|Low energy induced homolytic fragmentation of flavonol 3-O-glycosides by negative electrospray ionization tandem mass spectrometry|
|Yang, Wen-Zhi1; Qiao, Xue1; Bo, Tao2; Wang, Qing1; Guo, De-An1; Ye, Min1|
|刊名||RAPID COMMUNICATIONS IN MASS SPECTROMETRY|
|WOS标题词||Science & Technology|
|类目[WOS]||Biochemical Research Methods ; Chemistry, Analytical ; Spectroscopy|
|研究领域[WOS]||Biochemistry & Molecular Biology ; Chemistry ; Spectroscopy|
|关键词[WOS]||COLLISION-INDUCED DISSOCIATION ; STRUCTURAL-CHARACTERIZATION ; ION ELECTROSPRAY ; O-GLYCOSIDES ; GLYCOSYLATION ; DIFFERENTIATION ; EXTRACTION ; SEPARATION ; CLEAVAGE|
RATIONALENegative ESI-QIT-MS of several subtypes of flavonoid O-glycosides is known to produce deprotonated molecular ions which undergo homolytic fragmentation at the glycosidic bond upon collision-induced dissociation (CID). However, these subtypes have never been simultaneously compared under unified MS conditions.
METHODSThe (-)-ESI-MSn fragmentations of 69 flavonoid O-glycosides, involving eight subtypes, were analyzed using a quadrupole ion-trap mass spectrometer with collision energies varying from 18-44%. Factors influencing the homolytic glycosidic bond fragmentation, such as collision energy, hydroxylation of aglycone, and glycosylation pattern, were comprehensively studied.
RESULTSUnder the unified CID-QIT-MS2 conditions, the precursor deprotonated molecular ions [M-H](-) for 3-O-glycosyl, 3,7-di-O-glycosyl and 3,6,7-tri-O-glycosyl flavonols experienced homolytic fragmentation at the glycosidic bond and generated the radical aglycone ion [Y-0-H](-center dot). This gas-phase CID fragmentation behavior was not observed for the other subtypes. A general trend was found that hydroxyl substitution at C-6, glycosylation at C-6/C-7, and acetylation of the saccharide moiety remarkably suppressed this fragmentation. In addition, flavonol 3-O-diglycosides (disaccharides) possessing a 12 glycosidic bond generated more abundant [Y-0-H](-center dot) product ions than those with a 13 or 16 bond. The terminal sugar triggered the homolytic fragmentation in the order Rha>Xyl>Glc. Moreover, new counterexamples were found for previously reported fragmentation rules.
CONCLUSIONSThe low-energy CID homolytic fragmentation was diagnostic for structural identification of flavonol 3-O-glycosides. We have summarized key factors affecting this fragmentation. The results could be useful for rapid characterization of flavonoid O-glycosides in complicated herbal extracts. Copyright (c) 2014 John Wiley & Sons, Ltd.
|项目编号||81222054 ; NCET-11-0019|
|资助机构||National Natural Science Foundation of China ; Program for New Century Excellent Talents in University from the Chinese Ministry of Education|
|作者单位||1.Agilent Technol, Beijing 100102, Peoples R China|
2.Peking Univ, Sch Pharmaceut Sci, State Key Lab Nat & Biomimet Drugs, Beijing 100191, Peoples R China
|Yang, Wen-Zhi,Qiao, Xue,Bo, Tao,et al. Low energy induced homolytic fragmentation of flavonol 3-O-glycosides by negative electrospray ionization tandem mass spectrometry[J]. RAPID COMMUNICATIONS IN MASS SPECTROMETRY,2014,28(4):385-395.|
|APA||Yang, Wen-Zhi,Qiao, Xue,Bo, Tao,Wang, Qing,Guo, De-An,&Ye, Min.(2014).Low energy induced homolytic fragmentation of flavonol 3-O-glycosides by negative electrospray ionization tandem mass spectrometry.RAPID COMMUNICATIONS IN MASS SPECTROMETRY,28(4),385-395.|
|MLA||Yang, Wen-Zhi,et al."Low energy induced homolytic fragmentation of flavonol 3-O-glycosides by negative electrospray ionization tandem mass spectrometry".RAPID COMMUNICATIONS IN MASS SPECTROMETRY 28.4(2014):385-395.|