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Nucleic Acids Research 2006 34(5):1501-1511; doi:10.1093/nar/gkl026
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Published online 14 March 2006

© The Author 2006. Published by Oxford University Press. All rights reserved
The online version of this article has been published under an open access model. Users are entitled to use, reproduce, disseminate, or display the open access version of this article for non-commercial purposes provided that: the original authorship is properly and fully attributed; the Journal and Oxford University Press are attributed as the original place of publication with the correct citation details given; if an article is subsequently reproduced or disseminated not in its entirety but only in part or as a derivative work this must be clearly indicated. For commercial re-use, please contact journals.permissions@oxfordjournals.org

Article

C5'- and C3'-sugar radicals produced via photo-excitation of one-electron oxidized adenine in 2'-deoxyadenosine and its derivatives

Amitava Adhikary, David Becker, Sean Collins, Jessica Koppen and Michael D. Sevilla*

Department of Chemistry, Oakland University Rochester, MI 48309, USA

*To whom correspondence should be addressed. Tel: +1 248 370 2328; Fax: +1 248 370 2321; Email: sevilla{at}oakland.edu

Received January 5, 2005. Revised February 16, 2006. Accepted February 16, 2006.

We report that photo-excitation of one-electron-oxidized adenine [A(-H)•] in dAdo and its 2'-deoxyribonucleotides leads to formation of deoxyribose sugar radicals in remarkably high yields. Illumination of A(-H)• in dAdo, 3'-dAMP and 5'-dAMP in aqueous glasses at 143 K leads to 80-100% conversion to sugar radicals at C5' and C3'. The position of the phosphate in 5'- and 3'-dAMP is observed to deactivate radical formation at the site of substitution. In addition, the pH has a crucial influence on the site of sugar radical formation; e.g. at pH ~5, photo-excitation of A(-H)• in dAdo at 143 K produces mainly C5'• whereas only C3'• is observed at high pH ~12. 13C substitution at C5' in dAdo yields 13C anisotropic couplings of (28, 28, 84) G whose isotropic component 46.7 G identifies formation of the near planar C5'•. A ß-13C 16 G isotropic coupling from C3'• is also found. These results are found to be in accord with theoretically calculated 13C couplings at C5' [DFT, B3LYP, 6-31(G) level] for C5'• and C3'•. Calculations using time-dependent density functional theory [TD-DFT B3LYP, 6-31G(d)] confirm that transitions in the near UV and visible induce hole transfer from the base radical to the sugar group leading to sugar radical formation.


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