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浙江大学学报（理学版）
浙江大学学报（理学版）  2019, Vol. 46 Issue (1): 48-57    DOI: 10.3785/j.issn.1008-9497.2019.01.007
物理学     
水环境下羧基与氨基间为单氢键的α-Ala旋光异构及羟自由基和氢氧根的作用
闫红彦1, 王佐成2, 佟华2, 杨晓翠2
1.白城师范学院 计算机科学学院，吉林 白城 137000
2.白城师范学院物理学院，吉林 白城 137000
Effect of optical isomerism of α-Ala molecules with hydrogen bonds between carboxyl groups and amino and the roles of hydroxyl radicals and hydroxyl group in water environment
YAN Hongyan1, WANG Zuocheng2, TONG Hua2, YANG Xiaocui2
1.Computer Science College, Baicheng Normal University, Baicheng 137000, Jilin Province, China
2.College of Physics, Baicheng Normal University, Baicheng 137000, Jilin Province, China
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摘要： 采用密度泛函理论的B3LYP方法、微扰理论的MP2方法和自洽反应场（SCRF）理论的SMD模型方法，研究了水环境下羧基与氨基间为单氢键的α-Ala旋光异构及羟自由基和氢氧根作用的反应。研究发现：α-Ala的旋光异构可在a和b两个通道实现，a通道为羧基顺反异构后，水分子簇作媒介质子以氨基为桥从α碳的一侧向另一侧迁移；b通道为水分子簇作媒介，质子从α碳向氨基氮的迁移与羧基顺反异构协同进行。在a通道，羟自由基水分子簇可致α-Ala损伤。势能面计算表明：水环境下，在a通道3个水分子簇作氢迁移媒介，决速步能垒为113.37 kJ·mol-1，氢氧根水分子簇的催化使该能垒降到64.45 kJ·mol-1；在b通道2个水分子簇作氢迁移媒介，决速步能垒为135.00 kJ·mol-1。羟自由基水分子簇致α-Ala损伤的能垒在水分子抽氢和羟自由基抽氢时分别为24.47和 80.60 kJ·mol-1。
关键词： α-丙氨酸;  羟自由基;  氢氧根;  密度泛函理论;  过渡态;  微扰理论;  自洽反应场;  旋光异构    
Abstract: The title reaction is studied by using the B3LYP method of density functional theory, the MP2 method of perturbation theory and the SMD model method based on self-consistent reaction field (SCRF) theory. The research shows that there are two channels a and b in the optical isomer reaction of α-Ala. In channel a, the proton is transferred from the side of the α-carbon to the other side with the amino as the bridge after the carboxyl anti-isomeric using water clusters as medium, and hydroxyl radicals of water clusters can damage the α-Ala. In channel b, the transfer of proton from chiral carbon to amino groups is coordinated with the anti-isomerism of carboxyl groups with water clusters as medium. The potential energy surface calculation shows that the energy barrier of rate-limiting step is 113.37 kJ·mol－1 with three water molecule clusters as hydrogen transfer agents in channel a, while the hydroxyl groups reduce the barrier to 64.45 kJ·mol－1 in water liquid environment. In channel b, the energy barrier of rate-limiting step is 135.00 kJ·mol－1 with two water molecule clusters as hydrogen transfer agents. The energy barrier of hydrogen abstraction reaction which damage the α-Ala molecules is 24.47 kJ·mol－1 by water molecules and 80.60 kJ·mol－1 by hydroxyl radicals, relatively.
Key words: α-Ala    hydroxyl radical    hydroxyl group    density functional theory    transition state    perturbation theory    self-consistent reaction field    optical isomerism
收稿日期: 2017-12-10 出版日期: 2019-01-25
CLC:  O641.12  
基金资助: 吉林省科技发展计划项目（20130101308JC）.
作者简介: 闫红彦（1979—），ORCID：http：//orcid.org/0000-0002-3710-4669. 男，硕士，副教授，主要从事计算机及应用化学相关研究，E- mail：40591830@qq.com.
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引用本文:

闫红彦, 王佐成, 佟华, 杨晓翠. 水环境下羧基与氨基间为单氢键的α-Ala旋光异构及羟自由基和氢氧根的作用[J]. 浙江大学学报（理学版）, 2019, 46(1): 48-57.

YAN Hongyan, WANG Zuocheng, TONG Hua, YANG Xiaocui. Effect of optical isomerism of α-Ala molecules with hydrogen bonds between carboxyl groups and amino and the roles of hydroxyl radicals and hydroxyl group in water environment. Journal of ZheJIang University(Science Edition), 2019, 46(1): 48-57.

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https://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2019.01.007    或    https://www.zjujournals.com/sci/CN/Y2019/V46/I1/48

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