THERMODYNAMIC, THERMOMECHANICAL, AND STRUCTURAL-PROPERTIES OF A HYDRATED ASYMMETRIC PHOSPHATIDYLCHOLINE

1-Behenyl-2-lauryl-sn-glycero-3-phosphocholine (22/12PC) belongs to a unique group of phospholipids in which the molecule has one acyl chain almost twice as long as the other. The temperature-composition phase diagram for this lipid in the range of 25-65-degrees-C, and 0 to 84.3% (w/w) water has been constructed by using the isoplethal method in the heating direction and x-ray diffraction for phase identification and structure characterization. At water contents between 10.3 and 34% (w/w) and at temperatures below 43-degrees-C, a single mixed interdigitated lamellar gel phase (L(beta)m, [GRAPHICS] of the type described by Hui et al. (1984. Biochemistry. 23:5570-5577) and McIntosh et al. (1984. Biochemistry. 23:4038-4044) was found. A second phase consisting of bulk aqueous solution coexists with the Lm phase at hydration levels above 34% (w/w) water in the temperature range between 25 and 43-degrees-C. Above 43-degrees-C, a partially interdigitated lamellar liquid crystalline (L(alpha)p) phase [ GRAPHICS] is seen in the water concentration range extending from 0 to 84.3% (w/w). The pure LP phase is found below 43% (w/w) water, while coexistence of the LP phase and the bulk aqueous solution is observed above this water concentration which marks the hydration boundary. Interestingly, the latter boundary for both Lm and LP phases is nearly vertical in the temperature range studied. Furthermore, the lamellar chain-melting transition temperature appears to be relatively insensitive to hydration in the range 0-85% (w/w) water. We have confirmed the identity of the L(beta)m phase by constructing a 5.7-A resolution electron density profile on oriented samples by the swelling method. Temperature-induced chain melting effects an increase in lipid bilayer thickness suggesting that the LP phase has chains packed in the partially as opposed to the mixed interdigitated configuration. Unlike the symmetric phosphatidylcholines a ripple (P(beta')) phase was not found as an intermediate between the low and high temperature lamellar phases of 22/12 PC. The specific volume of 22/12 PC is 940 (+/- 1) mul/g and 946 (+/- 1) mul/g in the hydrated lamellar gel state at 28 (+/- 2) and 40 (+/- 2)-degrees-C, respectively, from neutral buoyancy experiments. Based on measurements of the temperature dependence of the various lattice parameters of the different phases encountered in this study the corresponding lattice thermal expansion coefficients have been measured. These are discussed and their dependence on lipid hydration is reported.