title: A novel trisaccharide glycolipid biosurfactant containing trehalose bears ester-linked hexanoate, succinate, and acyloxyacyl moieties: NMR and MS characterization of the underivatized structure.
abstract: A Gram-positive actinomycete growing on n-hexadecane secreted a family of anionic glycolipid surfactant homologs. The major homolog, with a molecular weight of 1210.6347, had the formula C58H98O26. Following mild alkaline saponification, 1H and 13C NMR spectroscopy were used to characterize the non-reducing trisaccharide backbone: beta-Glcp-(1-->3)-alpha-Glcp-(1<-->1)-alpha-Glcp ('laminaratrehalose'). Hexanoate, succinate, 3-hydroxyoctanoate, and 3-hydroxydecanoate were found in 3:1:1:1 molar ratio using GC-EIMS analysis of fatty acid methyl esters (FAME) prepared by transesterification. We found that the beta-hydroxy acids bore secondary hexanoate chains in 3-O-ester linkage, giving acyloxyacyl anions of appropriate m/z in FABMS and FABMS/MS spectra. COSY, HETCOR, HMBC, and HMQC NMR experiments established the acylation pattern: succinate at C-2 of the terminal alpha-glucopyranose ring; hexanoate at C-3" of the beta-glucopyranose ring; 3-hexanoyloxyoctanoate and 3-hexanoyloxydecanoate at the 2'- and 4-positions. In FABMS spectra, the homologs flanked the molecular ion by +/- 14 and +/- 28 amu, suggesting heterogeneity in acyl chain length.
authors.affiliation: Higuchi Biosciences Center, University of Kansas, Lawrence 66047, USA.
authors.forename: S W
authors.initials: SW
authors.lastname: Esch
authors.forename: M D
authors.initials: MD
authors.lastname: Morton
authors.forename: T D
authors.initials: TD
authors.lastname: Williams
authors.forename: C S
authors.initials: CS
authors.lastname: Buller
mesh_terms: D000215:Acylation; D002208:Caproates / Q000737:chemistry; D002236:Carbohydrate Conformation; D004952:Esters / Q000737:chemistry*; D006017:Glycolipids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D019802:Succinic Acid / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry*; D014199:Trehalose / Q000032:analysis*; D014312:Trisaccharides / Q000737:chemistry*
chemical_list: D002208:Caproates; D004952:Esters; D006017:Glycolipids; D013501:Surface-Active Agents; D014312:Trisaccharides; C037652:hexanoic acid; D019802:Succinic Acid; D014199:Trehalose