of copper at chemically modified electrodes based on crown ethers

The feasibility of fabricating copper-sensitive chemically modified electrodes (CMEs) for trace analysis in aqueous and in 40% (v/v) ethanol-water media was investigated. Carbon paste electrodes modified with crown ethers were constructed by mixing the crown ethers into a graphite powder-paraffin oil matrix. The electrodes so formed were able to bind Cu(II) ions chemically and gave better voltammetric responses than the unmodified ones. The crown ethers studied and compared were 15-crown-5, benzo-15-crown-5 and dibenzo-18-crown-6. With a 3% benzo-15-crown-5 CME, Cu(II) could be quantified at sub-ppm levels by differential pulse voltammetry with a detection limit of 0.05 ppm. By differential pulse anodic stripping voltammetry Cu(II) could be quantified over the range I to 100 ppb. Interference from metal ions like Ni(II), Co(II), Mn(II), Fe(II), etc. have also been studied. The method was successfully applied to artificial as well as commercial samples of alcoholic beverages.     

Carbon Nanotubes Modified Graphite Electrodes for Monitoring of Biointeraction Between 6‐Thioguanine and DNA

In this present study, single‐walled carbon nanotubes (SWCNT) modified disposable pencil graphite electrodes (SWCNT‐PGEs) were developed for the electrochemical monitoring of anticancer drug, and its interaction with double stranded DNA (dsDNA). Under this aim, SWCNT‐PGEs were applied for the first time in the literature to analyse of 6‐Thioguanine (6‐TG), and also to investigate its interaction with DNA by voltammetric and impedimetric methods. The surface morphologies of PGE and SWCNT‐PGE were explored using scanning electron microscopy (SEM) and electrochemical characterization of unmodified/modified electrodes was performed by cyclic voltammetry (CV). Experimental parameters; such as, the concentration of 6‐TG and its interaction time with dsDNA were optimized by using differential pulse voltammetry (DPV). Additionally, the interaction of 6‐TG with dsDNA was studied in case of different interaction times by electrochemical impedance spectroscopy (EIS) in contrast to voltammetric results. The detection limit of 6‐TG was found to be 0.25 μM by SWCNT‐PGE.     

Electrochemical Behavior and Voltammetric Determination of Curcumin at Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of curcumin by using a electrochemically reduced graphene oxide (ERGO) modified glass carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The electrochemical behaviors of curcumin at ERGO/GCE were investigated by cyclic voltammetry, suggesting that the ERGO/GCE exhibits excellent electrocatalytic activity towards curcumin, compared with bare GCE and GO/GCE electrodes. The electrochemical reaction mechanisms of curcumin, demethoxycurcumin and bisdemethoxycurcumin at the ERGO/GCE were also investigated and discussed systematically. Under physiological condition, the modified electrode showed linear voltammetric response from 0.2 μM to 60.0 μM for curcumin, with the detection limit of 0.1 μm. This work demonstrates that the graphene‐modified electrode is a promising strategy for electrochemical determination of biological important phenolic compounds.     

Topography changes of rhodium electrodes induced by the application of fast periodic potential routines

The surface structure of polycrystalline rhodium electrodes in contact with aqueous sulfuric acid was modified by chemical etching with hot concentrated acid or by applying fast square waves with an upper potential equal to 1.55 V and a lower potential within the –0.75 V to –0.35 V range. Polycrystalline rhodium and chemical etched electrodes were characterized by voltammetry, Cu underpotential deposition (upd) and X-ray diffraction. For electrofaceted surfaces were used voltammetry, Cu upd and SEM, revealing that two modified rhodium electrodes exhibit similar voltammetric characteristics as those found for Rh(111) and Rh(110) single crystals, and a third surface with an equal distribution of (110) and (111) planes. In addition, the upd of Cu on those surfaces corroborated the existence of those crystallographic planes. SEM micrographs show surface structures with a high density of terraces and steps. A mechanism of faceting is proposed. Electronic Publication     

A simple and sensitive portable system for a rapid evaluation of bisphenol A contamination in potable and environmental waters using a mesoporous silica-modified carbon paste electrode

In this work, two ordered mesoporous silicas (HMS and SBA-15) were prepared and incorporated into carbon paste electrodes (CPEs) to obtain mesostructured sensors for a rapid determination of bisphenol A (BPA) in waters by voltammetric techniques. The materials were characterised by nitrogen adsorption-desorption measurements, transmission electron microscopy and scanning electron microscopy. The electrochemical properties of the modified carbon paste electrodes were studied by differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Results showed that the sensor modified with HMS (HMS-CPE) exhibited strong adsorption activity toward the oxidation of BPA, with a well-defined voltammetric peak at +0.6 V. Moreover, the HMS-CPE exhibited a wider linearity range, from 0.44 to 3.5 μM BPA, with a detection limit of 61 nM (S/N = 3) and good reproducibility by DPV. The enhanced performance of the HMS-CPE could be attributed to its high surface area, with a 3 D wormhole-like channel structure that favoured an excellent accessibility, high adsorption capacity and faster adsorption rate of BPA. This novel sensor was coupled to a portable system and successfully applied for a rapid determination of BPA in tap, mineral, well and river water samples with good recovery, ranging from 98 ± 12 to 103 ± 7%.