首页 | 本学科首页   官方微博 | 高级检索  
     

密度泛函理论辅助研究大黄素型蒽醌化合物电喷雾质谱的裂解过程
引用本文:牛燕燕,陈光英,罗由萍,郑彩娟,周学明. 密度泛函理论辅助研究大黄素型蒽醌化合物电喷雾质谱的裂解过程[J]. 分析科学学报, 2017, 33(3). DOI: 10.13526/j.issn.1006-6144.2017.03.015
作者姓名:牛燕燕  陈光英  罗由萍  郑彩娟  周学明
作者单位:海南师范大学化学与化工学院,海南海口,571158
摘    要:从红树植物尖瓣海莲(Bruguiera sexangula var.rhynchopetala)来源的一株青霉菌属真菌Penicillium sp.次级代谢产物中,分离鉴定出三个大黄素型蒽醌化合物,分别为:大黄素1,3,8-三-羟基-6-甲基蒽醌(1,3,8-trihydroxy-6-methyl anthraquinone,JGWY-C)、1,3,5,8-四羟基-6甲基蒽醌(1,3,5,8-tetrahydroxy-6-methyl-anthraquinone,JGWY-D)和1,3,8-三羟基6-羟甲基蒽醌(1,3,8-trihydroxy-6 hydroxymethyl-anthraquinone,JGWY-B).采用电喷雾离子阱质谱技术(ESI-IT-MSn)对三个化合物的裂解过程及碎片离子结构进行研究,并运用密度泛函理论计算方法,优化各碎片离子的稳定几何构型和裂解过程的能量变化,进一步验证裂解途径分析的可靠性.实验结果表明:大黄素型蒽醌化合物中酚羟基具有一定的酸性,更容易在负离子模式下形成氧负离子,A环和B环酚羟基在多级裂解过程中易脱去CO和CO2小分子.这一裂解过程可以作为药物快速检测和药代动力学研究中质谱的特征碎片离子峰.此外,化合物JGWY-B碰撞诱导裂解α位-CH2OH脱去H2形成醛基,这一过程也得到理论计算的支持.该研究为大黄素型蒽醌化合物的结构鉴定和检测提供了有用的质谱依据.

关 键 词:大黄素型蒽醌化合物  次级代谢产物  电喷雾多级质谱  裂解途径

Study on the Pyrolysis Processes of Emodin-type Anthraquinone Compounds by Electrospray Ionization Mass Spectrometry Combined with Density Functional Theory
NIU Yan-yan,CHEN Guang-ying,LUO You-ping,ZHENG Cai-juan,ZHOU Xue-ming. Study on the Pyrolysis Processes of Emodin-type Anthraquinone Compounds by Electrospray Ionization Mass Spectrometry Combined with Density Functional Theory[J]. Journal of Analytical Science, 2017, 33(3). DOI: 10.13526/j.issn.1006-6144.2017.03.015
Authors:NIU Yan-yan  CHEN Guang-ying  LUO You-ping  ZHENG Cai-juan  ZHOU Xue-ming
Abstract:A fungus identified as penicillium sp.was obtained from a mangrove plant Bruguiera sexangula var.rhynchopetala.Three emodin-type anthraquinone compounds were identified as 1,3,8-trihydroxy-6-methyl-anthraquinone (JGWY-C),1,3,5,8-tetrahydroxy-6-methyl-anthraquinone (JGWY-D) and 1,3,8-trihydroxy-6-hydroxymethyl-anthraquinone (JGWY-B) by NMR spectroscopic analysis.Fragmentation pathway and fragment ion structure of these compounds were further investigated by electrospray ionization ion trap mass spectrometry (ESI IT-MSn) in negative ion mode with the collision induced dissociation (CID),and the stable geometry and energy were optimized based on density functional theory (DFT).The results indicated that the phenolic hydroxyl group connected in anthraquinone compounds had certain acidity and it was easier to form negative oxygen ion in the negative ion mode by dehydrogenation.Dehydrogenated ions could be further induced to crack and take off CO or CO2 neutral molecule in ring A.These data could be used for the rapid detection of related drugs and the study of pharmacokinetics.In addition,H2 could be removed from-CH2OH group of JGWY-B at beta site by CID-MS2 and aldehyde group formed,and the process was also supported by theoretical calculation.The study could provide a useful basis of mass spectrometry in identification and detection of emodin-type anthraquinone compounds.
Keywords:Emodin-type anthraquinone compounds  Secondary metabolites  Electrospray ionization mass spectrometry  Fragmentation pathway
本文献已被 万方数据 等数据库收录!
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号