Electrocatalytic oxidation and flow-injection determination of sulfur amino acids on a glassy carbon electrode modified by a nickel(II) polytetrasulfophthalocyanine film

The electrochemical oxidation of sulfur amino acids, i.e., cysteine, cystine, and methionine, is studied on a glassy carbon electrode modified by a film of nickel(II) polytetrasulfophthalocyanine (poly-NiTsPc). Poly-NiTsPc demonstrates a selective mediator activity in the oxidation of sulfur amino acids, depending on the pH of solution. The proper conditions for fabricating a polymer film on the surface of glassy carbon are found and the conditions of registering the maximal electrocatalytic effect on the modified electrode are determined. A procedure is proposed for the voltammetric determination and amperometric detection of cysteine, cystine, and methionine on an electrode coated by a poly-NiTsPc film under the conditions of flow-injection analysis (FIA). The linear relation of the electrocatalytic response of a composite electrode to amino acid concentration is observed to the level n × 10^?6 M in the static mode and n × 10^?9 M under FIA conditions.     

Electrocatalytic Oxidation of Cysteine and Cystine at a Carbon-Paste Electrode Modified with Ruthenium(IV) Oxide

The electrocatalytic activity of ruthenium(IV) oxide incorporated into a carbon-paste electrode was studied in the oxidation of cysteine and cystine. The oxidation potentials of the amino acids decreased and the current peaks of their oxidation increased at a modified electrode as compared to an unmodified one. Procedures for the voltammetric determination of cysteine and cystine with the use of electrodes chemically modified with ruthenium(IV) oxide were proposed.     

Electrocatalytic Oxidation of Sulfur Containing Amino Acids at Renewable Ni‐Powder Doped Carbon Ceramic Electrode: Application to Amperometric Detection L‐Cystine,L‐Cysteine and L‐Methionine

A sol‐gel technique was used here to prepare a renewable carbon ceramic electrode modified with nickel powder. Cyclic voltammograms of the resulting modified electrode show stable and a well defined redox couple due to Ni(II)/Ni(III) system with surface confined characteristics. The modified electrode shows excellent catalytic activity toward L ‐cystine, L ‐cysteine and L ‐methionine oxidation at reduced overpotential in alkaline solutions. In addition the antifouling properties at the modified electrode toward the above analytes and their oxidation products increases the reproducibility of results. L ‐cystine, L ‐cysteine and L ‐methionine were determined chronoamperometricaly at the surface of this modified electrode at pH range 9–13. Under the optimized conditions the calibration curves are linear in the concentration range 1–450 μM, 2–90 μM and 0.2–75 μM for L ‐cystine, L ‐methionine and L ‐cysteine determination, respectively. The detection limit and sensitivity were 0.64 μM, 3.8 nA/ μM for L ‐cystine, 2 μM, 5.6 nA/ μM for L ‐methionine and 0.2 μM and 8.1 nA/μM for L ‐cysteine. The advantageous of this modified electrode is high response, good stability and reproducibility, excellent catalytic activity for oxidation inert molecules at reduced overpotential and possibility of regeneration of the electrode surface by potential cycling for 5 minutes. Furthermore, the modified electrode has been prepared without using specific reagents. This sensor can be used as an amperometric detector for disulfides detection in chromatographic or flow systems.     

Flow-injection determination of water-soluble vitamins B1, B2, and B6 from the electrocatalytic response of a graphite electrode modified with a ruthenium(III) hexacyanoruthenate(II) film

The electrochemical behavior of water-soluble vitamins B₁, B₂, and B₆ at an unmodified graphite electrode and a graphite electrode modified with an inorganic film of ruthenium(III) hexacyanoruthenate(II) was studied. The electrocatalytic activity of the metal complex in the oxidation of vitamins was found. Ru(IV) species act as a catalyst. Conditions for recording voltammograms and hydrodynamic conditions for detecting the maximum catalytic current in flow-injection analysis (FIA) were selected. Procedures for the amperometric detection of thiamine, riboflavin, and pyridoxine were proposed.     

