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Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions
Author(s) -
Mengele Alexander K.,
Weixler Dominik,
Chettri Avinash,
Maurer Maite,
Huber Fabian Lukas,
Seibold Gerd M.,
Dietzek Benjamin,
Eikmanns Bernhard J.,
Rau Sven
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202103029
Subject(s) - nad+ kinase , chemistry , supramolecular chemistry , redox , cofactor , photochemistry , photocatalysis , phenazine , ligand (biochemistry) , substrate (aquarium) , electron transfer , catalysis , stereochemistry , combinatorial chemistry , enzyme , crystallography , crystal structure , organic chemistry , biochemistry , receptor , oceanography , geology
A series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P) + in water. A combination of (time‐resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a 1 O 2 pathway was found. Rudppz ([(tbbpy) 2 Ru(dppz)]Cl 2 , tbbpy=4,4'‐di‐ tert ‐butyl‐2,2'‐bipyridine, dppz=dipyrido[3,2‐ a :2′,3′‐ c ]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P) + from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H 2 O 2 as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.