Selective oxyfunctionalisation reactions catalysed by P450 monooxygenases and peroxygenases – A bright future for sustainable chemical synthesis

Heme-dependent oxygenases (i.e. P450 monooxygenases and peroxygenases) are highly selective catalysts for the selective oxyfunctionalisation or organic compounds. Both enzyme classes exhibit mechanistic similarities (i.e. using so-called compound I (CpdI) as active oxidation species) and differences in how CpdI is formed. From the differences...

Pilot-scale production of peroxygenase from agrocybe aegerita

The pilot-scale production of the peroxygenase from Agrocybe aegerita (rAaeUPO) is demonstrated. In a fed-batch fermentation of the recombinant Pichia pastoris, the enzyme was secreted into the culture medium to a final concentration of 0.29 g L-1 corresponding to 735 g of the peroxygenase in 2500 L of the fermentation broth after 6 days. Due...

FOx News: Towards Methanol-driven Biocatalytic Oxyfunctionalisation Reactions

The novel formate oxidase from Aspergillus oryzae (AoFOx) is a useful catalyst to promote H₂O₂-dependent oxyfunctionalisation reactions. In this contribution we exploit the substrate promiscuity of AoFOx to fully oxidise methanol and formaldehyde to CO₂ and drive peroxygenase-catalysed stereoselective...

Energising the E-factor: The E⁺-factor

The E-factor has become an important measure for the environmental impact of (bio)chemical reactions. However, summing up the obvious wastes generated in the laboratory neglects energy-related wastes (mostly greenhouse gases) which are generated elsewhere. To estimate these wastes, we propose to extend the E-factor by an energy-term (E<sup>+<...

Natural Deep Eutectic Solvents as Performance Additives for Peroxygenase Catalysis

Natural deep eutectic solvents (NADES) are proposed as alternative solvents for peroxygenase-catalysed oxyfunctionalization reactions. Choline chloride-based NADES are of particular interest as they can serve as solvent, enzyme-stabiliser and sacrificial electron donor for the in situ H₂O₂ generation. This report...

Peroxygenase-Catalysed Epoxidation of Styrene Derivatives in Neat Reaction Media

Biocatalytic oxyfunctionalisation reactions are traditionally conducted in aqueous media limiting their production yield. Here we report the application of a peroxygenase in neat reaction conditions reaching product concentrations of up to 360 mM.