Chemiluminescent determination of glucose with a modified carbon paste electrode

A flow injection analysis detection method for glucose is presented which is based on the oxidation of glucose by glucose oxidase followed by chemiluminescent detection of hydrogen peroxide. Both glucose oxidase and hematin, a chemiluminescent reaction catalyst, were bulk-immobilized conveniently by direct mixing with carbon paste, which allows renewal of the electrode surface by simply polishing or cutting to expose a new and fully active surface in the case of fouling. Luminol in reagent solution passed through the flow cell and reacted with hydrogen peroxide produced by the enzyme reactor in the presence of the catalyst to yield light. An applied potential of -0.4 V avoided the electrode fouling effectively. The log-log plot of the emitted light intensity vs glucose concentration was linear over the range of 1-100 mmol L-1 with a correlation coefficient of 0.992. Application of this method to other chemiluminescent and bioluminescent systems is suggested. (C) 1999 Academic Press.

In-situ Fourier transform infrared spectroelectrochemistry as a probe of the glassy carbon electrode chemically modified by nickel (II)-cyanometallates

A new nickel (II)-cyanometallates modified on glassy carbon electrode was prepared by a new method and studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroelectrochemistry. It was found that the NiHCF film existed in two forms: Ni2Fe(II)-(CN)(6) and M2NiFe(II)(CN)(6), Fe(CN)(3)(6-) codeposited in the NiHCF film existing in free cation or bridged-bond state depended on the property of the cations in electrolyte: in NaCl and LiCl solution, it is in bridges-bonded, but in HCl and KCl, it is free.

Simultaneous voltammetric determination of acetophenetidin, aminopyrine, acetaminophenol and aminophenol on a glassy carbon electrode

The voltammetric behaviour of acetophenetidin(A(1)) aminopyrine(A(2)) acetaminophenol(A(3)) and aminophenol(A(4)) was investigated by linear-sweep, differential-pulse, cyclic voltammetry at a glassy carbon electrode. In a medium of 0.1 mol/L NaOH solution, 4 high sensitivity and resolution anodic peaks were obtained. Their peak potentials are about at 0.68 V, 0.51, 0.22 and - 0.06 V( vs. Ag/AgCl). They can be used for direct determination of A(1), A(2),A(3),A(4) in samples respectively. The method is simple and rapid. The mechanism of the electrode reaction was discussed.

Voltammetric study of vitamin K-3 at interdigitated array microelectrodes

Cyclic voltammetry of Vitamin K-3 (V-K3) was measured with Pt disk electrode, platinum interdigitated array (Pt-IDA) and Au-IDA microelectrodes in single and dual modes. The effects of pH, scan rate and collector potential on the current of generator and collector were studied. The collection efficiency of V-K3 at IDA electrodes was measured. The linear ranges for current response as a function of V-K3 concentration were found to he 10 mu M-1 mM (i(g)) and 1 mu M - 1 mM (i(c)) for the generator and collector of the Pt-IDA electrode, respectively. The effects of waiting time, potential difference and pulse electrolysis time in differential pulse voltammetry (DPV) on the peak current of V-K3 were studied to get the optimal condition at 0.1 M Na2HPO4, pH 11.50 and 11.0 for Au-IDA and Pt-IDA, respectively.

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.

Potential-dependent adsorption/desorption of organic adsorbate at HOPG electrode and accompanying delamination of graphite surface

In situ electrochemical scanning tunneling microscopy, alternating current voltammetry, and electrochemical quartz crystal microbalance have been employed to follow the potential-dependent adsorption/desorption processes of nucleic acid bases on highly oriented pyrolytic graphite (HOPG) electrode. The results show that (i) potential-dependent adsorption/desorption of nucleic acid bases on HOPG electrode was accompanied by delamination of the HOPG surface, and the delamination initiates from steps or kinks on the electrode surface, which provide highly active sites for adsorption; (ii) the delamination usually occurred when the electrode potential was changed or when the electrode was at potentials where the phase transition of adsorbate occurred. These results suggest that the surface stress resulting from the interaction between the substrate and adsorbate, as well as the interaction due to potential-induced surface charge distribution and the hysteresis of charge equilibrium are the main factors resulting in HOPG delamination. (C) 1999 The Electrochemical Society. S0013-4651(97)12-013-4. All rights reserved.

