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• W2057709596 startingPage "8183" @default.
• W2057709596 abstract "The question of how NA base sequence influences the yield of DNA strand breaks produced by the direct effect of ionizing radiation was investigated in a series of oligodeoxynucleotides of the form (d(CG)n)2 and (d(GC)n)2. The yields of free base release from X-irradiated DNA films containing 2.5 waters/nucleotide were measured by HPLC as a function of oligomer length. For (d(CG)n)2, the ratio of the Gua yield to Cyt yield, R, was relatively constant at 2.4−2.5 for n = 2−4 and it decreased to 1.2 as n increased from 5 to 10. When Gua was moved to the 5′ end, for example going from d(CG)5 to d(GC)5, R dropped from 1.9 ± 0.1 to 1.1 ± 0.1. These effects are poorly described if the chemistry at the oligomer ends is assumed to be independent of the remainder of the oligomer. A mathematical model incorporating charge transfer through the base stack was derived to explain these effects. In addition, EPR was used to measure the yield of trapped-deoxyribose radicals at 4 K following X-irradiation at 4 K. The yield of free base release was substantially greater, by 50−100 nmol/J, than the yield of trapped-deoxyribose radicals. Therefore, a large fraction of free base release stems from a nonradical intermediate. For this intermediate, a deoxyribose carbocation formed by two one-electron oxidations is proposed. This reaction pathway requires that the hole (electron loss site) transfers through the base stack and, upon encountering a deoxyribose hole, oxidizes that site to form a deoxyribose carbocation. This reaction mechanism provides a consistent way of explaining both the absence of trapped radical intermediates and the unusual dependence of free base release on oligomer length." @default.
• W2057709596 created "2016-06-24" @default.
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• W2057709596 date "2009-05-19" @default.
• W2057709596 modified "2023-10-17" @default.
• W2057709596 title "Mechanisms of Strand Break Formation in DNA due to the Direct Effect of Ionizing Radiation: The Dependency of Free Base Release on the Length of Alternating CG Oligodeoxynucleotides" @default.
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• W2057709596 doi "https://doi.org/10.1021/jp900803b" @default.
• W2057709596 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/2791348" @default.
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