Separation of promethazine and thioridazine using capillary electrophoresis with end-column amperometric detection

Promethazine and thioridazine were separated and detected by capillary electrophoresis with end-column amperometric detection. The influence of pH Value on oxidation potential, the peak current and the resolution were studied and the following conditions was selected: 0.03 M Na2HPO4 and 0.015 M citric acid at pH 3.0, detection potential at 1.10 V. The detection limits of these two substances were in the range of 10(-8) mol/l. The linear range spanned two to three orders of magnitude. This method was applied to the detection of promethazine and thioridazine spiked in urine. (C) 1999 Elsevier Science B.V. All rights reserved.

Amperometric glucose biosensor based on sol-gel organic-inorganic hybrid material

A new type of sol-gel organic-inorganic hybrid material was developed and used for the production of biosensors. This material is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. It prevents the cracking of conventional sol-gel-derived glasses and eliminates the swelling of the hydrogel. The optimum composition of the hybrid material was first examined, and then glucose oxidase was immobilized in this matrix to demonstrate its application. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The biosensor exhibited a series of good properties: high sensitivity (600 nA mmol(-1)L(-1)), short response time (11 s) and remarkable long-term stability in storage (at least 5 months). In addition, the characteristics of the second-generation biosensor with the use of tetrathiafulvalene as a mediator mere discussed.

Electrocatalytic oxidation of hydrazines at a 4-pyridyl hydroquinone self-assembled platinum electrode and its application to amperometric detection in capillary electrophoresis

4-Pyridyl hydroquinone on a platinum electrode adsorbs through the pyridine nitrogen forming stable self-assembled layers. The electrocatalytical oxidation of hydrazines was performed by the modified electrode. The overpotential of hydrazines was decreased markedly at the self-assembled monolayer (SAM) electrode. The mechanism of hydrazine oxidation was also investigated. Amperometric detection of hydrazine under zero potential (vs Ag\AgCI\sat. KCl) was exhibited by the SAM electrode used as an electrochemical detector in a flow system. (C) 1998 Elsevier Science S.A. All rights reserved.

An amperometric detector with a tubular electrode deposited on the capillary for capillary liquid chromatography

A procedure is described for the preparation of a tubular electrode by chemical deposition of platinum at the end of a fused-silica capillary. The properties of the electrode were tested under liquid chromatographic conditions, demonstrating that both the static and the dynamic behaviour of the detection system satisfy the requirements of capillary chromatographic separations and compare well with a wall-jet amperometric system and with UV photometric detection. The detection system described is easy to prepare and does not require any time-consuming positioning of the electrode system as it is integrated into the separation part of the apparatus. (C) 1998 Elsevier Science B.V.

Electrocatalytic oxidation and flow amperometric detection of hydrazine at an electropolymerized 4-vinylpyridine/palladium film electrode

A poly(4-vinyl)pyridine (PVP)/Pd film electrode was constructed for the electrocatalytic detection of hydrazine. The preparation of the PVP/GC electrode was performed by electropolymerization of the monomer 4-vinylpyridine onto the surface of a glassy carbon electrode. Subsequently, palladium is electrodeposited onto the polymer modified electrode surface. The ion-exchange function of PVP polymer is helpful to this process in view of the tetrachlorapalladate anion. Compared with the Pd/GC electrode, the modified electrode displays a better mechanical stability in a flowing stream. The PVP/Pd film electrode exhibits higher sensitivity when detecting hydrazine with a detection limit of 0.026 ng (S/N=3).

