Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
BCSJ Award Article
Computational Study on the Mechanism of the Electron-Transfer-Induced Repair of the (6–4) T–T Photoproduct of DNA by Photolyase: Possibility of a Radical Cation Pathway
Toshiaki MatsubaraNozomi AraidaDaichi HayashiHatsumi Yamada
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2014 Volume 87 Issue 3 Pages 390-399


The oxetane and the non-oxetane mechanisms of the electron-transfer-driven repair of the (6–4) T–T photolesion of DNA by photolyase are examined by density functional theory (B3LYP). We calculated the radical cation pathway in addition to the radical anion and the neutral pathways for both mechanisms in order to assess the possibility of the radical cation pathway, because relatively large energy barriers have been found for the radical anion pathway. As a result, the radical anion pathway showed a large energy barrier in both the oxetane and the non-oxetane mechanisms in agreement with previous calculations. However, it was found that the radical cation pathway of the oxetane mechanism has a realistic low energy barrier. This advantage of the radical cation pathway was ascribed to the position of the radical before the formation of the oxetane and the stability of the oxetane in energy.

The mechanism of the electron-transfer-induced repair of the (6–4) photoproduct of DNA by photolyase was examined by density functional theory. As a result, the radical cation pathway of the oxetane mechanism was found to be the most favorable in energy. Fullsize Image
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© 2014 The Chemical Society of Japan
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