水液相下脯氨酸Cu^(2+)配合物手性反转的密度泛函理论研究  

A Density Functional Theory Study of Chiral Inversion of Pro·Cu^(2+) Complex in Water-Liquid Phase

作　　者：孙士红 陈凤清[2] 高浩溟 王亚玲[4] 姜春旭 王佐成[2] SUN Shihong;CHEN Fengqing;GAO Haoming;WANG Yaling;JIANG Chunxu;WANG Zuocheng(Department of Basic Medicine,Baicheng Medical College,Baicheng Jilin 137000,China;Theoretical Computing Center,Baicheng Normal University,Baicheng Jilin 137000,China;Ophthalmology Department,PLA 321st Hospital,Baicheng Jilin 137000,China;Department of Informatization,Baicheng Medical College,Baicheng Jilin 137000,China)

机构地区：[1]白城医学高等专科学校基础医学院,吉林白城137000 [2]白城师范学院理论计算中心,吉林白城137000 [3]解放军第三二一医院眼科,吉林白城137000 [4]白城医学高等专科学校信息化学院,吉林白城137000

出　　处：《复旦学报（自然科学版）》2022年第4期472-484,共13页Journal of Fudan University：Natural Science

基　　金：吉林省教育厅科学研究项目(JJKH20200002KJ);吉林省自然科学基金(20130101131JC)。

摘　　要：采用密度泛函理论的M06和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水液相下脯氨酸二价铜(Pro·Cu^(2+))配合物的手性反转反应。研究发现:Pro·Cu^(2+)的手性反转可以在H质子利用水分子(簇)做媒介,以氨基N、羰基O和Cu为桥梁迁移的反应通道实现。势能面计算表明:H质子以氨基N为桥迁移的反应通道最具优势,反应的吉布斯自由能垒是121.4kJ·mol^(-1)。结果表明,水液相下的Pro·Cu^(2+)分子只能极缓慢地旋光异构。We have studied the chiral inversion reaction of Pro·Cu(Ⅱ)complex in water-liquid phase using the methods of M06 and MN15 based on the density functional theory combining with SMD model of self-consistent reaction field theory.The study reveals that chiral inversion of Pro·Cu(Ⅱ)can be realized in the reaction channel in which H proton is transferred using water molecules(clusters)as the medium and amino N,carbonyl O and Cu as a bridge.The potential energy surface shows the reaction channel in which H proton is transferred with amino N as a bridge is the most advantageous,and the Gibbs free energy barrier of the reaction is 121.4 kJ·mol^(-1).The results show that Pro·Cu(Ⅱ)molecules in water-liquid phase can only be optically isomerized very slowly.

关 键 词：脯氨酸 Cu^(2+) 密度泛函理论 自洽反应场理论 过渡态 手性反转 能垒 

分 类 号：O641.12[理学—物理化学]