Sulfur-centered hemi-bond radicals as active intermediates in S-DNA phosphorothioate oxidation
文献类型:期刊论文
作者 | Jie, Jialong; Xia, Ye; Huang, Chun-Hua; Zhao, Hongmei1; Yang, Chunfan; Liu, Kunhui; Song, Di1; Zhu, Ben-Zhan; Su, Hongmei |
刊名 | NUCLEIC ACIDS RESEARCH
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出版日期 | 2019-12-16 |
卷号 | 47期号:22页码:11514-11526 |
ISSN号 | 0305-1048 |
英文摘要 | Phosphorothioate (PS) modifications naturally appear in bacteria and archaea genome and are widely used as antisense strategy in gene therapy. But the chemical effects of PS introduction as a redox active site into DNA (S-DNA) is still poorly understood. Herein, we perform time-resolved spectroscopy to examine the underlying mechanisms and dynamics of the PS oxidation by potent radicals in free model, in dinucleotide, and in S-oligomer. The crucial sulphur-centered hemi-bonded intermediates P-S therefore S-P- were observed and found to play critical roles leading to the stable adducts of -P-S-S-P-, which are backbone DNA lesion products. Moreover, the oxidation of the PS moiety in dinucleotides d[G(PS)G], d[A(PS)A], d[G(PS)A], d[A(PS)G] and in S-oligomers was monitored in real-time, showing that PS oxidation can compete with adenine but not with guanine. Significantly, hole transfer process from A(+center dot) to PS and concomitant -P-S therefore S-P- formation was observed, demonstrating the base-to-backbone hole transfer unique to S-DNA, which is different from the normally adopted backbone-to-base hole transfer in native DNA. These findings reveal the distinct backbone lesion pathway brought by the PS modification and also imply an alternative -P-S therefore S-P-/-P-S-S-P- pathway accounting for the interesting protective role of PS as an oxidation sacrifice in bacterial genome. |
源URL | [http://ir.rcees.ac.cn/handle/311016/42598] ![]() |
专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
作者单位 | 1.Chinese Acad Sci, Res Ctr Ecoenvironm Sci, State Key Lab Environm Chem & Ecotoxicol, Beijing 100085, Peoples R China 2.Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China 3.Chinese Acad Sci, Inst Chem, BNLMS, Beijing 100190, Peoples R China |
推荐引用方式 GB/T 7714 | Jie, Jialong,Xia, Ye,Huang, Chun-Hua,et al. Sulfur-centered hemi-bond radicals as active intermediates in S-DNA phosphorothioate oxidation[J]. NUCLEIC ACIDS RESEARCH,2019,47(22):11514-11526. |
APA | Jie, Jialong.,Xia, Ye.,Huang, Chun-Hua.,Zhao, Hongmei.,Yang, Chunfan.,...&Su, Hongmei.(2019).Sulfur-centered hemi-bond radicals as active intermediates in S-DNA phosphorothioate oxidation.NUCLEIC ACIDS RESEARCH,47(22),11514-11526. |
MLA | Jie, Jialong,et al."Sulfur-centered hemi-bond radicals as active intermediates in S-DNA phosphorothioate oxidation".NUCLEIC ACIDS RESEARCH 47.22(2019):11514-11526. |
入库方式: OAI收割
来源:生态环境研究中心
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