水液相下两性Lys→Mg(Ⅱ)配合物对映异构的理论研究  

Theoretical Study on the Enantiomerism of Amphoteric Lys→Mg(Ⅱ)Complex in Aqueous-liquid Environment

作　　者：崔金玉 黄筱珂 张方坚 王丽 王佐成[4] 张雪娇[4] 赵丽红[5] Cui Jinyu;Huang Xiaoke;Zhang Fangjian;Wang Li;Wang Zuocheng;Zhang Xuejiao;Zhao Lihong(Basic Courses Teaching and Research Department,Yingkou Institute of Technology,Yingkou 115014,Liaoning,China;Qianguo County of Jilin province,Physics Group of No.3 Middle School,Songyuan 138000,China;Institute of Atomic and Molecular Physics,Jilin University,Changchun 130000,Jilin,China;College of Computer Science,Baicheng Normal University,Baicheng 137000,China;College of Pharmacy,Baicheng Medical College,Baicheng 137000,Jilin,China)

机构地区：[1]营口理工学院基础教研部,辽宁营口115014 [2]吉林省前郭县第三中学物理组,吉林松原138000 [3]吉林大学原子与分子物理研究所,吉林长春130012 [4]白城师范学院理论计算中心,吉林白城137000 [5]白城医学高等专科学校药学院,吉林白城137000

出　　处：《南开大学学报(自然科学版)》2023年第5期99-112,共14页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：辽宁省教育厅科研项目(LJKMZ20221858);营口理工学院科研团队项目(TD202003);辽宁省自然科学基金项目(2020-BS-287);白城医学高等专科学校科研平台重点项目(BYKPT202207);白城医学高等专科学校高层次人才团队建设项目(BCYZ20220408)。

摘　　要：采用基于密度泛函理论的M06-2X和MN15方法,结合处理溶剂效应的SMD模型方法,研究了水液相下两性赖氨酸二价镁配合物(Lys→Mg(Ⅱ))的对映异构.发现Lys→Mg(Ⅱ)的对映异构可通过质子转移和R基的CC键旋转过程实现.考察了3个反应通道a、b和c,它们分别是S-Lys→Mg(Ⅱ)先失去手性,然后R-基C-C键旋转,最后实现对映体异构;S-Lys→Mg(Ⅱ)先手性转变,然后R-基C-C键旋转实现对映体异构;S-Lys→Mg(Ⅱ)先从两性向中性异构,然后实现手性转变,最后通过R-基C-C键旋转实现对映体异构.计算表明,c通道最优势,隐性溶剂效应下决速步的自由能垒是204.4 k J/mol,显性溶剂效应下该能垒降到103.9-109.9 k J/mol之间.结果表明,水液相下Lys→Mg(Ⅱ)的对映异构过程很慢,赖氨酸二价镁可短期用于生命体同补赖氨酸和二价镁.The enantiomerism of amphoteric lysine and magnesium bivalent complexes(Lys→Mg(Ⅱ))in aqueous-liquid environment was studied by using M06-2X and MN15 methods based on density functional theory and SMD model method to deal with solvent effect.It was found that the enantiomerism of Lys Mg(II)can be achieved through the process of proton transfer and the rotation of R group C-C bond.Three reaction channels a,b and c were investigated.In channel a,S-Lys→Mg(Ⅱ)loses its chirality first,then C-C bond of R group totates,and it achieves enantiomerism process finally.The reaction be achieved through the chiral flip of S-Lys→Mg(Ⅱ)and the rotation of R group C-C bond in channel b.S-Lys→Mg(Ⅱ)isomerisms from amphoteric to neutral first,then achieves chiral flip and through the rotation of R group C-C bond achieves enantiomerism reaction finally in channel c.The calculation shows that the channel c has the most advantage,its free energy barriers of step-determining is 204.4 kJ/mol under the effect of recessive solvent,the barrier could be reduced to between 103.9 and 109.9 kJ/mol under the effect of dominant solvent.The results show that the enantiomerism process of Lys→Mg(Ⅱ)is slow in aqueous-liquid environment,lysine magnesium divalent can be used to supply lysine and magnesium divalent for life simultaneously in short-term dimensions.

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

分 类 号：O641.12[理学—物理化学]