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Eletron Transfer in DNA from Guanine and 8-Oxoguanine to a Radical Cation of the Carbohydrate Backbone

机译:电子从鸟嘌呤和8-氧鸟嘌呤转移到碳水化合物骨架的阳离子上

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摘要

Photolysis of a 4ft-pivaloylsubstituted nucleotide in single- and double-stranded DNA (1) generated an enol ether radical cation 4 that was reduced to enol ether 17 by electron transfer from the nearest guanoside (G). Variation of the nucleotide sequence demonstrated a strong distance dependence of this electron-transfer rate with #beta#=1.0+-0.1 A~(-1). When 8-oxoguanosine (G~oxo) was used as the electron donor, the rate of the electron donor, the rate of the electron transfer increased by a factor of 4 but the distance dependence of the transfer remained unchanged within experimental error. In single strands, the number of intervening A, T, and C nucleotides had a much smaller effect; the rate remained nearly constant for two, three, or four intervening nucleotides. This is explained by the flexibility of the single-stranded oligonucleotides.
机译:在单链和双链DNA(4)中4ft-新戊酰取代的核苷酸的光解产生了烯醇醚自由基阳离子4,该阳离子通过电子从最近的鸟苷(G)转移而还原为烯醇醚17。核苷酸序列的变化表明该电子传输速率与#beta#= 1.0 + -0.1 A〜(-1)有很强的距离依赖性。当使用8-氧代鸟苷(G_oxo)作为电子供体时,电子供体的速率,电子转移的速率增加了4倍,但转移的距离依赖性在实验误差内保持不变。在单链中,中间的A,T和C核苷酸的数量影响较小;对于两个,三个或四个插入核苷酸,该速率几乎保持恒定。单链寡核苷酸的灵活性解释了这一点。

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