ELECTROCATALYTIC OXIDATION AND AMPEROMETRIC DETERMINATION OF SULFHYDRYL COMPOUNDS AT A COPPER HEXACYANOFERRATE FILM GLASSY-CARBON ELECTRODE IN LIQUID-CHROMATOGRAPHY

Electrocatalytic oxidation of sulfhydryl compounds was effective on a copper hexacyanoferrate (CuHCF) film glassy carbon electrode, at a significantly reduced overpotential (0.55 to 0.65 V) and for a broader pH range (2.0 to 7.0). The electrocatalysis was

DETERMINATION OF CATECHOL DERIVATIVES ON PRETREATMENT AND COPOLYMER COATED GLASSY-CARBON ELECTRODE

A glassy carbon electrode was pretreated electrochemically and was coated with a copolymer of maleic acid anhydride attached with Eastman-AQ55D (MA/AQ). The voltammetric behavior of a series of biologically important compounds, such as dopamine, L-DOPA, D

RAPID-DETERMINATION OF KINETIC-PARAMETERS FOR THE ELECTROCATALYTIC REDUCTION OF DIOXYGEN BY VITAMIN-B12 ADSORBED ON GLASSY-CARBON ELECTRODE

In this paper, the electrochemical behavior of vitamin B-12, ie cyanocobalamin (abbr. VB12) in a weak acidic aqueous solution and adsorbed on glassy carbon (GC) surface (abbr. VB12(ad)/GC) in different pH buffer solutions have been described by using cyclic voltammetry (cv). It is found that VB12 and VB12(ad)/GC exhibit catalytic activity for the electroreduction of O2 according to two reduction peaks at -0.50 and -1.00 V vs. sce; but their electrocatalytic activity is very unstable. Based on the method of hydrodynamic amperometry [B. Miller and S. Bruckenstein, J. electrochem. Soc. 117, 1033 (1970)], some kinetic parameters for the electrocatalytic reduction of O2 by VB12(ad)/GC have been determined rapidly by using a linear rotation-scan method [Rongzhong Jiang and Shaojun Dong, Electrochim. Acta 35, 1451 (1990)]. These kinetic parameters indicate that the reduction of O2 on VB12(ad)/GC gives water predominantly in both potential ranges which correspond to those two reduction peaks. Possible reaction mechanisms have been suggested.

PREPARATION AND CHARACTERIZATION OF A MULTICYLINDER MICROELECTRODE COUPLED WITH A CONVENTIONAL GLASSY-CARBON ELECTRODE AND ITS APPLICATION TO THE DETECTION OF DOPAMINE

A multi-cylinder microelectrode coupled with a conventional glassy carbon disc electrode (MCM/GC) was prepared and characterized using cyclic voltammetry and chronoamperometry. It was demonstrated that in the same way as one observed a steady-state current at closely spaced microelectrodes when redox recycling takes place, the same effect can be obtained with the MCM/GC device. The experimental results obtained with K3Fe(CN)6 solutions were compared with a previously developed theory. Further, it was demonstrated that with a carbon fibre MCM/GC device, the voltammetric behaviour of dopamine is greatly improved by virtue of redox recycling, hence giving high sensitivity. The steady-state collection current was linearly related to dopamine concentration in the range 1 X 10(-4) to 5 x 10(-7) Mol l-1, and the detection limit was 2 x 10(-7) mol l-1. The influence of coexisting ascorbic acid was also investigated. This device was applied successfully in the determination of dopamine hydrochloride in pharmaceutical preparations.

FLOW-INJECTION ANALYSIS OF GLUCOSE AT AN AMPEROMETRIC GLUCOSE SENSOR-BASED ON ELECTROCHEMICAL CODEPOSITION OF PALLADIUM AND GLUCOSE-OXIDASE ON A GLASSY-CARBON ELECTRODE

A glassy carbon electrode (GCE) modified with palladium provides excellent electrocatalytic oxidation of hydrogen peroxide. When the electrolyte contains palladium chloride and glucose oxidase, the GCE can be modified by electrochemical codeposition at a given potential. The resulting modified surface was coated with a thin film of Nation to form a glucose sensor. Such a glucose sensor was successfully used in the flow-injection analysis of glucose with high stability and anti-poisoning ability. It gave a detection limit of 1 X 10(-7) M injected glucose, with a linear concentration range of 0.001-8 mM. There is no obvious interference from substances such as ascorbate and saccharides.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

THE ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON ELECTRODE

The anodic oxidation kinetics of hydrazine (N2H4) on glassy carbon (GC) electrode was examined by cyclic voltammetry, rotating disk and ring-disc electrode techniques. The possible mechanisms of N2H4 oxidation in both aqueous and nonaqueous solutions are proposed.

