黑沙蒿黄酮抗氧化性能的构效关系分析  

Structure and Antioxidant Activities Relationship of Artemisia Ordosica Flavonoids

作　　者：杨怡萌 黎可 姜显琼 陈聪梅 王强 YANG Yimeng;LI Ke;JIANG Xianqiong;CHEN Congmei;WANG Qiang(College of Biological&Chemical Engineering,Chongqing University of Education,Chongqing 400067;Cooperative Innovation Center of Lipid Resources and Children’s Daily Chemicals,Chongqing University of Education,Chongqing 400067;National Supercomputing Center in Shenzhen,Shenzhen 518055,Guangdong)

机构地区：[1]重庆第二师范学院生物与化学工程学院,重庆400067 [2]重庆第二师范学院脂质资源与儿童日化品协同创新中心,重庆400067 [3]国家超级计算深圳中心,深圳518055

出　　处：《四川师范大学学报（自然科学版）》2022年第5期688-695,共8页Journal of Sichuan Normal University（Natural Science）

基　　金：重庆市教委科学技术研究项目(KJQN201901613)。

摘　　要：基于密度泛函理论,针对4种黑沙蒿黄酮化合物(芫花素、羟基芫花素、芹菜素-7,4′-二甲醚、鼠李素)的抗氧化活性的构效关系进行深入研究,通过优化构型的结构参数、抽氢反应的热力学能量分析、黄酮化合物中酚羟基氢原子的NBO电荷分析、黄酮自由基稳定性分析、溶剂极性的影响等方面展开,剖析调控黑沙蒿黄酮抗氧化活性的关键位点及内在规律.结果表明4种黑沙蒿黄酮抗氧化活性顺序为:鼠李素>羟基芫花素>芫花素>芹菜素-7,4′-二甲醚.酚羟基的位置是影响黑沙蒿黄酮抗氧化活性差异的主要因素,黑沙蒿黄酮不同位点抗氧化性能的高低与其酚羟基上氢原子的电荷分布成正比关系,与黄酮半醌式自由基氧原子的自旋密度分布成反比关系.黑沙蒿黄酮自由基单电子的离域程度和分子内氢键的稳定化作用共同决定了B环4′—OH是黑沙蒿黄酮的关键活性位点.4种黑沙蒿黄酮的抗氧化性能在不同极性溶剂中,随着溶剂极性的减弱而增强.With the aid of density functional theory(DFT),the antioxidant properties of the four artemisia ordosica flavonoids(genkainin,hydroxygenkwanin,apigenin-7,4′-dimethylether and rhamnetin)were studied.The optimized geometric configuration,the relative change in energy(ΔH)associated with the formation of various flavonoid radicals,the NBO charges,the stability analysis of flavonoid radicals and the solvent effects of the four aforementioned flavonoids were conducted.The results showed that the order of antioxidant activity of the four flavonoids was as follows:rhamnetin>hydroxygenkwanin>genkainin>apigenin-7,4′-dimethylether.Furthermore,it found that the position of phenol hydroxyl group was the main factor influencing the difference of antioxidant activity of the artemisia ordosica flavonoids.The antioxidant activities at different sites of artemisia ordosica flavonoids were directly proportional to the charges on H atom of the phenol hydroxyl group,and inversely proportional to the spin densities on O atom of flavonoid radicals.The electron delocalization and intramolecular hydrogen bond finally results in the high activity of 4′-OH in ring B of artemisia ordosica flavonoids.Finally,the solvent phase optimized calculation results indicates that the antioxidant activity of artemisia ordosica flavonoids was enhanced with the weakening of the polarity of the solvent phase.

关 键 词：黑沙蒿黄酮 抗氧化 密度泛函计算 溶剂极性 

分 类 号：O64[理学—物理化学]