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Protonation of nucleobase anions in gamma-irradiated DNA and model systems. Which DNA base is the ultimate sink for the electron

Journal Article · · Radiation Research; (United States)
DOI:https://doi.org/10.2307/3578841· OSTI ID:6480145
;  [1]
  1. Oakland Univ., Rochester, MI (United States)

Electron spin resonance (ESR) spectroscopy has been used to investigate irreversible protonations of the nucleobase anions in [gamma]-irradiated frozen aqueous solutions of dGMP[center dot]dCMP, polyG[center dot]polyC, poly[dGdC][center dot]poly[dGdC], dAMP[center dot]dTMP, poly[dAdT][center dot]poly-[dAdT] and DNA itself. Analysis of the ESR spectra at a dose of 22 kGy shows that fractional conversion of total radicals to carbon-protonated species on annealing is in the order: dAMP[center dot]dTMP (43%) > pdAdT = DNA (23%) > dGMP[center dot]dCMP (15%) > poly-dGdC[center dot]polydGdC (6%) > polyG[center dot]polyC (3%). Two hydrogen addition radicals make contributions to the polyG[center dot]polyC, poly[dGdC][center dot]poly[dGdC] and dGMP[center dot]dCMP spectra in H[sub 2]O on annealing. They are those formed by protonations at C6 of the cytosine anion radical, C(C6)H[sup *], and at C8 of the guanine anion radical, G(c8)H[sup *]. Computer analysis reveals that anion protonation reaction in dGMP[center dot]dCMP results in mainly C(C6)H[sup *], whereas protonation reaction in polyG[center dot]polyC and poly[dGdC][center dot]poly-[dGdC] yields mainly G(C8)H[sup *]. In dAMP[center dot]dTMP and poly[dAdT][center dot]poly[dAdT] as in DNA itself, the only DNA itself, the only DNA base found to undergo an irreversible protonation at a carbon site is thymine, resulting in T(C6)H[sup *]. The conversion of DNA anion to T(C6)H[sup *] is found to be dependent on dose. At low doses (5 kGy), about 30% conversion to T(C6)H[sup *] is found, whereas at high doses (94 kGy), only 13% conversion is found. The dose dependence is ascribed in part to ion radical recombinations whose probabilities are increased at high doses. 33 refs., 8 figs., 1 tab.

OSTI ID:
6480145
Journal Information:
Radiation Research; (United States), Journal Name: Radiation Research; (United States) Vol. 138:1; ISSN 0033-7587; ISSN RAREAE
Country of Publication:
United States
Language:
English