大黄蒽醌类化合物电喷雾质谱研究

采用电喷雾-离子阱质谱(ESI-ITMS)法,通过一级质谱全扫描和二级质谱碰撞诱导解离技术,研究5种大黄蒽醌衍生物(大黄素、芦荟大黄素、大黄酸、大黄素甲醚、大黄酚)的质谱行为及分子结构与裂解规律间的关系,并对大黄药材中总游离蒽醌提取物进行了电喷雾质谱检测.实验结果显示,5种大黄蒽醌类化合物一级质谱负离子出峰较好,被测样品均为基峰或第二强峰,未发现聚合体离子及加合离子产生,二级质谱各碎片离子归属明确,特征性强.实验结果可应用于大黄蒽醌类化合物的结构分析及进一步的代谢产物研究,并为大黄药材有效成分的鉴定提供了一种快速,灵敏的检测方法.

The electrospray ionization - mass spectra of Radix et rhizoma rhei anthraquinones

Five anthraquinones(Emodin,Chrysophanol,Rheni,Physcion,Aloe-emodin) in Radix et rhizoma rhei were analysed by ESI-ITMS detector to study their relationship between molecular structure and MS behavior,and Radix et rhizoma rhei extract of anthraquinones was also detected in MS full scan mode and CID MS~2 mode.The results showed that these five anthraquinones were easily to lose H~+ and become negative ions,the semi-molecular ions of the anthraquinones were base peaks or second strong peaks in MS spectra,no polymerized ions were found.In CID mode detection,the MS~2 spectra is of high specificity and the assignments of fragmentation of the five anthraquinones were clearly analysed.This characteristic anthraquinones mass specctra will be helpful reference for further study on their molecular struture analysis and metabolite substance detection,and it also offer a rapid,sensitive method for identification of medicinal plant Radix et rhizoma rhei.