ELECTROCATALYTIC OXIDATION AND FLOW DETECTION OF HYDRAZINE COMPOUNDS IN LIQUID-CHROMATOGRAPHY AT A VITAMIN-B-12 ADSORBED GLASSY-CARBON ELECTRODE

A vitamin B-12 chemically modified electrode (CME) was constructed by adsorption of vitamin B-12 onto a glassy carbon surface. The electrode catalyzes the electrooxidation of hydrazine compounds over a wide pH range. The electrocatalytic behavior of hydrazines is elucidated with respect to the CME preparation conditions, solution pH, operating potential, mobile phase flow rate, and other variables. When applied to liquid chromatographic detection of the analytes, the vitamin B-12 CME yielded a linear response range over 2 orders of magnitude, and detection limits at the picomole level. The vitamin B-12 CME offers acceptable catalytic stability in both batch and flow systems.

A GLASSY-CARBON ELECTRODE MODIFIED BY DISPERSED ALPHA-ALUMINA AS AN ENHANCED ELECTROCHEMICAL DETECTOR IN LIQUID-CHROMATOGRAPHY FOR CYSTEINE AND GLUTATHIONE

The dispersion of alumina particles on a glassy-carbon surface serving as a modified electrode significantly enhances the amperometric detection of cysteine and glutathione following liquid chromatography. With an applied potential of 0.8 V vs. SCE, the detection limits were 1.2 ng for cysteine and 8 ng for glutathione and the electrode response was linear up to 600 ng for cysteine and 1.8-mu-g for glutathione. The modified electrode displayed high sensitivity and stability and was easy and inexpensive to prepare.

INVESTIGATION OF CETYLPYRIDINIUM BROMIDE ADSORPTION AT A GLASSY-CARBON ELECTRODE SURFACE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

The adsorption of cationic surfactant cetylpyridinium bromide (CPB) on a glassy carbon (GC) electrode surface has been studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. A fine adsorption isotherm of CPB molecules from an aqueous solution containing 0.10 M KBr has been obtained over the range of (1.00-8.00) x 10(-5) M. From theoretical calculation and experimental data, adsorption of CPB on the GC electrode surface shows four distinct orientations and three large orientation transitions. Compared with the ordinary isotherm, the differential isotherm is more characteristic and would be suitable for the study of orientation transitions of organic compounds. With a theoretical treatment of the adsorption isotherm, four orientations of adsorbed CPB on a GC electrode surface coincide with the Frumkin-Langmuir type. From adsorption parameters the Frumkin-Langmuir equations, the adsorption free energy and, therefore, the equilibrium constants of orientation transitions of the CPB molecule can be obtained.

SURFACE CHARACTERIZATION OF COBALT TETRAPHENYLPORPHYRIN MODIFIED GLASSY CARBON ELECTRODE BY XPS

Surface structure of the glassy carbon surface modified with cobalt tetraphenyl-porphyrin (CoTPP) by thermal-treatment has been studied by XPS, DTA and TG. During the thermal treatment a bond can be formed between the glassy carbon surface and TPP. Therefore the stability of electrode for the catalysis of dioxygen reduction is improved. Upon thermal treatment at 600 degrees C, FWHM of Co(2p(2/2)) is broadened, the reason is due to overlapping of peaks of multiple states, the spin orbit separation between Co (2p(1/2)) and Co (2p(3/2)) increases to 15.5-16.3eV, which indicated a change from low spin divalent states, the kinetic energy of Co L3VV Auger line and Auger parameter also increase. These changes of central cobalt ion provide a suitable redox potential for Co(III)/Co(II) which is related to the activity for catalysis of dioxygen reduction.

ELECTROCATALYSIS ON ELECTROCHEMICALLY PRETREATED GLASSY-CARBON ELECTRODE

The surface structure of glassy carbon electrode subjected to "galvanostat" pretreat- ment and its electrocatalytic behaviour in the presence of ascorbic acid, catechol and hydroquinone were studied by means of cyclic voltammetry, chronoamperometry, chronocoulometry and scanning electron microscopy. The electrocatalytic mechanism was discussed, which was due to the adsorption and the catalysis of functional groups at the electrode surface. Three separated peaks from the mixture of catecnol, hydroq...