Studies on the kinetics of ascorbate oxidation at a ruthenium oxide hexacyanoferrate modified electrode towards the detection at microenvironments

The electrocatalytic oxidation of ascorbate on a ruthenium oxide hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was investigated at pH 6.9 by using rotating disc electrode (RDE) voltammetry. The influence of the systematic variation of rotation rate, film thickness, ascorbate concentration and the electrode potential indicated that the rate of cross-chemical reaction between Ru(III) centres immobilized into the film and ascorbate controls the overall process. The kinetic regime may be classified as a Sk″ mechanism and the second order rate constant for the surface electrocatalytic reaction was found to be 1.56 × 10⁻³ mol⁻¹ L¹ s⁻¹ cm. A carbon fibre microelectrode modified with the RuOHCF film was successfully used as an amperometric sensor to monitor the ascorbate diffusion in a simulated microenvironment experiment.     

Electrocatalytic oxidation and amperometric detection of ethanol on graphite electrodes modified with a coating composed of hexacyanometallates

The electrochemical behavior of methanol on graphite electrodes modified with a coating composed of (III) hexacyanoferrate and ruthenium(III) hexacyanoferrate(II) and hexacyanoruthenate(II) was studied. A method for electrochemical determination of ethanol on a carbon-paste electrode modified with a coating composed of ruthenium(III) hexacyanoruthenate(II) under stationary and flow-injection conditions was suggested.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 1974–1979.Original Russian Text Copyright © 2004 by Shaidarova, Gedmina, Chelnokova, Budnikov.     

Electrocatalytic oxidation of hydrazine at cobalt hexacyanoferrate- modified glassy carbon, Pt and Au electrodes

The electrocatalytic oxidation of hydrazine has been studied on glassy carbon, Pt and Au electrodes modified by cobalt hexacyanoferrate (CoHCF) using cyclic voltammetry and rotating disc techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at the potential coinciding with that of Co(II) to Co(III) transformation in a CoHCF film, where no oxidation signal is observed at a bare glassy carbon electrode. A Tafel plot, derived from RDE voltammograms, exhibits a slope of 150 mV, indicating a one-electron charge transfer process to be the rate-limiting step. The electrocatalytic efficiency of the modified electrode towards hydrazine oxidation depends on solution pH, and the optimum range was found to be located between pH 5 and pH 7. The kinetic behaviour and location of the electrocatalytic process were examined using the W.J. Albery diagnosis table, and it was concluded that the reaction has either a “surface” or a “layer” reaction mechanism. Pt- and Au-CoHCF-modified electrodes show no significant electrocatalytic activity towards hydrazine oxidation. Received: 25 April 1997 / Accepted: 12 August 1997     

Boron doped diamond and glassy carbon electrodes comparative study of the oxidation behaviour of cysteine and methionine

The electrochemical oxidation behaviour at boron doped diamond and glassy carbon electrodes of the sulphur-containing amino acids cysteine and methionine, using cyclic and differential pulse voltammetry over a wide pH range, was compared. The oxidation reactions of these amino acids are irreversible, diffusion-controlled pH dependent processes, and occur in a complex cascade mechanism. The amino acid cysteine undergoes similar three consecutive oxidation reactions at both electrodes. The first step involves the oxidation of the sulfhydryl group with radical formation, that undergoes nucleophilic attack by water to give an intermediate species that is oxidized in the second step to cysteic acid. The oxidation of the sulfhydryl group leads to a disulfide bridge between two similar cysteine moieties forming cysteine. The subsequent oxidation of cystine occurs at a higher potential, due to the strong disulfide bridge covalent bond. The electro-oxidation of methionine at a glassy carbon electrode occurs in two steps, corresponding to the formation of sulfoxide and sulfone, involving the adsorption and protonation/deprotonation of the thiol group, followed by electrochemical oxidation. Methionine undergoes a one-step oxidation reaction at boron doped diamond electrodes due to the negligible adsorption, and the oxidation also leads to the formation of methionine sulfone.     

