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Taxonomic group: fungi / Ascomycota (Phylum: Ascomycota)
Associated disease: aspergillosis [ICD11: 1F20

, ICD11: XN0WC

]; infection due to Aspergillus fumigatus [ICD11: XN5Z7

]

The structure was elucidated in this paper
NCBI PubMed ID: 17488996
Publication DOI: 10.1194/jlr.M700149-JLR200
Journal NLM ID: 0376606
Publisher: ASBMB
Correspondence: Levery SB <slevery

cisunix.unh.edu>, Takahashi HK <takahashi.bioq

epm.br>
Institutions: Department of Biochemistry and Molecular Biology, University of Georgia, Athens, Georgia, USA, Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, São Paulo, Brazil, Department of Chemistry, University of New Hampshire, Durham, North Carolina, USA, Department of Plant Biology, University of Georgia, Athens, Georgia, USA

Acidic glycosphingolipid components were extracted from the opportunistic mycopathogen Aspergillus fumigatus and identified as inositol phosphorylceramide and glycosylinositol phosphorylceramides (GIPCs). Using nuclear magnetic resonance sppectroscopy, mass spectrometry, and other techniques, the structures of six major components were elucidated as Ins-P-Cer (Af-0), Manp(α1→3)Manp(α1→2)Ins-P-Cer (Af-2), Manp(α1→2)Manp(α1→3)Manp(α1→2)Ins-P-Cer (Af-3a), Manp(α1→3)[Galf(β1→6)]Manp(α1→2)-Ins-P-Cer (Af-3b), Manp(α1→2)-Manp(α1→3)[Galf(β1→6)]Manp(α1→2)Ins-P-Cer (Af-4), and Manp(α1→3)Manp(α1→6)GlcpN(α1→2)Ins-P-Cer (Af-3c) (where Ins = myo-inositol and P = phosphodiester). A minor A. fumigatus GIPC was also identified as the N-acetylated version of Af-3c (Af-3c*), which suggests that formation of the GlcNα1→2Ins linkage may proceed by a two-step process, similar to the GlcNα1→6Ins linkage in glycosylphosphatidylinositol (GPI) anchors (transfer of GlcNAc, followed by enzymatic de-N-acetylation). The glycosylinositol of Af-3b, which bears a distinctive branching Galf(β1→6) residue, is identical to that of a GIPC isolated previously from the dimorphic mycopathogen Paracoccidioides brasiliensis (designated Pb-3), but components Af-3a and Af-4 have novel structures. Overlay immunostaining of A. fumigatus GIPCs separated on thin-layer chromatograms was used to assess their reactivity against sera from a patient with aspergillosis and against a murine monoclonal antibody (MEST-1) shown previously to react with the Galf(β1→6) residue in Pb-3. These results are discussed in relation to pathogenicity and potential approaches to the immunodiagnosis of A. fumigatus.

monoclonal antibody, NMR spectroscopy, mass spectrometry, galactofuranose, glycolipid, Electrospray Ionization, fungus, sphingolipid, ion trap

Structure type: oligomer
Location inside paper: abstract, p.1817, table 4, p.1818, scheme 6, fraction Af-3c
Compound class: glycosphingolipid, glycosylinositolphosphoceramide (GIPC)
Contained glycoepitopes: IEDB_130701,IEDB_1394182,IEDB_141807,IEDB_144983,IEDB_151531,IEDB_152206,IEDB_164174,IEDB_983930,SB_197,SB_44,SB_67,SB_72

Methods: 13C NMR, 1H NMR, methylation, NMR-2D, GC-MS, ESI-MS, composition analysis, serological methods, HPLC, ion-exchange chromatography, extraction, CID-MS, HPTLC, ESI-QTOF-MS, HPTLC immunostaining
Biological activity: comparison of the immunoreactivity of A. fumigatus and A. nidulans GIPCs with monoclonal antibody MEST-1
Comments, role: major component

Related record ID(s): 41798, 42014, 42015, 42016, 42018
NCBI Taxonomy refs (TaxIDs): 746128
Show glycosyltransferases

NMR conditions: in vol 98%DMSO-d6 / vol 2%D2O at 308 K [as TSV]

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
2	lXLig
1,0,2,6,3	a?Manp	102.49	70.60	71.43	67.42	73.72	61.27-61.39
1,0,2,6	a?Manp	100.12	69.64	79.31	66.06	74.07	61.27-61.39
1,0,2	a?GlcpN	100.12	56.49	74.07	70.24	71.12	65.73
1,0	xLmyoIno	75.83	79.96	70.60	72.64	75.70	71.43
1	P
	xXphSph	64.48	50.60	73.20	70.60


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
2	lXLig
1,0,2,6,3	a?Manp	4.883	3.741	3.555	3.422	3.602	3.498-3.628
1,0,2,6	a?Manp	4.622	3.882	3.618	3.512	3.428	3.462-3.630
1,0,2	a?GlcpN	5.034	2.460	3.295	3.135	4.040	3.564-3.675
1,0	xLmyoIno	3.793	4.000	3.241	3.329	2.974	3.555
1	P
	xXphSph	3.689-4.021	3.849	3.455	3.350


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
2	lXLig
1,0,2,6,3	a?Manp	102.49/4.883	70.60/3.741	71.43/3.555	67.42/3.422	73.72/3.602	61.27-61.39/3.498-3.628
1,0,2,6	a?Manp	100.12/4.622	69.64/3.882	79.31/3.618	66.06/3.512	74.07/3.428	61.27-61.39/3.462-3.630
1,0,2	a?GlcpN	100.12/5.034	56.49/2.460	74.07/3.295	70.24/3.135	71.12/4.040	65.73/3.564-3.675
1,0	xLmyoIno	75.83/3.793	79.96/4.000	70.60/3.241	72.64/3.329	75.70/2.974	71.43/3.555
1	P
	xXphSph	64.48/3.689-4.021	50.60/3.849	73.20/3.455	70.60/3.350

¹H NMR data:

Linkage	Residue	H1	H2	H3	H4	H5	H6
2	lXLig
1,0,2,6,3	a?Manp	4.883	3.741	3.555	3.422	3.602	3.498 3.628
1,0,2,6	a?Manp	4.622	3.882	3.618	3.512	3.428	3.462 3.630
1,0,2	a?GlcpN	5.034	2.460	3.295	3.135	4.040	3.564 3.675
1,0	xLmyoIno	3.793	4.000	3.241	3.329	2.974	3.555
1	P
	xXphSph	3.689 4.021	3.849	3.455	3.350

¹³C NMR data:

Linkage	Residue	C1	C2	C3	C4	C5	C6
2	lXLig
1,0,2,6,3	a?Manp	102.49	70.60	71.43	67.42	73.72	61.27 61.39
1,0,2,6	a?Manp	100.12	69.64	79.31	66.06	74.07	61.27 61.39
1,0,2	a?GlcpN	100.12	56.49	74.07	70.24	71.12	65.73
1,0	xLmyoIno	75.83	79.96	70.60	72.64	75.70	71.43
1	P
	xXphSph	64.48	50.60	73.20	70.60

There are 8 chemically distinct structures. Please, select:

CCCCCCCCCCCCCCCCCCCCCCCC(=O)O[1*]OP(=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](O[C@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]3O)[C@@H]2O)[C@@H](O)[C@H](O)[C@H]1N

SVG MW SMILES 3D mol Ionize

R1 = xXphSph (phSphC18 or phSphC20)