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Issue 10, 2019
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Boosting photobioredox catalysis by morpholine electron donors under aerobic conditions

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Abstract

Light-driven reduction of flavins, e.g. FAD or FMN, by sacrificial electron donors emerged as a convenient method to promote biocatalytic transformations. However, flavin activation has been restricted to oxygen-free conditions to prevent enzyme deactivation caused by reactive oxygen species (ROS). Herein, we show that the photoreduction of FMN by morpholines, including 3-(N-morpholino)propanesulfonic acid (MOPS), lessens the deactivation of the enoate reductase XenB from Pseudomonas sp. during the stereoselective asymmetric enzymatic reduction of a model α,β-unsaturated diketone under aerobic conditions, leading to a 91% GC-yield and a stereoselectivity greater than 94%. The kinetic stability of the thermolabile XenB was increased by more than 20-fold in MOPS buffer compared to that in Tris-HCl buffer, and a pronounced positive effect on the transition midpoint temperature was observed. The reactive form of the FMN photocatalyst is stabilized by the formation of a 3[FMN˙–MOPS˙+] ensemble, which reduces the formation of hydrogen peroxide and other ROS in the presence of oxygen. These results contribute to broaden the application of photobiocatalytic transformations using flavin-dependent reductases.

Graphical abstract: Boosting photobioredox catalysis by morpholine electron donors under aerobic conditions

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Publication details

The article was received on 12 Mar 2019, accepted on 22 Apr 2019 and first published on 23 Apr 2019


Article type: Paper
DOI: 10.1039/C9CY00496C
Catal. Sci. Technol., 2019,9, 2682-2688
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    Boosting photobioredox catalysis by morpholine electron donors under aerobic conditions

    L. C. P. Gonçalves, H. R. Mansouri, S. PourMehdi, M. Abdellah, B. S. Fadiga, E. L. Bastos, J. Sá, M. D. Mihovilovic and F. Rudroff, Catal. Sci. Technol., 2019, 9, 2682
    DOI: 10.1039/C9CY00496C

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