Enzyme-Based Electrobiotechnological Synthesis.

Oxidoreductases are enzymes with a high potential for organic synthesis, as their selectivity often exceeds comparable chemical syntheses. The biochemical cofactors of these enzymes need regeneration during synthesis. Several regeneration methods are available but the electrochemical approach offers an efficient and quasi mass-free method for providing the required redox equivalents. Electron transfer systems involving direct regeneration of natural and artificial cofactors, indirect electrochemical regeneration via a mediator, and indirect electroenzymatic cofactor regeneration via enzyme and mediator have been investigated. This chapter gives an overview of electroenzymatic syntheses with oxidoreductases, structured by the enzyme subclass and their usage of cofactors for electron relay. Particular attention is given to the productivity of electroenzymatic biotransformation processes. Because most electroenzymatic syntheses suffer from low productivity, we discuss reaction engineering concepts to overcome the main limiting factors, with a focus on media conductivity optimization, approaches to prevent enzyme inactivation, and the application of advanced cell designs. Graphical Abstract.