The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry

The oxidation of cysteine by ferricyanide is well established. However, electrochemical studies of the mechanism have to date been underdeveloped due to the lack of resolution between the oxidation waves of the ferrocyanide and cysteine on most electrode materials. It is shown that on boron doped di...

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Автори: Nekrassova, O, Allen, G, Lawrence, N, Jiang, L, Jones, T, Compton, R
Формат: Journal article
Мова:English
Опубліковано: 2002
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author Nekrassova, O
Allen, G
Lawrence, N
Jiang, L
Jones, T
Compton, R
author_facet Nekrassova, O
Allen, G
Lawrence, N
Jiang, L
Jones, T
Compton, R
author_sort Nekrassova, O
collection OXFORD
description The oxidation of cysteine by ferricyanide is well established. However, electrochemical studies of the mechanism have to date been underdeveloped due to the lack of resolution between the oxidation waves of the ferrocyanide and cysteine on most electrode materials. It is shown that on boron doped diamond electrode, unlike for example platinum electrodes, the voltammetric responses of the ferrocyanide wave and the targets are sufficiently different, with the former at a lower oxidizing potential, to permit examination of the kinetics of the homogeneous oxidation via voltammetric methods. Accordingly conventional cyclic voltammetry using a BDD electrode is used to show that an EC′ mechanism occurs and rate constants deduced. Both the protonated and de-protonated forms of cysteine (pKa = 10.5) are shown to undergo oxidation by ferricyanide. The cyclic voltammetry data obtained is corroborated by use of channel flow cell experiments with excellent agreement shown between the two techniques for deduced values of the homogeneous electrocatalytic rate constants: Channel electrodes are seen to provide a convenient means to allow quantitative mechanistic hydrodynamic voltammetry at BDD electrods.
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spelling oxford-uuid:bef01ab8-6499-4652-882c-8c52f6aa84fb2022-03-27T05:43:46ZThe oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetryJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:bef01ab8-6499-4652-882c-8c52f6aa84fbEnglishSymplectic Elements at Oxford2002Nekrassova, OAllen, GLawrence, NJiang, LJones, TCompton, RThe oxidation of cysteine by ferricyanide is well established. However, electrochemical studies of the mechanism have to date been underdeveloped due to the lack of resolution between the oxidation waves of the ferrocyanide and cysteine on most electrode materials. It is shown that on boron doped diamond electrode, unlike for example platinum electrodes, the voltammetric responses of the ferrocyanide wave and the targets are sufficiently different, with the former at a lower oxidizing potential, to permit examination of the kinetics of the homogeneous oxidation via voltammetric methods. Accordingly conventional cyclic voltammetry using a BDD electrode is used to show that an EC′ mechanism occurs and rate constants deduced. Both the protonated and de-protonated forms of cysteine (pKa = 10.5) are shown to undergo oxidation by ferricyanide. The cyclic voltammetry data obtained is corroborated by use of channel flow cell experiments with excellent agreement shown between the two techniques for deduced values of the homogeneous electrocatalytic rate constants: Channel electrodes are seen to provide a convenient means to allow quantitative mechanistic hydrodynamic voltammetry at BDD electrods.
spellingShingle Nekrassova, O
Allen, G
Lawrence, N
Jiang, L
Jones, T
Compton, R
The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title_full The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title_fullStr The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title_full_unstemmed The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title_short The oxidation of cysteine by aqueous ferricyanide: A kinetic study using boron doped diamond electrode voltammetry
title_sort oxidation of cysteine by aqueous ferricyanide a kinetic study using boron doped diamond electrode voltammetry
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