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...

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...

Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene epoxides generated by fungal peroxygenases can...

Plasma-Driven in Situ Production of Hydrogen Peroxide for Biocatalysis

Peroxidases and peroxygenases are promising classes of enzymes for biocatalysis because of their ability to carry out one-electron oxidation reactions and stereoselective oxyfunctionalizations. However, industrial application is limited, as the major drawback is the sensitivity toward the required peroxide substrates. Herein, we report a...

Enzymatic Oxidation of Butane to 2-Butanol in a Bubble Column

Unspecific peroxygenases have recently gained significant interest due to their ability to catalyse the hydroxylation of non-activated C−H bonds using only hydrogen peroxide as a co-substrate. However, the development of preparative processes has so far mostly concentrated on benzylic hydroxylations using liquid substrates. Herein, we...

Piezobiocatalysis: Ultrasound-Driven Enzymatic Oxyfunctionalization of C-H Bonds

Peroxygenases have long inspired the selective oxyfunctionalization of various aliphatic and aromatic compounds, because of their broad substrate spectrum and simplicity of catalytic mechanism. This study provides a proof-of-concept of piezobiocatalysis by demonstrating peroxygenase-catalyzed oxyfunctionalization reactions fueled by...

Microscale Atmospheric Pressure Plasma Jet as a Source for Plasma-Driven Biocatalysis

The use of a microscale atmospheric pressure plasma jet (μAPPJ) was investigated for its potential to supply hydrogen peroxide in biocatalysis. Compared to a previously employed dielectric barrier discharge (DBD), the μAPPJ offered significantly higher H₂O₂ production rates and better handling of larger reaction volumes....

Multienzymatic in situ hydrogen peroxide generation cascade for peroxygenase-catalysed oxyfunctionalisation reactions

There is an increasing interest in the application of peroxygenases in biocatalysis, because of their ability to catalyse the oxyfunctionalisation reaction in a stereoselective fashion and with high catalytic efficiencies, while using hydrogen peroxide or organic peroxides as oxidant. However, enzymes belonging to this class exhibit a very...