Structural determination of glucosylceramides isolated from marine sponge by fast atom bombardment collision-induced dissociation linked scan at constant B/E

Abstract

Five glucosylceramides (GlcCers) were isolated by reversed phase high-performance liquid chromatography from the MeOH extracts of amarine sponge, Haliclona (Reniera) sp., collected from the coast of Ulleung Island, Korea, and analyzed by fast atom bombardmentmass spectrometry (FAB-MS) in positive-ionmode. FAB-mass spectra of these compounds included protonated molecules [M+H]+ andabundant sodiatedmolecules[M+Na]+ from amixture of m-NBA and NaI. The structures of theseGlcCers, which were similar, were elucidated by FAB-linked scan at constant B/E. To find diagnostic ions for their characterization, the GlcCers were analyzed by collision-induced dissociation (CID) linked scan at constant B/E. The CID-linked scan at constant B/E of [M+H]+ and [M+Na]+ precursor ions resulted in the formation of numerous characteristic product ions via a series of dissociative processes. The product ions formed by charge-remote fragmentation provided important information for the characterization of the fatty N-acyl chain moiety and the sphingoid base, commonly referred to as the long-chain base. The product ions at m/z 203 and 502 were diagnostic for the presence of a sodiated sugar ring and β-D-glucosylsphinganine, respectively. For further confirmation of the structure of the fatty N-acyl chain moiety in each GlcCer, fatty acid methyl esters were obtained from the five GlcCers by methanolysis and analyzed by FAB-MS in positive-ion mode. On the basis of these dissociation patterns, the structures of the five GlcCers from marine sponge were elucidated. In addition, the accurate mass measurement was performed to obtain the elemental composition of the GlcCers isolated from marine sponge. Copyright © 2009 John Wiley & Sons, Ltd.