Structure elucidation of sphingolipids from the mycopathogen Sporothrix schenckii: identification of novel glycosylinositol phosphorylceramides with core manalpha1-->6Ins linkage.
Acidic glycosphingolipid components were extracted from the mycelium form of the thermally dimorphic mycopathogen Sporothrix schenckii. Two fractions from the mycelium form (Ss-M1 and Ss-M2), having the highest Rf values on HPTLC analysis, were isolated and their structures elucidated by 1- and 2-D 13C- and 1H-nuclear magnetic resonance spectroscopy, and electrospray ionization mass spectrometry with lithium adduction of molecular ions. The structures of Ss-M1 and Ss-M2 were determined to be Manalpha1-->Ins1-P-1Cer and Manalpha1--> 3Manalpha1-->Ins1-P-1Cer, respectively (where Ins = myo-inositol, P = phosphodiester). The Manalpha1-->6Ins motif is found normally in diacylglycerol-based glycophosphatidylinositols of Mycobacteria, but this is the first unambiguous identification of the same linkage making up the core structure of fungal glycosylinositol phosphorylceramides (GIPCs). These results are discussed in relation to the structures of GIPCs of other mycopathogens, including Histoplasma capsulatum and Paracoccidioides brasiliensis.
Toledo
M S
MS
Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, Rua Botucatu 862, São Paulo, SP, 04023-900, Brazil.
Levery
S B
SB
Glushka
J
J
Straus
A H
AH
Takahashi
H K
HK
D000364:Agaricus / Q000737:chemistry; D002247:Carbon Isotopes; D002518:Ceramides / Q000737:chemistry* / Q000302:isolation & purification; D002851:Chromatography, High Pressure Liquid; D002855:Chromatography, Thin Layer; D006859:Hydrogen; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D021241:Spectrometry, Mass, Electrospray Ionization; D013107:Sphingolipids / Q000737:chemistry* / Q000302:isolation & purification; D013175:Sporothrix / Q000737:chemistry*
D002247:Carbon Isotopes; D002518:Ceramides; D013107:Sphingolipids; D006859:Hydrogen