Electrochemical behavior and voltammetric determination of cysteine and cystine at carbon-paste electrodes modified with metal phthalocyanines

The electrochemical behavior of cysteine and cystine on carbon-paste electrodes modified with Fe(II), Co(II), Ni(II), and Cu(II) phthalocyanines is studied. Metal phthalocyanines exhibit catalytic activity in the electrooxidation of cysteine and cystine and in the reduction of cystine. The best catalyst is the cobalt complex. In the electrooxidation of cysteine, the catalysts are electrogenerated complex species of Co(II)Pc or Co(III)Pc⁺, and in the oxidation of cystine, oxidized or reduced forms of the coordinated ligand. Various versions of the determination of cysteine and cystine by the electrocatalytic reactions on the modified electrodes are proposed.     

Surface-renewable cobalt(II) hexacyanoferrate-modified graphite organosilicate electrode and its electrocatalytic oxidation of thiosulfate

Cobalt(II) hexacyanoferrate (CoHCF) was deposited on graphite powder by an in situ chemical deposition procedure and then dispersed into methyltrimethoxysilane-derived gels to prepare a surface-renewable CoHCF-modified electrode. The electrochemical behavior of the modified electrode in different supporting electrolyte solutions was characterized by cyclic voltammetry. In addition, square-wave voltammetry was employed to investigate the pNa-dependent electrochemical behavior of the electrode. The CoHCF-modified electrode showed a high electrocatalytic activity toward thiosulfate oxidation and could thus be used as an amperometric thiosulfate sensor.     

Amperometric sensor for the determination of ascorbic acid based on Cobalt hexacyanoferrate modified electrode fabricated through a new route

A new approach was attempted to prepare a chemically modified electrode using Cobalt hexacyanoferrate (CoHCF) as the redox mediator and to study its stability and electrocatalytic activity for ascorbic acid (AA) oxidation. The basic principle underlying the electrode modification is the coordination of cobalt ion with the amino nitrogen of aniline adsorbed on the surface of a graphite rod. This surface was subsequently derivatized with ferrocyanide to get CoHCF film on the electrode surface. The CoHCF modified electrode as prepared above was characterized using cyclic voltammetry. The effect of scan rate, supporting electrolyte and pH of the medium on the performance of the modified electrode was investigated. The CoHCF modified electrode exhibited good electrocatalytic activity towards the oxidation of ascorbic acid and gave a linear response from 5.52 x 10(-5) M to 3.23 x 10(-2) M with a correlation coefficient of 0.9929. The detection limit was found to be 3.33 x 10(-5) M. Hydrodynamic voltammetry and chronoamperometry studies for the oxidation of ascorbic acid were also carried out. The electrode was highly stable and exhibited good reproducibility. This modified electrode was also applied for the determination of ascorbic acid in commercial samples.     

Simple and low-cost electrochemical sensor based on nickel nanoparticles for the determination of cabergoline

Cabergoline (CAB) is an ergot alkaloid derivative with dopamine agonist activity. In this work for the first time the electrocatalytic oxidation of CAB was carried out with nickel nanoparticles-modified carbon paste electrode using cyclic voltammetry, chronoamperometry, chronocoulometry and amperometry methods. At first, nickel nanoparticles were synthesized by non-aqueous polyol method and these nanoparticles were mixed with graphite powder to form modified carbon paste electrode. The resulting modified electrode was characterized by scanning electron microscope images. In the presence of 0.1 M NaOH a good redox behavior of the Ni(III)/Ni(II) couple at the surface of the electrode can be observed. CAB was successfully oxidized at the surface of the modified electrode. The electrocatalytic oxidation peak current of this drug was linearly dependent on its concentration. The proposed sensor exhibited a high sensitivity and was successfully applied for the determination of CAB in real samples.     

