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  • Phase behavior of palmitoyl...
    Arsov, Zoran; González-Ramírez, Emilio J.; Goñi, Felix M.; Tristram-Nagle, Stephanie; Nagle, John F.

    Chemistry and physics of lipids, July 2018, 2018-07-00, 20180701, Letnik: 213
    Journal Article

    Display omitted •X-ray scattering from hydrated, oriented sphingomyelin (SM) samples clearly distinguishes phases.•Egg SM (ESM) forms a stable ripple phase in a wide temperature range below TM.•Palmitoyl SM (PSM) displays the usual gel- > ripple- > fluid phases upon heating.•Ripple wavelength is temperature-dependent, decreasing with increasing T.•Fluid phase area is ∼64 Å2 for both ESM and PSM; gel phase area/lipid for PSM is 45 Å2. Despite the biological significance of sphingomyelins (SMs), there is far less structural information available for SMs compared to glycerophospholipids. Considerable confusion exists in the literature regarding even the phase behavior of SM bilayers. This work studies both palmitoyl (PSM) and egg sphingomyelin (ESM) in the temperature regime from 3 °C to 55 °C using X-ray diffraction and X-ray diffuse scattering on hydrated, oriented thick bilayer stacks. We observe clear evidence for a ripple phase for ESM in a large temperature range from 3 °C to the main phase transition temperature (TM) of ∼38 °C. This unusual stability of the ripple phase was not observed for PSM, which was in a gel phase at 3 °C, with a gel-to-ripple transition at ∼24 °C and a ripple-to-fluid transition at ∼41 °C. We also report structural results for all phases. In the gel phase at 3 °C, PSM has chains tilted by ∼30° with an area/lipid ∼45 Å2 as determined by wide angle X-ray scattering. The ripple phases for both PSM and ESM have temperature dependent ripple wavelengths that are ∼145 Å near 30 °C. In the fluid phase, our electron density profiles combined with volume measurements allow calculation of area/lipid to be ∼64 Å2 for both PSM and ESM, which is larger than that from most of the previous molecular dynamics simulations and experimental studies. Our study demonstrates that oriented lipid films are particularly well-suited to characterize ripple phases since the scattering pattern is much better resolved than in unoriented samples.