Redox enzymes electrochemistry

In this chapter we first describe components and the organization of some important biological redox systems. We then discuss advantages of electroactive polymers for this type of application and review the work so far in different areas of redox protein electrochemistry, redox enzyme electrochemistry, and redox... 

In contrast to the area of redox protein electrochemistry, redox enzyme electrochemistry has received much greater attention, driven in many cases by the desire to construct practical, self-contained enzyme electrodes for commercial applications. Redox enzyme electrochemistry is also easier to study in many ways because the substrate or product is often detected electrochemically rather than the enzyme itself. Various types of electroactive polymers have been used with redox enzymes, including redox polymers, redox-active hydrogels, and electropolymer-ized films of conducting and nonconducting, polymers. We discuss each type of polymer in turn, starting with electropolymerized films. 

To predict systems most likely to yield meaningful and useful direct electrochemistry, redox enzymes may be divided into two categories. The first comprises those for which one of the redox processes in the catalytic cycle is a discrete outer-sphere (and probably long-range) electron-transfer reaction. Examples include the blue Cu oxidases, ferredoxin-linked reductases, and cytochrome c oxidase and other enzymes of electron-transport chains. In such systems there is exchange of electrons with an extrinsic agent, i.e. one that does not form... 

Moreover, it has been demonstrated that CNTs promote the direct electrochemistry of enzymes. Dong and coworkers have reported the direct electrochemistry of microperoxidase 11 (MP-11) using CNT-modified GC electrodes [101] and layer-by-layer self-assembled films of chitosan and CNTs [102], The immobilized MP-11 has retained its bioelectrocatalytic activity for the reduction of H202 and 02, which can be used in biosensors or biofuel cells. The direct electrochemistry of catalase at the CNT-modified gold and GC electrodes has also been reported [103-104], The electron transfer rate involving the heme Fe(III)/Fe(II) redox couple for catalase on the CNT-modified electrode is much faster than that on an unmodified electrode or other... 

The use of redox enzymes in organic synthesis, while having a large potential for broad application in the selective formation of high-value compounds, has been limited by the necessity of cofactor regeneration or enzyme reactivation. Electrochemistry offers an attractive and, in principle, simple way to solve this problem because the mass-free electrons are used as regenerating agents. No... 

A number of nitrogen heterocyclic, aromatic compounds, riboflavin 26, folic acid 27a and biopterin 27b, isolated from natural sources, are related in structure to natural redox enzyme cofactors. The electrochemistry of these and related compounds has been studied extensively. 

Electrochemistry of Enzymes at Electrodes Functionalized with Monolayers of Redox Relays... 

Diffusional electrochemistry of enzymes functionalized with tethered redox relays... 

C. The Microscopic Model in Protein Electrochemistry Electrochemistry of Protein-Protein Complexes Electrochemistry of Redox Enzymes... 

Direct, unmediated electrochemistry of redox enzymes has interested many researchers in several aspects. Understanding of the thermodynamics, kinetics, stoichiometry, and interfacial properties of redox enzymes is obviously important. The most attractive aspect, however, is the use of enzyme electrodes as novel electrochemical biosensors and their applications to bioreactors and biofuel cells. Although the observation of direct electrochemistry of small redox proteins has become almost commonplace as the consequence of extensive research over the past decade, the corresponding study with larger redox enzymes has proved more elusive. The difficulty lies mainly in that the redox centers are located sufficiently far from the outermost... 

The direct electrochemistry of redox proteins has developed significantly in the past few years. Conditions now exist that permit the electrochemistry of all the proteins to be expressed at a range of electrodes, and important information about thermodynamic and kinetic properties of these proteins can be obtained. More recently, direct electron transfer between redox enzymes and electrodes has been achieved due to the more careful control of electrode surfaces. The need for biocompatible surfaces in bioelectrochemistry has stimulated the development of electrode surface engineering techniques, and protein electrochemistry has been reported at conducting polymer electrodes 82) and in membranes 83, 84). Furthermore, combination of direct protein electrochemistry with spectroscopic methods may offer 85) a novel way of investigating structure-function relationships in electron transport proteins. 

Leger, C. and Bertrand, P. (2008) Direct electrochemistry of redox enzymes as a tool for mechanistic studies. Chemical Reviews, 108 (7), 2379-2438. 

Since the establishment of spectroelectrochemistry very little effort has been devoted to the direct electrochemistry of redox proteins. Although many thermodynamic and kinetic parameters can be determined by UV-VIS spectroelectrochemistry, the electrochemical reaction mechanisms for redox proteins are not well understood. New techniques md new theoretical treatments are needed to address this issue. Moreover, most attention has been placed on relatively simple electron transfer proteins to date no one has reported the direct electrochemistry of a more complex system (e.g., a redox enzyme system) which unequivocally undergoes electron transfer to (or from) its active site. Considerable experimental work is needed to develop more fully spectroelectrochemical methods for biological systems. 

An important application of CyD complexes is in the field of mediated electrocatalysis and bioelectrocatalysis. Detection of a target analyte using a biosensor based on a redox enzyme is well recognized as a more convenient solution than one based on the electrochemistry of reaction products. An ideal mediator for electrocatalysis should be soluble in water or easily anchored on an electrode surface. CyDs have often been employed in solubilizing hydrophobic molecules used either as mediators in catalysis or occurring as the products of catalytic reactions. In the latter case, their role was to avoid fouling of the electrode surface. 

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