High-energy collision-induced dissociation of ceramide ions from permethylated glycosphingolipids.

Ceramide fragments from permethylated glycosphingolipids (GSLs) were studied by highenergy collision-induced dissociation (CID). In comparison with ceramlde fragments of underivatized GSLs, many more product ions including charge-remote fragment ions were observed. These ions provided detailed structural information on the ceramides. The relative intensity and the mass interval between the L and M ions were used to assign the position of the double bond. The position of the hydroxyl group was assigned with the Ln and K ions. Because the ceramide fragments and not the pseudomolecular ions were selected as the precursor ions, the size of GSLs had little effect on the quality of the product ion spectra. The sensitivity of this approach was in the range of picomoles.