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...

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...

Enhancing the ROS Sensitivity of a Responsive Supramolecular Hydrogel Using Peroxizyme Catalysis

Hydrogels that can disintegrate upon exposure to reactive oxygen species (ROS) have the potential for targeted drug delivery to tumor cells. In this study, we developed a diphenylalanine (FF) derivative with a thioether phenyl moiety attached to the N-terminus that can form supramolecular hydrogels at neutral and mildly acidic pH. The...

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...

Assessing Peroxygenase-Mediated Oxidations in the Presence of High Concentrations of Water-Miscible Co-Solvents

The use of water-miscible organic co-solvents in biocatalysis is a simple procedure for obtaining higher enzymatic activities toward hydrophobic substrates. However, effects on activity and stability have to be carefully evaluated, also with regard to the type and concentration of the respective co-solvent. In this contribution, we investigated...

Towards Biocatalytic Oxidation of Secondary Alcohols to Carbonyl Products of Relevance for Flavors and Fragrances

Non-enantioselective alcohol dehydrogenases (ADHs) are rarely found in the biocatalysis portfolio. Generally, highly enantioselective ADHs are sought for. Using such ADHs for the oxidation of racemic alcohols generally results in a kinetic resolution of the starting material, which is unfavourable if the ketone represents the product of interest...

A Photochemoenzymatic Hunsdiecker-Borodin-Type Halodecarboxylation of Ferulic Acid

A photochemoenzymatic halodecarboxylation of ferulic acid was achieved using vanadate-dependent chloroperoxidase as (bio)catalyst and oxygen and organic solvent as sole stoichiometric reagents in a biphasic system. Performance and selectivity were improved through a phase transfer catalyst, reaching a turnover number of 660.000 for the enzyme...

Heat-fueled enzymatic cascade for selective oxyfunctionalization of hydrocarbons

Heat is a fundamental feedstock, where more than 80% of global energy comes from fossil-based heating process. However, it is mostly wasted due to a lack of proper techniques of utilizing the low-quality waste heat (<100 °C). Here we report thermoelectrobiocatalytic chemical conversion systems for heat-fueled, enzyme-catalyzed...

Unbiased Photoelectrode Interfaces for Solar Coupling of Lignin Oxidation with Biocatalytic C=C Bond Hydrogenation

The pulp and paper manufacturers generate approximately 50 million metric tons of lignin per annum, most of which has been abandoned or incinerated because of lignin's recalcitrant nature. Here, we report bias-free photoelectrochemical (PEC) oxidation of lignin coupled with asymmetric hydrogenation of C=C bonds. The PEC platform consists of a...