Hybrid Organometallic and Enzymatic Tandem Catalysis for Oxyfunctionalisation Reactions

Unspecific peroxygenases (UPOs) are promising biocatalysts for oxyfunctionalisation reactions, owing to their simplicity of handling, stability and robustness. A limitation of using UPOs on a large scale is their deactivation in the presence of even rather modest concentrations of H₂O₂, requiring a constant and...

Structure-Based Redesign of a Methanol Oxidase into an “Aryl Alcohol Oxidase” for Enzymatic Synthesis of Aromatic Flavor Compounds

Alcohol oxidases (AOxs) catalyze the aerobic oxidation of alcohols to the corresponding carbonyl products (aldehydes or ketones), producing only H₂O₂ as the byproduct. The majority of known AOxs, however, have a strong preference for small, primary alcohols, limiting their broad applicability, e.g., in the food industry....

Peroxygenase-Promoted Enzymatic Cascades for the Valorisation of Fatty Acids

Utilisation of fatty acids generally relies on pre-existing functional groups such as the carboxylate group or C=C-double bonds. Addition of new functionalities into the hydrocarbon part opens up new possibilities for fatty acid valorisation. In this contribution we demonstrate the synthetic potential of a peroxygenase mutant AaeUPO−Fett for...

A novel unspecific peroxygenase from Agaricus bisporus var. bisporus for biocatalytic oxyfunctionalisation reactions

Unspecific peroxygenases (UPOs) represent an emerging class of catalysts for the selective oxyfunctionalisation of C–H- and C = C groups. Until now, only a few UPOs have been characterised. In this study, we report a new peroxygenase identified from the Unspecific Peroxygenase Database. The UPO from Agaricus bisporus var. bisporus (AbvbUPO)...

Biosynthesis of cyclic ketones by a H₂O₂ self-sufficient cascade reaction

In the present work we propose a bienzymatic cascade for the oxyfunctionalisation of cycloalkanes to cyclic alcohols/cyclic ketones. By combining a H₂O₂-dependent peroxygenase with a O₂-consuming and H₂O₂-producing alcohol oxidase an overall aerobic oxidation system was established. A...

Mirror, mirror on the wall which is the greenest of them all? A critical comparison of chemo- and biocatalytic oxyfunctionalisation reactions

This review article critically compares two widely used types of catalysis, chemo- and biocatalysis, and provides insights on their greenness according to specified parameters. A comparative analysis of the environmental impact of chemo- and biocatalytic oxyfunctionalisation reactions based on published experimental data reveals that both...

Engineering a Highly Regioselective Fungal Peroxygenase for the Synthesis of Hydroxy Fatty Acids

The hydroxylation of fatty acids is an appealing reaction in synthetic chemistry, although the lack of selective catalysts hampers its industrial implementation. In this study, we have engineered a highly regioselective fungal peroxygenase for the ω-1 hydroxylation of fatty acids with quenched stepwise over-oxidation. One single mutation near...

A photodecarboxylase from Micractinium conductrix active on medium and short-chain fatty acids

Hydrocarbons are essential base chemicals as energy carriers and starting materials for chemical manufacture. So-called fatty acid photodecarboxylases (FAPs) represent interesting catalysts for the conversion of natural fatty acids into hydrocarbons thereby giving access to alkanes from renewable feedstock. Today, however, only few FAPs are...

A Novel Unspecific Peroxygenase from Galatian marginata for Biocatalytic Oxyfunctionalization Reactions

Unspecific peroxygenases (UPOs, EC 1.11.2.1) are promising oxyfunctionalization catalysts because of their unique stereoselectivity. However, so far only a few UPOs have been reported. In this study, gene mining was used to identify a gene from Galerina marginata that coded for a novel UPO (GmaUPO). GmaUPO was expressed in Pichia pastoris X...

More efficient enzymatic cascade reactions by spatially confining enzymes via the SpyTag/SpyCatcher technology

Hydrocarbon synthesis from (waste)oils enabled by a cascade of lipase-catalysed hydrolysis and decarboxylase-catalysed decarboxylation has become an active area of research en route to alternative, biobased fuels. However, Poor substrate transport efficiency is a major issue causing low reaction rates. This study focused on a protein self...

A Biocatalytic Platform for the Synthesis of Enantiopure Propargylic Alcohols and Amines

Propargylic alcohols and amines are versatile building blocks in organic synthesis. We demonstrate a straightforward enzymatic cascade to synthesize enantiomerically pure propargylic alcohols and amines from readily available racemic starting materials. In the first step, the peroxygenase from Agrocybe aegerita converted the racemic...

Intensification of Photobiocatalytic Decarboxylation of Fatty Acids for the Production of Biodiesel

Light-driven biocatalytic processes are notoriously hampered by poor penetration of light into the turbid reaction media. In this study, wirelessly powered light-emitting diodes are found to represent an efficient and scalable approach for process intensification of the photobiosynthetic production of diesel alkanes from renewable fatty acids...

Stabilisation of the Fatty Acid Decarboxylase from Chlorella variabilis by Caprylic Acid

The fatty acid photodecarboxylase from Chlorella variabilis NC64 A (CvFAP) catalyses the light-dependent decarboxylation of fatty acids. Photoinactivation of CvFAP still represents one of the major limitations of this interesting enzyme en route to practical application. In this study we demonstrate that the photostability of CvFAP can easily...

An alginate-confined peroxygenase-CLEA for styrene epoxidation

Oxyfunctionalisation reactions in neat substrate still pose a challenge for biocatalysis. Here, we report an alginate-confined peroxygenase-CLEA to catalyse the enantioselective epoxidation of cis-β-methylstyrene in a solvent-free reaction system achieving turnover numbers of 96 000 for the biocatalyst and epoxide concentrations of 48 mM.