中山大学学报（自然科学版）2018，Vol.57Issue(3)：96-107,12.DOI:10.13471/j.cnki.acta.snus.2018.03.014
水环境下具有氨基和羧基间双氢键的缬氨酸旋光异构及羟自由基致损伤的机理
Mechanism of optical isomerization of valine molecules with dual-hydrogen bonds between amino and carboxyl groups and the damage induced by hydroxyl radicals in water environment
摘要
Abstract
The mechanism of optical isomerization of valine molecules with dual-hydrogen bonds between amino and carboxyl groups and the damage induced by hydroxyl radicals in water environment were stud-ied by using MP2/6-311 ++G(2df,pd)//B3LYP/6-31 +G(d,p)dual-theory and SMD model method for self consistent reaction field(SCRF)theory.The study of reaction channels showed that there were three channels a,b and c in the optical isomer reaction of valine in water environment.Using water cluster as medium,the protons transfered from one side of the α-carbon to the other side with N atom of amino group,O atom of carbonyl group and carboxyl group as bridges.The hydrogen abstraction reaction which damaged the valine molecules happened in channel a,and the water molecules were assistants. The potential energy surface calculation showed that when two or three water clusters were used as hydro-gen transport medium,they acted a good catalytic action on the process of hydrogen-transfer of Optical I-somerization,and reduced the barrier of reaction vs naked reaction.Water solution effect had good cata-lytic activity in channel a,but catalytic activities were not obvious in channel b and c.The reaction bar-rier of hydrogen abstraction reaction which damaged the valine molecules with water molecules as assis-tants was low.The water solution effect has a big impediment effect on this reaction.关键词
旋光异构/缬氨酸/密度泛函理论/过渡态/微扰论/溶剂效应/羟自由基/损伤Key words
optical isomerization/valine/density functional theory/transition state/perturbation theo-ry/solvent effect/hydroxyl radical/damage分类
化学化工引用本文复制引用
赵宇,汤振宇,吴怡,张育凯,杨晓翠,王佐成..水环境下具有氨基和羧基间双氢键的缬氨酸旋光异构及羟自由基致损伤的机理[J].中山大学学报（自然科学版）,2018,57(3):96-107,12.基金项目
吉林省科技发展计划自然科学基金(20130101308JC) （20130101308JC）
