Discovery and Structural Characterization of Fucosylated Oligomannosidic N-Glycans in Mushrooms

Department of Chemistry, University of Natural Resources and Life Sciences, 1190 Vienna, Austria.
Journal of Biological Chemistry (Impact Factor: 4.57). 02/2011; 286(8):5977-84. DOI: 10.1074/jbc.M110.191304
Source: PubMed


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.

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    • "Thus, GnT I is a key enzyme since it is the first glycosyltransferase occurring in the Golgi apparatus in the GnT I-dependent pathway giving rise to complex N-glycans that are required for normal morphogenesis in pluricellular organisms (Ioffe and Stanley, 1994; Metzler et al., 1994). A sequence encoding for a GnT I is predicted in P. tricornutum (Baïet et al., 2011) but not in C. reinhardtii (Mathieu-Rivet et al., 2013) suggesting that N-linked glycans from these two microalgae could be processed in the Golgi apparatus according to two different pathways, referred to as GnT I-dependent and GnT I-independent pathways (Zhu et al., 2004; Crispin et al., 2006; Grass et al., 2011). "
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    • "UEA-I binding was associated with increased adherence to epithelial cells [39]. Recently mass spectrometry identified í µí»¼1,6-fucose residues in oligomannosylated N-linked glycans of the fungi Cantharellus cibarius [40]. This raises the question on how this type of glycans are presented in the surface of mushrooms, as no FUT8 family member of fucosyltransferases responsible for this linkage has been identified in yeast nor mushrooms [38]. "
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