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.

Flow injection amperometric detection of ascorbic acid using a Prussian Blue film-modified electrode

The PB film-modified electrode was used as an amperometric detector for flow injection analysis of ascorbic acid. The modified electrode detector showed good sensitivity, stability and reproducibility. The calibration curve for ascorbic acid was linear over the concentration range from 5.0 x 10(-6) to 1.0 x 10(-3) mol l(-1) with a slope of 19.9 mA mol(-1) per litre and a correlation coefficient of 0.999. The detection limit of this method was 2.49 x 10(-6) mol l(-1). The relative standard deviation of six replicate injections of 2.5 x 10(-4) mol l(-1) ascorbic acid was 2.5%. The results obtained for ascorbic acid determination in pharmaceutical products are in good agreement with those obtained by using the procedure involving the reaction between triiodide and ascorbic acid. (C) 2001 Elsevier B.V. B.V. All rights reserved.

AMPEROMETRIC DETECTION OF AMINO-ACIDS IN A FLOW-INJECTION SYSTEM WITH A NICKEL(II)-MODIFIED ELECTRODE WITH AN EASTMAN-AQ POLYMER FILM

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l-1 KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 X 10(-6)-0.1 mol 1-1 with a detection limit of 1.0 X 10(-6) mol l-1. A 1 X 10(-4) mol 1-1 mixture of serine and tyrosine was also detected after separation on an Nucleosil C18 column.

Quantification of terbinafine in pharmaceutical tablets using capillary electrophoresis with contactless conductivity detection and batch injection analysis with amperometric detection

Terbinafine hydrochloride (TerbHCl) is an allylamine derivative with fungicidal action, especially against dermatophytes. Different analytical methods have been reported for quantifying TerbHCl in different samples. These procedures require time-consuming sample preparation or expensive instrumentation. In this paper, electrochemical methods involving capillary electrophoresis with contactless conductivity detection, and amperometry associated with batch injection analysis, are described for the determination of TerbHCl in pharmaceutical products. In the capillary electrophoresis experiments, terbinafine was protonated and analyzed in the cationic form in less than 1 min. A linear range from 1.46 to 36.4 mu g mL(-1) in acetate buffer solution and a detection limit of 0.11 mu g mL(-1) were achieved. In the amperometric studies, terbinafine was oxidized at +0.85 V with high throughput (225 injection h(-1)) and good linear range (10-100 mu mol L-1). It was also possible to determine the antifungal agent using simultaneous conductometric and potentiometric titrations in the presence of 5% ethanol. The electrochemical methods were applied to the quantification of TerbHCl in different tablet samples; the results were comparable with values indicated by the manufacturer and those found using titrimetry according to the Pharmacopoeia. The electrochemical methods are simple, rapid and an appropriate alternative for quantifying this drug in real samples. (C) 2012 Elsevier B.V. All rights reserved.

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of >80% was achieved when applied to the analysis of curcumin in extracts of turmeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 W, injection for 6 s at 9 W and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 - 10(-8) mol/l (SIN = 3), high efficiency of 1.0(.)10(5) N, linear range of 7(.)10(-4) -3(.)10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.

Simultaneous determination of 2-aminothiazole, 2-aminobenzothiazole and 2-mercaptobenzothiazole by capillary electrophoresis with end-column amperometric detection

Capillary electrophoresis with amperometric detection is evaluated for the simultaneous determination of 2-aminothiazole (A), 2-amino-benzothiazole (AB), 2-mercaptobenzothiazole (AM). The cyclic voltammogram, hydrodynamic voltammogram, effect of pH, concentration of buffer and separation voltage on the separation and the detection were studied. The conditions were optimized as follows: 50 mM phosphate buffet; pH 6.0, 2s at 17.5 kV sample injection, separation at 17.5 kV, 1.2 V as detection potential. The method provided low detection limit as 0.5 mu M, 0.05 mu M and 0.01 mu M, wide linear range 2-200 mu M, 10-200 mu M and 0.025-100 mu M for A, AB, and AM, respectively. The variations in peak current and migration time for 15 consecutive injections of a standard containing 5 mu M each compound were 3.7, 2.1, and 3.9%, and 1.2, 0.8, and 1.2%, for A, AB and AM, respectively. This method was employed to analyze river water.

Determination of propranolol by capillary electrophoresis with end-column amperometric detection

A capillary electrophoresis-amperometric detection system was developed for the determination of propranolol (PRO) at a 33 mu m carbon fiber microdisk electrode (CFE). The cyclic voltammogram, the hydrodynamic voltammograms and the effect of pH were studied. Under the optimum conditions: separation Voltage 15 kV; injection 3 s at 15 kV; 10 mM pH 7.5 phosphate buffer, 1.15 V (vs. Ag/AgCl) detection potential, the detection limit (LOD) for PRO was 0.05 mu M (S/N = 3). The response for PRO was linear over two orders of magnitude with a linear correlation coefficient of 0.994. The feasibility of this method was demonstrated by the detection of PRO in urine sample.

