Molecular dynamics simulations for aq solutions of methyl-alpha- and -
beta-D-glucopyranoside, galactopyranoside and talopyranoside have been
carried out. A single molecule surrounded by 252 SPC water molecules
was used under periodic boundary conditions. Preference for the gr and
gg orientations for the hydroxymethyl groups in solution has been con
firmed. Examination of the extent and pattern of hydrogen bonding betw
een water and the sugar molecule hydroxyl groups showed that the galac
tose and glucose derivatives were substantially better hydrogen-bond d
onors at OH-2 and OH-4 than the respective ones of talose. Intramolecu
lar hydrogen bonding involving OH-2 and OH-4 of the talosides persiste
d for some 40% of the 100 ps simulation time in water. The remarkably
long retention times (on reversed-phase HPLC in pure water) of the tal
osides relative to the galactosides and glucosides were rationalised i
n terms of differing extents of hydration, intramolecular hydrogen bon
ding, and compatibility with the structure of water.