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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: abstract, p.9C, table III, table IV, PI-oligosaccharide
Compound class: glycosphingolipid, glycoinositolphosphoryl ceramide (GIPC)
Contained glycoepitopes: IEDB_114701,IEDB_130701,IEDB_136044,IEDB_137472,IEDB_1394182,IEDB_140116,IEDB_141793,IEDB_141794,IEDB_144983,IEDB_145668,IEDB_152206,IEDB_153220,IEDB_164174,IEDB_167188,IEDB_174332,IEDB_190606,IEDB_983930,SB_165,SB_166,SB_187,SB_195,SB_197,SB_198,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 wild strain; the NMR solvent was not indicated.

Related record ID(s): 42033, 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
0,2,6,4,2	b?Xylp	105.77	75.41	78.21	72.93	67.87
0,2,6,4,3,6	a?Manp	102.39	72.63	73.36	69.45	75.35	63.69
0,2,6,4,3	a?Manp	105.77	72.79	73.42	68.68	72.96	68.79
0,2,6,4	a?Manp	101.93	80.76	80.00	68.80	74.17	62.81
0,2,6	b?Galp	106.23	73.57	74.78	79.84	75.20	63.20
0,2	a?Manp	104.24	72.79	72.95	69.31	74.49	71.47
0	xLmyoIno	77.81	82.29	76.25	73.08	77.20	73.02
	P


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
0,2,6,4,2	b?Xylp	4.354	3.268	3.405	3.609	3.248-3.963
0,2,6,4,3,6	a?Manp	4.893	4.004	3.852	3.665	3.650	3.742-3.876
0,2,6,4,3	a?Manp	5.103	4.056	3.819	3.820	3.889	3.651-3.859
0,2,6,4	a?Manp	4.972	4.047	4.010	3.867	4.058	3.804-3.833
0,2,6	b?Galp	4.479	3.574	3.732	4.067	3.738	3.725-3.760
0,2	a?Manp	5.188	4.147	3.846	3.740	4.154	3.875-4.154
0	xLmyoIno	3.974	4.248	3.612	3.731	3.320	3.856
	P


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
0,2,6,4,2	b?Xylp	105.77/4.354	75.41/3.268	78.21/3.405	72.93/3.609	67.87/3.248-3.963
0,2,6,4,3,6	a?Manp	102.39/4.893	72.63/4.004	73.36/3.852	69.45/3.665	75.35/3.650	63.69/3.742-3.876
0,2,6,4,3	a?Manp	105.77/5.103	72.79/4.056	73.42/3.819	68.68/3.820	72.96/3.889	68.79/3.651-3.859
0,2,6,4	a?Manp	101.93/4.972	80.76/4.047	80.00/4.010	68.80/3.867	74.17/4.058	62.81/3.804-3.833
0,2,6	b?Galp	106.23/4.479	73.57/3.574	74.78/3.732	79.84/4.067	75.20/3.738	63.20/3.725-3.760
0,2	a?Manp	104.24/5.188	72.79/4.147	72.95/3.846	69.31/3.740	74.49/4.154	71.47/3.875-4.154
0	xLmyoIno	77.81/3.974	82.29/4.248	76.25/3.612	73.08/3.731	77.20/3.320	73.02/3.856
	P

¹H NMR data:

Linkage	Residue	H1	H2	H3	H4	H5	H6
0,2,6,4,2	b?Xylp	4.354	3.268	3.405	3.609	3.248 3.963
0,2,6,4,3,6	a?Manp	4.893	4.004	3.852	3.665	3.650	3.742 3.876
0,2,6,4,3	a?Manp	5.103	4.056	3.819	3.820	3.889	3.651 3.859
0,2,6,4	a?Manp	4.972	4.047	4.010	3.867	4.058	3.804 3.833
0,2,6	b?Galp	4.479	3.574	3.732	4.067	3.738	3.725 3.760
0,2	a?Manp	5.188	4.147	3.846	3.740	4.154	3.875 4.154
0	xLmyoIno	3.974	4.248	3.612	3.731	3.320	3.856
	P

¹³C NMR data:

Linkage	Residue	C1	C2	C3	C4	C5	C6
0,2,6,4,2	b?Xylp	105.77	75.41	78.21	72.93	67.87
0,2,6,4,3,6	a?Manp	102.39	72.63	73.36	69.45	75.35	63.69
0,2,6,4,3	a?Manp	105.77	72.79	73.42	68.68	72.96	68.79
0,2,6,4	a?Manp	101.93	80.76	80.00	68.80	74.17	62.81
0,2,6	b?Galp	106.23	73.57	74.78	79.84	75.20	63.20
0,2	a?Manp	104.24	72.79	72.95	69.31	74.49	71.47
0	xLmyoIno	77.81	82.29	76.25	73.08	77.20	73.02
	P

There are 64 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]5O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]5O)[C@@H](O)[C@H](O)[C@@H]4O)[C@@H]3O[C@@H]3OC[C@@H](O)[C@H](O)[C@H]3O)[C@H](O)[C@H]2O)[C@@H](O)[C@H](O)[C@@H]1O

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