Electron transfer mediated by glucose oxidase at the liquid/liquid interface.

In order to establish an experimental basis for exploring the reactivity of membrane-bound redox enzymes using electrochemistry at an organic/aqueous interface, the reactivity of glucose oxidase adsorbed at the dichloroethane/water interface has been studied. Turnover of glucose in the aqueous phase mediated by dimethyl ferricenium electrogenerated in the organic phase was measured by measuring the feedback current caused by recycling the mediator as the generator electrode approached close to the interface from the organic side. An unexpected self-exchange reaction of the ferrocene at the interface was suppressed by adsorption of a surfactant. The interfacial enzyme reaction could be distinguished from reaction within the bulk of the aqueous phase. Reaction within a protein-surfactant film formed at the interface is conjectured.

[1]  David E. Williams,et al.  Digital Simulation of Two-Dimensional Mass Transfer Problems in Electrochemistry Using the Extrapolation Method , 1999 .

[2]  Fraser A Armstrong Electron transfer and coupled processes in protein film voltammetry. , 1999, Biochemical Society transactions.

[3]  K. Kontturi,et al.  Enhanced ion transfer rate due to the presence of zwitterionic phospholipid monolayers at the ITIES , 2000 .

[4]  P. Unwin,et al.  A new approach to the measurement of transfer rates across immiscible liquid/liquid interfaces , 1996 .

[5]  F. Armstrong,et al.  KINETICS AND MECHANISM OF REDOX-COUPLED, LONG-RANGE PROTON TRANSFER IN AN IRON-SULFUR PROTEIN. INVESTIGATION BY FAST-SCAN PROTEIN-FILM VOLTAMMETRY , 1998 .

[6]  P. Mitchell Keilin's respiratory chain concept and its chemiosmotic consequences. , 1979, Science.

[7]  H. Hill,et al.  Electrochemistry of horse heart cytochrome c , 1979 .

[8]  M. Mirkin,et al.  LONG-RANGE ELECTRON TRANSFER THROUGH A LIPID MONOLAYER AT THE LIQUID/LIQUID INTERFACE , 1997 .

[9]  M. Almgren,et al.  Interactions of Globular Proteins with Surfactants Studied with Fluorescence Probe Methods , 1999 .

[10]  F. Armstrong,et al.  Fast-scan cyclic voltammetry of protein films on pyrolytic graphite edge electrodes: characteristics of electron exchange. , 1998, Analytical chemistry.

[11]  K. Kontturi,et al.  Potential Dependence of Transmembrane Electron Transfer across Phospholipid Bilayers Mediated by Ubiquinone 10 , 1996 .

[12]  Jose H. Hodak,et al.  Layer-by-Layer Self-Assembly of Glucose Oxidase with a Poly(allylamine)ferrocene Redox Mediator , 1997 .

[13]  H. Girault,et al.  Second harmonic generation of glucose oxidase at the air/water interface. , 1999, Biophysical journal.

[14]  H. Heering,et al.  Redox properties of flavocytochrome c3 from Shewanella frigidimarina NCIMB400. , 1999, Biochemistry.

[15]  David E. Williams,et al.  Probing adsorption reactions at the liquid/liquid interface by area-step experiments , 2000 .

[16]  A. Volkov,et al.  Charge transfer between water and octane phases by soluble mitochondrial ATPase (F1), bacteriorhodopsin and respiratory chain enzymes , 1975, FEBS letters.

[17]  K. Kontturi,et al.  Phospholipid monolayers studied by a combination of cyclic voltammetry and Langmuir techniques at the water ∣ 1,2-dichloroethane interface , 1999 .

[18]  L. Yaguzhinsky,et al.  Synthesis of ATP coupled with action of membrane protonic pumps at the octane–water interface , 1976, Nature.

[19]  A. Bard,et al.  Scanning Electrochemical Microscopy. 17. Studies of Enzyme-Mediator Kinetics for Membrane= and Surface- Immobilized Glucose Oxidase , 1992 .

[20]  E. Landau,et al.  ELECTROCHEMISTRY AT THE AIR/WATER INTERFACE. LATERAL DIFFUSION OF AN OCTADECYLFERROCENE AMPHIPHILE IN LANGMUIR MONOLAYERS , 1991 .

[21]  C. Koval,et al.  Electron Transfer Reactions of Hydrophobic Metallocenes with Aqueous Redox Couples at Liquid−Liquid Interfaces. 1. Solvent, Electrolyte, Partitioning, and Thermodynamic Issues , 2000 .

[22]  C. Bourdillon,et al.  Electrochemical measurements of the lateral diffusion of electroactive amphiphiles in supported phospholipid monolayers. , 1994, Biophysical journal.

[23]  David E. Williams,et al.  The kinetics of ionic transfer across adsorbed phospholipid layers , 1988 .

[24]  V. Cunnane,et al.  Electron and ion transfer potentials of ferrocene and derivatives at a liquid-liquid interface , 1995 .

[25]  A. Turner,et al.  Ferrocene-mediated enzyme electrode for amperometric determination of glucose. , 1984, Analytical chemistry.

[26]  Adam Heller,et al.  Electrical Connection of Enzyme Redox Centers to Electrodes , 1992 .

[27]  J. K. Hurst,et al.  Mechanisms of viologen-mediated charge separation across bilayer membranes deduced from mediator permeabilities , 1992 .

[28]  P. Unwin,et al.  Lateral Proton Diffusion Rates along Stearic Acid Monolayers , 2000 .

[29]  Ole Østerby,et al.  Some numerical investigations of the stability of electrochemical digital simulation, particularly as affected by first-order homogeneous reactions , 1994 .

[30]  David E. Williams,et al.  Dynamic effects at the interface between two immiscible electrolyte solutions (ITIES) , 1996 .

[31]  A. Bard,et al.  Scanning electrochemical microscopy. 34. Potential dependence of the electron-transfer rate and film formation at the liquid/liquid interface , 1996 .

[32]  A. Hillman,et al.  Mechanism of the reduction and oxidation reaction of cytochrome c at a modified gold electrode , 1981 .