水液相环境α-丙氨酸Ni(Ⅱ)配合物的对映异构机理  

Enantiomerization Mechanism ofα-Alanine Ni(Ⅱ)Complex in Water-Liquid Environment

作　　者：高峰[1] 徐亚华 孙永欣[1] 杨清荟 张雪娇[3] 佟华[1] 王佐成[1] GAO Feng;XU Yahua;SUN Yongxin;YANG Qinghui;ZHANG Xuejiao;TONG Hua;WANG Zuocheng(College of Physics,Baicheng Normal University,Baicheng 137000,Jilin,China;Department of Cardiology,Baicheng Central Hospital,Baicheng 137000,Jilin,China;Network Center,Baicheng Normal University,Baicheng 137000,Jilin,China)

机构地区：[1]白城师范学院物理学院,吉林白城137000 [2]白城市中心医院心血管内科,吉林白城137000 [3]白城师范学院网络中心,吉林白城137000

出　　处：《武汉大学学报（理学版）》2022年第6期655-664,共10页Journal of Wuhan University:Natural Science Edition

基　　金：吉林省教育厅科学研究规划项目(JJKH20210010KJ);吉林省科技发展计划自然科学基金(20130101131JC)

摘　　要：采用密度泛函理论(DFT)的M06和MN15方法,结合极化连续介质的SMD模型方法,研究了水液相下α-丙氨酸(α-Ala)二价镍(α-Ala·Ni^(2+))配合物的对映异构化机制。反应通道研究发现:α-Ala·Ni^(2+)可以在以羰基O、氨基N和Ni作H质子迁移桥梁的3个通道实现。势能面计算表明:以氨基N作质子迁移桥梁的反应通道最具优势,反应的决速步能垒是92.6 kJ/mol。结果表明:水液相下α-Ala·Ni^(2+)会缓慢地消旋,因此只能短期且少量地用于生命体同补α-丙氨酸和二价镍。We have studied the enantiomerization mechanism ofα-alanine nickelous complex(α-Ala·Ni^(2+))in water-liquid environment using the methods of M06 and MN15 based on the density functional theory(DFT)combining with polarized continuum of SMD model.It is identified thatα-Ala·Ni^(2+)could be realized when hydrogen proton is transferred using the carbonyl oxygen,the amino nitrogen or Ni as a bridge in three pathways respectively.The calculations of potential energy surface show that the pathway that hydrogen proton is transferred using the amino nitrogen as a bridge is the most advantageous.The energy barrier of the reaction rate-determining steps is 92.6 kJ/mol.The results show thatα-Ala·Ni^(2+)can be racemized slowly in water-liquid environment,and then it can only be used for a short time and in small amounts in living bodies to supplementα-alanine and Ni^(2+)simultaneously.

关 键 词：Α-丙氨酸 Ni(Ⅱ) 密度泛函理论 对映异构 能垒 

分 类 号：O641.4[理学—物理化学]