title: Separation of electron-transfer and coupled chemical reaction components of biocatalytic processes using Fourier transform ac voltammetry.
abstract: The underlying electron-transfer and coupled chemical processes associated with biologically important catalytic reactions can be resolved using a combination of Fourier transform ac voltammetry with an analysis of the separated dc and ac components. This outcome can be achieved because the response associated with generation of the catalytic current is essentially confined to the steady-state dc component, whereas the electron-transfer step is dominant in the fundamental and higher harmonics. For the mediated oxidation of glucose with glucose oxidase, it was found that the underlying reversible redox chemistry of the mediator, ferrocenemonocarboxylic acid, as detected in the third and higher harmonics, was totally unaffected by introduction of the catalytic process. In contrast, for the catalytic reduction of molecular oxygen by cytochrome P450, slight changes in the P450 redox process were detected when the catalytic reaction was present. Simulations of a simple catalytic reaction scheme support the fidelity of this novel FT ac voltammetric approach for examining mechanistic nuances of catalytic forms of electrochemical reaction schemes.
authors.affiliation: School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
authors.forename: Barry D
authors.initials: BD
authors.lastname: Fleming
authors.forename: Jie
authors.initials: J
authors.lastname: Zhang
authors.forename: Alan M
authors.initials: AM
authors.lastname: Bond
authors.forename: Stephen G
authors.initials: SG
authors.lastname: Bell
authors.forename: Luet-Lok
authors.initials: LL
authors.lastname: Wong
mesh_terms: D002384:Catalysis; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D004579:Electron Transport; D005296:Ferrous Compounds / Q000032:analysis / Q000737:chemistry*; D005583:Fourier Analysis; D005947:Glucose / Q000737:chemistry*; D005949:Glucose Oxidase / Q000737:chemistry; D000075163:Metallocenes; D010084:Oxidation-Reduction; D010100:Oxygen / Q000032:analysis*; D012680:Sensitivity and Specificity; D013499:Surface Properties; D013997:Time Factors
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; C032949:ferrocenecarboxylic acid; D003577:Cytochrome P-450 Enzyme System; D005949:Glucose Oxidase; D005947:Glucose; D010100:Oxygen