Bioelectrocatalysis is a phenomenon of acceleration of electrode reactions by the enzymes. Direct bioelectrocatalysis presumes the direct electron exchange between the enzyme active site and the electrode without any use of diffusion free mediators.

Direct bioelectrocatalysis is a discovery of Russian enzymologists and electrochemists. The discovery of the phenomenon in late 70-s realized in elaboration of oxygen enzyme electrode based on laccase. Later several other enzymes were involved in direct bioelectrocatalysis. The achievement of the substrate equilibrium potential was first shown with hydrogen enzyme electrode.

The history of direct bioelectrocatalysis, starting form electrochemistry of redox enzymes will be presented. The most successful examples for the enzymes in direct bioelectrocatalysis (including information on the structure of the enzymes) will be outlined. The approaches, how to involve enzymes in direct bioelectrocatalysis and the fundamentals of this phenomenon will be discussed.

Special attention will be paid to describe the novel approach: enzyme orientation during immobilization to improve efficiency of bioelectrocatalysis. The example of achievement of limiting performance characteristics of the enzymes in bioelectrocatalysis will be shown.

A rather novel phenomenon, the direct bioelectrocatalysis by intact cells, will be presented. An evidence for electroactivity of intact cells will be outlined, and the pictures, how bacteria are using electrode as an electron acceptor will be shown.

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