摘要
采用密度泛函理论(DFT)的M06-2X和MN15方法,结合自洽反应场理论的SMD(solvationmodeldensity)模型方法,研究水液相下依达拉奉(Eda)消除超氧阴离子自由基(O_(2)^(·-))的反应机理.结果表明:Eda消除O_(2)^(·-)的反应有3个通道,分别是O_(2)^(·-)抽H原子、O_(2)^(·-)加成到不饱和C和单电子从Eda向O_(2)^(·-)转移;O_(2)^(·-)抽H反应的最低能垒为12.2kJ/mol,O_(2)^(·-)加成反应的最低能垒为110.2kJ/mol,单电子从Eda向O_(2)^(·-)转移的能垒为408.5kJ/mol,抽H反应最具优势.水液相下Eda消除O_(2)^(·-)的反应主要在抽H通道实现,因此Eda可作为O_(2)^(·-)自由基清除剂.
We studied the reaction mechanism of Edaravone(Eda)scavenging superoxide anion free radical(O_(2)^(·-))in aqueous liquid phase by using M06-2X and MN15 methods of DFT(density functional theory)and SMD(solvation model density)model method of self-consistent reaction field theory.The results show that the reaction of Eda scavenging O_(2)^(·-)has three channels,which are extraction of H atom by O_(2)^(·-),addition of O_(2)^(·-)to unsaturated C and single electron transfer from Eda to O_(2)^(·-).The lowest energy barrier of O_(2)^(·-)extracting H reaction is 12.2 kJ/mol,the lowest energy barrier of O_(2)^(·-)addition reaction is 110.2 kJ/mol,the energy barrier of single electron transfer from Eda to O_(2)^(·-)is 408.5 kJ/mol,and the reaction of extracting H has the most advantage.The reaction of Eda scavenging O_(2)^(·-)is mainly achieved in channel of extracting H in aqueous liquid phase,and Eda can be used as O_(2)^(·-)free radical scavenger.
作者
张雪娇
杨应
杨文富
张勇
姜春旭
王佐成
董雷刚
ZHANG Xuejiao;YANG Ying;YANG Wenfu;ZHANG Yong;JIANG Chunxu;WANG Zuocheng;DONG Leigang(Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,Jilin Province,China;Department of Media,Baicheng Normal University,Baicheng 137000,Jilin Province,China)
出处
《吉林大学学报(理学版)》
CAS
北大核心
2023年第6期1489-1500,共12页
Journal of Jilin University:Science Edition
基金
吉林省自然科学基金(批准号:YD2J2022012YTS666)。
关键词
依达拉奉
超氧阴离子自由基
密度泛函理论
过渡态
Marcus理论
电子转移
能垒
Edaravone
superoxide anion free radical
density functional theory
transition state
Marcus theory
electron transfer
energy barrier