Structure and dynamics in oligomannose-type oligosaccharides.

Using a combination of 1H NMR nuclear Overhauser effect measurements, molecular orbital calculations, and molecular dynamics simulations, we have determined the tertiary structure and dynamic properties of the oligomannose oligosaccharide Man alpha 6(Man alpha 3)Man alpha 6(Man alpha 3)Man beta 4GlcNAc beta 4GLcNAc. While the calculated potential surfaces for the majority of the glycosidic linkages could be described by a single deep potential well, similar calculations for the Man alpha 1-6Man alpha and Man alpha 1-6Man beta linkages described a diffuse, shallow well, suggesting that a larger degree of flexibility exists about the latter. These conclusions are supported by the results of molecular dynamics simulations, which suggest that the NMR data should be interpreted in terms of a degree of flexibility about the Man alpha 1-6Man beta and Man alpha 1-6Man alpha linkages. In contrast, a similar series of investigations suggests that the conformation of the Man alpha 1-6Man beta linkage in Man alpha 2Man6(Man alpha 2Man alpha 3)Man alpha 6 (Man alpha 2Man alpha 2Man alpha 3)Man beta 4GlcNAc beta 4GlcNAc is more restricted, resulting in an overall structure that is "restrained".