Preparation of multiwall carbon nanotubes film modified electrode and its application to simultaneous determination of oxidizable amino acids in ion chromatography

A multiwall carbon nanotubes (MWNTs) film modified electrode was prepared and used as an amperometric sensor for the simultaneous determination of oxidizable amino acids including cysteine, tryptophane and tyrosine. The electrochemical behaviors of these amino acids at this modified electrode were studied by cyclic voltammetry (CV). The results indicated that the MWNTs chemically modified electrode (CME) exhibited efficient electrocatalytic activity towards the oxidation of these amino acids with relatively high sensitivity, stability and long-life. Following separation by ion chromatography (IC) with 2.0×10⁻³ mol l⁻¹ citric acid buffer solution (pH 6.5) as eluent, cysteine, tryptophane and tyrosine could be determined by the MWNTs CME successfully. Under the optimal conditions, the detection limits were 7.0×10⁻⁷ mol l⁻¹ for cysteine, 2.0×10⁻⁷ mol l⁻¹ for tryptophane and 3.5×10⁻⁷ mol l⁻¹ for tyrosine at the signal-to-noise of 3, respectively. The method was applied successfully to the determination of these substances in plasma.     

Direct Electrocatalytic Oxidation of Cysteine and Cystine Based on Nafion/Lead Oxide‐Manganese Oxide Combined Catalyst

This article reports direct electrocatalytic oxidation of cysteine (CySH) and cystine (CyS‐SCy) at an inexpensive Nafion/lead oxide‐manganese oxide combined catalyst in physiological pH. The synthesized lead oxide‐manganese oxide material is simply mixed with Nafion in the form of cast solution and modified on a disposable screen‐printed carbon electrode (designated as SPE/Nf‐PMO) for biosensing application. Electrochemical study with a standard redox couple of quinone/hydroquinone demonstrates an enhanced current response at the combined catalyst compared to its individual component. Surface characterization further provides information regarding the structural morphology of the catalyst to its catalytic performance. Direct electrocatalytic oxidation signals are observed at +0.75 and +1.20 V vs. Ag/AgCl for cysteine and cystine, respectively, at the SPE/Nf‐PMO. To extend the applicability, we further apply the proposed system for the detection of cysteine and cystine by flow injection analysis (FIA). Under optimized conditions, the detection limit (S/N=3) is 0.43 μM and 0.33 μM for cysteine and cystine, respectively.     

Electrocatalytic oxidation of nitric oxide at indium hexacyanoferrate film-modified electrodes

The electrocatalytic oxidation of nitric oxide (NO) by indium (III) hexacyanoferrate (III) films has been studied. These films are electrodeposited onto glassy carbon electrodes through potential cycling in acidic solutions containing a potassium electrolyte, indium (III), and potassium hexacyanoferrate. The resulting modified electrodes exhibit a reversible redox response ascribed to the oxidation/reduction of iron atoms presents in the electrodeposited film. The films have a potent and persistent electrocatalytic activity towards NO oxidation at neutral pH. The electrocatalytic oxidation of NO takes place at potentials around +0.75 V which represents a moderate diminution in the overpotential. In addition, interferences due to the presence of nitrate and nitrite have been significantly reduced. According to these results, the described modified electrodes have been used as sensors for the determination of NO generated by decomposition of a typical NO-donor, such as S-nitroso- N -acetyl- d, l -penicillamine (SNAP).     

Electrocatalytic Oxidation and Determination of Sulfite with a Novel Copper‐Cobalt Hexacyanoferrate Modified Carbon Paste Electrode

The electrocatalytic oxidation of sulfite has been studied at a stable electroactive thin film of copper‐cobalt hexacyanoferrate (CuCoHCF) hybrid electrodeposited on a carbon paste electrode (ECMCPE). A linear range of 5 μM to 5 mM of sulfite, with an experimental detection limit of 1 μM, was obtained using the cyclic voltammetric method. The oxidation of sulfite showed no significant fouling effect on the modified electrode surface at sulfite concentrations below 5 mM. The proposed modified electrode exhibited several attractive features, including simple preparation, fast response, good stability and repeatability, and could be applied to sulfite determination in real samples.     

