生理环境下缬氨酸二价钴配合物对映体异构的密度泛函理论研究  

The Density Functional Theory Study on Enantiomerism of Valine Cobaltous Complexes in Physiological Environment

作　　者：王佐成 杨应[2] 孙冠军 程志刚 林哲 何星炜 戴文娟 WANG Zuocheng;YANG Ying;SUN Guanjun;CHENG Zhigang;LIN Zhe;HE Xingwei;DAI Wenjuan(College of Medicine,Hainan Vocational University of Science and Technology,Haikou Hainan 571126,China;Theoretical Computing Center,Baicheng Normal University,Baicheng Jilin 137099,China;College of Mechanical and Electrical Engineering,Hainan Vocational University of Science and Technology Haikou Hainan 571126,China;Community Physical Examination Center,Yingkou Traditional Chinese Medicine Hospital,Yingkou Liaoning 115014,China)

机构地区：[1]海南科技职业大学医药学院,海南海口571126 [2]白城师范学院理论计算中心,吉林白城137099 [3]海南科技职业大学机电工程学院,海南海口571126 [4]营口中医院社区体检中心,辽宁营口115014

出　　处：《江西师范大学学报(自然科学版)》2024年第6期557-566,共10页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：海南科技职业大学校级科研基金(HKKY2024-TD-02);吉林省自然科学基金(YDZJ20241628ZYTS)资助项目.

摘　　要：采用密度泛函理论(DFT)的M06方法,结合处理溶剂效应的SMD模型方法(基于自洽反应场理论),该文对在生命体内环境(水液相、1个标准大气压、310.15 K)下缬氨酸二价钴(Val→Co^(2+))的对映体异构反应机制进行研究.研究发现:Val→Co^(2+)的对映异构过程可通过氨基N原子、羰基O原子或羰基O原子与氨基N原子联合作为H质子转移的桥梁实现.异构反应相关驻点的能量图计算结果表明:H只以N作桥迁移的对映异构反应具有绝对的优势.在生命体内水的极性以及水分子(簇)的共同作用下,反应优势通道速率控制步骤的能垒为111.3~112.5 kJ·mol^(-1).研究结果表明:在生命体内环境下Val→Co^(2+)手性对映体的异构反应速率比较缓慢,短期利用缬氨酸二价钴给生命体补充二价钴离子和缬氨酸具有安全性.The enantiomerism reaction mechanism of valine cobaltous(Val→Co^(2+))is investigated by using M06 method of density functional theory(DFT)and SMD model method(based on self-consistent reaction field theory)to deal with solvent effects in physiological environment(aqueous liquid phase,1 standard atmosphere,310.15 K).It is found that the enantiomerism process of Val→Co^(2+)can be realized by amino N atom,carbonyl O atom or carbonyl O atom combined with amino N atom as the bridge for H proton transfer.The energy diagram calculation of the relative stagnation point of enantiomerism reaction shows that the enantiomerism reaction has absolute advantage when H only uses N as the transfer bridge.Under the combined effect of the polarity of water in living organisms and the water molecules(clusters),the energy barrier of the rate-determining step of the dominant reaction channel is from 111.3 to 112.5 kJ·mol^(-1).The results show that the isomerization rate of Val→Co^(2+)chiral enantio-mers is relatively slow in physiological environment,and it is safe to use valine cobaltous to supplement cobaltous ion and valine in the short and medium term.

关 键 词：缬氨酸 二价钴离子 密度泛函理论 溶剂效应 对映异构 

分 类 号：O641.12[理学—物理化学]