LC−MSn Methods for Saccharide Characterization of Monoglycosyl Flavonoids Using Postcolumn Manganese Complexation

A simple tandem mass spectrometry method for differentiating isomeric monoglycosyl flavonols, flavones, and flavanones using manganese complexation is reported. Dissociation of the [Mn(II) (L) (L - H)]+ and [Mn(II) (L)2 (L - H)]+ species provides unique fragment ions that allow the identification of the saccharide moiety as glucose, galactose, arabinose, or xylose. The glycosylation site of the flavonoid can also be determined by the fragmentation pathways of the Mn complexes. The Mn complexation method was adapted for on-line liquid chromatography-mass spectrometry analysis and tested using flavonoid extracts from Fuji apples (Malus domestica Borkh. cv. Fuji) and red onions (Allium cepa L.). Using fragmentation data obtained from collisional activated dissociation of the deprotonated flavonoid glycosides and their Mn complexes, the major flavonoid species in these extracts were identified.