水液相下二价镁缬氨酸配合物(Val·Mg^(2+))对映异构的密度泛函理论  

Density Functional Theory of Enantiomerism of Bivalent Magnesium Valine Complexes(Val·Mg^(2+))in Aqueous Liquid Phase

作　　者：曲亚楠 杨文富[2,3] 杨应 刘芳[2] 王佐成[2] 姜春旭[2,3] 丛建民 杨震 QU Yanan;YANG Wenfu;YANG Ying;LIU Fang;WANG Zuocheng;JIANG Chunxu;CONG Jianmin;YANG Zhen(Department of Civil Engineering,Baicheng Normal University,Baicheng 137000,Jilin Province,China;Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,Jilin Province,China;Department of Media,Baicheng Normal University,Baicheng 137000,Jilin Province,China;Crop Research Institute,School of Agricultural and Biological Engineering,Taizhou Vocational College of Science and Technology,Taizhou 318020,Zhejiang Province,China;National Quality Inspection and Testing Center for Biobased Products,Jilin Province Product Quality Supervision and Inspection Institute,Changchun 130103,China)

机构地区：[1]白城师范学院土木工程学院,吉林白城137000 [2]白城师范学院理论计算中心,吉林白城137000 [3]白城师范学院传媒学院,吉林白城137000 [4]台州科技职业学院农业与生物工程学院作物研究所,浙江台州318020 [5]吉林省产品质量监督检验院国家生物基产品质量检验检测中心,长春130103

出　　处：《吉林大学学报（理学版）》2024年第6期1479-1490,共12页Journal of Jilin University:Science Edition

基　　金：吉林省教育厅科研重点项目(批准号:JJKH20240033KJ);吉林省科技发展计划项目(批准号:232681JC0103115076);大学生创新创业训练项目(批准号:202310206018).

摘　　要：采用密度泛函理论中处理远程弱作用的M06-2X和MN15杂化交换泛函方法以及SMD模型方法(处理溶剂效应),对生理环境下二价镁缬氨酸(Val·Mg^(2+))的对映异构(S手性→R手性)转变过程的机制进行研究.对映异构反应通道研究结果表明:手性Val·Mg^(2+)对映异构反应通道分别是H质子以羰基O为桥、羰基O与氨基N联合为桥以及氨基N独自为桥迁移.反应过程的自由能势能面计算表明:H质子以N独自为桥的迁移反应具有优势;在水溶剂的极性作用下,优势反应通道速度控制步骤的能垒为210.4 kJ/mol,水分子(簇)的催化使该能垒降至116.1~118.3 kJ/mol.水液相下二价镁缬氨酸配合物对映异构的速度极缓慢,其可安全用于生命体,二价镁离子和缬氨酸同补.The enantiomerism transformation mechanism of bivalent magnesium valine complexes(Val·Mg^(2+))in physiological environment was studied by using M06-2X and MN15 hybrid exchange functional methods for dealing with remote weak interactions of density functional theory and SMD model method(for solvent effects).The results of the study on enantiomerism reaction channels show that there are three enantiomerism reaction channels of chiral Val·Mg^(2+),which are H proton uses carbonyl O as a bridge,carbonyl O combined with amino N as a bridge,and amino N as a bridge alone.The calculation of free energy potential energy surface of the reaction process shows that it is advantageous for H proton using amino N as a bridge alone for migration reaction.Under the polarity of the water solvent,the energy barrier for speed control step of the dominant reaction channel is 210.4 kJ/mol,and the catalysis of water molecules(clusters)reduces the energy barrier to 116.1-118.3 kJ/mol.The enantiomization rate of bivalent magnesium valine complexes in the aqueous liquid phase is extremely slow,and it can be safely used to complement bivalent magnesium ions and valine in living organisms.

关 键 词：缬氨酸 二价镁 配合物 溶剂效应 密度泛函理论 对映异构 自由能垒 

分 类 号：O641.12[理学—物理化学]