Fungal glycosylinositolphosphoceramides (GIPCs) are involved in cell growth and fungal–host interactions. In this study, six GIPCs from the mycelium of the human pathogen Aspergillus fumigatus were purified and characterized using Q-TOF mass spectrometry and 1H, 13C, and 31P NMR. All structures have the same inositolphosphoceramide moiety with the presence of a C18:0-phytosphingosine conjugated to a 2-hydroxylated saturated fatty acid (2-hydroxy-lignoceric acid). The carbohydrate moiety defines two types of GIPC. The first, a mannosylated zwitterionic glycosphingolipid contains a glucosamine residue linked in α1-2 to an inositol ring that has been described in only two other fungal pathogens. The second type of GIPC presents an α-Manp-(1→3)-α-Manp-(1→2)-IPC common core. A galactofuranose residue is found in four GIPC structures, mainly at the terminal position via a β1-2 linkage. Interestingly, this galactofuranose residue could be substituted by a choline–phosphate group, as observed only in the GIPC of Acremonium sp., a plant pathogen.

NMR, galactofuranose, glycosphingolipid, Aspergillus fumigatus, glycosylinositolphosphoceramide

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
2	l?2HOLig
1,0,2,6,3	a?Manp	105.26	73.56	74.07	70.57	76.66	64.41
1,0,2,6	a?Manp	103.51	72.54	82.24	69.06	76.80	64.41
1,0,2	a?GlcpN	101.32	57.91	73.83	72.97	74.30	68.29
1,0	xLmyoIno	79.86	85.22	73.38	75.18	78.03	75.11
1	P
	xXphSphC18


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
2	l?2HOLig
1,0,2,6,3	a?Manp	4.925	3.781	3.606	3.440	3.468	3.524-3.695
1,0,2,6	a?Manp	4.666	3.932	3.656	3.576	3.468	3.518-3.665
1,0,2	a?GlcpN	5.222	2.923	3.652	3.320	3.994	3.594-3.799
1,0	xLmyoIno	3.825	4.168	3.278	3.371	3.048	3.776
1	P
	xXphSphC18


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
2	l?2HOLig
1,0,2,6,3	a?Manp	105.26/4.925	73.56/3.781	74.07/3.606	70.57/3.440	76.66/3.468	64.41/3.524-3.695
1,0,2,6	a?Manp	103.51/4.666	72.54/3.932	82.24/3.656	69.06/3.576	76.80/3.468	64.41/3.518-3.665
1,0,2	a?GlcpN	101.32/5.222	57.91/2.923	73.83/3.652	72.97/3.320	74.30/3.994	68.29/3.594-3.799
1,0	xLmyoIno	79.86/3.825	85.22/4.168	73.38/3.278	75.18/3.371	78.03/3.048	75.11/3.776
1	P
	xXphSphC18

There are 8 chemically distinct structures. Please, select:
l?2HOLig?(1-2)[aDManp(1-3)aDManp(1-6)aDGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aDManp(1-3)aDManp(1-6)aLGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aDManp(1-3)aLManp(1-6)aDGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aDManp(1-3)aLManp(1-6)aLGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aLManp(1-3)aDManp(1-6)aDGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aLManp(1-3)aDManp(1-6)aLGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aLManp(1-3)aLManp(1-6)aDGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18? l?2HOLig?(1-2)[aLManp(1-3)aLManp(1-6)aLGlcpN(1-2)xLmyoIno?(1-P-1)]xXphSphC18?

SVGMWSMILES3D molIonize

 

CCCCCCCCCCCCCCCCCCCCCCC(O)C(=O)N[C@@H](COP(=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)[C@H](O)[C@H](O)CCCCCCCCCCCCCC

1411.703 g/mol (C₆₆H₁₂₇N₂O₂₇P)