Biotransformation of cyclohexene to value-added oxygenated derivative catalyzed by chloroperoxidase in the presence of small quantities of quaternary ammonium salts

Biotransformation of cyclohexene catalyzed by chloroperoxidase (CPO) from Caldariomyces fumago was employed to prepare value-added oxygenated derivative: trans-1,2-cyclohexanediol (CHD) using H2O2 as oxidants. The conversion of substrate was enhanced to 89.2% in the presence of small quantities of quaternary ammonium salts (QAS) compared to that of only 48.1% in aqueous phosphate buffer after 150 min. The enhancement was dependent on the concentration and alkyl group length of QAS. QAS were found playing multiple functions in reaction media: phase transfer catalysis and tuning the composition of product. UV–vis, fluorescence and circular dichroism (CD) spectral assay were employed to investigate the effect of QAS on micro-environment around active center and structure of protein. The strengthening of α-helix structure of CPO and more exposure heme for easily access of substrate was found responsible for the improvement of catalytic performance of CPO. Moreover, the determined kinetic parameters indicated the affinity and selectivity of CPO to substrate was improved according to the observation of a decrease of Michaelis constant Km while an increase of the second order rate constants kcat/Km.The strategy reported in this work is environment-friendly, straightforward and applicable to large scale preparation.

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► Cyclohexene was turned to value-added derivative by CPO-catalyzed biotransformation.
► Small quantity of introduced quaternary ammonium salts played multiple functions.
► The strategy is environment-friendly, straightforward and applicable to large scale.