超高效液相色谱-四极杆-飞行时间全信息串联质谱技术分析黄芪中黄酮类及皂苷类化合物质谱裂解规律

Fragmentation pattern of flavonoids and saponins in Astragali Radix by mass spectrum based on ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry

中文关键词:  黄芪  UPLC-Q-TOF-MSE  裂解规律  黄酮  皂苷

英文关键词:Astragali Radix  ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry  fragmentation pattern  flavonoids  saponins

中文摘要:

      目的 应用超高效液相色谱-四极杆-飞行时间全信息串联质谱(ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry, UPLC-Q-TOF-MSE)技术分析黄芪中10个黄酮化合物、5个皂苷化合物的质谱裂解规律。方法 在电喷雾离子源正、负离子模式下, 分别对黄芪中10个黄酮化合物、5个皂苷化合物的主要特征碎片进行检测, 依据获得的特征碎片分析裂解途径, 归纳裂解规律。结果 在正离子模式下, 黄芪中的15种化合物均取得了较好的质谱信息。黄酮类化合物主要裂解规律为先脱去C6H10O5生成相应的苷元, 其次是失去·CH3、CO、H2O、CH4O、C2H4O等官能团。同时, 黄酮类化合物经逆-狄尔斯-阿尔德反应裂解(retro Diels-Alder reaction, RDA)后形成相应的片段离子。黄芪皂苷Ⅰ、黄芪皂苷Ⅱ、黄芪皂苷Ⅲ、黄芪甲苷和环黄芪醇在正离子模式下产生相同的裂解碎片m/z 473、455、437、419、143、125。结论 该研究获得了黄芪中黄酮类、皂苷类化合物的质谱裂解特征, 可为挖掘黄芪作为药食同源药材, 其功能成分对机体的保健作用机制研究提供参考依据, 为保障黄芪动物性食品安全提供技术支撑。

英文摘要:

      Objective To analyse the mass spectrometry fragmentation pattern of 10 kinds of flavonoids, 5 kinds of saponins in Astragali Radix by ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry (UPLC-Q-TOF-MSE). Methods In the positive and negative ion modes of the electrospray ion source, the main characteristic fragments of 10 kinds of flavonoids, 5 kinds of saponins were detected respectively, and the cracking process was inferred according to the characteristic fragments, and the cracking rules were summarized. Results Good mass spectrum information was obtained for all 15 kinds of components in positive ion mode. The main fragmentation pattern of flavonoids was to remove C6H10O5 to generate the corresponding aglycones firstly, followed by the loss of ·CH3, CO, H2O, CH4O, C2H4O and other functional groups. At the same time, flavonoids were cleaved by retro Diels-Alder reaction (RDA) to form corresponding fragment ions. In addition, the same fragmentation m/z 473, 455, 437, 419, 143, 125 were produced by astragaloside I, astragaloside II, astragaloside III, astragaloside IV and cycloastragenol in positive ion mode. Conclusion In this study, the mass spectrum cracking characteristics of flavonoids and saponins in Astragali Radix are obtained, which can provide reference for exploring Astragali Radix as a homologous medicinal material and the study on the mechanism of its functional components’ health care on the organism, and provide technical support for ensuring the safety of Astragali Radix animal food.