文献类型：期刊文献

中文题名：Cu(Ⅱ)结合对3种黄酮醇分子结构与抗氧化活性影响的理论分析

英文题名：Theoretical Analysis of the Effect of Cu(Ⅱ)Binding on the Molecular Structure and Antioxidant Activity of Three Flavonols

作者：管勤昊[1] 汤丽华[1] 徐曼[1] 张亮亮[2] 黄立新[1]

第一作者：管勤昊

机构：[1]中国林业科学研究院林产化学工业研究所、江苏省生物质能源与材料重点实验室、国家林业和草原局林产化学工程重点实验室、林木生物质低碳高效利用国家工程研究中心、江苏省林业资源高效加工利用协同创新中心,江苏南京210042;[2]华侨大学先进碳转化技术研究院,福建厦门361021

年份：2024

卷号：44

期号：4

起止页码：130-138

中文期刊名：林产化学与工业

外文期刊名：Chemistry and Industry of Forest Products

收录：CSTPCD;;Scopus;北大核心:【北大核心2023】；CSCD:【CSCD2023_2024】；

基金：国家重点研发计划资助项目(2022YFD1300903);华侨大学引进人才科研启动经费(22BS133);江苏省生物质能源与材料重点实验室资助项目(JSBEM-S-202322)。

语种：中文

中文关键词：密度泛函理论;林源膳食黄酮醇;分子结构;抗氧化

外文关键词：density functional theory;forest-derived dietary flavonol;molecular structure;antioxidant

分类号：TQ35

摘要：为揭示黄酮醇与Cu(Ⅱ)之间的相互作用机制,进而提升黄酮醇-Cu(Ⅱ)配位化合物的抗氧化活性,采用密度泛函理论B3LYP方法,分析了羟基去质子化及结合Cu(Ⅱ)对水溶液中3种林源膳食黄酮醇山奈酚、槲皮素、杨梅素分子结构与抗氧化活性的影响。结果表明:羟基去质子化后,黄酮醇分子内其他O—H键键长减小、苯环结构二面角发生改变、分子偶极矩增加、最高占有分子轨道(HOMO)与最低未占有分子轨道(LUMO)能级差(ΔE)减小、分子内其他羟基氢原子正电荷数减小;结合Cu(Ⅱ)后,黄酮醇分子内其他O—H键键长增加、二面角与偶极矩改变、ΔE减小、氢原子正电荷数增大。研究还发现:去质子化后的黄酮醇主要通过改变分子结构和减小ΔE提升离子活性,于去质子化位点形成较高负电势,从而通过静电相互作用与Cu(Ⅱ)发生配位;结合Cu(Ⅱ)后的黄酮醇主要通过增加键长、改变分子结构、增加氢原子正电荷数促进与自由基结合,减小ΔE提升分子活性,增强其抗氧化能力。
By revealing the interaction mechanism between flavonols and Cu(Ⅱ),the antioxidant activity of flavonol-Cu(Ⅱ)coordination compounds was enhanced.The effects of hydroxyl deprotonation and bound Cu(Ⅱ)on the molecular structure and antioxidant activity of three forest-derived dietary flavonols,namely,kaempferol,quercetin,and myricetin,in aqueous solution were analyzed by density-functional theory B3LYP method.The results showed that after deprotonation of hydroxyl group,the length of other O—H bonds in the molecule decreased,the dihedral angle of the benzene ring structure changed,the dipole moment of the molecule increased,the energy level difference(ΔE)between the highest occupied molecular orbital(HOMO)and the lowest unoccupied molecular orbital(LUMO)decreased,and the positive charge number of other hydroxyl atoms in the molecule decreased.The other O—H bond lengths in the molecule increased,the dihedral angle and dipole moment changed,ΔE decreased,and the positive charge number of hydroxyl atoms increased after combining with Cu(Ⅱ).It was also found that the deprotonated flavonols mainly enhanced the ionic activity by changing the molecular structure and decreasing theΔE,and formed a higher negative potential at the deprotonation site,thereby coordinating with Cu(Ⅱ)through electrostatic interactions.The flavonols bound to Cu(Ⅱ)mainly promoted the binding with free radicals by increasing the bond lengths,changing the molecular structure,and increasing the number of positive charges of the hydrogen atoms,while decreasing theΔE to enhance the molecular activity and strengthen its antioxidant ability.