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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
23
pubmed:dateCreated
2001-12-17
pubmed:abstractText
Glycosylinositol phosphorylceramides (GIPCs) are a class of acidic glycosphingolipids (GSLs) expressed by fungi, plants, and certain parasitic organisms, but not found in cells or tissues of mammals or other higher animals. Recent characterizations of fungal GIPCs point to an emerging diversity which could rival that already known for mammalian GSLs, and which can be expected to present a multitude of challenges for the analytical chemist. Previously, the use of Li(+) cationization, in conjunction with electrospray ionization mass spectrometry (ESI-MS) and low-energy collision-induced dissociation tandem mass spectrometry (ESI-MS/CID-MS), was found to be particularly effective for detailed structural analysis of monohexosylceramides (cerebrosides) from a variety of sources, including fungi, especially minor components present in mixtures at extremely low abundance. In applying Li(+) cationization to characterization of GIPCs, a substantial increase in both sensitivity and fragmentation was observed on collision-induced dissociation of [M + Li](+) versus [M + Na](+) for the same components analyzed under similar conditions, similar to results obtained previously with cerebrosides. Molecular adduct fragmentation patterns were found to be systematic and characteristic for both the glycosylinositol and ceramide moieties with or without phosphate. Interestingly, significant differences were observed in fragmentation patterns when comparing GIPCs having Manalpha1 --> 2 versus Manalpha1 --> 6Ins core linkages. In addition, it was useful to perform tandem product ion scans on primary fragments generated in the orifice region, equivalent to ESI-(CID-MS)(2) mode. Finally, precursor ion scanning from appropriate glycosylinositol phosphate product ions yielded clean molecular ion profiles in the presence of obscuring impurity peaks. The methods were applied to detailed characterization of GIPC fractions of increasing structural complexity from a variety of fungi, including a non-pathogenic Basidiomycete (mushroom), Agaricus blazei, and pathogenic Euascomycete species such as Aspergillus fumigatus, Histoplasma capsulatum, and Sporothrix schenckii. The analysis confirmed a remarkable diversity of GIPC structures synthesized by the dimorphic S. schenckii, as well as differential expression of both glycosylinositol and ceramide structures in the mycelium and yeast forms of this mycopathogen. Mass spectrometry also established that the ceramides of some A. fumigatus GIPC fractions contain very little 2-hydroxylation of the long-chain fatty-N-acyl moiety, a feature that is not generally observed with fungal GIPCs.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:issn
0951-4198
pubmed:author
pubmed:copyrightInfo
Copyright 2001 John Wiley & Sons, Ltd.
pubmed:issnType
Print
pubmed:volume
15
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2240-58
pubmed:dateRevised
2007-11-14
pubmed:meshHeading
pubmed:year
2001
pubmed:articleTitle
Comparative analysis of glycosylinositol phosphorylceramides from fungi by electrospray tandem mass spectrometry with low-energy collision-induced dissociation of Li(+) adduct ions.
pubmed:affiliation
The Complex Carbohydrate Research Center and Department of Biochemistry and Molecular Biology, University of Georgia, 220 Riverbend Road, Athens, GA 30602-4712, USA. leverysb@ccrc.uga.edu
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, Non-U.S. Gov't