中山大学学报（自然科学版）2016，Vol.55Issue(5)：57-65,9.DOI:10.13471/j.cnki.acta.snus.2016.05.011
水环境下基于氨基作氢迁移桥梁α－丙氨酸的手性转变机制
Chiral transition mechanism of α-lalanine molecule under the water environment based on anmino used as hydrogen transfer bridges
摘要
Abstract
Based on anmino used as hydrogen transfer bridges,chiral transition mechanism of α-alanine molecule was studied under the water environment through the B3LYP methods of density functional theo-ry and the MP2 methods of perturbation theory as well as the smd models of SCRF.The result of structur-al analysis suggested that the bond angles 1 C -1 3H -1 4O and 1 8O -1 5H -6N between transition state aTS2·2H2 O of seven membered ring and aTS2·3H2 O of nine membered ring were significantly larger than that 1 C -1 3H -1 4O and 1 4O -1 5H -6N of transition state aTS2·1 H2 O of five membered ring. There were two channels in the chiral transition reaction,in which one the hydrogen of chiral carbon used the imino N as a bridge and was transferred to the other side to achieve chiral transition,the other that was firstly transferred to carbonyl and then to the other side using amino as a bridge.Calculations of po-tential energy surface showed that the first channel was the dominant reaction channel,where the process of the hydrogen from chiral carbon to amino was the rate determining step and the energy barrier is re-duced to 1 22.5 kJ·mol -1 when using three water molecules as transfer media.The water molecules had good catalytic effect on the proton transfer in α-Ala molecule,and the solvent effect on water made the energy barrier of the non proton transfer reaction increase slightly.关键词
手性转变/α-Ala/密度泛函理论/微扰理论/自洽反应场/过渡态Key words
chiral transition/α-Ala/density functional theory/perturbation theory/SCRF/transi-tion state分类
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王彦全,王佐成,闫红彦,佟华..水环境下基于氨基作氢迁移桥梁α－丙氨酸的手性转变机制[J].中山大学学报（自然科学版）,2016,55(5):57-65,9.基金项目
吉林省科技发展计划资助项目 （）
