羟基自由基和鸟嘌呤-胞嘧啶碱基对反应的密度泛函理论研究
为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶（GC）碱基对上5个氢原子的反应机理.研究结果表明,所有的脱氢反应路径都是放热过程,热力学上五个脱氢反应路径形成自由基的稳定性顺序是（H2b-GC）·〉（GC-H4b）·〉（GC-H6）·〉（GC-H5）·（H8-GC）·,其中H2b反应路径的能量变化最大,说明该反应平衡时的转化率最高.动力学上,相对于反应复合物的局部反应能垒大小顺序是H2b〈H4b〈H5〈H6〈H8．可以看出在H2b夺取路径中能垒最小，表明了该反应能在室温下迅速完成，和...
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| Published in | 物理化学学报 Vol. 31; no. 6; pp. 1007 - 1014 |
|---|---|
| Main Author | |
| Format | Journal Article |
| Language | Chinese |
| Published |
上海大学化学系，创新药物研究中心，上海200444
2015
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| Subjects | |
| Online Access | Get full text |
| ISSN | 1000-6818 |
| DOI | 10.3866/PKU.WHXB201504171 |
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| Abstract | 为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶（GC）碱基对上5个氢原子的反应机理.研究结果表明,所有的脱氢反应路径都是放热过程,热力学上五个脱氢反应路径形成自由基的稳定性顺序是（H2b-GC）·〉（GC-H4b）·〉（GC-H6）·〉（GC-H5）·（H8-GC）·,其中H2b反应路径的能量变化最大,说明该反应平衡时的转化率最高.动力学上,相对于反应复合物的局部反应能垒大小顺序是H2b〈H4b〈H5〈H6〈H8．可以看出在H2b夺取路径中能垒最小，表明了该反应能在室温下迅速完成，和实验结果一致．综合考虑热力学和动力学方面的分析，发现H2b夺取反应最容易进行，次之是H4b夺取反应，然后是H6和H5．而H8的夺取反应很难发生，和实验观察到的8位加成产物现象一致． |
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| AbstractList | 为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶（GC）碱基对上5个氢原子的反应机理.研究结果表明,所有的脱氢反应路径都是放热过程,热力学上五个脱氢反应路径形成自由基的稳定性顺序是（H2b-GC）·〉（GC-H4b）·〉（GC-H6）·〉（GC-H5）·（H8-GC）·,其中H2b反应路径的能量变化最大,说明该反应平衡时的转化率最高.动力学上,相对于反应复合物的局部反应能垒大小顺序是H2b〈H4b〈H5〈H6〈H8．可以看出在H2b夺取路径中能垒最小，表明了该反应能在室温下迅速完成，和实验结果一致．综合考虑热力学和动力学方面的分析，发现H2b夺取反应最容易进行，次之是H4b夺取反应，然后是H6和H5．而H8的夺取反应很难发生，和实验观察到的8位加成产物现象一致． O641; 为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶(GC)碱基对上5个氢原子的反应机理.研究结果表明,所有的脱氢反应路径都是放热过程,热力学上五个脱氢反应路径形成自由基的稳定性顺序是(H2b-GC)?>(GC-H4b)?>(GC-H6)?>(GC-H5)?~(H8-GC)?,其中H2b反应路径的能量变化最大,说明该反应平衡时的转化率最高.动力学上,相对于反应复合物的局部反应能垒大小顺序是H2b<H4b<H5<H6<H8,可以看出在H2b夺取路径中能垒最小,表明了该反应能在室温下迅速完成,和实验结果一致.综合考虑热力学和动力学方面的分析,发现H2b夺取反应最容易进行,次之是H4b夺取反应,然后是H6和H5.而H8的夺取反应很难发生,和实验观察到的8位加成产物现象一致. |
| Abstract_FL | To address problems such as aging, mutation, and cancer, it is of great importance to understand the damage mechanism of DNA induced by hydroxyl radical. In this study, the abstraction reaction mechanism of hydroxyl radical with guanine-cytosine (GC) base pair in aqueous phase under the polarized continuum model (PCM) has been explored by using density functional theory (DFT). The results indicated that al the abstraction reactions in GC base pair were thermodynamical y exothermic, and the stability of dehydrogenation radicals decreased in the order of (H2b-GC)?>(GC-H4b)?>(GC-H6)?>(GC-H5)?~(H8-GC)?. The reaction energy of H2b abstraction pathway was the lowest among al investigated pathways, thus indicating that the reaction conversion of (H2b-GC)?was the highest. In the five hydrogen abstraction pathways, the local energy barriers with respect to the corresponding reactant complexes increased in the fol owing order:H2b<H4b<H5<H6<H8, thereby suggesting that the H2b abstraction pathway was the most rapid. Thus, H2b abstraction process was the most likely favorable reaction pathway. Another compatible pathway would be the H4b abstraction, fol owed by H6 and H5 abstraction pathways in thermodynamics and in kinetics. H8 abstraction process was the least favorable pathway, as consistent with the formation of hydroxylation adduct observed experimental y rather than the hydrogen abstraction radical. |
