小檗碱和9-O取代衍生物紫外光谱及构效研究  

Ultraviolet spectra and structure-activity of berberine and 9-O-substituted derivatives

作　　者：李会吉 孙海杰 张丽丽[2] 栗婧 LI Hui-Ji;SUN Hai-Jie;ZHANG Li-Li;LI Jing(School of Chemistry and Chemical Engineering,Zhengzhou Nornal University,Zhengzhou 450044,China;Molecular Science and Biomedicine Laboratory,Hunan University,Changsha 410082,China)

机构地区：[1]郑州师范学院化学化工学院,郑州450044 [2]湖南大学分子科学与生物医学实验室,长沙410082

出　　处：《原子与分子物理学报》2021年第6期1-7,共7页Journal of Atomic and Molecular Physics

基　　金：河南省科技攻关项目(202102310592);河南省高等学校重点科研项目(20A150045);郑州师范学院环境催化科研创新团队(702010)。

摘　　要：在水溶剂中,采用含时密度泛函理论(TD-DFT)和Multiwfn波函数分析软件中空穴-电子分析探究小檗碱及其衍生物紫外光谱电子激发特征,进而讨论构效关系.理论紫外光谱与实验光谱吻合较好,其中243 nm和416 nm处的两个吸收峰可认为是与小檗碱及其衍生物药性相关的特征吸收峰.小檗碱9-O处3-溴代丙基的取代不仅未引起吸收峰位置的变化,且提高O供电子能力,增强吸收峰强度;而2-氯代乙酰基、2-溴代乙酰基、环丙沙星的取代使9-O处氧对小檗碱母体无供电子能力,导致吸收峰红移. a、b环及9-O处氧是小檗碱及其衍生物激发过程中供电子体,c环是电子受体,尤其N处.有望对今后小檗碱衍生物合成设计提供一定的理论指导.In water-rich solvent, the electron excitation characteristics of ultraviolet spectra for berberine and its derivatives were studied by time-dependent density functional theory(TD-DFT) and hole-electron analysis in Multiwfn wave function analysis software, and then the structure-activity relationship was discussed. The ultraviolet spectra by theoretical calculations are in good agreement with the experimental data. Two absorption peaks at 243 nm and 416 nm can be considered to be the characteristic absorption peaks, associated with medicinal properties of berberine and its derivatives. The 3-bromopropoxy substituent at 9-O of berberine does not cause the change in the peak positions, and enhances the peak strength. However, 2-chloroacetyl and 2-bromoacetyl and ciprofloxacin substituents make the oxygen at 9-O unable to supply electrons to berberine, leading to the red-shift of absorption peak. The a, b rings and 9-O are the electron donors in the excitation process of berberine and its derivatives, while c ring is the electron acceptor, especially at N. It is expected to provide some theoretical guidance for the synthetic design of berberine derivatives in the future.

关 键 词：9-O-取代的小檗碱衍生物 紫外光谱 构效关系 

分 类 号：O561[理学—原子与分子物理]