Discovery and structural characterization of fucosylated oligomannosidic N-glycans in mushrooms

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Grass, Josephine
Pabst, Martin
Kolarich, Daniel
Poeltl, Gerald
Leonard, Renaud
Brecker, Lothar
Altmann, Friedrich
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2011
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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 1H 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.

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Journal of Biological Chemistry

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286

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8

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This research was originally published in Journal of Biological Chemistry (JBC). Grass et al, Discovery and structural characterization of fucosylated oligomannosidic N-glycans in mushrooms, Journal of Biological Chemistry (JBC) 2011; 286: 5977-5984 Copyright the American Society for Biochemistry and Molecular Biology. Reproduced in accordance with the copyright policy of the publisher. Please refer to the journal's website for access to the definitve version.

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Chemical sciences

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