Issue 6, 2019

Morpholine-based buffers activate aerobic photobiocatalysis via spin correlated ion pair formation

Abstract

The use of enzymes for synthetic applications is a powerful and environmentally-benign approach to increase molecular complexity. Oxidoreductases selectively introduce oxygen and hydrogen atoms into myriad substrates, catalyzing the synthesis of chemical and pharmaceutical building blocks for chemical production. However, broader application of this class of enzymes is limited by the requirements of expensive cofactors and low operational stability. Herein, we show that morpholine-based buffers, especially 3-(N-morpholino)propanesulfonic acid (MOPS), promote photoinduced flavoenzyme-catalyzed asymmetric redox transformations by regenerating the flavin cofactor via sacrificial electron donation and by increasing the operational stability of flavin-dependent oxidoreductases. The stabilization of the active forms of flavin by MOPS via formation of the spin correlated ion pair 3[flavin˙–MOPS˙+] ensemble reduces the formation of hydrogen peroxide, circumventing the oxygen dilemma under aerobic conditions detrimental to fragile enzymes.

Graphical abstract: Morpholine-based buffers activate aerobic photobiocatalysis via spin correlated ion pair formation

Supplementary files

Article information

Article type
Paper
Submitted
14 Dec 2018
Accepted
08 Feb 2019
First published
11 Feb 2019
This article is Open Access
Creative Commons BY license

Catal. Sci. Technol., 2019,9, 1365-1371

Morpholine-based buffers activate aerobic photobiocatalysis via spin correlated ion pair formation

L. C. P. Gonçalves, H. R. Mansouri, E. L. Bastos, M. Abdellah, B. S. Fadiga, J. Sá, F. Rudroff and M. D. Mihovilovic, Catal. Sci. Technol., 2019, 9, 1365 DOI: 10.1039/C8CY02524J

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