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.

Detection of neurotransmitters by a light scattering technique based on seed-mediated growth of gold nanoparticles

A simple light scattering detection method for neurotransmitters has been developed, based on the growth of gold nanoparticles. Neurotransmitters (dopamine, L-dopa, noradrenaline and adrenaline) can effectively function as active reducing agents for generating gold nanoparticles, which result in enhanced light scattering signals. The strong light scattering of gold nanoparticles then allows the quantitative detection of the neurotransmitters simply by using a common spectrofluorometer.

Quality analysis of herbal medicine products prepared from Herba sarcandrae by capillary electrophoresis with electrochemical detection

A capillary electrophoresis with electrochemical detection(CE-ED) method was developed for the quality analysis of herbal medicine products prepared from the same herb of Herba Sarcandrae: Fufang Caoshanhu tablets, Qingrexiaoyanning capsules, and Xuekang oral liquids. Under the optimal analysis conditions, the low detection limit[1.0x10(-7) mol/L(S/N=3)] and the wide linear range(1.0x10(-7)-1.0x10(-4) mol/L) were obtained for quality standard compound of isofraxidin. The precisions of the peak current and the migration time(as RSDs) for the real sample analysis were 2.0%-2.6%, and 1.2%-1.8% for isofraxidin, respectively.

Polyelectrolyte-functionalized ionic liquid for electrochemistry in supporting electrolyte-free aqueous solutions and application in amperometric flow injection analysis

As a green process, electrochemistry in aqueous solution without a supporting electrolyte has been described based on a simple polyelectrolyte-functionalized ionic liquid (PFIL)-modified electrode. The studied PFIL material combines features of ionic liquids and traditional polyelectrolytes. The ionic liquid part provides a high ionic conductivity and affinity to many different compounds. The polyelectrolyte part has a good stability in aqueous solution and a capability of being immobilized on different substrates. The electrochemical properties of such a PFIL-modified electrode assembly in a supporting electrolyte-free solution have been investigated by using an electrically neutral electroactive species, hydroquinone ( HQ) as the model compound. The partition coefficient and diffusion coefficient of HQ in the PFIL film were calculated to be 0.346 and 4.74 X 10(-6) cm(2) s(-1), respectively. Electrochemistry in PFIL is similar to electrochemistry in a solution of traditional supporting electrolytes, except that the electrochemical reaction takes place in a thin film on the surface of the electrode. PFILs are easily immobilized on solid substrates, are inexpensive and electrochemically stable. A PFIL-modified electrode assembly is successfully used in the flow analysis of HQ by amperometric detection in solution without a supporting electrolyte.

Analysis of nephroloxic and carcinogenic aristolochic acids in Aristolochia plants by capillary electrophoresis with electrochemical detection at a carbon fiber microdisk electrode

Aristolochic acids (AAs) are the main bioactive ingredients in the most of Aristolochia plants, which are used to make dietary supplements, slimming pills and Traditional Chinese Medicines (TCMs). Excessive ingestion of AAs can lead to serious nephropathy. Therefore, quantitative analysis and quality control for the plants containing AAs is of great importance. In this paper, capillary electrophoresis (CE) with electrochemical detection (ED) at a 33 mu m carbon fiber microdisk electrode (CFE) has been applied to detect AA-I and AA-II in Aristolochia plants. Under the optimum conditions: detection potential at 1.20 V, 2.0 x 10(-2) mol L-1 phosphate buffer solution (PBS) (pH 10.0), injection time 25 s at a height of 17 cm and separation voltage at 12.5 kV, the AA-I and AA-II were baseline separated within 5 min. Low detection limits for AA-I and AA-II were 4.0 x 10(-8) mol L-1 and 1.0 x 10(-7) mol L-1, respectively. Wide linear ranges were from 4.0 x 10(-8) mol L-1 to 1.9 x 10(-5) mol L-1 and 1.0 X 10(-7) mol L-1 to 5.0 x 10(-5) mol L-1 for AA-I and AA-II, respectively. The proposed method has been successfully applied to analyze AAs contents in plant extracts. The results indicated that the contents of AAs in each part of Aristolochia debilis Sieb. Et Zucc.

