Mediated electron transfer Mediators

Directed evolution and rational design have become common techniques to improve enzyme properties such as activity, selectivity, and stability and will also gain impact in the improvement of mediated electron transfer. Mediator-enzyme interactions, electron-transfer path and rate, as well as the redox center itself are all properties of the enzyme that could be optimized. A comprehensive review covering different approaches and examples thereof to improve the electron-transfer rate between enzyme and electrode has been published by Giiven et al. [13]. 

The pathway model makes a number of key predictions, including (a) a substantial role for hydrogen bond mediation of tunnelling, (b) a difference in mediation characteristics as a function of secondary and tertiary stmcture, (c) an intrinsically nonexponential decay of rate witlr distance, and (d) patlrway specific Trot and cold spots for electron transfer. These predictions have been tested extensively. The most systematic and critical tests are provided witlr mtlrenium-modified proteins, where a syntlretic ET active group cair be attached to the protein aird tire rate of ET via a specific medium stmcture cair be probed (figure C3.2.5). 

DeRege P J F, Williams S A and Therien M J 1995 Direct evaluation of electronic coupling mediated by hydrogen bonds—implications for biological electron transfer Sc/e/ ce 269 1409-13... 

The next generation of amperomethc enzyme electrodes may weU be based on immobilization techniques that are compatible with microelectronic mass-production processes and are easy to miniaturize (42). Integration of enzymes and mediators simultaneously should improve the electron-transfer pathway from the active site of the enzyme to the electrode. 

Most of the free-radical mechanisms discussed thus far have involved some combination of homolytic bond dissociation, atom abstraction, and addition steps. In this section, we will discuss reactions that include discrete electron-transfer steps. Addition to or removal of one electron fi om a diamagnetic organic molecule generates a radical. Organic reactions that involve electron-transfer steps are often mediated by transition-metal ions. Many transition-metal ions have two or more relatively stable oxidation states differing by one electron. Transition-metal ions therefore firequently participate in electron-transfer processes. 

Novel electron-transfer reactions mediated by alkali metals complexed with crown ethers as macrocyclic ligands 98ACR55. 

The redox properties of quinones are crucial to the functioning of living cells, where compounds called ubiquinones act as biochemical oxidizing agents to mediate the electron-transfer processes involved in energy production. Ubiquinones, also called coenzymes Q, are components of the cells of all aerobic organisms, from the simplest bacterium to humans. They are so named because of their ubiquitous occurrence in nature. 

S.3.3 Electrocatalytic Modified Electrodes Often the desired redox reaction at the bare electrode involves slow electron-transfer kinetics and therefore occurs at an appreciable rate only at potentials substantially higher than its thermodynamic redox potential. Such reactions can be catalyzed by attaching to the surface a suitable electron transfer mediator (45,46). Knowledge of homogeneous solution kinetics is often used to select the surface-bound catalyst. The function of the mediator is to facilitate the charge transfer between the analyte and the electrode. In most cases the mediated reaction sequence (e.g., for a reduction process) can be described by... 

Mediated electrolyses make use of electron transfer mediators PjQ that shuttle electrons between electrodes and substrates S, avoiding adverse effects encountered with the direct heterogeneous reaction of substrates at electrode surfaces (Scheme 6). In recent years this mode of electrochemical synthesis has been widely studio and it is becoming increasingly well understood. A review is given in vol 1 of the present electrochemistry series... 

The oxidation or reduction of a substrate suffering from sluggish electron transfer kinetics at the electrode surface is mediated by a redox system that can exchange electrons rapidly with the electrode and the substrate. The situation is clear when the half-wave potential of the mediator is equal to or more positive than that of the substrate (for oxidations, and vice versa for reductions). The mediated reaction path is favored over direct electrochemistry of the substrate at the electrode because, by the diffusion/reaction layer of the redox mediator, the electron transfer step takes place in a three-dimensional reaction zone rather than at the surface Mediation can also occur when the half-wave potential of the mediator is on the thermodynamically less favorable side, in cases where the redox equilibrium between mediator and substrate is disturbed by an irreversible follow-up reaction of the latter. The requirement of sufficiently fast electron transfer reactions of the mediator is usually fulfilled by such revemible redox couples PjQ in which bond and solvate... 

A general theory based on the quantitative treatment of the reaction layer profile exists for pure redox catalysis where the crucial function of the redox mediator is solely electron transfer and where the catalytic activity largely depends only on the redox potential and not on the structure of the catalyst This theory is consistent... 

The beauty of bromide-mediated oxidations is that they combine mechanistic complexity with practical simplicity and, hence, utility. They involve an intricate array of electron transfer steps in which bromine atoms function as go-betweens in transfering the oxidizing power of peroxidic intermediates, via redox metal ions, to the substrate. Because the finer mechanistic details of these elegant processes have often not been fully appreciated we feel that their full synthetic potential has not yet been realized. Hence, we envision further practical applications in the future. 

The spatial arrangement of the Fe-S clusters in D. gigas NiFe-hydrogenase (see Fig. 1) suggests an active role for the [Fe3S4] ° cluster in mediating electron transfer from the NiFe active site to the... 

Such reduction In overpotentlal Is the largest observed for a bare glassy carbon electrode. The presence of surface qulnones may be Indicative of activation but does not appear to mediate the heterogeneous electron transfer. XFS results support the presence of qulnones as a minor constituent on the surface. 

Several mechanisms have been proposed to explain the activation of carbon surfaces. These have Included the removal of surface contaminants that hinder electron transfer, an Increase In surface area due to ralcro-roughenlng or bulld-up of a thin porous layer, and an Increase In the concentrations of surface functional groups that mediate electron transfer. Electrode deactivation has been correlated with an unintentional Introduction of surface contaminants (15). Improved electrode responses have been observed to follow treatments which Increase the concentration of carbon-oxygen functional groups on the surface (7-8,16). In some cases, the latter were correlated with the presence of electrochemical surface waves (16-17). However, none of the above reports discuss other possible mechanisms of activation which could be responsible for the effects observed. 

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