Capturing the radical ion-pair intermediate in DNA guanine oxidation
文献类型:期刊论文
作者 | Jie, Jialong1,3; Liu, Kunhui2; Wu, Lidan1; Zhao, Hongmei1; Song, Di1; Su, Hongmei1,2,3 |
刊名 | SCIENCE ADVANCES
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出版日期 | 2017-06-01 |
卷号 | 3期号:6 |
英文摘要 | Although the radical ion pair has been frequently invoked as a key intermediate in DNA oxidative damage reactions and photoinduced electron transfer processes, the unambiguous detection and characterization of this species remain formidable and unresolved due to its extremely unstable nature and low concentration. We use the strategy that, at cryogenic temperatures, the transient species could be sufficiently stabilized to be detectable spectroscopically. By coupling the two techniques (the cryogenic stabilization and the time-resolved laser flash photolysis spectroscopy) together, we are able to capture the ion-pair transient G(+_). Cl-in the chlorine radical-initiated DNA guanine (G) oxidation reaction, and provide direct evidence to ascertain the intricate type of addition/charge separation mechanism underlying guanine oxidation. The unique spectral signature of the radical ion-pair G(+_). Cl-is identified, revealing a markedly intense absorption feature peaking at 570 nm that is distinctive from G(+_) alone. Moreover, the ion-pair spectrum is found to be highly sensitive to the protonation equilibria within guanine-cytosine base pair (G:C), which splits into two resolved bands at 480 and 610 nm as the acidic proton transfers along the central hydrogen bond from G(+_) to C. We thus use this exquisite sensitivity to track the intrabase-pair proton transfer dynamics in the double- stranded DNA oligonucleotides, which is of critical importance for the description of the proton-coupled charge transfer mechanisms in DNA. |
语种 | 英语 |
源URL | [http://ir.iccas.ac.cn/handle/121111/39189] ![]() |
专题 | 化学研究所_光化学实验室 |
作者单位 | 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 2.Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
推荐引用方式 GB/T 7714 | Jie, Jialong,Liu, Kunhui,Wu, Lidan,et al. Capturing the radical ion-pair intermediate in DNA guanine oxidation[J]. SCIENCE ADVANCES,2017,3(6). |
APA | Jie, Jialong,Liu, Kunhui,Wu, Lidan,Zhao, Hongmei,Song, Di,&Su, Hongmei.(2017).Capturing the radical ion-pair intermediate in DNA guanine oxidation.SCIENCE ADVANCES,3(6). |
MLA | Jie, Jialong,et al."Capturing the radical ion-pair intermediate in DNA guanine oxidation".SCIENCE ADVANCES 3.6(2017). |
入库方式: OAI收割
来源:化学研究所
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