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Taxonomic group: fungi / Basidiomycota (Phylum: Basidiomycota)
Associated disease: infection due to Cryptococcus neoformans [ICD11: XN3EH

]

The structure was elucidated in this paper
NCBI PubMed ID: 17369287
Publication DOI: 10.1093/glycob/cwm030
Journal NLM ID: 9104124
Publisher: IRL Press at Oxford University Press
Correspondence: luciamp

biof.ufrj.br
Institutions: Instituto de Biofísica Carlos Chagas Filho, Universidade Federal do Rio de Janeiro, Cidade Universitária, Rio de Janeiro, Brasil, Unité de Glycobiologie, Structurale et Fonctionnelle, Université des Sciences et Technologies de Lille, Villeneuve D'Ascq, France

In fungi, glycoinositolphosphoryl ceramide (GIPC) biosynthetic pathway produces essential molecules for growth, viability, and virulence. In previous studies, we demonstrated that the opportunistic fungus Cryptococcus neoformans synthesizes a complex family of xylose-(Xyl) branched GIPCs, all of which have not been previously reported in fungi. As an effort to understand the biosynthesis of these sphingolipids, we have now characterized the structures of GIPCs from C. neoformans wild-type (KN99α) and mutant strains that lack UDP-Xyl, by disruption of either UDP-glucose dehydrogenase (NE321) or UDP-glucuronic acid decarboxylase (NE178). The structures of GIPCs were determined by a combination of nuclear magnetic resonance (NMR) spectroscopy, tandem mass spectrometry (MS), and gas chromatography-MS. The main and largest GIPC from wild-type strain was identified as an α-Manp(1→6)α-Manp(1→3)α-Manp[β-Xylp(1→2)]α-Manp(1→4)β-Galp(1→6)α-Manp(1→2)Ins-1-P-Ceramide, whereas the most abundant GIPC from both mutant strains was found to be an α-Manp(1→3)α-Manp(1→4)β-Galp(1→6)α-Manp(1→2)Ins-1-P-Ceramide. The ceramide moieties of C. neoformans wild-type and mutant strains were composed of a C(18) phytosphingosine, which was N-acylated with 2-hydroxy tetra-, or hexacosanoic acid, and 2,3-dihydroxy-tetracosanoic acid. Our structural analysis results indicate that the C. neoformans mutant strains are unable to complete the assembly of the GIPC-oligosaccharide moiety due the absence of Xyl side chain.

NMR spectroscopy, mass spectrometry, Cryptococcus neoformans, Cryptococcus mutants, glycoinositolphosphoryl ceramide, UDP-Xyl

Structure type: oligomer
Location inside paper: p.5C, p.8C, table II, p.9C, table IV, PI-oligosaccharide
Compound class: glycosphingolipid, glycoinositolphosphoryl ceramide (GIPC)
Contained glycoepitopes: IEDB_130701,IEDB_136044,IEDB_137472,IEDB_1394182,IEDB_141794,IEDB_144983,IEDB_152206,IEDB_164174,IEDB_190606,IEDB_983930,SB_165,SB_166,SB_187,SB_195,SB_197,SB_44,SB_67,SB_7,SB_72,SB_88

Methods: 13C NMR, 1H NMR, GC-MS, ESI-MS/MS, GC, composition analysis, methanolysis, GPC, alkaline hydrolysis, extraction, permethylation, CID-MS, HPTLC, nESI-QTOF-MS, MALDI-TOF-MS
Comments, role: C. neoformans mutant strains major component GIPC. The NMR solvent was not indicated. NMR spectra are given for C. neoformans NE178. Very similar NMR data for C. neoformans NE321 are present in the paper.

Related record ID(s): 41805, 42034, 42035, 43707, 43708, 43709, 43710
NCBI Taxonomy refs (TaxIDs): 5207
Show glycosyltransferases

NMR conditions: at 303 K [as TSV]

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
0,2,6,4,3	a?Manp	104.97	72.76	73.01	69.26	75.86	63.83
0,2,6,4	a?Manp	104.33	72.37	81.04	68.49	75.86	63.18
0,2,6	b?Galp	106.13	73.66	74.70	80.26	75.10	63.18
0,2	a?Manp	104.32	72.76	73.02	69.26	74.44	71.34
0	xLmyoIno	77.80	82.16	76.08	73.01	77.23	73.04
	P


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
0,2,6,4,3	a?Manp	5.127	4.052	3.855	3.742	4.070	3.732-3.874
0,2,6,4	a?Manp	4.818	4.172	3.956	3.792	4.068	3.793-3.806
0,2,6	b?Galp	4.465	3.564	3.714	4.024	3.735	3.733-3.734
0,2	a?Manp	5.171	4.131	3.855	3.740	4.151	3.872-4.140
0	xLmyoIno	3.962	4.257	3.610	3.743	3.324	3.874
	P


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
0,2,6,4,3	a?Manp	104.97/5.127	72.76/4.052	73.01/3.855	69.26/3.742	75.86/4.070	63.83/3.732-3.874
0,2,6,4	a?Manp	104.33/4.818	72.37/4.172	81.04/3.956	68.49/3.792	75.86/4.068	63.18/3.793-3.806
0,2,6	b?Galp	106.13/4.465	73.66/3.564	74.70/3.714	80.26/4.024	75.10/3.735	63.18/3.733-3.734
0,2	a?Manp	104.32/5.171	72.76/4.131	73.02/3.855	69.26/3.740	74.44/4.151	71.34/3.872-4.140
0	xLmyoIno	77.80/3.962	82.16/4.257	76.08/3.610	73.01/3.743	77.23/3.324	73.04/3.874
	P

¹H NMR data:

Linkage	Residue	H1	H2	H3	H4	H5	H6
0,2,6,4,3	a?Manp	5.127	4.052	3.855	3.742	4.070	3.732 3.874
0,2,6,4	a?Manp	4.818	4.172	3.956	3.792	4.068	3.793 3.806
0,2,6	b?Galp	4.465	3.564	3.714	4.024	3.735	3.733 3.734
0,2	a?Manp	5.171	4.131	3.855	3.740	4.151	3.872 4.140
0	xLmyoIno	3.962	4.257	3.610	3.743	3.324	3.874
	P

¹³C NMR data:

Linkage	Residue	C1	C2	C3	C4	C5	C6
0,2,6,4,3	a?Manp	104.97	72.76	73.01	69.26	75.86	63.83
0,2,6,4	a?Manp	104.33	72.37	81.04	68.49	75.86	63.18
0,2,6	b?Galp	106.13	73.66	74.70	80.26	75.10	63.18
0,2	a?Manp	104.32	72.76	73.02	69.26	74.44	71.34
0	xLmyoIno	77.80	82.16	76.08	73.01	77.23	73.04
	P

There are 16 chemically distinct structures. Please, select:

O=P(O)(O)O[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@@H]1O[C@H]1O[C@H](CO[C@@H]2O[C@H](CO)[C@H](O[C@H]3O[C@H](CO)[C@@H](O)[C@H](O[C@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]4O)[C@@H]3O)[C@H](O)[C@H]2O)[C@@H](O)[C@H](O)[C@@H]1O

SVG MW SMILES 3D mol Ionize