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ESR study of DNA base cation radicals produced by attack of oxidizing radicals

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j150608a021· OSTI ID:6507558

ESR investigations of ..gamma..-irradiated aqueous glasses (8 M NaClO/sub 4/, 12 M LiCl) containing DNA bases and analogues show that oxidizing species produced in the glasses (hydroxyl radicals and Cl/sub 2//sup -/) at 77 K attack a number of the bases and their analogues after warming to produce ..pi..-cation radicals. Compounds which produce ..pi.. cations include thymine, uracil, 3-methyluracil, 6-methyluracil, orotic acid, isoorotic acid, guanine, and adenine. Compounds which are not found to produce ..pi.. cations are 1-methylthymine, thymidine, and 1-methyluracil. The overall reaction for formation of the ..pi.. cations is as follows: base + OH.(Cl/sub 2//sup -/) ..-->.. OH/sup -/(2Cl/sup -/) + base cation. A pH and substituent dependence is also noted for the pyrimidines. At pHs where the nitrogen at position 1 is protonated, ..pi..-cation radicals are not formed. In addition, when there are substituents at position 1, ..pi.. cations are not found. Analysis of the ESR spectra of the DNA base ..pi.. cations for hyperfine splittings and g values were performed by aid of computer simulations. The analyses are in agreement with values found for several DNA base cations produced by photolysis and by direct ..gamma.. irradiation.

Research Organization:
Oakland Univ., Rochester, MI
OSTI ID:
6507558
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:8; ISSN JPCHA
Country of Publication:
United States
Language:
English