生理环境下二价铜苯丙氨酸配合物对映体异构的DFT研究  

DFT Study of the Enantiomeric Isomerization of Divalent Copper Phenylalanine Complexes in Physiological Environment

作　　者：王佐成 张雪娇 张一鸣[3] 孙彦慧 赵红迪 姜春旭 Wang Zuocheng;Zhang Xuejiao;Zhang Yiming;Sun Yanhui;Zhao Hongdi;Jiang Chunxu(Collegel of Medicine,Hainan Vocational University of Science and Technology,Haikou 571126,China;Information Construction Management Office,Baicheng Normal University,Baicheng 137000,China;Media School,Baicheng Normal University,Baicheng 137000,China;Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,China)

机构地区：[1]海南科技职业大学医药学院,海南海口571126 [2]白城师范学院信息化建设管理处,吉林白城137000 [3]白城师范学院传媒学院,吉林白城137000 [4]白城师范学院理论计算中心,吉林白城137000

出　　处：《南开大学学报（自然科学版）》2024年第5期57-67,共11页Journal of Nankai University(Natural Sience)

基　　金：全国大学生创新项目(202310206116);吉林省教育厅科研项目(JJKH20240033KJ);吉林省自然科学基金(YDZJ202401628ZYTS)。

摘　　要：采用基于DFT(密度泛函理论)的M06杂化交换泛函方法,对生理环境(水液相、310.15 K、1个标准大气压)下二价铜苯丙氨酸配合物(Phe→Cu^(2+))对映体之间的手性异构进行研究.反应通道研究发现:Phe→Cu^(2+)的手性对映异构可通过羰基的O原子或氨基的N原子做为H(质子)转移桥梁实现.异构过程的驻点能量图研究表明:H以N做为迁移桥梁的异构反应具有明显优势.在水分子(簇)及水的强极性的双重作用下,优势反应通道速控制骤的自由能能垒是116.6 kJ/mol.研究结果表明:在生命体内二价铜苯丙氨酸配合物的手性对映体异构速度极慢,用苯丙氨酸铜给生命体同时补充铜元素和苯丙氨酸比较安全.The chiral isomerism between enantiomers of divalent copper phenylalanine complexes(Phe→Cu^(2+)))in physiological environment(aqueous-liquid phase,310.15 K,1 standard atmospheric pressure)was investigated by using the M06 hybridized exchange flooding method based on DFT(Density Functional Theory).The reaction channel study reveals that the chiral enantiomerism of Phe→Cu^(2+))can be realized by the O atom of the carbonyl group or the N atom of the amino group acting as an H(proton)transfer bridge.The stationary energy maps of the isomerization process show that the isomerization reaction in which H uses N as a migration bridge has a clear advantage.The free energy barrier of the dominant reaction channel velocity control qubit is 116.6 kJ/mol under the dual effect of water molecules(clusters)and the strong polarity of water.The results of the study show that the chiral enantiomer isomerization of divalent copper phenylalanine complexes is extremely slow in the living body,and that it is safer to use copper phenylalanine to give the living body a supplement of both elemental copper and phenylalanine at the same time.

关 键 词：二价铜苯丙氨酸 手性对映体 密度泛函理论 溶剂效应 自由能能垒 

分 类 号：O641.12[理学—物理化学]