Thermal transitions in the bilayer assembly of dimyristoylphosphatidylglycerol sodium salt dispersion in water: a new phase transition through an intermediate state.
The thermal properties of the dispersion of sodium salt of dimyristoylphosphatidylglycerol (NaDMPG) in water have been investigated as functions of incubation temperature and aging time by DSC, XRD, sodium ion activity, pH, zeta-potential, and IR measurements. The DSC charts for NaDMPG dispersions incubated below 30 degrees C showed an endothermic peak at 31.7 degrees C with a small shoulder peak at Tm (gel-liquid crystal transition temperature: 23.5 degrees C). The temperature of 31.7 degrees C coincides with the T* temperature at which a high-order transition in the NaDMPG bilayer assembly has been found to occur in our previous studies. However, no peak was observed for the dispersions incubated above 32 degrees C. These results indicate that thermal properties of NaDMPG bilayers definitely differ below and above the T* temperature. The dispersion which had been once incubated at 40 degrees C for 24 h never showed the endothermic peak at T* even after the further aging at 3 degrees C for 12-day. Namely, the NaDMPG bilayer assembly exhibits an intensive thermohysteresis. The XRD charts for the NaDMPG dispersions incubated at 25 degrees C showed a sharp X-ray diffraction pattern corresponding to the repeat distance of d = 4.75 nm regardless of their aging time, while the dispersions incubated at 40 degrees C had no diffraction peak until 9-day elapsed. After 10-day aging at 40 degrees C, however, a diffraction peak corresponding to d = 5.55 nm clearly appeared. In the DSC measurements for the dispersion incubated at 40 degrees C, a few endothermic peaks began to appear between Tm and T* after approximately 7-day aging. Then, they shifted toward higher temperatures and finally converged into a single peak at 40-42 degrees C after 14-day aging. These XRD and DSC peaks observed after a long period of aging time above T* suggest that conformations of the hydrophilic groups and the hydrocarbon chains in the NaDMPG bilayers take a more tight and closer arrangement very slowly via an intermediate state above T*, and a new gel phase of the bilayers is consequently formed, the transition temperature (T(I) temperature) of which is 40-42 degrees C. A molecular interpretation for such transition processes in the bilayer assembly of NaDMPG dispersions has been proposed on the basis of pH, sodium ion activity, zeta-potential, IR data, etc.
Tajima
K
K
Faculty of Engineering, Kanagawa University, Japan. ktajima@cc.kanagawa-u.ac.jp
Imai
Y
Y
Nakamura
A
A
Koshinuma
M
M
D002152:Calorimetry, Differential Scanning; D007700:Kinetics; D008051:Lipid Bilayers / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010715:Phosphatidylglycerols / Q000737:chemistry*; D012492:Salts; D012964:Sodium; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics; D014867:Water; D014961:X-Ray Diffraction
D008051:Lipid Bilayers; D010715:Phosphatidylglycerols; D012492:Salts; D014867:Water; D012964:Sodium; C002773:dimyristoylphosphatidylglycerol