Determination of allopurinol and its active metabolite oxypurinol by capillary electrophoresis with end-column amperometric detection

A simple method was proposed for the separation of allopurinol (AP) and its active metabolite oxypurinol (OP) by capillary electrophoresis with end-column amperometric detection. A running buffer composed of 15 rum Na2HPO4/NaH2PO4 at a pH 9.55, electrokinetic injection 7 s at 5 kV, separation voltage at 15 kV and detection potential at 1.20 V were investigated to be the optimal condition for the separation. The method exhibited low detection Emit (S/N = 3) as 1 x 10(-8) mol/l for AP and OP, wide linearity range of 2 x 10(-7) to 1 x 10(-4) mol/l, 1 x 10(-7) to 1 x 10(-4) and high efficiency of 1.2 x 10(5) and 1.8 x 10(5) N/m for AP and OP, respectively. The potential application examined for the method was the determination of the spiked urine sample, which was proved to be sensitive and efficient. (C) 2001 Elsevier Science B.V. All rights reserved.

New microsystem of capillary electrophoresis with amperometric detection

We have made a cheap microsystem of capillary electrophoresis with a new method, integrating the electrodes, injection channel, separation channel, buffer reservoirs and detection cell on a polymethylmethacrylate (PMMA) chip. Using an integrated micro carbon fiber disk electrode as the working electrode in three electrodes system, 1 x 10(-4) mol/L dopamine(DA) could be detected with end-column amperometric detection. The reproducibility was good. Peak current was 6.73 nA,theoretical plate number was 71300/m and height equivalent of one theoretical plate height was 14.0 mum for 1 x 10(-4) mol/L DA. The limit of detection was 3.6 x 10(-8) mol/L and the linear range was extended from 5 x 10(-7) mol/L to 1 x 10(-4) mol/L for DA. 1 x 10(-4) mol/L catechol (CA) and 5 x 10(-5) mol/L DA were also separated completely with R-s = 10.1.

End-column amperometric detection of aesculin and aesculetin by capillary electrophoresis

Determination of aesculin (AL) and aesculetin (AT) by capillary electrophoresis with end-column amperometric detection using a 33 mu m microdisk carbon fiber electrode is described. The HDVs, the effect of pH, buffer concentration, injection voltage, injection time and separation voltage on the peak current response (i(p)) of the analytes and the number of theoretical plates (N) were studied. The method has high sensitivity and good reproducibility. Under the optimum condition - 10 mM, pH 9.00 phosphate buffer, 4 s at 9 kV injection, separation at 15 kV and +1.0 V as the detection potential - low detection limits (S/N = 3) of 0.06 and 0.3 mu M were obtained for AL and AT, respectively. The calibration curve was linear over three orders of magnitude. The relative standard deviations (n = 15) of peak current and migration time were 3.9% and 4.6%, and 0.96% and 0.75% for 15 consecutive injections of 5 mu M AL and AT, respectively. The use of this method for the separation and detection of the two compounds present in the traditional Chinese medicine and human urine samples is also reported. (C) 1999 Elsevier Science B.V. All rights reserved.

End-column amperometric detection of 6-mercaptopurine by capillary zone electrophoresis

End-column amperometric detection of 6-mercaptopurine by capillary zone electrophoresis was described with high resolution and speed. The detection conditions were optimized and the electrochemical behavior was observed. Under the optimal conditions: detection potential of 1.2 V ( vs. Ag/AgCl), operating voltage of 15 kV, sample injection of 3 s at 15 kV and 10 mmol/l Na2HPO4 buffer, the detection limit for 6-MP was as low as 1 x 10(-7) mol/L and the linear range was from 5 x 10(-4) to 5 x 10(-6) mol/L with the relative coefficient of 0.995. The RSD of reproducibility for peak current and migration time was 2.5% and 1.2%, respectively. This method was utilized in assay real sample of human mine and bovine serum albumin containing 6-mercaptopurine.

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.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

LIQUID-CHROMATOGRAPHY AMPEROMETRIC DETECTION OF CARBOXYLIC-ACIDS AND PHENOLIC-ACIDS WITH A COPPER-BASED CHEMICALLY-MODIFIED ELECTRODE

A copper-based chemically-modified electrode has been constructed and characterized by various experimental parameters in flow-through amperometric detection of carboxylic acids and phenolic acids. Novel hydrodynamic voltamperograms were first obtained in flow-through amperometric detection with the Cu-based CME and subsequently negative and positive peaks were observed in a single chromatogram. This unique and flexible potential dependence could be of great benefit in chromatographic speciation and quantification. These observations suggest that the detector response was governed by the complexation reaction of copper ions with the solutes.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.