Chemical and electrochemical approaches to the investigation of redox reactions of simple electron transfer metalloproteins

The redox chemistry of simple metalloproteins such as cytochrome, plastocyanin and ferredoxin has been studied extensively by both chemically and electrochemically based techniques. However, despite the fact that complementary information can be obtained, in practice the results of the two methods generally have been reported and interpreted in an independent manner. In this paper an overview of the information that can be gained from the two approaches is presented. In both areas, a complex range of problems exists that are often considerably more challenging than those commonly encountered in studies on smaller redox active molecules. Consequently, interpretation of data obtained from either method when based on standard approaches and concepts is often fraught with danger. Nevertheless, knowledge related to important thermodynamic relationships, rates of electron transfer and structural changes associated with electron transfer processes are slowly being unravelled from both fields of endeavour. It is therefore proposed that the inherently difficult challenge of using both forms of methodology could now be attempted more frequently than currently is the case and that the dual approach provides an opportunity to synergistically enhance knowledge related to biologically important electron transfer processes of redox active metalloproteins.