Comparison of the 13C-n.m.r. spectra of gangliosides GM1 with those of GM1-oligosaccharide and asialo-GM1

The ¹³C-n.m.r. spectra of asialo-G_M1 and G_M1-oligosaccharide are completely assigned and compared to those previously found for intact G_M1 and for the series G_M4, G_M3, G_M2, G_M1, G_D1a, G_D1b, and G_T1b. Removal of the ceramide residue from G_M1 liberated a free, reducing aldehyde group, which was reflected in a doubling of the ¹³C-n.m.r. signals assignable to the d-glucose residue because of α,β equilibrium. The spectrum of asialo-G_M1 lacks the resonances from the sialic acid residue, as expected; in addition, several resonances from the neutral gangliotetraglycosyl residue shifted to different field positions after removal of sialic acid from G_M1. These resonances include that of C-4 of the inner β-d-galactosyl residue, and C-1 of the 2-acetamido-2-deoxy-d-galactosyl residue that is near the site of attachment of the sialosyl residue. The differences between the chemical shifts of the carbon resonances of oligomeric and monomeric saccharides, termed linkage shifts, provide a quantitative assignment aid. They are ～ $\text{1}\text{3}$ of those for residues linked to sialic acid than those for residues linked to the neutral hexose chain. Correlations among linkage shifts for pairs of glycosidically-linked carbon atoms for asialo-G_M1 and G_M1-oligosaccharide were compared with those for the series of gangliosides G_M4 to G_T1b, and differences are noted for resonances for carbon atoms near the sialic acid residue. The spectrum of ganglioside G_M1b, a positional isomer of G_M1 whose ¹³C-n.m.r. spectrum has not yet been observed, is predicted.