title: Discovery and structural characterization of fucosylated oligomannosidic N-glycans in mushrooms.
abstract: L-fucose is a common constituent of Asn-linked glycans in vertebrates, invertebrates, and plants, but in fungal glycoproteins, fucose has not been found so far. However, by mass spectrometry we detected N-glycans and O-glycans containing one to six deoxyhexose residues in fruit bodies of several basidiomycetes. The N-glycans of chanterelles (Cantharellus cibarius) contained a deoxyhexose chromatographically identical to fucose and sensitive to α-L-fucosidase. Analysis of individual glycan species by tandem MS, glycosidase digestion, and finally (1)H NMR revealed the presence of L-fucose in α1,6-linkage to an α1,6-mannose of oligomannosidic N-glycans. The substitution by α1,6-mannose of α1,2-mannosyl residues of the canonical precursor structure was yet another hitherto unknown modification. No indication for the occurrence of yet other modifications, e.g. bisecting N-acetylglucosamine, was seen. Besides fucosylated N-glycans, short O-linked mannan chains substituted with fucose were present on chanterelle proteins. Although undiscovered so far, L-fucose appears to represent a prominent feature of protein-linked glycans in the fungal kingdom.
authors.affiliation: Department of Chemistry, University of Natural Resources and Life Sciences, 1190 Vienna, Austria.
authors.forename: Josephine
authors.initials: J
authors.lastname: Grass
authors.forename: Martin
authors.initials: M
authors.lastname: Pabst
authors.forename: Daniel
authors.initials: D
authors.lastname: Kolarich
authors.forename: Gerald
authors.initials: G
authors.lastname: Pöltl
authors.forename: Renaud
authors.initials: R
authors.lastname: Léonard
authors.forename: Lothar
authors.initials: L
authors.lastname: Brecker
authors.forename: Friedrich
authors.initials: F
authors.lastname: Altmann
mesh_terms: D001487:Basidiomycota / Q000737:chemistry* / Q000378:metabolism; D002236:Carbohydrate Conformation; D005643:Fucose / Q000737:chemistry* / Q000378:metabolism; D008358:Mannose / Q000737:chemistry* / Q000378:metabolism; D013058:Mass Spectrometry; D009844:Oligosaccharides / Q000737:chemistry* / Q000378:metabolism; D011134:Polysaccharides / Q000737:chemistry* / Q000378:metabolism; D005644:alpha-L-Fucosidase / Q000737:chemistry* / Q000378:metabolism
chemical_list: D009844:Oligosaccharides; D011134:Polysaccharides; C028569:oligomannoside; D005643:Fucose; D005644:alpha-L-Fucosidase; D008358:Mannose