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端粒 G-四链体结构中低能 UV 光子直接吸收产生的鸟嘌呤自由基：钾离子的影响。

Guanine Radicals Generated in Telomeric G-Quadruplexes by Direct Absorption of Low-Energy UV Photons: Effect of Potassium Ions.

机构信息

LIDYL, CEA, CNRS, Université Paris-Saclay, F-91191 Gif-sur-Yvette, France.

Univ Lyon, ENS de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, F-69342 Lyon, France.

出版信息

Molecules. 2020 Apr 30;25(9):2094. doi: 10.3390/molecules25092094.

DOI:10.3390/molecules25092094
PMID:32365780
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7248781/
Abstract

The study deals with the primary species, ejected electrons, and guanine radicals, leading to oxidative damage, that is generated in four-stranded DNA structures (guanine quadruplexes) following photo-ionization by low-energy UV radiation. Performed by nanosecond transient absorption spectroscopy with 266 nm excitation, it focusses on quadruplexes formed by folding of GGG(TTAGGG) single strands in the presence of K ions, . The quantum yield for one-photon ionization (9.4 × 10) was found to be twice as high as that reported previously for . The overall population of guanine radicals decayed faster, their half times being, respectively, 1.4 and 6.7 ms. Deprotonation of radical cations extended over four orders of magnitude of time; the faster step, concerning 40% of their population, was completed within 500 ns. A reaction intermediate, issued from radicals, whose absorption spectrum peaked around 390 nm, was detected.

摘要

该研究涉及在低能紫外辐射光致电离后，在四条链 DNA 结构（鸟嘌呤四链体）中产生的引发氧化损伤的原始物种、射出电子和鸟嘌呤自由基。采用 266nm 激发的纳秒瞬态吸收光谱进行研究，重点关注在 K 离子存在下通过单链 GGG(TTAGGG)折叠形成的四链体。单光子电离的量子产率（9.4×10）是先前报道的的两倍。鸟嘌呤自由基的整体衰减速度更快，其半衰期分别为 1.4ms 和 6.7ms。自由基阳离子的去质子化过程扩展到时间的四个数量级；其中涉及 40%自由基的较快步骤在 500ns 内完成。检测到一种从自由基产生的反应中间体，其吸收光谱在 390nm 左右达到峰值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/c072613c5489/molecules-25-02094-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/0a68b209d98f/molecules-25-02094-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/d4458a40c47e/molecules-25-02094-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/2493afa447a8/molecules-25-02094-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/ac816a46fcb8/molecules-25-02094-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/073db8ffd125/molecules-25-02094-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/1b28be453abc/molecules-25-02094-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/c22065cce7f5/molecules-25-02094-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/71d4fd0beed2/molecules-25-02094-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/c072613c5489/molecules-25-02094-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/0a68b209d98f/molecules-25-02094-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/d4458a40c47e/molecules-25-02094-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/2493afa447a8/molecules-25-02094-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/ac816a46fcb8/molecules-25-02094-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/073db8ffd125/molecules-25-02094-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/1b28be453abc/molecules-25-02094-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/c22065cce7f5/molecules-25-02094-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/71d4fd0beed2/molecules-25-02094-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5819/7248781/c072613c5489/molecules-25-02094-g009.jpg

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