Two galactofuranomannans, Ths-4 and Ths-5, were isolated from the lichen, Thamnolia vermicularis var. subuliformis, using ethanol fractionation and anion-exchange and size-exclusion chromatography. The average molecular weights of Ths-4 and Ths-5 were estimated to be 19 and 200 kDa, respectively. Structural characterisation of Ths-4, Ths-5 and their partially hydrolysed derivatives was performed by methanolysis and methylation analysis. The intact and partially hydrolysed Ths-4 was further analysed using NMR spectroscopy (1D, COSY, NOESY, TOCSY, HSQC and HMBC). According to the data obtained, the heteroglycans Ths-4 and Ths-5 have similar structures, but have large differences in molecular weight. The structure is composed of 3-O-linked and 5-O-linked galactofuranosyl chains linked to a mannan core. The mannan core consists of a main chain of α-(1→6)-linked mannopyranosyl residues, substituted at O-2 with either a single α-mannopyranosyl unit or an α-Manp-(1→2)-α-Manp-(1→2)-α-Manp group in the ratio of approximately 1:3, respectively. The polysaccharides have idealised repeating blocks as is shown.

methylation analysis, NMR spectroscopy, lichens, Galactofuranomannan, Thamnolia

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
	bDGalf	107.6	81.8	77.1	82.1	76.1	61.2


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
	bDGalf	5.13	4.09	4.05	4.10	3.89	3.75


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
	bDGalf	107.6/5.13	81.8/4.09	77.1/4.05	82.1/4.10	76.1/3.89	61.2/3.75

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

[*]O[C@H](CO)[C@@H]1O[C@@H]([*])[C@H](O)[C@H]1O

162.141 g/mol (C₆H₁₀R₂O₅, R = next and previous repeats, not counted in mol weight)

Two galactofuranomannans, Ths-4 and Ths-5, were isolated from the lichen, Thamnolia vermicularis var. subuliformis, using ethanol fractionation and anion-exchange and size-exclusion chromatography. The average molecular weights of Ths-4 and Ths-5 were estimated to be 19 and 200 kDa, respectively. Structural characterisation of Ths-4, Ths-5 and their partially hydrolysed derivatives was performed by methanolysis and methylation analysis. The intact and partially hydrolysed Ths-4 was further analysed using NMR spectroscopy (1D, COSY, NOESY, TOCSY, HSQC and HMBC). According to the data obtained, the heteroglycans Ths-4 and Ths-5 have similar structures, but have large differences in molecular weight. The structure is composed of 3-O-linked and 5-O-linked galactofuranosyl chains linked to a mannan core. The mannan core consists of a main chain of α-(1→6)-linked mannopyranosyl residues, substituted at O-2 with either a single α-mannopyranosyl unit or an α-Manp-(1→2)-α-Manp-(1→2)-α-Manp group in the ratio of approximately 1:3, respectively. The polysaccharides have idealised repeating blocks as is shown.

methylation analysis, NMR spectroscopy, lichens, Galactofuranomannan, Thamnolia

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
	bDGalf	107.6	80.1	82.5	82.6	71.3	63.4


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
	bDGalf	5.14	4.23	4.13	3.97	3.84	3.61-3.65


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
	bDGalf	107.6/5.14	80.1/4.23	82.5/4.13	82.6/3.97	71.3/3.84	63.4/3.61-3.65

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

[*]O[C@@H]1[C@@H](O)[C@H]([*])O[C@H]1[C@H](O)CO

162.141 g/mol (C₆H₁₀R₂O₅, R = next and previous repeats, not counted in mol weight)

Two galactofuranomannans, Ths-4 and Ths-5, were isolated from the lichen, Thamnolia vermicularis var. subuliformis, using ethanol fractionation and anion-exchange and size-exclusion chromatography. The average molecular weights of Ths-4 and Ths-5 were estimated to be 19 and 200 kDa, respectively. Structural characterisation of Ths-4, Ths-5 and their partially hydrolysed derivatives was performed by methanolysis and methylation analysis. The intact and partially hydrolysed Ths-4 was further analysed using NMR spectroscopy (1D, COSY, NOESY, TOCSY, HSQC and HMBC). According to the data obtained, the heteroglycans Ths-4 and Ths-5 have similar structures, but have large differences in molecular weight. The structure is composed of 3-O-linked and 5-O-linked galactofuranosyl chains linked to a mannan core. The mannan core consists of a main chain of α-(1→6)-linked mannopyranosyl residues, substituted at O-2 with either a single α-mannopyranosyl unit or an α-Manp-(1→2)-α-Manp-(1→2)-α-Manp group in the ratio of approximately 1:3, respectively. The polysaccharides have idealised repeating blocks as is shown.

methylation analysis, NMR spectroscopy, lichens, Galactofuranomannan, Thamnolia

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6
6,6,6,2	a?Manp	102.8	70.5	71.2	67.4	73.9	61.5
6,6,6	a?Manp	98.8	79.2	70.7	66.8	71.1	66.0
6,6,2,2,2	a?Manp	102.8	70.5	71.2	67.4	73.9	61.5
6,6,2,2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
6,6,2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
6,6	a?Manp	98.8	79.2	70.7	66.8	71.1	66.0
6,2,2,2	a?Manp	102.8	70.5	71.2	67.4	73.9	61.5
6,2,2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
6,2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
6	a?Manp	98.8	79.2	70.7	66.8	71.1	66.0
2,2,2	a?Manp	102.8	70.5	71.2	67.4	73.9	61.5
2,2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
2	a?Manp	101.3	78.8	70.7	67.5	78.9	61.5
	a?Manp	98.8	79.2	70.7	66.8	71.1	66.0


