Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions

in: Chemistry-A European Journal (2021)
Mengele, Alexander; Weixler, Dominik; Chettri, Avinash; Maurer, Maite; Huber, Fabian Lukas; Seibold, Gerd M.; Dietzek, Benjamin; Eikmanns, Bernhard J.; Rau, Sven
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 (timeresolved) 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 1O2 pathway was found. Rudppz ([(tbbpy)2Ru(dppz)]Cl2, 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 H2O2 as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.

Third party cookies & scripts

This site uses cookies. For optimal performance, smooth social media and promotional use, it is recommended that you agree to third party cookies and scripts. This may involve sharing information about your use of the third-party social media, advertising and analytics website.
For more information, see privacy policy and imprint.
Which cookies & scripts and the associated processing of your personal data do you agree with?

You can change your preferences anytime by visiting privacy policy.