Chinese Academy of Medical Sciences and Peking Union Medical College, Institute of Medicinal Plant Development, Malianwa North Road 151#, Haidian District, Beijing 100193, China.
J Pharm Biomed Anal. 2013 Mar 5;75:55-63. doi: 10.1016/j.jpba.2012.11.015. Epub 2012 Nov 16.
Ultra high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC/ESI-Q-TOF MS/MS) was used to investigate the MS fragmentation behaviors of flavone C-glycosides present in the extracts of five Trollius species. In this study, the primary MS fragmentation pathways and key diagnostic fragment ions of flavone C-glycosides were systematically investigated and summarized to distinguish different types of derivatives and to trace other analogs in Trollius species. This method was useful, rapid, efficient and sensitive and allowed the simultaneous identification of different types of flavone C-glycosides present in other medicinal plants. The features of the MS fragmentation of these compounds indicated that the product ions were primarily the result of cleavage in the saccharide moiety, followed by hydrogen rearrangement and dehydration. In this study, thirty-six components including thirty-two flavone C-glycosides, two flavone O-glycosides and two phenylethanoid glycosides, were identified in the extracts of five Trollius species. Eleven of the flavone C-glycosides were identified by comparison with reference standards, and twenty-one flavone C-glycosides were tentatively identified based on their retention times, exact mass information and fragment ions. Two potentially new flavone C-glycosides (2″-O-vanilloylorientin and 2″-O-feruloylvitexin) were successfully characterized based on the summarized fragmentation pathways, and six known flavone C-glycosides (2″-O-glucosylvitexin, 2″-O-acetylorientin, 2″-O-acetylvitexin, 3″-O-acetylorientin, 3″-O-acetylvitexin and 6″-O-acetylvitexin) were identified in these plant species for the first time. In conclusion, the fragmentation pathways proposed in this paper were helpful for the identification of different types of flavone C-glycosides when no reference standards were available.
超高效液相色谱-电喷雾串联四极杆飞行时间质谱联用（UHPLC/ESI-Q-TOF MS/MS）用于研究五种翠雀属植物提取物中类黄酮 C-糖苷的 MS 碎裂行为。在这项研究中，系统地研究和总结了类黄酮 C-糖苷的主要 MS 碎裂途径和关键诊断碎片离子，以区分不同类型的衍生物，并追踪翠雀属植物中的其他类似物。该方法快速、高效、灵敏，可同时鉴定其他药用植物中不同类型的类黄酮 C-糖苷。这些化合物的 MS 碎裂特征表明，产物离子主要是糖基部分断裂的结果，随后是氢重排和脱水。在这项研究中，从五种翠雀属植物提取物中鉴定出包括三十二种类黄酮 C-糖苷、两种黄酮 O-糖苷和两种苯乙醇苷在内的三十六个成分。其中十一种类黄酮 C-糖苷通过与对照品比较进行鉴定，二十一种类黄酮 C-糖苷根据保留时间、精确质量信息和碎片离子进行了初步鉴定。基于总结的碎裂途径，成功表征了两种潜在的新类黄酮 C-糖苷（2″-O-香草酰基木犀草素和 2″-O-阿魏酰牡荆素），并在这些植物中首次鉴定出六种已知的类黄酮 C-糖苷（2″-O-葡萄糖基牡荆素、2″-O-乙酰基橙皮苷、2″-O-乙酰基牡荆素、3″-O-乙酰基橙皮苷、3″-O-乙酰基牡荆素和 6″-O-乙酰基牡荆素）。总之，当没有对照品时，本文提出的碎裂途径有助于鉴定不同类型的类黄酮 C-糖苷。
