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采用液相色谱-电喷雾电离质谱联用技术分析大黄中的酚类化合物。

Analysis of phenolic compounds in rhubarbs using liquid chromatography coupled with electrospray ionization mass spectrometry.

作者信息

Ye Min, Han Jian, Chen Hubiao, Zheng Junhua, Guo Dean

机构信息

The State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing, People's Republic of China.

出版信息

J Am Soc Mass Spectrom. 2007 Jan;18(1):82-91. doi: 10.1016/j.jasms.2006.08.009. Epub 2006 Oct 6.

Abstract

Rhubarb is an important herbal medicine for the treatment of constipation, inflammation, and cancer. In this study, a facile method based on liquid chromatography coupled with electrospray ionization tandem mass spectrometry has been established for the analysis of bioactive phenolic compounds in rhubarbs. From six rhubarb species, official (Rheum officinale, R. palmatum, and R. tanguticum) and unofficial (R. franzenbachii, R. hotaoense, and R. emodi), a total of 107 phenolic compounds were identified or tentatively characterized based on their mass spectra. These compounds include sennosides, anthraquinones, stilbenes, glucose gallates, naphthalenes, and catechins. Ion chromatograms for the identified compounds of different rhubarbs were then compared. Consistent with previous reports, sennosides and rhein were only detected in official rhubarbs. Unexpectedly, we found that R. officinale contained very different phenolic compounds from the other two official species. Sennoside A, which has been considered as the major purgative component of rhubarb, was only detected in R. officinale, while its close isomers were observed in R. palmatum and R. tanguticum. In addition, the predominant anthraquinone glycosides in R. officinale were found to be rhein 8-O-glucoside and emodin 1-O-glucoside, whereas those in R. palmatum and R. tanguticum were rhein 1-O-glucoside and emodin 8-O-glucoside. Stilbenes, which are the major constituents of unofficial rhubarbs, were also different among the species. Our results clarify the chemical composition of rhubarbs comprehensively for the first time. Due to the significant differences in chemical components of rhubarbs, we suggest that different Rheum species be used separately in clinical practice.

摘要

大黄是治疗便秘、炎症和癌症的一种重要草药。在本研究中,已建立了一种基于液相色谱联用电喷雾电离串联质谱的简便方法,用于分析大黄中的生物活性酚类化合物。从六种大黄品种,即正品大黄(药用大黄、掌叶大黄和唐古特大黄)和非正品大黄(河套大黄、波叶大黄和喜马拉雅大黄)中,基于质谱共鉴定或初步表征了107种酚类化合物。这些化合物包括番泻苷、蒽醌、芪类、没食子酸葡萄糖酯、萘类和儿茶素。然后比较了不同大黄中已鉴定化合物的离子色谱图。与先前报道一致,番泻苷和大黄酸仅在正品大黄中检测到。出乎意料的是,我们发现药用大黄所含的酚类化合物与其他两种正品大黄有很大不同。番泻苷A,一直被认为是大黄的主要泻下成分,仅在药用大黄中检测到,而在掌叶大黄和唐古特大黄中观察到其相近的异构体。此外,药用大黄中主要的蒽醌苷为大黄酸8-O-葡萄糖苷和大黄素1-O-葡萄糖苷,而掌叶大黄和唐古特大黄中的主要蒽醌苷为大黄酸1-O-葡萄糖苷和大黄素8-O-葡萄糖苷。芪类是非正品大黄的主要成分,在不同品种间也存在差异。我们的结果首次全面阐明了大黄的化学成分。由于大黄化学成分存在显著差异,我们建议在临床实践中分别使用不同的大黄品种。

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