Liquid chromatography amperometric detection of nitrite using a polypyrrole modified glassy carbon electrode doped with tungstodiphosphate anion

Chromatography-amperometric detection of nitrite with a polypyrrole modified glassy carbon electrode doped with tungstodiphosphate anion (Dawson-type P2W18O626-/PPy/GC electrode) based on its electrocatalytic reduction of nitrite is described. The cyclic and hydrodynamic voltammetry of nitrite at the P2W18O626-/PPy/GC electrode was studied. The factors affecting the detection of nitrite and the analytical performance of the modified electrode in flowing stream were investigated. The results show that the modified electrode has a good sensitivity (the limit of detection is 1 mu mol dm(-3)) and a satisfactory reproducibility (RSD = 3.78%, N = 21). The modified electrode was used in the chromatographic detection of nitrite spiked in the liquid from a tin of mushrooms and the mineralized spring water. It was found that the modified electrode exhibited good selectivity for nitrite.

Detection of menadione sodium bisulfite (vitamin K-3) by reversed-phase high performance liquid chromatography with series dual-electrode amperometric detector

A reversed-phase high-performance liquid chromatography with series dual glassy carbon electrodes for the amperometric detection of water-soluble menadione is described. The complex post-column derivatization reaction and the high background currents were avoided. The menadione sodium bisulfite was reduced at -0.3 V vs. SCE at the upstream (generator) electrode and oxidized at +0.2V vs. SCE at the downstream (collector) electrode. The mobile phase was 0.2moll(-1) HAc-NaAc aqueous buffer (pH 5.50) and 40% (v/v) methanol. The linear response was in the range of 35 ng to 15 mu g, with a detection Limit of 15 ng (S/N=3). The correlation coefficient was 0.9997 (n=6). The electrochemical detection with series dual electrodes has a higher selectivity for menadione (vitamin K-3) compound than with UV detection.

Amperometric biosensor for tyrosinase inhibitors in a pure organic phase

The determination of benzoic acid, thiourea and 2-mercaptoethanol in three pure organic solvents, viz., chloroform, chlorobenzene and 1,2-dichlorobenzene, by using an amperometric cryohydrogel tyrosinase biosensor is described. Measurements were carried out with phenol as the enzyme substrate. Kinetic parameters (K-i and I-50) were determined in the three solvents for various inhibitors. The sensor showed the most sensitive measurements to these inhibitors in pure chloroform. The solvent-induced deviation of the biosensor to thiourea was evaluated by means of Hill coefficients. The smallest deviation as observed in 1,2-dichlorobenzene, owing to the high hydrophobicity of this solvent. The nature of the inhibition process and its reversibility mere also examined.

Acetylcholinesterase amperometric detection system based on a cobalt(II) tetraphenylporphyrin-modified electrode

An acetylcholinesterase (AChE) activity detection system was fabricated based on the electrocatalysis of cobalt(II) tetraphenylporphyrin of the electrooxidation of thiocholine chloride, which is the product of the hydrolysis of acetylthiocholine chloride by AChE. A simple modified method was used to form the base electrode. AChE was cross-linked on the base electrode by glutaraldehyde. The optimum working conditions are discussed and the characteristics of the detection system are evaluated.

Determination of isoniazid and hydrazine by capillary electrophoresis with amperometric detection at a Pt-particle modified carbon fiber microelectrode

Capillary electrophoresis (CE)/electrochemical detection (EC) for the simultaneous determination of hydrazine and isoniazid has been developed. The electrochemical method uses a novel modified electrode dispersed with ultrafine platinum particles on the surface of a 30 mu m carbon fiber microelectrode. The unique characteristic of the Pt-particles modified carbon fiber microelectrode is its excellent stability. The current measurement for hydrazine is more sensitive than that of isoniazid. Selective determination of trace amount of free hydrazine in isoniazid and its formulation can be achieved at applied potential of 0.5 V.

