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 of Amphoteric Lysine Molecule in Water-Liquid Phase Environment
崔金玉 1蒋倩云 1王丽 1王聪 1邵思佳 1王佐成 2姜春旭 2李冰2
作者信息
- 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
- 折叠
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.
Abstract
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 at α-H,the amino group N as the bridge at α-H or amino group H transfers to α-C after the α-H transferring to carbonyl O atom.The potential energy surface shows that there is al-most 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 at α-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Key words
lysine/chiral flip/density functional theory/transition state/solvent effect/energy barrier引用本文复制引用
基金项目
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项目(LJKMZ20221858)
辽宁省教育厅科学技术研究项目(L2020006)
出版年
2024
NETL
NSTL
万方数据