LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CATECHOL, RESORCINOL, AND HYDROQUINONE WITH A COPPER-BASED CHEMICALLY MODIFIED ELECTRODE

A copper-based chemically modified electrode (CME) has been constructed and characterized for flow-through amperometric detection of catechol, resorcinol, and hydroquinone. Novel potential dependence of the detector response was first obtained for these analytes at the Cu CME, where negative peaks together with positive ones were observed in one definite chromatogram using amperometric detection. Its advantages in chromatographic applications were demonstrated. From these observations it is proposed that the detector response was governed by formation of copper complexes with the solutes. A dynamic linear range over two orders of magnitude was obtained, when operating the detector at +0.10 V vs. SCE, from which ng detection limits were achieved.

INTERPRETATION OF THE PHOTOREDUCTION CURRENT RESPONSE ON POLYANILINE MODIFIED ELECTRODE

The photoreduction current response on a polyaniline modified electrode is interpreted as photo-assisted reduction of oxygen dissolved in the electrolyte solution but not due to the excited species PAn* and PAn* dagger. The effect of light is just the same as that of the electrode rotating or of stirring of the electrolyte which accelerates the oxygen dissolved in the electrolyte solution to react with leucoemeraldine (reduced polyaniline). The potentiostat is set to reduce the oxidized polyaniline at constant potential, thus producing a reduction current.

CATALYTIC REDUCTION OF HEMOGLOBIN AT THIONINE CHEMICALLY MODIFIED ELECTRODE AND FIA APPLICATIONS

Thionine-containing chemically modified electrode (cme) was constructed with glassy carbon substrate by potential sweep oxidation, electrodeposition and adsorption procedures, and electrocatalytic reduction of hemoglobin was carried out and characterized at the cme under batch and flow conditions. Comparison of the catalytic response toward hemoglobir obtained at the cme was made mainly in terms of the potential dependence, the detectability and long-term stability. When used in flow injection analysis (FIA) experiments with the detector monitored at a constant potential applied at -0.35 V vs sce, detection limit of 0.15-1.5 pmol level of hemoglobin injected was achieved at the cme, with linear response range over 2 orders of magnitude. All the cme s retained more than 70% of their initial hemoglobin response level over 8 h of continuous service in the flow-through system.

AMPEROMETRIC DETECTION OF CATECHOLAMINES WITH LIQUID-CHROMATOGRAPHY AT A NOVELLY CONSTRUCTED PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.

FLOW-INJECTION AMPEROMETRIC DETECTION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

A Prussian Blue-modified glassy carbon electrode prepared by simple adsorption exhibited excellent electrocatalytic activity in the oxidation of hydrazine in acidic media. A film of the perfluorosulphonic acid polymer Nafion coated on top of the Prussian Blue-modified glassy carbon electrode can improve the mechanical stability of the Prussian Blue layer in the flow stream. Hydrazine was detected by flow-injection analysis at the modified electrode with high sensitivity. The limit of detection was 0.6 ng.

AMPEROMETRIC FLOW-INJECTION ANALYSIS OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT COBALT TETRAPHENYLPORPHYRIN MODIFIED ELECTRODE WITH HEAT-TREATMENT

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750-degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH3OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4-mu-g. The method is very sensitive and selective.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

LIQUID-CHROMATOGRAPHY WITH ELECTROCATALYTIC DETECTION OF CYSTEINE, N-ACETYLCYSTEINE AND GLUTATHIONE BY A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

Chemically modified electrodes prepared by adsorbing prussian blue on a glassy carbon electrode are shown to catalyse the electro-oxidation of cysteine, N-acetylcysteine and glutathione in acidic media. The catalytic response is evaluated with respect to the potential scan rate, the solution pH, the concentration dependence, and other variables. Covering the electrode with Nafion(R) film improved the stability and reproducibility in liquid chromatography with electrochemical detection to the extent that repetitive sample injections produced relative standard deviations of less than 5% over several hours of operation. The limit of detection was 4 pmol for cysteine, 33 pmol for glutathione and 61 pmol for N-acetylcysteine.

POLYANILINE CHEMICALLY MODIFIED ELECTRODE FOR DETECTION OF ANIONS IN FLOW-INJECTION ANALYSIS AND ION CHROMATOGRAPHY

An electrochemical detector based on a polyaniline conducting polymer chemically modified electrode (PAn CME) was developed for use in flow-injection analysis and ion chromatography. Iodide, bromide, thiocyanate and thiosulphate are detected by using ion chromatography with a PAn CME electrochemical detector. The detection limits are 1, 5, 10 and 10 mgl-1, respectively. The CME response for electroinactive anions varies selectively with the mobile phase composition in flow-injection analysis. By this approach, perchlorate, sulphate, nitrate, iodide, acetate and oxalate can be detected conveniently and reproducibly over a linear concentration range of at least 3 orders of magnitude. The electrode is stable for over 2 weeks with no evidence of chemical or mechanical deterioration.

ELECTROCATALYTIC OXIDATION OF ASCORBIC-ACID AT A PRUSSIAN BLUE FILM MODIFIED MICRODISK ELECTRODE

The preparation and the behaviour of a Prussian Blue (PB) film on a platinum microdisk electrode has been described. Electrocatalytic oxidation of ascorbic acid has occurred at the PB film modified microelectrode. This shows a typical example of a modified microelectrode in electrocatalysis following our previous theoretical studies (J. Electroanal. Chem., 309 (1991) 103) and the related catalytic reaction rate constant was determined.

COBALT PORPHYRIN NAFION FILM ON CARBON MICROARRAY ELECTRODE TO MONITOR OXYGEN FOR ENZYME ANALYSIS OF GLUCOSE

A microcarbon array electrode was modified by the placement of a Nafion film containing cobalt tetramethylpyridyl phorphyrin on its surface. This electrode was applied to the analysis of solution glucose when it was further modified by the immobilization of glucose oxidase on the outermost surface of the Nafion by the cross-linking of serum albumin with glutaraldehyde. The concomitant decrease in the concentration of oxygen, as it was consumed in the enzymatic reaction of glucose with glucose oxidase, was determined by either cyclic voltammetry or a double potential step method at the porphyrin-Nafion catalytic electrode. Glucose could be determined in the range of 0.01-4 mM rapidly, without interference from substances such as ascorbate or other saccharides.