Fast atom bombardment mass spectrometry of N-acetylated neoglycolipids of the 1-deoxy-1-phosphatidylethanolamino-lactitol-type.

N-Acetylated neoglycolipids (neoGL) of the 1-deoxy-1-phosphatidylethanolamino-lactitol-type (Lac-PtdEtn) carrying lactose, sialyllactose, disialyllactose, II3sialylgangliotetraose, II3,IV3disialylgangliotetraose, lacto-N-tetraose, IV6sialyllacto-N-tetraose, lacto-N-triaose, and bloodgroup A determinant as carbohydrate moieties were synthesized either chemically or enzymatically by glycosylation or deglycosylation of the parent compounds. The neoGL were then analyzed by fast atom bombardment mass spectrometry (FAB MS) with positive (FAB(+)) and negative ion (FAB(-)) detection. The resulting spectra showed intense pseudomolecular ions and characteristic fragmentations. FAB(-) spectra of the N-acetylated Lac-PtdEtn-type neoGL showed pseudomolecular ions (M-H)- of one magnitude higher intensity compared to those from the corresponding non-acetylated compounds. The main fragment ions were obtained from successive cleavage of the sugar units, thereby indicating the monosaccharide sequence. In FAB(+) spectra of the title compounds clearly detectable pseudomolecular ions were observed. The most prominent peaks, however, were obtained from cleavage of phosphatidic acid. The N-acetyl-ethyleneamine moieties of the corresponding glycosyl-Etn-fragments most probably formed five membered rings and thereby mesomery-stabilized cations. Secondary ions resulting from loss of the respective terminal sugars demonstrated the monosaccharide sequence.