水液相下两性Lys分子手性反转的密度泛函理论研究  

The Density Function Theoretical Study on the Chiral Flip ofAmphoteric Lysine Molecule in Water-Liquid Phase Environment

作　　者：崔金玉 蒋倩云 王丽 王聪 邵思佳 王佐成[2] 姜春旭 李冰[2] CUI Jinyu;JIANG Qianyun;WANG Li;WANG Cong;SHAO Sijia;WANG Zuocheng;JIANG Chunxu;LI Bing(Basic Courses Teaching and Research Department,Yingkou Institute of Technology,Yingkou Liaoning 115014,China;Theoretical Computing Center,Baicheng Normal University,Baicheng Jilin 137099,China)

机构地区：[1]营口理工学院基础教研部,辽宁营口115014 [2]白城师范学院理论计算中心,吉林白城137099

出　　处：《江西师范大学学报（自然科学版）》2024年第1期83-93,共11页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：吉林省自然科学基金(20160101308JC),营口理工学院科研团队课题(TD202003);辽宁省教育厅科学技术研究课题(LJKMZ20221858,L2020006)资助项目.

摘　　要：该文采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了在水液相下两性赖氨酸分子的手性反转.反应通道研究发现:反应可以在α-H以羰基O为桥、以氨基N为桥以及α-H迁移到羰基O后氨基H再向α-C迁移的3个通道上实现.势能面计算结果表明:在隐性溶剂效应下3个反应通道基本没有优劣之分,速度决定步骤能垒为233.6~243.0 kJ·mol^(-1);在显性溶剂效应下α-H以氨基N为桥的反应通道为优势通道,速度决定步骤能垒为110.0~114.3 kJ·mol^(-1).计算结果表明:在水液相下光学纯的手性赖氨酸分子可以缓慢地消旋,生命体不宜长期补充赖氨酸.The chiral flip of amphoteric lysine molecule has been studied in water-liquid phase environment by means of M06-2X and MN15 methods based on density functional theory and SMD model method of self consistent reaction field theory.The study of reaction channels shows that the reaction can be achieved in the following three channels that are the carbonyl O atom as the bridge atα-H,the amino group N as the bridge atα-H or amino group H transfers toα-C after theα-H transferring to carbonyl O atom.The potential energy surface shows that there is almost no distinction of good or bad among these three channels under the effect of recessive solvent,and the energy barrier of the rate-determining step is between 233.6 kJ·mol^(-1)and 243.0 kJ·mol^(-1).The reaction channel that the amino group N as the bridge atα-H has advantages under the effect of recessive solvent and the energy barrier of the rate-determining step is between 110.0 kJ·mol^(-1)and 114.3 kJ·mol^(-1).The results show that optically pure chiral lysine molecule can racemize slowly in water-liquid phase environment,long-term supplementation of lysine is not suitable for life.

关 键 词：赖氨酸 手性反转 密度泛函理论 过渡态 溶剂效应 能垒 

分 类 号：O641.12[理学—物理化学]