Selective Activation of C−H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis

Selective oxyfunctionalizations of inert C−H bonds can be achieved under mild conditions by using peroxygenases. This approach, however, suffers from the poor robustness of these enzymes in the presence of hydrogen peroxide as the stoichiometric oxidant. Herein, we demonstrate that inorganic photocatalysts such as gold–titanium dioxide...

Bias-Free in Situ H₂O₂ Generation in a Photovoltaic-Photoelectrochemical Tandem Cell for Biocatalytic Oxyfunctionalization

Peroxygenases catalyze selective oxyfunctionalization of hydrocarbons with high conversion efficiencies using H₂O₂ as a key cosubstrate. Here, we report an unbiased photoelectrochemical (PEC) tandem structure consisting of a FeOOH/BiVO₄ photoanode, a Cu(In,Ga)Se₂ solar absorber, and a graphitic...

Photoenzymatic Hydroxylation of Ethylbenzene Catalyzed by Unspecific Peroxygenase: Origin of Enzyme Inactivation and the Impact of Light Intensity and Temperature

Photoenzymatic cascades can be used for selective oxygenation of C−H-Bonds under mild conditions circumventing the hydrogen peroxide mediated peroxygenase inactivation via in situ H₂O₂ generation. Here, we report the “on demand” production of hydrogen peroxide via methanol assisted reduction of molecular oxygen using UV...

Nuclear Waste and Biocatalysis: A Sustainable Liaison?

It is well-known that energy-rich radiation induces water splitting, eventually yielding hydrogen peroxide. Synthetic applications, however, are scarce and to the best of our knowledge, the combination of radioactivity with enzyme-catalysis has not been considered yet. Peroxygenases utilize H2O2 as an oxidant to promote highly selective...

Enantioselective Sulfoxidation of Thioanisole by Cascading a Choline Oxidase and a Peroxygenase in the Presence of Natural Deep Eutectic Solvents

A bienzymatic cascade for selective sulfoxidation is presented. The evolved recombinant peroxygenase from Agrocybe aegeritra catalyses the enantioselective sulfoxidation of thioanisole whereas the choline oxidase from Arthrobacter nicotianae provides the H2 O2 necessary via reductive activation of ambient oxygen. The reactions are performed...