Electron-transfer pathways in amperometric biosensors. Ferrocene-modified enzymes entrapped in conducting-polymer layers

Abstract The development of non-leaking amperometric enzyme electrodes is a fundamental prerequisite for the application of biosensors. However, a contradiction between the accessibility of the enzyme's active site and the mobility of immobilized redox mediators has to be overcome. Entrapment of glucose oxidase with ferrocene derivatives attached to its outer surface via long and flexible spacer chains within conducting polymer films ( e.g. polypyrrole) is used to evaluate electron-transfer pathways between enzymes and electrode surfaces. It can be demonstrated that electron transfer occurs from the enzyme's active site via electron hopping between the enzyme-linked ferrocene derivatives and/or directly using the conducting polymer backbone as a molecular wire, presuming that the redox properties of the polypyrrole layer have not been destroyed by enzymatically produced H 2 O 2 .

[1]  Adam Heller,et al.  High current density "wired" quinoprotein glucose dehydrogenase electrode , 1993 .

[2]  Christopher R. Lowe,et al.  Covalent electropolymerization of glucose oxidase in polypyrrole , 1992 .

[3]  M. C. Feiters,et al.  Glucose sensor utilizing polypyrrole incorporated in tract-etch membranes as the mediator , 1992 .

[4]  D. Bélanger,et al.  Electrochemistry of the polypyrrole glucose oxidase electrode , 1989 .

[5]  W. Schuhmann,et al.  New principles of amperometric enzyme electrodes and of reagentless oxidoreductase biosensors , 1993 .

[6]  G. Jobst,et al.  New microminiaturized glucose sensors using covalent immobilization techniques , 1990 .

[7]  W. Schuhmann,et al.  Amperometric polypyrrole enzyme electrodes: effect of permeability and enzyme location , 1992 .

[8]  D. Bélanger,et al.  Optimization of a polypyrrole glucose oxidase biosensor. , 1990, Biosensors & bioelectronics.

[9]  W. Schuhmann Amperometric substrate determination in flow-injection systems with polypyrrole—enzyme electrodes , 1991 .

[10]  A. Cass,et al.  Ferricinium ion as an electron acceptor for oxido-reductases , 1985 .

[11]  J. Kulys,et al.  Oxidation of glucose oxidase from Penicillium vitale by one- and two-electron acceptors , 1983 .

[12]  W. Holle Vergleichende Beurteilung des Blutglucosemeßsystems ExacTech® auf der Basis von Präzisionsprofilen , 1990 .

[13]  N F de Rooij,et al.  In-vivo behaviour of hypodermically implanted microfabricated glucose sensors. , 1991, Biosensors & bioelectronics.

[14]  W. Schuhmann,et al.  Polypyrrole, a new possibility for covalent binding of oxidoreductases to electrode surfaces as a base for stable biosensors , 1990 .

[15]  H. van Kempen,et al.  Polypyrrole microtubules and their use in the construction of a third generation biosensor , 1992 .

[16]  N. F. Rooij,et al.  Planar Amperometric Enzyme-Based Glucose Microelectrode , 1989 .

[17]  A. Ryabov,et al.  Chemical Attachment of Organometallics to Proteins in Reverse Micelles , 1992 .

[18]  G. S. Wilson,et al.  Design and in vitro studies of a needle-type glucose sensor for subcutaneous monitoring. , 1991, Analytical chemistry.

[19]  R. Nolte,et al.  Amperometric biosensor based on direct communication between glucose oxidase and a conducting polymer inside the pores of a filtration membrane , 1991 .

[20]  Adam Heller,et al.  Electrical Wiring of Redox Enzymes , 1990 .

[21]  M. Umaña,et al.  Protein-modified electrodes. The glucose oxidase/polypyrrole system , 1986 .

[22]  Philip N. Bartlett,et al.  Electrochemical immobilisation of enzymes: Part II. Glucose oxidase immobilised in poly-N-methylpyrrole , 1987 .

[23]  N. D. de Rooij,et al.  In vivo response of microfabricated glucose sensors to glycemia changes in normal rats. , 1989, Biomedica biochimica acta.

[24]  D. Bélanger,et al.  Characterization of the biochemical behavior of glucose oxidase entrapped in a polypyrrole film , 1991, Biotechnology and bioengineering.

[25]  W. Schuhmann Functionalized polypyrrole. A new material for the construction of biosensors , 1991 .

[26]  Christopher R. Lowe,et al.  Enzyme entrapment in electrically conducting polymers. Immobilisation of glucose oxidase in polypyrrole and its application in amperometric glucose sensors , 1986 .

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

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

[29]  Adam Heller,et al.  Electron Transfer between Glucose Oxidase and Electrodes via Redox Mediators Bound with Flexible Chains to the Enzyme Surface , 1991 .

[30]  C. Lowe,et al.  Immobilization of glucose oxidase in ferrocene-modified pyrrole polymers. , 1988, Analytical chemistry.

[31]  A Heller,et al.  Cross-linked redox gels containing glucose oxidase for amperometric biosensor applications. , 1990, Analytical chemistry.

[32]  W. Göpel,et al.  Leaching of dimethylferrocene, a redox mediator in amperometric enzyme electrodes , 1990 .

[33]  Christopher R. Lowe,et al.  Covalent electropolymerization of glucose oxidase in polypyrrole. Evaluation of methods of pyrrole attachment to glucose oxidase on the performance of electropolymerized glucose sensors , 1993 .

[34]  P. Hale,et al.  Amperometric glucose sensors based on ferrocene-modified poly(ethylene oxide) and glucose oxidase , 1991 .

[35]  Christine Kranz,et al.  Conducting polymer-based amperometric enzyme electrodes. Towards the development of miniaturized reagentless biosensors , 1993 .

[36]  Paul D. Hale,et al.  A new class of amperometric biosensor incorporating a polymeric electron-transfer mediator , 1989 .

[37]  D. Bélanger,et al.  Fast and easy preparation of an amperometric glucose biosensor , 1988 .