In-situ FTIR spectroelectrochemical study of chromium hexacyanoferrate on glassy carbon electrode

Chromium hexacyanoferrate (CrHCF) modified grassy carbon electrode (GC) in different electrolytes was studied by cyclic voltammetry and in situ FTIR spectroelectrochemistry. The results indicate that the behavior of CrHCF firm can be understood in term of two structures: Cr1/3Cr(III)Fe(II)(CN), and MCr(III)Fe(II)(CN)(6). Besides,the film exists in amorphous state: the outer layer is porous film, while the inner layer is relatively compact. According to the electrochemical reaction of CrHCF, the lattice can contract and expand with the cations' diffusion.

Electrochemical behavior of 3,4-dihydroxybenzoic acid in self-assembled monolayer electrode system

The self-assembled monolayer of cystamine was prepared on gold electrode and 3,4-dihydroxybenzoic acid (DHBA) was electrochemically deposited on cystamine surface as a functional group by electrostatic adsorption, namely, molecular deposition. It shows that the MD/SAM structure has a higher stability, and E-1/2 of the DBAH in MD/SAM shifts more negative than that of on naked gold electrode, The n-decanethiol was also used to fill defects in MD/SAM, it results in much better cyclic voltermmetric behavior.

Preparation of a composite film electrode containing 12-tungstosilicic acid and its electrocatalytic reduction for nitrite

A novel organic-inorganic composite film was formed by attaching Keegin-type heteropolyanion, SiW12O404- (devoted briefly as SiW12), on a glassy carbon electrode derivatized by 4-aminophenyl group. The composite film has an ionic bonding character between SiW12 and the surface amino group, which greatly improves the Blm stability and exhibits a more reversible electrochemical behavior. The modified electrode offers an excellent and stable electrocatalytic response for the reduction of nitrite. Possible mechanism was provided for the reaction of nitrite with SiW12O404-/aminophenyl composite film.

Self-gelatinizable copolymer immobilized glucose biosensor based on Prussian Blue modified graphite electrode

A novel poly(vinyl alcohol) grafting 4-vinylpyridine self-gelatinizable copolymer was adapted to immobilize glucose oxidase. The reduction of hydrogen peroxide (H2O2) was detected at a Prussian Blue (PB) modified graphite electrode. A stable and sensitive glucose amperometric biosensor is described. The copolymer is a good biocompatible polymer in which the glucose oxidase retains high activity. Moreover, the copolymer can adhere firmly to the inorganic PB membrane. The sensor showed an apparent Michaelis-Menten constant of 18 +/- 0.2 mM and a maximum current density of 1.14 mu A cm(-2) mM(-1). The linear range is from 5 mu M to 4.5 mM glucose and the detection limit is 0.5. mu M glucose. The catalytic efficiency of PB for the reduction of H2O2 is higher than that for the oxidation of H2O2. Glucose concentrations in serum samples from healthy persons and diabetic patients were determined using the sensor. The results compared well with those provided by the hospital using a spectroscopy method.

Investigation of oxygen- and hydrogen peroxide-reduction on platinum particles dispersed on poly(o-phenylenediamine) film modified glassy carbon electrodes

Composite membrane modified electrodes were prepared by electrochemical deposition of platinum particles in a poly(o-phenylenediamine) (PPD) him coated on glassy carbon (GC) electrodes. The modified electrodes showed high catalytic activity towards the reduction of oxygen and hydrogen peroxide. A four-electron transfer process predominated the reduction process. The pH dependence and the stability of the electrodes were also studied.

Electrochemical studies of a lanthanide heteropoly tungstate/molybdate complex in polypyrrole film electrode and its electrocatalytic reduction of bromate

An electrode modified with a polybasic lanthanide heteropoly tungstate/molybdate complex K10H3[Nd(SiMo7W4O39)(2)] entrapped into polypyrrole (PPy) film, denoted as Nd(SiMo7W4)(2)-PPy, exhibits three couples of two-electron redox waves in pH 1-5 buffer solutions. The redox waves are surface-controlled at lower scan rates and diffusion-controlled at higher scan rates. The effects of pH on the electrochemical behavior of Nd(SiMo7W4)(2) in PPy film were investigated in detail and compared with that of Nd(SiMo7W4)(2) in aqueous solution. The various charge states of PPy during its redox process have peculiar effects on the relationship between pH and formal potentials of Nd(SiMo7W4)(2)-PPy at different acidities. The Nd(SiMo7W4)(2)-PPy cme can remarkably catalyze the electrochemical reduction of bromate with good stability. (C) 1997 Elsevier Science Ltd.

Electrochemical investigation of DNA adsorbed on conducting polymer modified electrode

Detection of DNA is a very important task for molecular biology and biomedical field. We have investigated electrochemical behavior of double-stranded DNA and single-stranded DNA adsorbed on conducting polymer modified electrode in presence of cobalt complex. The possibility of using such electrode as gene detector is discussed.