Study of the collision‐induced radical cleavage of flavonoid glycosides using negative electrospray ionization tandem quadrupole mass spectrometry

Abstract

Negative electrospray ionization tandem quadrupole mass spectrometry was used to study the collision-induced dissociation (CID) of the O-glycosidic bond from different commercially available flavonoid glycosides. Depending on the structure, flavonoid glycosides can undergo both a collision-induced homolytic and heterolytic cleavage of the O-glycosidic bond producing deprotonated radical aglycone ((Y₀ − H)^−·) and aglycone (Y₀⁻) product ions. The relative abundance of the radical aglycone to the aglycone fragment from flavonol-3-O-glycosides increased with increasing number of hydroxyl substituents in the B ring and in the order kaempferol − O-glycoside. The nature and position of the sugar substitution of the flavonol glycosides also affected the fragmentation to the radical aglycone. Obtained under similar conditions, the product ion spectrum of kaempferol-7-O-neohesperidoside showed only a minor radical aglycone product ion as opposed to kaempferol-3-O-rutinoside. The relative abundance of the radical aglycone to the aglycone fragment from flavone-7-O-glycosides was also dependent on the substitution in the B ring. CID of apigenin-7-O-glucoside produced relatively more of the radical aglycone fragment than luteolin-7-O-glucoside, while only the aglycone fragment was found from diosmetin-7-O-rutinoside. The position of the sugar substitution also affected the fragmentation of the flavone glycosides, such that the product ion spectrum of luteolin-4^′-O-glucoside showed only the aglycone fragment as opposed to luteolin-7-O-glucoside. No radical aglycone fragments were found from the flavanone-7-O-glycosides and dihydrochalcone glycoside investigated in the study. Copyright © 2003 John Wiley & Sons, Ltd.