Intermolecular Interactions in Systems Containing Bi(III) – ClO−4 – H2O – Selected Amino Acids in the Aspect of Catalysis of Bi(III) Electroreduction

The paper describes recent results of studies on the accelerating effect of sulfur‐containing protein amino acids and water activity on multistep Bi(III) ion electroreduction at mercury electrode. The catalytic effect of methionine (Mt), cystine (CY) and cysteine (CE) was analyzed based on kinetic and thermodynamic parameters, which correlated with water activity. Investigations of adsorption of those amino acids at the electrode/solution interface provided information for the analysis of the electrical double layer and its influence on the kinetics of the electrode process. The multistep Bi(III) electroreduction process is controlled by the kinetics of active complexes formation, which precedes transfer of consecutive electrons.     

Effects of a Surfactant on the Electrocatalytic Activity of Cobalt Hexacyanoferrate Modified Glassy Carbon Electrode Towards the Oxidation of Dopamine

The cobalt hexacyanoferrate film (CoHCF) was deposited on the surface of a glassy carbon (GC) electrode with a potential cycling procedure in the presence and absence of the cationic surfactant, cetyl trimethylammonium bromide (CTAB), to form CoHCF modified GC (CoHCF/GC) electrode. It was found that CTAB would affect the growth of the CoHCF film, the electrochemical behavior of the CoHCF film and the electrocatalytic activity of the CoHCF/GC electrode towards the electrochemical oxidation of dopamine (DA). The reasons of the electrochemical behavior of CoHCF/GC electrode influenced by CTAB were investigated using FTIR and scanning electron microscope (SEM) techniques. The apparent rate constant of electrocatalytic oxidation of DA catalyzed by CoHCF was determined using the rotating disk electrode measurements.     

Voltammetric and potentiometric study of cysteine at cobalt(II) phthalocyanine modified carbon-paste electrode

Cyclic voltammetry and potentiometry were used to investigate the electrochemical behavior of cysteine at a chemically modified electrode prepared by incorporating cobalt(II) phthalocyanine [Co(II)Pc] into carbon paste matrix. The modified electrode showed high electrocatalytic activity toward cysteine; the overpotential for the oxidation of cysteine was decreased by more than 100 mV, and the corresponding peak current increased significantly. The electrocatalytic process was highly dependent on the pH of the supporting electrolyte. The peak currents decreased when the pH was raised to 6 and totally disappeared at pH≥ 7, resulting from the autocatalytic oxidation of cysteine by Co(II)Pc at the electrode surface. Therefore, at pH values of 6 to 8, the modified electrode was used as a potentiometric sensor for quantitative measurement of cysteine in the presence of oxygen in air saturated solutions. In fact, the Co(II)Pc/Co(I)Pc couple acts as a suitable mediator for indirect oxidation of cysteine by dissolved oxygen at approximately neutral pH values. Under the optimized conditions, the potentiometric response of the modified electrode was linear against the concentration of cysteine in the range of 0.6 μM to 2 mM. The limit of detection was found to be 0.5 μM. The potentiometric response time was ≤15 s. The electrode showed long term stability; the standard deviation of the slope obtained after repeated calibration during a period of two months was 2.8% (n = 7). Application of the electrode in a recovery experiment for the determination of cysteine added to a synthetic serum sample is described.     

Electrocatalytic oxidation of thiosulfate on a modified nickel hexacyanoferrate film electrode

Summary A modified nickel hexacyanoferrate film glassy carbon electrode is prepared by the electrochemical deposition technique. The film is very stable upon voltammetric scanning in the potential range of 1.0 to –0.5 V (vs. SCE) and an oxidation peak occurs at 0.35 V (vs. SCE) (1 mol/l NaNO₃). The effects of electrolyte, solvent, coexisting ions and other variables on the voltammetric behaviour of the modified film have been studied. The thickness of the resulting film can be controlled by changing the number of voltammetric cycles and the concentrations of nickel(II) and hexacyanoferrate(III) ions. The film shows catalytic activity towards electrooxidation of thiosulfate with a peak potential +0.5 V (K^–-containing media). This oxidation potential of thiosulfate on the modified electrode is shifted negatively by about 550 mV as compared to the naked glassy carbon electrode. For practical application, the modified electrode can be used for the determination of thiosulfate in concentrations from 5.0×10^–5 to 1.0×10^–1 mol/l. This method has been successfully applied to the determination of thiosulfate in photographic waste effluents.