Photoenzymatic cascade reactions: Coupling photocatalytic in-situ generation of hydrogen peroxide with peroxidase-based enzymatic reactions

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Peroxygenases catalyze a variety of oxyfunctionalizations for the synthesis of chemical and pharmaceutical building blocks. In contrast to many co-factor dependent Oxidoreductases they use the inexpensive and easily producible hydrogen peroxide (H2O2) as a cosubstrate. However, their instability against H2O2 currently makes the application rather complicated. In the previous project we could show that heterogeneous photocatalysis is an excellent tool for the adequate in-situ H2O2 supply. However, an unexpected inactivation through photocatalytically generated hydroxyl radicals leads to the somewhat lower performance compared to the alternative enzymatic or electrochemical H2O2 generation methods. A further development of this proof of principle study with the development of a detailed kinetic model, the optimization of the photocatalysts and the use of immobilized enzymes shall further improve the efficiency of the overall process. In a later stage of the project an online H2O2 and product analysis will be used to regulate the whole process. In the end more efficient photoreactors will be used for an intensification of the process and their scalability shall be demonstrated.