A Concerted Synchronous [2 + 2] Cycloreversion Repair Catalyzed by Two Electrons

The current understanding of photoenzyme-catalyzed [2 + 2] cycloreversion repair of cyclobutane pyrimidine dimer (CPD) is that a photogenerated electron from the photolyase enzyme catalyzes the repair. This one-electron catalyzed repair is a sequential two-bond breaking cycloreversion of the cyclobu...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2018-12, Vol.9 (24), p.6973-6977
Main Authors: Davis, Daly, Bhushan, K. G, Sajeev, Y, Cederbaum, L. S
Format: Article
Language:English
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Summary:The current understanding of photoenzyme-catalyzed [2 + 2] cycloreversion repair of cyclobutane pyrimidine dimer (CPD) is that a photogenerated electron from the photolyase enzyme catalyzes the repair. This one-electron catalyzed repair is a sequential two-bond breaking cycloreversion of the cyclobutane center and involves a negative ion radical as an intermediate. Here, by resonantly capturing two exogenous low-energy electrons into the molecular field of a CPD, we show that the concerted synchronous two-bond breaking reaction, which is intermediate-free, and hence a safe repair, is feasible through two-electron catalysis.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.8b03256