山茱萸炮制过程中环烯醚萜苷类成分的质谱研究

Analysis on Iridoid Glycosides in Crude and Processed Extracts from Cornus Officinals by Liquid Chromatography-electrospray Ionization Mass Spectrometry

利用高效液相色谱-电喷雾多级串联质谱(HPLC-ESI-MSn)联用技术,对传统中药山茱萸炮制过程中环烯醚萜苷类成分的变化进行了研究.采用反相C18色谱柱,二元线性梯度洗脱,分离并获得了山茱萸中7个环烯醚萜苷类化合物.并通过电喷雾一级质谱获得了上述7种化合物的分子量信息,利用电喷雾质谱的源内碰撞诱导解离技术,获得了该类化合物在负离子模式下的碎裂特征,在此基础上,对其进行了结构鉴定和含量分析.首次发现了差向异构体7α-乙氧基莫诺苷和7β-乙氧基莫诺苷化合物.研究结果表明,当采用HPLC-ESI-MS法分析山茱萸环烯醚萜苷类化合物时,通过色谱保留时间色谱峰面积和质谱特征两方面信息能够提供更加准确可靠的定性定量结果.

The iridoid glycosides in crude and processed extracts from cornus officinals have been analyzed by high performance liquid chromatography-electrospray ionization mass spectrometry. Samples were analyzed by a reversed-phase C18 column using a binary eluent under gradient conditions. Seven iridoid glycosides could be separated and detected. The [M-H]-ions of iridoid glycosides in the negative ion mode were observed, which reflect their molecule mass information. An in-source collision induced dissociation （in-source CID） experiment was carried out in order to identify the structures and to measure the contents of iridoid glycosides. The epimers were discovered in the experiment for the first time, namely 7a-O-ethyl-morroniside and 7β-O-ethylmorroniside. The chromatographic and mass spectral characterization of iridoid glycosides in comus officinals was obtained via a high performance liquid chromatography-electrospray ionization mass spectrometry method, which provides an accurate and reliable result to the qualitative and quantitative analysis of cornus officinals.