Degree Name
MS (Master of Science)
Program
Chemistry
Date of Award
12-2014
Committee Chair or Co-Chairs
Marina Roginskaya
Committee Members
Scott Kirkby, David Close
Abstract
The carbonate radical anion (CO3•-, CR) is an important reactive oxygen species produced in vivo by one-electron oxidation of CO2 or bicarbonate, constituents of the major physiological buffer. It was demonstrated for the first time by using an HPLC-based analysis of low-molecular products of DNA damage that CRs react with DNA 2΄-deoxyribose by the hydrogen abstraction mechanism. CRs exhibit a ~ 800-fold preference for one-electron oxidation of guanine over hydrogen abstraction from DNA sugar, in sharp contrast with •OH. CRs also have, as compared to •OH, an increased preference for the H1΄ abstraction, which is the most thermodynamically favorable due to the highest stability of the respective deoxyribosyl radical but kinetically the slowest due to low solvent accessibility, by the expense of the decreased preference for the H5΄ abstraction. All these findings are in agreement with the characteristics of CR as a potent oxidant and selective hydrogen abstractor.
Document Type
Thesis - unrestricted
Recommended Citation
Moore, Terence J., "Oxidative Damage to DNA 2´-Deoxyribose by Carbonate Radicals: Reaction Mechanisms and Products" (2014). Electronic Theses and Dissertations. Paper 2445. https://dc.etsu.edu/etd/2445
Copyright
Copyright by the authors.