水液相下Eda酮式异构体与超氧化氢自由基反应的DFT理论计算  

DFT Theoretical Calculation of Reaction between Eda Keto Isomers and Superoxide Hydrogen Radical in Aqueous Liquid Phase

作　　者：潘宇[1,2] 姜春旭 王颢霖 杨应 董雷刚[1] 王佐成 李冰[1] PAN Yu;JIANG Chunxu;WANG Haolin;YANG Ying;DONG Leigang;WANG Zuocheng;LI Bing(Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,Jilin Province,China;College of Physics and Electronic Information,Baicheng Normal University,Baicheng 137000,Jilin Province,China;College of Forest,Beihua University,Jilin 132013,Jilin Province,China;College of Medicine,Hainan Vocational University of Science and Technology,Haikou 571126,China)

机构地区：[1]白城师范学院理论计算中心,吉林白城137000 [2]白城师范学院物理与电子信息学院,吉林白城137000 [3]北华大学林学院,吉林吉林132013 [4]海南科技职业大学医药学院,海口571126

出　　处：《吉林大学学报（理学版）》2024年第5期1254-1266,共13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);吉林省自然科学基金(批准号:YDZJ202201ZYTS666)。

摘　　要：在M06-2X/SMD/6-311+G(d,p)理论水平下,研究水液相1个大气压、 310.15 K温度下依达拉奉(Eda)酮式异构体与超氧化氢自由基(·HO_(2))的反应机理.结果表明:Eda酮式异构体与·HO_(2)的反应有抽H、加成和单电子转移3个过程;抽H反应主要通过·HO_(2)抽取杂环H和甲基H实现,反应的自由能垒为77.1~78.7 kJ/mol;加成反应可通过·HO_(2)加成不饱和C的过程实现,加成自由能垒为48.2~95.0 kJ/mol;加成到杂环上与甲基相连的C原子的放热反应最具优势,自由能垒为48.2 kJ/mol;单电子转移的自由能垒为141.1 kJ/mol,该过程不能实现.可见,水液相下Eda酮式异构体可通过抽H和加成反应消除·HO_(2).At the theoretical level of M06-2X/SMD/6-311+G(d,p),we studied the reaction mechanism between Edaravone(Eda)keto isomers and superoxide hydrogen radical·HO_(2) in aqueous liquid phase at 1 atmospheric pressure and 310.15 K temperature.The results show that there are three processes in the reaction of Eda keto isomers with·HO_(2):H extraction,addition and single electron transfer.The H extraction reaction is mainly achieved through·HO_(2) extraction of heterocyclic H and methyl H,and the free energy barrier of the reaction is 77.1—78.7 kJ/mol.The addition reaction can be realized by the process of·HO_(2) addition to unsaturated C,and the free energy barrier of addition is 48.2—95.0 kJ/mol.The most advantageous exothermic reaction is the addition of C atoms connected to methyl groups on heterocycles,with a free energy barrier of 48.2 kJ/mol.The free energy barrier of single electron transfer is 141.1 kJ/mol,which is impossible.Therefore,the Eda keto isomer in aqueous liquid phase can eliminate·HO_(2) by H extraction and addition reactions.

关 键 词：依达拉奉酮式异构体 超氧化氢自由基 密度泛函理论 过渡态 Marcus理论 电子转移 自由能垒 

分 类 号：O641.12[理学—物理化学]