Novel structures in galactoglucomannans of the lichens Cladonia substellata and Cladonia ibitipocae: significance as chemotypes.

The galactoglucomannans of two species of the lichen genus Cladonia, C. substellata and C. ibitipocae, were compared. They were homogeneous on gel-filtration chromatography and structurally related, having (1-->6)-linked alpha-D-mannopyranosyl main-chains, but were substituted in different patterns by alpha- and beta-D-galacto-, beta-D-gluco- and alpha-D-mannopyranosyl groups. The C-1 portions of their 13C-NMR spectra are typical of the lichen species and indicate differences between the two polysaccharides. Partial acetolysis of the galactoglucomannan from C. substellata gave rise to oligosaccharides and three were identified, namely alpha-D-Manp-(1-->3)-alpha beta-D-Galp, alpha-D-Manp-(1-->2)-alpha beta-D-Manp and alpha-D-Manp-(1-->2)-[beta-D-Glcp-(1-->4)]-alpha beta-D-Manp, whereas only the latter two were obtained from that of C ibitipocae. Methylation and Smith degradation data confirmed these results. Whereas the mannobiose represents a common structure in lichen heteropolysaccharides, it is the first time that the other oligosaccharides have been isolated from those of lichens.