Structure and Interactions in the Anomalous Swelling Regime of Phospholipid Bilayers

Abstract

We have carried out X-ray and neutron diffraction experiments, as a function of temperature, on fully hydrated samples of dimyristoyl phosphatidylcholine bilayers. The data show the following: (a) In the vicinity of the Lα to Pβ‘ transition, we find an anomalous expansion of the water layer of ∼1.7 A. (b) The lipid bilayer thickness increases quasi-linearly and is similar to the increase in the lamellar repeat spacing d found in dimyristoyl ethanolamine bilayers in the temperature range of TM to TM + 13 °C. (c) In contrast to an earlier study, we find no significant changes to the steric size of the phosphatidylcholine headgroup. The anomalous increase in d is thus dominated by an expansion of the water layer. This expansion is caused by a distinct increase in bilayer fluctuations as revealed by an analysis of the Caille parameter. Additional osmotic pressure experiments not only support this notion but have allowed us to further estimate the temperature dependence of both the bilayer bending rigidity, K...