Nuclear Magnetic Resonance (NMR) spectroscopy was used to probe the pr
imary structure of the glucan pullulan. Carbon-13 proton and phosphoru
s-31 NMR spectra in aqueous solution of the intact polysaccharide obta
ined from three different sources indicate that significant structural
differences can occur among these samples. In particular, two samples
consist solely of alpha(1-->6) linked maltotriose units, in accord wi
th the generally accepted structure. However a third sample has fewer
alpha(1-->6) linkages and appeals to consist of higher alpha(1-->6) li
nked maltooligosaccharides in addition to maltotriose. Unlike the othe
r samples, this sample was also phosphorylated. Enzymatic digestion of
pullulan followed by NMR spectroscopy using pullulanase confirmed the
se results, as did HPLC analysis of the resulting digest, which showed
the presence of maltooligosaccharides consisting of ten and more gluc
ose units. However, HPLC analysis of acid hydrolysed pullulan indicate
d that no sugars other than glucose were present in any of the samples
examined.