| Author | 李敏杰 刁玲 寇莉 李重杲 陆文聪 |
| AuthorAffiliation | 上海大学化学系,创新药物研究中心,上海200444 |
| AuthorAffiliation_xml | – name: 上海大学化学系，创新药物研究中心，上海200444 |
| Author_FL | LU Wen-Cong LI Zhong-Gao DIAO Ling KOU Li LI Min-Jie |
| Author_FL_xml | – sequence: 1 fullname: LI Min-Jie – sequence: 2 fullname: DIAO Ling – sequence: 3 fullname: KOU Li – sequence: 4 fullname: LI Zhong-Gao – sequence: 5 fullname: LU Wen-Cong |
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| ClassificationCodes | O641 |
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| Copyright | Copyright © Wanfang Data Co. Ltd. All Rights Reserved. |
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| DocumentTitleAlternate | Hydroxyl Radical Reaction with the Guanine-Cytosine Base Pair： A Density Functional Theory Study |
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| Keywords | Guanine-cytosine base pair DNA oxidative damage 反应机理 密度泛函理论 羟基自由基 DNA氧化损伤 Reaction mechanism Density functional theory 鸟嘌呤-胞嘧啶碱基对 Hydroxyl radical |
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| Notes | DNAoxidative damage; Hydroxyl radical; Guanine-cytosine base pair;Reaction mechanism; Density functional theory 11-1892/O6 LI Min-Jie DIAO Ling KOU Li LI Zhong-Gao LU Wen-Cong （Innovative Drug Research Center, Department of Chemistry, Shanghai University, Shanghai 200444, P. R. China） To address problems such as aging, mutation, and cancer, it is of great importance to understand the damage mechanism of DNA induced by hydroxyl radical. In this study, the abstraction reaction mechanism of hydroxyl radical with guanine-cytosine （GC） base pair in aqueous phase under the polarized continuum model （PCM） has been explored by using density functional theory （DFT）. The results indicated that all the abstraction reactions in GC base pair were thermodynamically exothermic, and the stability of dehydrogenation radicals decreased in the order of （H2b-GC）〉（GC-H4b）〉（GC-H6）〉（GC-H5）-（H8-GC）. The reaction energy of H2b abstraction pathway was the lowest among all investigated pathways, thus indicating that the reaction conversio |
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| Publisher | 上海大学化学系，创新药物研究中心，上海200444 |
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| Snippet | 为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶（GC）碱... O641; 为了解决年龄衰老、基因突变和癌症等问题,理解DNA的氧化损伤机理非常重要.本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧... |
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| SubjectTerms | DNA氧化损伤 反应机理 密度泛函理论 羟基自由基 鸟嘌呤-胞嘧啶碱基对 |
| Title | 羟基自由基和鸟嘌呤-胞嘧啶碱基对反应的密度泛函理论研究 |
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