气相α-丙氨酸二价锌配合物手性转变的密度泛函理论研究  

Chiral transition mechanism of Zn(Ⅱ) and α-Ala complexes in gas phase:A density functional theory study

作　　者：车立新[1] 张雪娇 刘芳[1] 徐锐英 马宏源[1] 潘宇[1] 佟华[1] 王佐成[1] CHE Li-xin;ZHANG Xue-jiao;LIU Fang;XU Rui-ying;MA Hong-yuan;PAN Yu;TONG Hua;WANG Zuo-cheng(College of Physics,Baicheng Normal University,Baicheng 137000,China;Communication College,Baicheng Normal University,Baicheng 137000,China)

机构地区：[1]白城师范学院物理学院,吉林白城137000 [2]白城师范学院传媒学院,吉林白城137000

出　　处：《云南大学学报（自然科学版）》2020年第5期966-976,I0002,共12页Journal of Yunnan University(Natural Sciences Edition)

基　　金：吉林省科技发展计划自然科学基金(20160101308JC);吉林省教育厅科学研究规划(JJKH20200002KJ)。

摘　　要：采用密度泛函理论的M06和MN15方法,研究了气相α-丙氨酸二价锌(α-Ala·Zn2+)配合物的2种稳定构型(两性的A1和中性的A2)的手性转变.研究发现,A1可通过以氧为桥、氮为桥、锌为桥、氧与氮联合为桥以及氧与甲基碳联合为桥等多种途径进行氢迁移,实现手性转变;A2可通过以氧为桥进行氢迁移,实现手性转变,还可以打开螯合环向A1异构,按A1手性转变的多种途径实现手性转变.势能面研究表明,A1以锌为桥进行氢迁移的手性转变反应具有优势,活化自由能垒是197.2 kJ·mol^-1,A2打开螯合环向A1异构后,再以锌为桥进行氢迁移的手性转变反应具有优势,活化自由能垒是228.7 kJ·mol^-1.结果表明:气相丙氨酸锌可以很好地保持其手性特征.The chiral transition of two stable conformations(amphoteric A1 and neutral A2) of α-Ala·Zn2+complex were investigated by means of M06 and MN15 method based on density functional theory. The study reveals that H of A1 can migrated to realize chiral transition with oxygen, nitrogen, zinc, oxygen with nitrogen and oxygen with methyl carbon as the bridge, respectively. As for A2, the chiral transition can be realized by H migration with oxygen as the bridge, and that can also be realized by various ways of A1 chiral transition after opening the chelate ring to A1 isomerism. The potential energy surface studies indicate that the chiral transition reaction of A1 with Zn atom as a bridge to realize H migration has advantage, and the activation energy is 197.2 kJ·mol^-1. The chiral transition reaction with A2 opening chelating ring to realize isomerization to A1 and then using Zn atom as a bridge to realize H migration has advantage, and the activation energy is 228.7 kJ·mol^-1. The results show that Ala·Zn2+ can maintain its chiral characteristics well.

关 键 词：密度泛函理论 丙氨酸 锌配合物 手性转变 自洽反应场理论 过渡态 能垒 

分 类 号：O641.12[理学—物理化学]