Phase transitions in phosphatidylcholine multibilayers.

The (2)H NMR spectrum of a multilamellar dispersion of 1-myristoyl-2-[14,14,14-(2)H(3)]myristoyl-sn-glycero-3-phosphocholine with 1 mol% cholesterol in excess water has been recorded at temperatures between -15 degrees C and 36 degrees C. Motionally averaged quadrupole coupling constants nu(Q) and motionally induced asymmetry parameters eta are obtained by spectral analysis. Values of these quantities indicate that, at temperatures below -4 degrees C, any rotational motion of the molecules about their molecular long axis is slow on the NMR time scale. At temperatures immediately above the pretransition these same parameters show that a fast-rotational motion is occurring about the molecular long axis. This rotational motion is hindered in that the molecules flip about a twofold symmetry axis. Between -4 degrees C and the pretransition, spectra appear as the superposition of two powder patterns, one corresponding to the pattern observed below -4 degrees C and the other to the pattern above the pretransition. The relative contribution of the latter increases with temperature until the pretransition is reached. These data have been interpreted in two ways: either the sample between -4 degrees C and the pretransition contains two populations of rapidly and slowly rotating molecules, or there is only a single population of molecules undergoing a 180 degrees flipping motion on the time scale of the NMR measurement. The latter interpretation is more consistent with other experimental findings. At the temperature of the main transition the hydrocarbon chains melt. In the absence of cholesterol, spectra are more complex in that the line shape is reproduced by the superposition of three spectral powder patterns between -4 degrees C and the pretransition and by the superposition of two spectral patterns above the pretransition. It is postulated that these two patterns observed above the pretransition are in direct correspondence to the two ripple structures observed by freeze-fracture electron microscopy in the absence of cholesterol.