SIMULTANEOUS DETERMINATION OF GUANINE, URIC-ACID, HYPOXANTHINE AND XANTHINE IN HUMAN PLASMA BY REVERSED-PHASE HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY WITH AMPEROMETRIC DETECTION

A reversed-phase high-performance liquid chromatographic method with amperometric detection is described for the separation and quantification of uric acid, guanine, hypoxanthine and xanthine. The isocratic separation of a standard mixture of the compounds was achieved in 5 min on a Spherisorb 5 C-18 reversed-phase column, with a mobile phase of NaH2PO4 (300 mmol dm(-3) pH 3.0)-methanol-acetonitrile-tetrahydrofuran (97.8 + 0.5 + 1.5 + 0.2). Uric acid, guanine, hypoxanthine and xanthine were completely separated, with detection limits in the range 2-20 pmol per injection. The effect of pH and the composition of the mobile phase on the separation are described. The hydrodynamic voltammograms of these compounds were recorded at a glassy carbon electrode. The linear range of the calibration graph for each compound was: uric acid; 1-5000 mu mol dm(-3); guanine, 0.5-2000 mu mol dm(-3); hypoxanthine, 0.1-500 mu mol dm(-3) and xanthine, 0.5-5000 mu mol dm(-3). The within- and between-day precision was good. The uric acid and hypoxanthine content in human plasma was measured using the proposed method. Good recoveries of uric acid (97.9-103%), hypoxanthine (98.0-99.2%), guanine (96.0-98.3%) and xanthine (96.0-102%) were obtained from human plasma. The results of electrochemical detection were in good agreement with those of UV detection.

DETERMINATION OF CYSTEINE AND REDUCED GLUTATHIONE IN HUMAN PLASMA BY LIQUID-CHROMATOGRAPHY WITH PULSED AMPEROMETRIC ELECTROCHEMICAL DETECTION USING A PLATINUM-PARTICLES MODIFIED GLASSY-CARBON ELECTRODE

An assay procedure utilizing pulsed amperometric detection at a platinum-particles modified electrode has been developed for the determination of cysteine and glutathione in blood samples following preliminary separation by reversed-phase liquid chromatography. A chemically modified electrode (CME) constructed by unique electroreduction from a platinum-salt solution to produce dispersed Pt particles on a glassy carbon surface was demonstrated to catalyze the electo-oxidation of sulfhydryl-containing compounds: DL-cysteine (CYS), reduced glutathione (GSH). When used as the sensing electrode in flow-system pulsed-amperometric detection (PAD), electrode fouling could be avoided using a waveform in which the cathodic reactivation process occurred at a potential of - 1.0 V vs. Ag/AgCl to achieve a cathodic desorption of atomic sulfur. A superior detection limit for these free thiols was obtained at a Pt particle-based GC electrode compared with other methods; this novel dispersed Pt particles CME exhibited high electrocatalytic stability and activity when it was employed as an electrochemical detector in FIA and HPLC for the determination of those organo-sulfur compounds.

AMPEROMETRIC BIOSENSORS BASED ON THE IMMOBILIZATION OF OXIDASES IN A PRUSSIAN BLUE FILM BY ELECTROCHEMICAL CODEPOSITION

Prussian blue has been formed by cyclic voltammetry onto the basal pyrolytic graphite surface to prepare a chemically modified electrode which provides excellent electrocatalysis for both oxidation and reduction of hydrogen peroxide. It is found for the first time that glucose oxidase or D-amino oxidase can be incorporated into a Prussian blue film during its electrochemical growth process. Two amperometric biosensors were fabricated by electrochemical codeposition, and the resulting sensors were protected by coverage with a thin film of Nafion. The influence of various experimental conditions was examined for optimum analytical performance. The glucose sensor responds rapidly to substrates with a detection limit of 2 x 10(-6) M and a linear concentration range of 0.01-3 mM. There was no interference from 2 mM ascorbic acid or uric acid. Another (D-amino acid) sensor gave a detection limit of 3 x 10(-5) M D-alanine, injected with a linear concentration range of 7.0 x 10(-5)-1.4 x 10(-2) M. Glucose and D-amino acid sensors remain relatively stable for 20 and 15 days, respectively. There is no obvious interference from anion electroactive species due to a low operating potential and excellent permselectivity of Nafion.