UV-Induced Adenine Radicals Induced in DNA A-Tracts: Spectral and Dynamical Characterization.

UV-Induced Adenine Radicals Induced in DNA A-Tracts: Spectral and Dynamical Characterization.
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DOI:
10.1021/acs.jpclett.6b01831
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发表时间:
2016-10-06
影响因子:
5.7
通讯作者:
Markovitsi, Dimitra
Markovitsi, Dimitra
中科院分区:
化学2区
文献类型:
--
作者:
Banyasz, Akos;Ketola, Tiia-Maaria;Munoz-Losa, Aurora;Rishi, Sunny;Adhikary, Amitava;Sevilla, Michael D.;Martinez-Fernandez, Lara;Improta, Roberto;Markovitsi, Dimitra

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由266 nm激光脉冲单光子和双光子电离产生的DNA单链和双链(Da)20和(Da)20·(Dt)20产生的腺基自由基在600 nm处衰减,半衰期分别为1.0±0.1ms和4±1ms。当电离最初形成阳离子自由基时,检测到的(Da)20的自由基通过它们的吸收光谱被定量地鉴定为N6去质子腺基自由基,这是用TD-DFT量子力学计算的。理论计算表明,阳离子自由基的去质子化只引起微弱的光谱变化,这与捕获在低温玻璃中的腺基自由基和去质子化自由基的光谱一致。
Adenyl radicals generated in DNA single and double strands, (dA)20 and (dA)20•(dT)20, by one- and two-photon ionization by 266 nm laser pulses decay at 600 nm with half-times of 1.0 ± 0.1 and 4 ± 1 ms, respectively. While ionization initially forms the cation radical, the radicals detected for (dA)20 are quantitatively identified as N6-deprotonated adenyl radicals by their absorption spectrum, which is computed quantum mechanically employing TD-DFT. Theoretical calculations show that deprotonation of the cation radical induces only weak spectral changes, in line with the spectra of the adenyl radical cation and the deprotonated radical trapped in low temperature glasses.
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