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

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

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.

Mansouri, Hanild R.TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria (författare)
Bastos, Erick L.Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, BR-03178200 Sao Paulo, Brazil (författare)
Abdellah, MohamedUppsala universitet,Fysikalisk kemi,South Valley Univ, Qena Fac Sci, Dept Chem, Qena 83523, Egypt (författare)
Fadiga, Bruma S.Uppsala universitet,Fysikalisk kemi,Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, BR-03178200 Sao Paulo, Brazil (författare)
Sá, JacintoUppsala universitet,Fysikalisk kemi,Polish Acad Sci, Inst Phys Chem, PL-01224 Warsaw, Poland(Swepub:uu)saaja288 (författare)
Rudroff, FlorianTU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria (författare)
Mihovilovic, Marko D.TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, Austria (författare)
TU Wien, Inst Appl Synthet Chem, Getreidemarkt 9-163, A-1060 Vienna, AustriaUniv Sao Paulo, Inst Chem, Dept Fundamental Chem, BR-03178200 Sao Paulo, Brazil (creator_code:org_t)

Ingår i:Catalysis Science & Technology: ROYAL SOC CHEMISTRY9:6, s. 1365-13712044-47532044-4761

Av författaren/redakt...: Goncalves, Letic ...; Mansouri, Hanild ...; Bastos, Erick L.; Abdellah, Mohame ...; Fadiga, Bruma S.; Sá, Jacinto; visa fler...; Rudroff, Florian; Mihovilovic, Mar ...; visa färre...

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