气相环境下丙氨酸Ca<sup>2+</sup>配合物的手性转变机理及水分子的催化作用

doi:10.3785/j.issn.1008-9497.2020.05.015

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摘要采用基于密度泛函理论的M06方法，研究了气相环境下2种稳定构型的丙氨酸（Ala）与Ca²⁺配合物的手性转变及水分子的催化。研究发现，Ala_1·Ca²⁺的手性转变有a和b 2个通道，a通道是α-氢只以羰基氧为桥迁移；b通道是α-氢迁移到羰基氧后，氨基上的质子在纸面内侧向α-碳迁移。Ala_2·Ca²⁺的手性转变有a、b、c、d 4个通道，a和b通道分别是羧基内质子迁移后，α-氢只以羰基氧为桥迁移和α-氢迁移到羰基氧接质子从氨基氮向α-碳迁移；c通道是钙与氮的配位键断裂后，α-氢向氨基氮迁移；d通道是钙与氮的配位键断裂后，Ala_2·Ca²⁺向Ala_1·Ca²⁺异构，再接Ala_1·Ca²⁺的手性转变。势能面计算表明，Ala_1·Ca²⁺手性转变的a通道具有优势，总包能垒为134.8 kJ·mol^－1，Ala_2·Ca²⁺手性转变的d通道具有优势，总包能垒为235.3 kJ·mol^－1；水分子的催化使能垒分别降至40.8和141.3 kJ·mol^－1。结果表明，Ca²⁺对Ala的手性转变具有催化作用，水分子对丙氨酸Ca²⁺配合物的手性转变具有极好的催化作用。

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关键词 ：丙氨酸, 钙离子（Ca²⁺）, 手性转变, 密度泛函理论, 过渡态, 能垒

Abstract：The catalysis of water molecules and the chiral transition of two stable configurations of alanine (Ala) and Ca²⁺ complexes in gas phase have been studied using the M06 method based on density functional theory. The study shows that the Ala_1·Ca²⁺ chiral transition has two pathways a and b. In pathway a, α-H is transferred merely using carbonyl O atom as a bridge. In pathway b, the proton on the amino group transfers to α-C from inside paper after α-H is transferred to carbonyl O atom. The Ala_2·Ca²⁺ chiral transition has four pathways a, b, c and d. In pathway a, α-H is transferred merely using carbonyl O atom as a bridge after the transition of proton on the carboxyl group. In pathway b, α-H is transferred to carbonyl O atom and then proton transfers from the amino group N atom to α-C after the transition of proton on the carboxyl group. In pathway c, α-H is transferred to the amino group N atom after the coordination bond between calcium and nitrogen is broken. In pathway d, the coordination bond between calcium and nitrogen is broken and Ala_2·Ca²⁺ is isomerized to Ala_1·Ca²⁺, then Ala_1·Ca²⁺achieves the chiral transition. The potential energy surface calculation shows that the dominant pathway of the chiral transition of Ala_1·Ca²⁺is pathway a, and the total energy barrier is 134.8 kJ·mol^－1. The dominant pathway of the chiral transition of Ala_2·Ca²⁺is pathway d, and the total energy barrier is 235.3 kJ·mol^－1. The catalysis of water molecules then reduces them to 40.8 kJ·mol^－1and 141.3 kJ·mol^－1respectively. The results show that Ca²⁺ has a catalytic effect on the chiral transition of Ala, and water molecule has an excellent catalytic effect on the chiral transition of Ala and Ca²⁺ complexes.

Key words： α-alanin(Ala) Ca²⁺ chiral transition density functional theory transition state energy barrier

收稿日期: 2019-11-16

ZTFLH:

O641.12

基金资助:吉林省科技发展计划自然科学基金项目（20130101308JC; 20160101308JC）.

通讯作者: ORCID：http://orcid.org/0000? 0003-2959-6190，E?mail：yxc0622@163.com E-mail: yxc0622@163.com

作者简介: 徐锐英（1979—），ORCID：http://orcid.org/0000?0002-6795-7558，男，硕士，副教授，主要从事计算化学研究，E?mail: 272754351@qq.com.。

引用本文:

徐锐英, 刘芳, 马宏源, 张雪娇, 潘宇, 杨晓翠, 王佐成. 气相环境下丙氨酸Ca²⁺配合物的手性转变机理及水分子的催化作用[J]. 浙江大学学报（理学版）, 2020, 47(5): 630-641.
XU Ruiying, LIU Fang, MA Hongyuan, ZHANG Xuejiao, PAN Yu, YANG Xiaocui, WANG Zuocheng. Chiral transition mechanism of Ala and Ca²⁺ complexes in gas phase and catalysis of water molecules. Journal of ZheJIang University(Science Edition), 2020, 47(5): 630-641.

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http://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2020.05.015 或 http://www.zjujournals.com/sci/CN/Y2020/V47/I5/630

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