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

Goncalves, Leticia C. P. (author): TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria

Mansouri, Hanild R. (author): TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria

Bastos, Erick L. (author): Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, BR-03178200 Sao Paulo, Brazil

Abdellah, Mohamed (author): Uppsala universitet,Fysikalisk kemi,South Valley Univ, Qena Fac Sci, Dept Chem, Qena 83523, Egypt

Fadiga, Bruma S. (author): Uppsala universitet,Fysikalisk kemi,Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, BR-03178200 Sao Paulo, Brazil

Sá, Jacinto (author): Uppsala universitet,Fysikalisk kemi,Polish Acad Sci, Inst Phys Chem, PL-01224 Warsaw, Poland

Rudroff, Florian (author): TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria

Mihovilovic, Marko D. (author): TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria

(creator_code:org_t)

2019
2019
English.
In: Catalysis Science & Technology. - : ROYAL SOC CHEMISTRY. - 2044-4753 .- 2044-4761. ; 9:6, s. 1365-1371

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Abstract Subject headings

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.

By the author/editor: Goncalves, Letic ...; Mansouri, Hanild ...; Bastos, Erick L.; Abdellah, Mohame ...; Fadiga, Bruma S.; Sá, Jacinto; show more...; Rudroff, Florian; Mihovilovic, Mar ...; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Physical Chemist ...

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