水液相环境下两性α-丙氨酸Fe(Ⅱ)配合物的构型反转  

Configuration Inversion of Amphotericα-Alanine Fe(Ⅱ)Complex in Water-Liquid Phase Environment

作　　者：刘军 姜春旭 胡燠铭 黄丽娟 高峰[3] 马宏源[3] 王佐成[3] LIU Jun;JIANG Chunxu;HU Yuming;HUANG Lijuan;GAO Feng;MA Hongyuan;WANG Zuocheng(College of Computer Science,Baicheng Normal University,Baicheng 137000,Jilin,China;College of Communication,Baicheng Normal University,Baicheng 137000,Jilin,China;College of Physics,Baicheng Normal University,Baicheng 137000,Jilin,China;Library of Baicheng Normal University,Baicheng 137000,Jilin,China)

机构地区：[1]白城师范学院计算机科学学院,吉林白城137000 [2]白城师范学院传媒学院,吉林白城137000 [3]白城师范学院物理学院,吉林白城137000 [4]白城师范学院图书馆,吉林白城137000

出　　处：《武汉大学学报（理学版）》2021年第4期375-385,共11页Journal of Wuhan University:Natural Science Edition

基　　金：吉林省教育厅科学研究规划项目(JJKH20200002KJ);吉林省大学生创新项目(202010206066);吉林省自然科学基金(20160101308JC)。

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,研究了水液相下两性α-丙氨酸与二价铁离子配合物(A·Fe)的构型反转。考察了a、b、c和d共4个反应通道,分别是:α-氢质子以羰基O为桥迁移;α-氢质子迁移到羰基O后,H质子再从氨基N向α-碳迁移;α-氢质子以氨基N为桥迁移;氢负离子以二价铁离子为桥迁移。隐性溶剂效应下d通道最具优势,决速步骤能垒为194.7 kJ/mol;c通道为第二优势通道,决速步骤能垒为222.2 kJ/mol;a和b为劣势通道,决速步骤能垒为262.7 kJ/mol。显性溶剂效应下c通道最具优势,决速步骤能垒降至145.1 kJ/mol;a和b为第二优势通道,决速步骤能垒降至160.4 kJ/mol;d通道为劣势通道,在此通道A·Fe无法消旋。结果表明:水液相环境下A·Fe可以很好地保持其旋光性,α-丙氨酸二价铁盐用于生命体补充二价铁和丙氨酸具有很高的安全性。The configuration inversion of amphotericα-alanine Fe(Ⅱ)(A·Fe)complex is studied in water-liquid phase environment by M06 and MN15 methods based on density functional theory and SMD model method of self consistent reaction field theory.Four reaction channels a,b,c and d are investigated.That the hydrogen is transferred with carbonyl oxygen as the bridge is channel a;that the hydrogen is transferred with carbonyl oxygen and amino nitrogen as the bridge is channel b;that the hydrogen is transferred with amino nitrogen as the bridge is channel c;and that the hydrogen is transferred with iron as the bridge is channel d.The results from potential energy surface show that channel d has the most advantages under the recessive solvent effect and the energy barrier of the rate-determining step is 194.7 kJ/mol;channel c is sub-dominant channel and the energy barrier of the ratedetermining step is 222.2 kJ/mol;a and b are the inferior channel and the energy barrier is 262.7 kJ/mol.But channel c has the most advantages under the dominant solvent effect and the energy barrier of the rate-determining step is reduced to 145.1 kJ/mol,a and b are the sub-dominant channels and the energy barrier is reduced to 160.4 k J/mol,and d is the inferior channel in which A·Fe can not be raced.The results imply that A·Fe can maintain its optical activity well in the water-liquid environment,and α-alanine divalent iron salt has a good safety when it is used to supplement divalent iron and alanine for life.

关 键 词：Α-丙氨酸 二价铁离子 密度泛函理论 自洽反应场理论 构型反转 

分 类 号：O641[理学—物理化学]