Electrochemical Activation of Cytochrome P450

This chapter reviews the efforts to develop catalytically competent P450 systems in which a simple electrode replaces NAD(P)H, and in some instances native reductase proteins, in the catalytic cycle. Notably, in evaluating the successes of P450 electrocatalytic methods, there is an important distinction to be made between mammalian and bacterial systems. While some mention of notable mammalian P450 electrocatalytic systems is made, the chapter focuses primarily on bacterial systems and specifically on the NADPH dependent flavocytochrome P450 from Bacillus megaterium (BM3). Harnessing P450 activity for in vitro applications may be most simply accomplished with electrochemical systems utilizing soluble mediators. Protein–surfactant film voltammetry has been widely used for studying the redox chemistry of P450s. Another striking aspect of P450 electrochemistry in surfactant films is the dramatic shift of the Fe^(III/II) couple to positive potentials. Finally, mediated electrochemical P450 systems are perhaps the best bets for large‐scale biocatalysis