The volume change in lipid bilayer lamellae at the crystalline-liquid crystalline phase transition

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Abstract

The volume change at the crystalline-liquid crystalline phase transition was measured for the dipalmitoylphosphatidylcholine-water system containing lamellar bimolecular structures. An abrupt volume increase of 0.011 ml/g (or ΔVV ≈ 1.4%) is observed at a transition temperature Tt ≈ 44°C. This value is about one order of magnitude smaller than the typical values for the melting dilation of hydrocarbon materials. This indicates that the hydrocarbon chains in the liquid crystalline phase are still in a relatively ordered state. The observed volume change is interpreted in terms of the formation of rotational isomers (kinks) in the hydrocarbon chains. The process of kink formation, which has been studied extensively in paraffins creates pockets of free volume within the lipid hydrocarbon phase and reduces the length of the hydrocarbon chains. The measured values taken together with published X-ray data indicate that the number n of kinks per hydrocarbon chain increases at the transition temperature from n ≈ 0.1 for T < Tt to n ≈ 0.6–2.0 for T >Tt. These data are in accord with the previously reported reduction in the bilayer thickness by about 5 Å at the phase transition. It is concluded that the phase transition is accompanied by an increase in the bilayer surface area per lipid molecule F from F = 48 Å2 for T < Tt to F = 58 Å2 for T >Tt. The consequences of these structural changes for the properties of lipid bilayer membranes (changes in affinity to ligands and changes in membrane permeability) are discussed.

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