生理环境下二价钙缬氨酸配合物(Val·Ca^(2+))对映异构的DFT研究  

DFT study on enantiomerism of calcium diatomic valine complexes(Val·Ca^(2+))in physiological environment

作　　者：陈静思 刘芳[2] 吴怡 赵宇[2] 王佐成[2] 杨应[2] 姜春旭 CHEN Jingsi;LIU Fang;WU Yi;ZHAO Yu;WANG Zuocheng;YANG Ying;JIANG Chunxu(College of Clinical Medicine,Baicheng Medical College,Baicheng 137000,China;Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,China;Liaoyuan City of Jilin province,Dongfeng County Experimental Middle School,Dongfeng 136300,China)

机构地区：[1]白城医学高等专科学校临床医学院,吉林白城137000 [2]白城师范学院理论计算中心,吉林白城137000 [3]吉林省辽源市东丰县实验中学,吉林东丰136300

出　　处：《中山大学学报(自然科学版)(中英文)》2025年第2期76-85,共10页Acta Scientiarum Naturalium Universitatis Sunyatseni

基　　金：吉林省教育厅科研重点项目(JJKH20240033KJ);吉林省自然科学基金(20160101308C)。

摘　　要：采用基于密度泛函理论(DFT)的M06-2X和MN15杂化交换泛函,结合基于自洽反应场理论处理溶剂效应的SMD模型方法,对生理环境[水液相、310.15 K和1.013×10^(5)Pa(1个标准大气压)]下二价钙缬氨酸(Val·Ca^(2+))手性对映体之间的异构机制进行研究。异构反应通道研究发现:Val·Ca^(2+)的对映异构可以通过羰基O或氨基N做H质子转移桥梁实现。异构过程中驻点的能量图计算表明:质子H以N原子做桥迁移的异构过程具有优势。在水的极性以及水分子(簇)的作用下,反应优势通道速度控制步骤的能垒为118.6~121.9 kJ/mol。研究结果表明:生理环境下二价钙缬氨酸配合物的对映异构速度很慢,其用于生命体补充二价钙和缬氨酸比较安全。The enantiomerism mechanism of chiral enantiomers of calcium diatomic valine(Val·Ca^(2+))was studied by using the hybrid exchange functional method of M06-2X and MN15 based on DFT(density functional theory)and SMD model method with self-consistent reaction field theory under physiological environment[(aqueous liquid phase,310.15 K and 1.013×10^(5) Pa)(1 standard atmosphere)].The observations on reaction channels found that the enantiomerism of Val·Ca^(2+)can be achieved by using carbonyl O or amino N as H proton transfer bridge.The energy diagram calculation of stagnation point in enantiomerism process showed that the enantiomerism process of proton H using N atom as bridge migration has advantages.Under the effect of water polarity and water molecules(clusters),the energy barrier of velocity determination step of the dominant reaction channel is between 118.6 and 121.9 kJ/mol.The results show that the enantiomerism rate of calcium diatomic valine complexes is very slow in physiological environment,and it is safe to supplement calcium bivalent ion and valine in living organisms.

关 键 词：二价钙缬氨酸 溶剂效应 密度泛函理论 对映异构 反应能垒 

分 类 号：O641.12[理学—物理化学]