Disaccharide conformational maps: how adiabatic is an adiabatic map?

Abstract

The ‘adiabatic’ ( φ, ψ) potential-energy surface of the disaccharide α- d-galactopyranosyl-(1→3)-β- d-galactopyranose was obtained by several established methods, using the MM3 molecular mechanics force field. The constrained minimizations throughout the whole grid were carried out using sharply different dielectric constants. The attainment of the ‘true’ adiabatic map is very difficult due to the ‘multiple minimum problem’, originating in the large number of exocyclic pendant groups present in a disaccharide. However, these results suggest that at low dielectric constants, the usual approach starting with conformers carrying cooperative hydrogen bonds results in a good approximation to the true adiabatic map, while at high dielectric constants this approach fails due to the damping of electrostatic and hydrogen-bonding interactions.