Binary mixtures of asymmetric phosphatidylcholines with one acyl chain twice as long as the other

High-resolution differential scanning calorimetry and 31P NMR spectroscopy have been used to study aqueous phosphatidylcholine (PC) dispersions prepared from colyophilized mixtures of C(10):C(22)PC/C(22):C(12)PC of various molar ratios. These two lipid species are highly asymmetric but have a common structural feature; namely, one acyl chain in the fully extended conformation is about twice as long as the other. Our experimental results support two conclusions: (1) These two component lipids are miscible in all proportions in both gel and liquid-crystalline states. This type of system behaves as a nearly ideal mixture. Its calorimetric parameters are those expected on the basis of the mole fraction weighted average of the corresponding parameters for the pure components. (2) The component lipids appear to self-assemble, at T less than Tm, into a mixed interdigitated bilayer in excess water. In a mixed interdigitated bilayer, the short acyl chain of one asymmetric phosphatidylcholine on one side of the bilayer leaflet is apposed with the short acyl chain of another lipid molecule on the other side of the bilayer leaflet, while the longer acyl chain from each of the two leaflets crosses the entire hydrocarbon width of the bilayer. The fundamental packing unit, as well as the dynamic unit describing the axial rotator motion about the bilayer normal for this mixed interdigitated bilayer, is thus a dimer, whereas the packing unit assigned for the noninterdigitated bilayer such as C(16):C(16)PC lamellae is a monomer.