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Abstract

The thermotropic phase behaviour and chain dynamics of the dimyristoylphosphatidylcholine/myristic acid (1:2, mol/mol) mixture at pH 4.0 have been studied with 31P-NMR and spin-label ESR. Broadline proton-dipolar decoupled 31P-NMR spectra show that the system undergoes a transition from a lamellar phase to a non-lamellar phase at 47° C. The 31P-NMR spectrum collapses, from a lamellar powder pattern with apparent chemical shift anisotropy Δσ = − 38 ppm below 47° C, to an isotropic spectrum with superimposed hexagonal powder pattern of Δσ = + 13 ppm above 47° C. With increasing temperature, the hexagonal component grows at the expense of the isotropic component, finally transforming to a single hexagonal phase at approximately 70° C. The ESR spectra from both fatty acid and phosphatidylcholine probes spin-labelled in the hydrocarbon chain have been used to study the ordering and mobility of the lipid chains through the lamellar-non lamellar transition. An abrupt increase in the chain mobility observed at approx. 47° C demonstrates that the lamellar-non lamellar phase transition coincides with chain melting. The apparent order parameter and polarity profiles, deduced from the ESR spectra of 11 different chain-labelled positional isomers, demonstrate flexibility and polarity gradients characteristic of a lyotropic liquid crystalline phase. The temperature dependence of the order parameters does not show any changes in the fluid phase, indicating that the conversion from the isotropic (cubic) phase to the inverted hexagonal phase is not accompanied by large changes in chain order. A comparison of the apparent order parameters and polarity profiles of the phosphatidylcholine and fatty acid spin labels indicates that the fatty acid spin labels are intercalated approximately one CH2 unit more deeply in the hydrocarbon region than are the positionally isomeric phosphatidylcholine spin labels.