摘要
本工作采用密度泛函理论的M06-2X和MN15方法结合自洽反应场理论的SMD模型方法,研究了水液相下羟基自由基(水分子簇)诱导的两性脯氨酸分子损伤。反应通道研究表明:Pro的损伤可以通过羟基自由基(水分子簇)抽取α-H原子和五元杂环上不同位置的H原子实现。势能面计算表明:羟基自由基(水分子簇)抽取α-H的自由能垒在41.3至48.3 kJ·mol^(-1)之间,抽取五元杂环上不同位置的H的自由能垒在33.3至48.9 kJ·mol^(-1)之间。抽取五元杂环的与α-C邻位C上的H的损伤反应最具优势,自由能垒在33.3至36.5 kJ·mol^(-1)之间。损伤修复的最低自由能垒是126.9 kJ·mol^(-1)。结果表明,水液相下羟基自由基存在时脯氨酸分子很容易损伤,且损伤后很难修复。
The damage of amphoteric proline induced by hydroxyl radicals(water clusters) is studied in water-liquid phase environment by means of M06-2 X and MN15 methods based on density functional theory and SMD model method of self-consistent reaction field theory. The study of reaction channels shows that the damage of proline can be achieved by hydroxyl radicals(water molecules clusters) extracting α-H atoms and H atoms at different positions on the five-membered heterocycle. The calculation of potential energy surface shows that the energy barrier of α-H-atom abstraction by hydroxyl radicals(water clusters) is between 41.3 and 48.3 kJ·mol^(-1), and the energy barrier of five-membered heterocycle-H atoms abstraction by hydroxyl radicals at different positions is between 33.3 and 48.9 kJ·mol^(-1). The damage reaction has the most advantages when extracting H on C that the ortho-position of five-membered heterocyclic α-C, with the energy barrier between 33.3 and 36.5 kJ·mol^(-1). The minimum energy barrier for damage repair is 126.9 kJ·mol^(-1). The results show that proline molecules are easily to be damaged in the presence of hydroxyl radicals in aqueous solution, and it is difficult to repair after damage.
作者
罗香怡
高浩溟
姜丰
刘军
范艳杰
姜春旭
王佐成
LUO Xiangyi;GAO Haoming;JIANG Feng;LIU Jun;FAN Yanjie;JIANG Chunxu;WANG Zuocheng(College of Physics, Baicheng Normal University, Baicheng, Jilin 137000, China;Ophthalmology Department, PLA 321st Hospital, Baicheng, Jilin 130700, China;Nadanbo Middle School, DongFeng, Liaoyuan, Jilin 136000, China;College of Computer Science, Baicheng Normal University, Baicheng, Jilin 137000, China)
出处
《复旦学报（自然科学版）》
CAS
CSCD
北大核心
2022年第1期104-114,共11页
Journal of Fudan University：Natural Science
基金
吉林省教育厅科学研究规划项目(JJKH20200002KJ)
吉林省科技厅自然科学基金(20160101308JC)。
关键词
脯氨酸
羟基自由基
损伤
密度泛函理论
自洽反应场理论
过渡态
自由能垒
proline
hydroxyl radicals
damage
density functional theory
self-consistent reaction field theory
transition state
energy barrier
