Wavelength-tunable ultraviolet photodissociation (UVPD) of heparin-derived disaccharides in a linear ion trap

A set of three heparin-derived disaccharide deprotonated ions was isolated in a linear ion trap and subjected to UV laser irradiation in the 220–290 nm wavelength range. The dissociation yields of the deprotonated molecular ions were recorded as a function of laser wavelength. They revealed maximum absorption at 220 nm for the nonsulfated disaccharide, but centered at 240 nm for the sulfated species. The comparison of the fragmentation patterns between ultraviolet photodissociation (UVPD) at 240 nm and CID modes showed roughly the same distribution of fragment ions resulting from glycosidic bond cleavages. Interestingly, UVPD favored additional cross ring cleavages of A and X type ion series enabling easier sulfate group location. It also reduced small neutral losses (H₂O).