Oxidation and Reduction of the 5-(2′-Deoxyuridinyl)methyl Radical

Authors

  • Dr. Gengjie Lin,

    1. Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis (IUPUI), 402 N. Blackford St., Indianapolis, IN 46202 (USA)
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  • Prof. Lei Li

    Corresponding author
    1. Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis (IUPUI), 402 N. Blackford St., Indianapolis, IN 46202 (USA)
    2. Department of Biochemistry and Molecular Biology, Indiana University School of Medicine, 635 Barnhill Drive, Indianapolis, IN 46202 (USA)
    • Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis (IUPUI), 402 N. Blackford St., Indianapolis, IN 46202 (USA)

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  • We thank all of the referees for their insightful suggestions and comments. We thank Professor Steven Rokita at the Johns Hopkins University for helpful discussions on the TpT radical reduction. We thank the National Institutes of Health (R00ES017177) as well as the IUPUI startup fund for financial support. The NMR and MS facilities are supported by the National Science Foundation MRI grants CHE-0619254 and DBI-0821661.

Abstract

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Sleeping beauty: The 5-(2′-Deoxyuridinyl)methyl radical 1 is a key intermediate in the thymine oxidative reaction mediated by reactive oxygen species. Evidence is presented that 1 is prone to both oxidation and reduction reactions at the absence of O2. These results question the current paradigm and suggest that the redox chemistry of 1, which has been largely overlooked in the past, may play a major role in determining the fate of 1.

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