Gel to liquid-crystalline phase transitions of aqueous dispersions of polyunsaturated mixed-acid phosphatidylcholines

The thermotropic properties of aqueous dispersions of synthetic mixed-acid polyunsaturated 1,2-diacyl-3-sn-phosphatidylcholines (PC) have been studied by differential scanning calorimetry. The gel to liquid-crystalline phase transition temperature (Tc) of 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine (SLPC) was -16.2 +/- 1.6 degrees C (means +/- SD, nine dispersions, three separate synthetic preparations); that for a preparation of 1-stearoyl-2-linolenoyl-PC (SLnPC) was -13 degrees C and for a preparation of 1-stearoyl-2-arachidonoyl-PC (SAPC) was -12.6 +/- 1.0 degrees C (three dispersions, one preparation). The temperatures of maximum heat flow (Tmax) for the lipid transitions were -14.4 +/- 1.3, -11, and -10.7 +/- 0.9 degrees C and the enthalpies were 3.3 +/- 1.0, 6.6, and 5.3 +/- 1.8 kcal X mol-1 for SLPC, SLnPC, and SAPC, respectively. The transition temperatures and enthalpies are rationalized on the basis of existing data on the effect of double-bond position on Tc and are interpreted with the use of a statistical mechanical model. The trend of the transition temperatures with the introduction of multiple double bonds reflects opposing effects due to increased molecular area and decreasing degrees of freedom of rotation about carbon-carbon bonds.