Can photolysis of the CoC bond in coenzyme B12-dependent enzymes be used to mimic the native reaction?

Publication date: Available online 21 December 2018Source: Journal of Photochemistry and Photobiology B: BiologyAuthor(s): Abdullah Al Mamun, Megan J. Toda, Pawel M. KozlowskiAbstractCoenzyme B12 (Adenosylcobalamin = AdoCbl)-dependent enzymes catalyze complex molecular transformations where cleavage of the CoC bond initiates the catalytic cycle. Alternatively, the CoC bond can be cleaved with light. In both cases, rupture of the CoC bond results in the formation of Co(II)/Ado radical pair (RP). Within the field of B12 chemistry, there has been a suspicion that photolytic cleavage can be used as a probe or a direct comparison of the native reaction. Herein, we seek to resolve what the connection between light-induced RP formation and the native catalytic cycle is. We used a combined QM/...

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