水液相下沙利度胺与羟基自由基反应的密度泛函理论研究  

The Density Functional Theory Study of Reaction Between Thalidomide andHydroxyl Radicals in Aqueous Liquid Phase

作　　者：王佐成 赵宇[2] 杨静 孙鸣 林哲 吴静 姜春旭 孙冠军 WANG Zuocheng;ZHAO Yu;YANG Jing;SUN Ming;LIN Ze;WU Jing;JIANG Chunxu;SUN Guanjun(Collegel of Medicine,Hainan Vocational University of Science and Technology,Haikou Hainan 571126,China;Theoretical Computing Center,Baicheng Normal University,Baicheng Jilin 137000,China;College of Information Engineering,Hainan Vocational University of Science and Technology,Haikou Hainan 571126,China;College of Mechanical and Electrical Engineering,Hainan Vocational University of Science and Technology,Haikou Hainan 571126,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137000 [3]海南科技职业大学信息工程学院,海南海口571126 [4]海南科技职业大学机电工程学院,海南海口571126

出　　处：《江西师范大学学报(自然科学版)》2025年第1期58-72,共15页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：海南科技职业大学校级科学研究基金(HKKY2024-02);吉林省教育厅科学技术研究课题(JJKH20240033KJ);吉林省自然科学基金(YDZJ202401628ZYTS)资助项目。

摘　　要：该文使用基于密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了在水液相下沙利度胺分子(Thd)与羟基自由基(OH)的反应机理.反应通道研究发现:Thd与OH的反应有抽氢、加成和单电子转移3个通道.反应势能面研究表明:OH抽H的自由能垒为15.0~56.6 kJ·mol^(-1),且均为热力学允许的过程;OH加成到不饱和C的自由能垒为15.4~67.8 kJ·mol^(-1),且均为热力学允许的过程;加成到不饱和N的吉布斯自由能垒在181.0 kJ·mol^(-1)以上,且为热力学不允许的过程;单电子从Thd向OH转移的吉布斯自由能垒是510.4 kJ·mol^(-1).研究结果表明:在水液相下Thd可以通过抽H和向不饱和C的加成过程清除羟自由基OH.Using M06-2X and MN15 methods based on density functional theory(DFT),combined with the SMD model of self-consistent reaction field theory,the reaction mechanism between thalidomide(Thd)and hydroxyl ra-dical(OH)in aqueous liquid phase is studied.The study of reaction pathways reveals three possible channels for the reaction between Thd and OH that are H extration,addition and single electron transfer.The potential energy surface(PES)analysis shows that the free energy barriers for H extration by OH range from 15.0 to 56.6 kJ·mol^(-1),all of which are thermodynamically favorable processes.The free energy barriers for OH addition to unsatura-ted carbon range from 15.4 to 67.8 kJ·mol^(-1),and these processes are also thermodynamically favorable.However,the Gibbs free energy barriers for addition to unsaturated nitrogen exceed 181.0 kJ·mol^(-1),rendering these processes thermodynamically unfavorable.The Gibbs free energy barrier for single electron transfer from Thd to OH is 510.4 kJ·mol^(-1).These results suggest that Thd can scavenge hydroxyl radicals(OH)via H extration and addition to unsaturated carbon in aqueous liquid phase.

关 键 词：沙利度胺 羟基自由基 密度泛函理论 自洽反应场理论 过渡态 单电子转移 吉布斯自由能垒 

分 类 号：O641.12[理学—物理化学]