Microelectrode voltammetric measurement of heterogeneous electron transfer rate constants for reduction of 7,7,8 ',8 '-tetracyanoquinodimethane in polymer electrolytes

This paper presents a microelectrode voltammetric determination of heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of 7,7,8',8 '-tetracyanoquinodimethane (TCNQ) in polyelectrolytes. The diffusion coefficients are estimated using cyclic voltammetry under linear diffusion conditions, and the heterogeneous electron transfer rate constants are obtained under mixed linear and radial diffusion in the polyelectrolyte. k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction for reduction of TCNQ are obtained. On the other hand, the dependencies of D and k(s) of TCNQ on the size and charge of the counterion are compared in the polyelectrolyte. (C) 1998 Elsevier Science Ltd. All rights reserved.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .2. Effect of the ionic size of supporting electrolytes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene in MPEG/salt electrolytes were determined by using steady-state voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equation. The effect of the ionic size of six supporting electrolytes on diffusion and electron transfer dynamics of ferrocene was discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .3. Effect of the polymer solvents

The diffusion coefficients(D-app) and the heterogeneous electron transfer rate constants(k(s)) for ferrocene in several polymer solvents were determined by using steady-state voltammetry. The temperature dependence of the two parameters indicates Arrhenius behavior, The polymer solvent effects on diffusion and electron transfer dynamics of ferrocene were discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .1. Effect of the nature of electroactive solutes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steady-state voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on D-app, k(s), and the half-wave potentials(E-1/2) are discussed.

An ultramicroelectrode study of ferrocene diffusion and heterogeneous electron transfer rate in polyelectrolyte

Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.

Electron transfer between Eu and Tb in MMgF(4) systems

Emission of europium(II) and europium(III) have been observed in SrMgF4 : xEu, yTb phosphors which are synthesized in Ar or Ar/H-2 flow. The valence state of Eu is influenced by terbium. It is notable that the intensities of the ESR peaks corresponding to EU(2+) are regularly changed when terbium ion is incorporated. The typical Tb3d XPS spectrum belonging to Tb4+ is also found when Eu is codoped. This phenomena can be explained by electron transfer mechanism Eu3+ + Tb3+-->EU(2+) + Tb4+. And its equilibrium constant is studied by ESR technique.

Direct electron communication between glucose oxidase and carbon electrode covered with polypyrrole

Glucose oxidase can be effectively adsorbed onto the polypyrrole(PPy) thin film electrochemically formed on an anodized galssy carbon electrode(GCEa). Direct electron communication between the redox of GOD and the modified electrode was successfully achieved, which was detected using cyclic voltammetry. GOD entrapped in PPy film still remained its biological activity and could catalyze the oxidation of glucose. As a third generation biosensor, GOD-PPy/GCEa responded linearly up to 20 mM glucose with a wider linear concentration range.

Electron transfer between Eu3+ and Tb3+ in BaB4O7 matrix

The BaB4O7:Eu, Tb phosphors are first synthesized in air atmosphere. We investigate their luminescent properties, and find that europium(II) and europium(III) can coexist in the BaB4O7:Eu phosphor. We observed that the relative intensity of europium(II) is increased when terbium(III) is incorporated. The electron spin resonance (ESR) spectra are carried out. The intensity of ESR peaks corresponding to europium(II) is also increased when terbium(III) is increased, so the valency state of europium is influenced by terbium(III). We explain these phenomena by an electron transfer mechanism. (C) 1996 Academic Press, Inc.

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

The direct electrochemistry of cryo-hydrogel immobilized myoglobin at a glassy carbon electrode

A cryo-hydrogel membrane (CHM) immobilized at a glassy carbon (GC) electrode is reported for the direct electron transfer of redox proteins. The most attractive characteristics of this CHM were its hydrophilic micro-environment for incorporated proteins to retain their activities, its high ability for protection against interference of denatured and adsorbed proteins at the electrode, its potential applications for various proteins or enzymes, as well as its high mechanical strength and thermal stability. A clear well developed and stable redox wave was obtained for commercially available horse heart myoglobin without further purification, giving a peak to peak separation Delta E(p) = 93 mV at 5 mV s(-1) and the formal electrode potential E(0)' = -0.158 V (vs. Ag/AgCl). The formal heterogeneous electron transfer rate constant was calculated as k(0)' = 5.7 X 10(-4) cm s(-1) at pH 6.5, showing rapid electron transfer was achieved. The pH controlled conformational equilibria, acid state --> natural state --> basic I state --> basic II state, of myoglobin at the CHM GC electrode in the pH range 0-13.8 were also observed and are discussed in detail.

ELECTRON-TRANSFER BETWEEN EU AND TB IN COMPLEX FLUORIDES

Europium (II) and europium (III) have been observed in MMgF(4):xEu, yTb (M=Ca, Sr, Ba) phosphors using their typical photoluminescence spectra when are synthesized in Ar or an Ar/H-2 stream. The valence state of Eu is influenced by terbium. It is notable that the intensities of the electron spin resonance peaks corresponding to Eu2+ change in a regular way when terbium ions are incorporated which can be explained by an electron transfer mechanism.

Electron transfer between Eu3+ and Ce3+ in SrM-F-4 matrix

Emissions of europium (II) and europium (III) have been observed in SrMgF4:Eu and SrMgF4:Eu,Ce phosphors which are synthesized in Ar flow, It is notable that the intensity of the ESR peaks corresponding to Eu2+ is increased when cerium ion is incorporated which can be explained by electron transfer mechanism.

Electron Transfer and its Equilibrium between Eu and Tb in SrMgF4 System

Emission of europium(II) and europium(III) have been observed in SrMgF4 xEu, yTb phosphors winch are synthesized in Ar flow. The valence state of En is influenced by terbium, It is noted that the intensities of the ESR peaks corresponding to Eu2+ are increased when terbium ion is codopech this can be explained by electron transfer mechanism which is Eu3++Tb3+-->Eu2++Tb4+. And its equilibrium constant is calculated.

DIRECT ELECTROCHEMICAL REACTIONS OF CYTOCHROME-C AT IODIDE-MODIFIED ELECTRODES

Quasi-reversible and direct electron transfer was observed between an iodide-modified Au electrode and cytochrome c, as well as between cytochrome c in an iodide-containing solution and a bare Au electrode. The results suggest that an electrostatic intera

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.