Dimorphic expression of cerebrosides in the mycopathogen Sporothrix schenckii

Abstract

Major neutral glycosphingolipid components were extracted from Sporothrix schenckii, a dimorphic fungus exhibiting a hyphal saprophytic phase and a yeast parasitic phase responsible for chronic mycotic infections in mammalian hosts. These components, one from the mycelial form and two from the yeast form, were purified and their structures were elucidated by 1H nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and tandem ESI-MS/MS. All three were characterized as cerebrosides (monohexosylceramides) containing (4E, 8E)-9-methyl-4,8-sphingadienine as the long-chain base attached to N-2′-hydroxyoctadecanoate and N-2′-hydroxy-(E)-Δ3-octadecenoate as the fatty acyl components. However, while the mycelial form expressed only β-glucopyranosylceramide, the yeast form expressed both β-gluco- and β-galactopyranosylceramides in approximately equal amounts. In addition, while the glucosylceramides of both mycelial and yeast forms had similar proportions of saturated and (E)-Δ3 unsaturated 2-hydroxy fatty acid, the galactocerebroside of the yeast form had significantly higher levels of (E)-Δ3 unsaturation. The differences in cerebroside hexose structure represent a novel type of glycosphingolipid dimorphism not previously reported in fungi. Possible implications of these findings with respect to regulation of morphological transitions in S. schenckii and other dimorphic fungi are discussed.—Toledo, M. S., S. B. Levery, A. H. Straus, and H. K. Takahashi. Dimorphic expression of cerebrosides in the mycopathogen Sporothrix schenckii. J. Lipid Res. 2000. 41: 797–806.

Keywords

• electrospray ionization
• mass spectrometry
• ESI-MS
• nuclear magnetic resonance spectroscopy
• NMR
• collision-induced dissociation