Ceramic carbon/polypyrrole materials for the construction of bienzymatic amperometric biosensor for glucose

A novel amperometric glucose biosensor was constructed by electrochemical formation of a polypyrrole (PPy) membrane in the presence of glucose oxidase (GOD) on the surface of a horseradish peroxidase (HRP) modified ferrocenecarboxylic acid (FCA) mediated sol-gel derived ceramic carbon electrode. The amperometric detection of glucose was carried out at +0.16 V (vs. SCE) in 0.1 mol/L phosphate buffer solution (pH 6.9) with a linear response range between 8.0x10(-5) and 1.3x10(-3) mol/L of glucose. The biosensor showed a good suppression of interference and a negligible deviation in the amperometric detection.

Detection of hydrazine, methylhydrazine and isoniazid by capillary electrophoresis with a 4-pyridyl hydroquinone self-assembled microdisk platinum electrode

Capillary electrophoresis (CE)/electrochemical detection (EC) for the simultaneous detection of hydrazine, methylhydrazine, and isoniazid has been developed with a 4-pyridyl hydroquinone self-assembled microdisk platinum electrode. Such an electrode has very high catalytic ability for hydrazines and they could be detected even at 0.0 V. The responses for hydrazine, methylhydrazine, and isoniazid are linear over 3 orders of detected concentration and of magnitude of 0.2-400 mu M, 0.2-400 mu M, 0.5 mu M-2 mM, with correlation coefficients of 0.9998, 0.9991, and 0.9982, respectively. And they could be detected to levels of 0.1, 0.1 and 0.2 mu M, respectively. This modified electrode was found to be very stable and reproducible when continuously used as detector for capillary electrophoresis for period of at least 4 weeks with no apparent loss of response. (C) 1999 Elsevier Science B.V. All rights reserved.

Determination of hydroxylamine by capillary electrophoresis electrochemical detection with a palladium-particle modified carbon fiber microdisk array electrode

A highly dispersed ultramicro palladium-particle modified carbon fiber microdisk array electrode (Pd-CFE) was employed for capillary electrophoresis-electrochemical (CEEC) detection of hydroxylamine (HA). The Pd particles obtained were in the nanometer scale, had a high electrocatalytic activity towards HA and exhibited good reproducibility and stability. A linear relationship between the current and the analyte concentration was found between 5 x 10(-6) and 1 x 10(-3) mol/l of HA with a correlation coefficient of 0.9992. The detection limit was 5 x 10(-8) mol/l. The applicability of the method for the determination of HA in river water and waste water was investigated.

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.

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.

Electrochemical characteristics of mediated laccase-catalysis and electrochemical detection of environmental pollutants

Laccase has been immobilized on the carbon nanotubes modified glassy carbon electrode surface by adsorption. As-prepared laccase retains good electrocatalytic activity to oxygen reduction by using 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) as the mediator. It can be used as a biosensor for the determination of catechol with broad linear range.

Synthesis of carbon nanofibers for mediatorless sensitive detection of NADH

Highly sensitive amperometric detection of dihydronicotinamide adenine dinucleotide (NADH) by using novel synthesized carbon nanofibers (CNFs) without addition of any mediator has been proposed. The CNFs were prepared by combination of electrospinning technique with thermal treatment method and were applied without any oxidation pretreatment to construct the electrochemical sensor. In amperometric detection of NADH, a linear range up to 11.45 mu M with a low detection limit of 20 nM was obtained with the CNF-modified carbon paste electrode (CNF-CPE).

CEC with tris(2,2 '-bipyridyl) ruthenium(II) electrochemiluminescent detection

For the first time, CEC was coupled with tris(2,2-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+) electrochemiluminescence detection. Efficient CEC separations of proline, putrescine, spermidine and spermine were achieved when the pH of the mobile phase is in the range of 3.5-7.0. The optimum mobile phase for CEC separation is much less acidic than that for CZE separation, which matches better with the optimum pH for Ru(bpy)(3)(2+) electrochemiluminescence detection and dramatically shortens the analysis time because of larger EOF at higher pH.