High-pressure proton NMR study of lateral self-diffusion of phosphatidylcholines in sonicated unilamellar vesicles

Effects of pressure on the lateral diffusion of phospholipid molecules in sonicated pure 1,2-dipalmitoylphosphatidylcholine (DPPC) and 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) vesicles (15 wt%) in D2O were examined using the high-pressure proton NMR rotating frame spin-lattice relaxation time (T1rho) method. Proton T1rho were measured at pressures from 1 bar to 5000 bar and at temperatures of 50 degrees C to 70 degrees C for DPPC and 5 degrees C to 35 degrees C for POPC. The T(-1)1rho values were plotted as a function of the square root of the spin-locking field angular frequency (omega1(1/2) and the lateral diffusion coefficient (D) calculated from the slope. Pressure effects on lateral diffusion were observed in the liquid-crystalline (LC) phase. The lateral diffusion coefficient exhibited sharp decreases in response to the various pressure-induced phase transitions encountered. However, pressure had little, if any, effect on lateral diffusion in the pressure-induced gel I (GI) phase and pressure-induced interdigitated gel (Gi) phase. The activation volumes for diffusion were calculated from the slopes from plots of In D versus pressure for both DPPC (37 ml/mol at 50 degrees C, 34 ml/mol at 60 degrees C and 25 ml/mol at 70 degrees C) and POPC (16 ml/mol at 5 degrees C, 9 ml/mol at 20 degrees C and 6 ml/mol at 35 degrees C) sonicated vesicles in the LC phase. The activation energy for diffusion (Ea) was calculated using the slopes from plots of In D versus the inverse of the temperature (1/T) for both DPPC and POPC in the LC phase (3.5 kcal/mol and 3.9 kcal/mol, respectively) and for both DPPC and POPC in the GI phase (6.0 kcal/mol and 4.4 kcal/mol, respectively). From the lateral diffusion coefficient and line width data pressure-temperature phase diagrams for sonicated pure DPPC and POPC vesicles were constructed. The values of the temperature to pressure equivalence of DPPC (dTm/dP) were estimated to be 22.1 degrees C/kbar for the LC to GI phase transition and 28.6 degrees C/kbar for the GI to Gi phase transition. The value of the temperature to pressure equivalence of POPC for the LC to GI phase transition was estimated to be 19.0 degrees C/kbar.