Structure and thermotropic behavior of phosphatidylserine bilayer membranes

The structure and thermotropic properties of a homologous series of diacylphosphatidylserines (PS) in the anhydrous and hydrated states have been examined with low-angle X-ray diffraction and differential scanning calorimetry. In the anhydrous state at low temperatures both acidic PS and its NH4+ salts exhibit lamellar bilayer crystal forms that transform to liquid-crystalline hexagonal (type II) structures at higher temperatures. The crystal leads to liquid-crystal transition temperature increases with increasing chain length, the transition temperature of an NH4+-PS being higher than that of its corresponding acidic form. In contrast, the transition enthalpies of the acidic PS are higher than those of the NH4+ salt forms. Hydrated cyclic PS and NH4+-PS exhibit reversible lamellar gel leads to liquid-crystal transitions. In this case the acidic form undergoes this chain length dependent transition at a higher temperature, but with a lower enthalpy change, than the NH4+-PS. Both below and above the hydrocarbon chain melting transition, hydrated lamellar bilayer structures are present. The temperature-composition phase diagram of the NH4+-dimyristoyl-PS/H2O system has been studied in detail. The chain melting transition decreases with increasing hydration, reaching a limiting value of 39 degrees C. X-ray diffraction shows that both the bilayer gel structure and the bilayer liquid-crystal form take up water continuously (i.e., no hydration limit), a characteristic of lipid bilayers with a net charge. Electron-density profiles a NH4+-dimyristoyl-PS at different hydration levels permit detailed analysis of the structural parameters of the PS bilayer.