UPLC-Q-TOF MS定性定量分析淫羊藿中淫羊藿苷类似物

利用超高效液相色谱-四极杆飞行时间质谱(UPLC-Q-TOF MS)法分析淫羊藿标准药材,并根据淫羊藿苷对照品的裂解规律及相关文献报道对朝鲜淫羊藿中淫羊藿苷类似物进行定性定量分析。采用加压溶剂提取系统提取淫羊藿标准药材中的有效成分,以液相色谱-质谱法进行分析,通过总结对照品淫羊藿苷和朝藿定C的质谱裂解规律,分析检测标准药材中的淫羊藿苷类似物。结果表明,从标准药材朝鲜淫羊藿中检测出42个淫羊藿苷类似物,它们主要集中在15%~70%乙腈洗脱部分,其中有4种化合物是首次发现。该方法通过检测一类标准品进而检测标准药材中的目标成分,可为淫羊藿其他药材中淫羊藿苷类似物的研究及先导药物开发提供必要依据。

Qualitative and Quantitative Analysis of Icariin Analogues in Epimedium koreanum by UPLC-Q-TOF MS

Herb Epimedii, the Chinese name is Yinyanghuo, is one of the most well-known and frequently used Chinese herbal medicine with tonic, antirheumatic and aphrodisiac effects. As the major bioactive constituents of Epimedium plants, the flavonoids compounds showed androgenic, anti-oxidant, antidepressant, anti-osteoporosis, anti-apoptotic, stimulate angiogenesis, and anti-tumor activities. According to the relevant reports, various compounds have been identified in Epimedium species, and most of them were phenolic compounds including flavonoids and quinic acids. However, even though the standard crude drug Epimedium koreanum has a wildly application in quality control study, the quantity detection of icariin analogues of Epimedium koreanum is quietly rare. In this paper, qualitative and quantitative analysis of icariin analogues in Epimedium koreanum Nakai was performed by using ultra performance liquid chromatography and quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF MS) technology based on icariin fragmentation and its analogues fragment pathway. In the experiment, the active components in Herb Epimedium koreanum were extracted by accelerated solvent extraction system with 70% acetonitrile at 120 ℃ for 10 min, and the chromatographic separation was used Waters Acquity UPLC BEH-C18 (2.1 mm×150 mm, 1.7 μm), mobile phase was 0.05% formic acid and acetonitrile, then analyzed by Q-TOF-MS. Furthermore, by analyzing the mass spectrometric fragmentations of Icariin and Epimedin C, the fragmentation rules of this kind of compound were summed up. To our knowledge, Icariin and Epimedin C obtained from were 3-O-, 7-O- or 3,7-di-O-glycosides, which frequently contained hexose, deoxyhexose, pentose. Therefore, based on the rules summarized the structures of unknown constituents of the icariin analogues in Epimedium koreanum could be detected. The results showed that Q-TOF MS provides abundant and stable information of fragment ions and 42 icariin analogues were identified, which were all eluted by 15%-70% acetonitrile. Among all these compounds, there are 4 compounds were firstly reported. This study is beneficial to discover icariin analogues in Epimedium and explore the leading compounds for drug development.