Characterization of aromatic glycosides in the extracts of Trollius species by ultra high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry

• Published in: Journal of pharmaceutical and biomedical analysis Vol. 75; pp. 55 - 63
• Main Authors: Wu, Li-Zhen, Zhang, Xiao-Po, Xu, Xu-Dong, Zheng, Qing-Xia, Yang, Jun-Shan, Ding, Wan-Long
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 05.03.2013
• Subjects: Anti-Infective Agents - analysis; Anti-Infective Agents - chemistry; Anti-Inflammatory Agents, Non-Steroidal - analysis; Anti-Inflammatory Agents, Non-Steroidal - chemistry; Aromatic glycosides; Chromatography, High Pressure Liquid; Drug Discovery; Drugs, Chinese Herbal - chemistry; Ethnopharmacology; Flavone C-glycosides; Flavones - analysis; Flavones - chemistry; Flavonoids - chemistry; Fragmentation pathway; glycosides; Glycosides - analysis; Glycosides - chemistry; hydrogen; ionization; ions; medicinal plants; Molecular Structure; Phenylethyl Alcohol - analogs & derivatives; Phenylethyl Alcohol - analysis; Phenylethyl Alcohol - chemistry; Ranunculaceae - chemistry; reference standards; Species Specificity; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry; Trollius; Trollius species; UHPLC/ESI-Q-TOF MS/MS; ultra-performance liquid chromatography; Aromatic glycosides; Fragmentation pathway; Flavone C-glycosides; UHPLC/ESI-Q-TOF MS/MS; Trollius species
• ISSN: 0731-7085; 1873-264X
• DOI: 10.1016/j.jpba.2012.11.015

[Display omitted] ► UHPLC–MS/MS was used to study the fragmentation behaviors of flavone C-glycosides. ► Diagnostic fragment ions were summarized to distinguish different type derivatives. ► Thirty-six components were identified in the extracts of five Trollius species. ► Two potentially new flavone C-glycosides were successfully identified. ► Six known flavone C-glycosides were firstly identified from Trollius species. 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.