Deprotonation Kinetics of 1-Methylguanine After One-Electron Oxidation

doi:10.6023/A14090666

Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (11): 1182-1186.DOI: 10.6023/A14090666 Previous Articles

Article

N¹-甲基鸟嘌呤阳离子脱质子动力学的研究

吴丽丹, 节家龙, 刘坤辉, 苏红梅

中国科学院化学研究所分子反应动力学国家重点实验室北京 100190

投稿日期:2014-09-28 发布日期:2014-10-22
通讯作者: 刘坤辉, 苏红梅 E-mail:khliu@iccas.ac.cn;hongmei@iccas.ac.cn
基金资助:
项目受国家自然科学基金(No. 21333012)、"973"基金(No. 2013CB834602)及中国科学院先导专项(No. XDB12020200)资助

Deprotonation Kinetics of 1-Methylguanine After One-Electron Oxidation

Wu Lidan, Jie Jialong, Liu Kunhui, Su Hongmei

State Key Laboratory of Molecular Reaction Dynamics, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2014-09-28 Published:2014-10-22
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21333012), the National Basic Research Program of China (No. 2013CB834602), and the Chinese Academy of Sciences (No. XDB12020200).

Among the four natural DNA bases, guanine (G) is the most sensitive to oxidation due to its lowest oxidation potential. When G base is oxidized to guanine cation radical (G^+·), it will deprotonate from both the imino proton N¹-H and the amino proton N²-H. According to the pKa values for N¹-H and N²-H deprotonation, the main deprotonation site in G base is N¹-H which would interfere with the N²-H deprotonation, making the kinetics of N²-H deprotonation difficult to be measured. Herein, the N²-H deprotonation kinetics is investigated using 1-methylguanosine (mG), where N¹-H is substituted by methyl group to avoid the N¹-H deprotonation and N⁹-H is substituted by ribose to ensure enough solubility of methylguanine in water, by nanosecond transient absorption (ns-TA) spectroscopy. By 355 nm photolysis of Na₂S₂O₈, the highly oxidizing radical SO₄^-· is generated, which will oxidize mG to mG^+· instantaneously. The time-resolved absorption spectra obtained for reaction of mG with SO₄^-· exhibits transient absorptions for mG(N²-H)^· featured by absorption band at 600 nm, indicating that the mG^+· deprotonation product is mG(N²-H)^· and the deprotonation site is therefore validated to be N²-H. The mG concentration dependence of mG(N²-H)^· formation rate constant is assessed through changing the mG concentration from 0.25 mmol·L^-1 to 5 mmol·L^-1. The concentration dependence experiment reveals that the rate-limiting step to form mG(N²-H)^· is the bimolecular reaction of mG with SO₄^-· when mG concentration is lower than 2 mmol·L^-1 and the bimolecular reaction rate constant to form mG^+· is (3.7±0.1)×10⁹ L·mol^-1·s^-1; when mG concentration is above 2 mmol·L^-1, the rate-limiting step to form mG(N²-H)^· is the first-order mG^+· deprotonation and the N²-H deprotonation rate constant is (7.1±0.2)×10⁶ s^-1. Furthermore, the N²-H deprotonation rate constant is measured at different temperatures varying from 278 K to 298 K. According to Arrhenius equation, the activation energy barrier for the N²-H deprotonation is determined to be 19.9±1.0 kJ· mol^-1. These results can provide valuable kinetic information on the oxidative damage of DNA.

Key words: 1-methylguanine, deprotonation, one-electron oxidation, rate constant, activation energy barrier

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Wu Lidan, Jie Jialong, Liu Kunhui, Su Hongmei. Deprotonation Kinetics of 1-Methylguanine After One-Electron Oxidation[J]. Acta Chimica Sinica, 2014, 72(11): 1182-1186.

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N¹-甲基鸟嘌呤阳离子脱质子动力学的研究

Deprotonation Kinetics of 1-Methylguanine After One-Electron Oxidation

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N1-甲基鸟嘌呤阳离子脱质子动力学的研究

Deprotonation Kinetics of 1-Methylguanine After One-Electron Oxidation

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N¹-甲基鸟嘌呤阳离子脱质子动力学的研究