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• W2334458135 endingPage "199" @default.
• W2334458135 startingPage "199" @default.
• W2334458135 abstract "The total free radical yield has been measured for crystals of five pyrimidine derivatives: thymine (T), 1-methylthymine (1MeT), 1-methyluracil (1MeU), 1-methylcytosine (1MeC) and cytosine monohydrate (C:HOH). Q-band EPR measurements were made on samples X-irradiated between 4 and 12 K. The G values in units of 10(-7) mol/J are 1MeC < 0.01, T < 0.04, 1MeU = 0.15, 1MeT = 0.25, and C:HOH = 0.8. The types of free radicals formed in these crystals are known through previous EPR investigations. A model is presented that attempts to identify the salient variables behind the large range in G values and, simultaneously, explain the variation in radical types. It is concluded that packing is a critical variable. Hydrogen-bonding networks promote the trapping of radicals through reversible proton transfer. In the absence of such a network less probable radical types are observed, such as radicals formed by irreversible protonation/deprotonation, higher-order reactions and homolytic bond cleavage. Crystals with low G values trap radicals formed predominantly by irreversible protonation/deprotonation at carbon positions and by excitation-spawned homolytic bond cleavage. In contrast, crystals with high G values trap radicals formed predominantly by reversible protonation/deprotonation at heteroatom positions. This model is extended to polynucleotides irradiated at low temperatures, where G values are typically 2-6. The high trapping efficiency seen in polynucleotides reflects highly efficient proton transfer. Consistent with this is the predominance of radicals formed by reversible protonation/deprotonation compared to those formed by irreversible protonation/deprotonation." @default.
• W2334458135 created "2016-06-24" @default.
• W2334458135 creator A5001405873 @default.
• W2334458135 creator A5010498609 @default.
• W2334458135 creator A5059533514 @default.
• W2334458135 creator A5075153396 @default.
• W2334458135 date "1994-11-01" @default.
• W2334458135 modified "2023-09-23" @default.
• W2334458135 title "The Influence of Packing on Free Radical Yields in Crystalline Nucleic Acids: The Pyrimidine Bases" @default.
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• W2334458135 doi "https://doi.org/10.2307/3578904" @default.
• W2334458135 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/7938469" @default.
• W2334458135 hasPublicationYear "1994" @default.
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