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6
6,6,6,2	a?Manp	4.99	4.03	3.76	3.62	3.71	3.70-3.84
6,6,6	a?Manp	5.06	3.98	3.88	3.78	3.76	3.65-3.96
6,6,2,2,2	a?Manp	4.99	4.02	3.79	3.62	3.71	3.70-3.84
6,6,2,2	a?Manp	5.18	4.05	3.90	3.62	3.68	3.70-3.84
6,6,2	a?Manp	5.18	4.06	3.91	3.63	3.72	3.70-3.84
6,6	a?Manp	5.06	3.98	3.92	3.78	3.76	3.65-3.96
6,2,2,2	a?Manp	4.99	4.02	3.79	3.62	3.71	3.70-3.84
6,2,2	a?Manp	5.18	4.05	3.90	3.62	3.68	3.70-3.84
6,2	a?Manp	5.18	4.06	3.91	3.63	3.72	3.70-3.84
6	a?Manp	5.06	3.98	3.92	3.78	3.76	3.65-3.96
2,2,2	a?Manp	4.99	4.02	3.79	3.62	3.71	3.70-3.84
2,2	a?Manp	5.18	4.05	3.90	3.62	3.68	3.70-3.84
2	a?Manp	5.18	4.06	3.91	3.63	3.72	3.70-3.84
	a?Manp	5.06	3.98	3.92	3.78	3.76	3.65-3.96


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6
6,6,6,2	a?Manp	102.8/4.99	70.5/4.03	71.2/3.76	67.4/3.62	73.9/3.71	61.5/3.70-3.84
6,6,6	a?Manp	98.8/5.06	79.2/3.98	70.7/3.88	66.8/3.78	71.1/3.76	66.0/3.65-3.96
6,6,2,2,2	a?Manp	102.8/4.99	70.5/4.02	71.2/3.79	67.4/3.62	73.9/3.71	61.5/3.70-3.84
6,6,2,2	a?Manp	101.3/5.18	78.8/4.05	70.7/3.90	67.5/3.62	78.9/3.68	61.5/3.70-3.84
6,6,2	a?Manp	101.3/5.18	78.8/4.06	70.7/3.91	67.5/3.63	78.9/3.72	61.5/3.70-3.84
6,6	a?Manp	98.8/5.06	79.2/3.98	70.7/3.92	66.8/3.78	71.1/3.76	66.0/3.65-3.96
6,2,2,2	a?Manp	102.8/4.99	70.5/4.02	71.2/3.79	67.4/3.62	73.9/3.71	61.5/3.70-3.84
6,2,2	a?Manp	101.3/5.18	78.8/4.05	70.7/3.90	67.5/3.62	78.9/3.68	61.5/3.70-3.84
6,2	a?Manp	101.3/5.18	78.8/4.06	70.7/3.91	67.5/3.63	78.9/3.72	61.5/3.70-3.84
6	a?Manp	98.8/5.06	79.2/3.98	70.7/3.92	66.8/3.78	71.1/3.76	66.0/3.65-3.96
2,2,2	a?Manp	102.8/4.99	70.5/4.02	71.2/3.79	67.4/3.62	73.9/3.71	61.5/3.70-3.84
2,2	a?Manp	101.3/5.18	78.8/4.05	70.7/3.90	67.5/3.62	78.9/3.68	61.5/3.70-3.84
2	a?Manp	101.3/5.18	78.8/4.06	70.7/3.91	67.5/3.63	78.9/3.72	61.5/3.70-3.84
	a?Manp	98.8/5.06	79.2/3.98	70.7/3.92	66.8/3.78	71.1/3.76	66.0/3.65-3.96

There are too many chemically distinct structures (~16384), so only one is shown:

-6)[aDManp(1-2)]aDManp(1-6)[aDManp(1-2)aDManp(1-2)aDManp(1-2)]aDManp(1-6)[aDManp(1-2)aDManp(1-2)aDManp(1-2)]aDManp(1-6)[aDManp(1-2)aDManp(1-2)aDManp(1-2)]aDManp(1-

SVGMWSMILES3D molIonize

 

[*]OC[C@H]1O[C@H](OC[C@H]2O[C@H](OC[C@H]3O[C@H](OC[C@H]4O[C@H]([*])[C@@H](O[C@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]5O[C@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]5O[C@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]5O)[C@@H](O)[C@@H]4O)[C@@H](O[C@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]4O[C@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]4O[C@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]4O)[C@@H](O)[C@@H]3O)[C@@H](O[C@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]3O[C@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]3O[C@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]3O)[C@@H](O)[C@@H]2O)[C@@H](O[C@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]2O)[C@@H](O)[C@@H]1O

2269.974 g/mol (C₈₄H₁₄₀R₂O₇₀, R = next and previous repeats, not counted in mol weight)