On the utility of 13C-n.m.r. spectroscopy in the identification of the primary structures of manno-oligosaccharides and glycopeptides.

The utility of 13C-n.m.r. spectroscopy in the identification of the primary structures of mannose-containing glycans is investigated. Unlike 1H resonances where the chemical shifts reflect multiple short- and long-range effects, the chemical shifts of 13C resonances are dependent largely upon short-range effects classified as glycosylation (linkage) and substitution effects. These effects are parametized for glycans composed of mannose and encoded in a FORTRAN algorithm. Applications of this program to "unknown" sets of experimental chemical shifts for the resonances of anomeric carbons gave the following conclusions. (1) This program can be used to produce a sub-set of possible structures inclusive of the "known" structure. (2) For other than simple oligosaccharides, it is unlikely that a single structure is consistent with the data for anomeric carbons alone, even when the linkage composition of the glycan has been assessed from other spectral data. (3) When used in conjunction with other chemical techniques, this program can provide a powerful tool for primary analysis of the structure of mannose-containing glycans.