• hydration;
  • dehydration;
  • surface chemistry;
  • liposomes;
  • calorimetry (DSC);
  • water in solids;
  • thermodynamics;
  • bilayer;
  • solid state;
  • physicochemical


Water vapor absorption and desorption at 25°C and phase transition temperatures of phospholipid bilayers were measured as a function of relative humidity (RH) to better understand how the patterns of water vapor absorption and desorption are linked to corresponding phase changes induced by the level of hydration. Comparisons were made of the dipalmitoyl and palmitoyloleyol esters of glycerol derivatized with phosphatidyl-choline, -glycerol, -ethanolamine and with phosphatidic acid. The results suggest that the extent of water vapor absorption and desorption at a given RH reflects the combined effects of water-polar group interaction and access of water to the polar region as controlled by intra- and interbilayer molecular packing and intermolecular attractive and repulsive interactions. The results further suggest that the extent of water vapor absorption and desorption over a range of relative humidities reflects the combined effects of the polar group's ability to interact with water, the access that water has to the polar groups as determined by molecular size and various intermolecular and intrabilayer forces of attraction and repulsion, and interbilayer interactions which influence the degree of order/disorder present in the overall solid-state structure. This behavior is also reflected in the changes observed in the various bilayer phase transition temperatures as a function of RH. Analyses of absorption isotherms suggests that after exceeding a critical RH, water initially interacting with these phospholipids most likely forms either stoichiometric or nonstoichiometric crystal hydrates, as with the disaturated derivatives, or hydrated mesophases, as with the gel states of the monounsaturated derivatives. ©2006 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96:377–396, 2007