The phase behavior of 1,1′-di-O-eicosamethylene-2,2′-di-O-decylbis(glycero-3-phosphocholine) (1) and 1,1′-di-O-hexadecamethylene-2,2′-di-O-octylbis(glycero-3-phosphocholine) (2) was studied at the air-water interface and in aqueous dispersions using monolayer film balance, small-angle X-ray scattering, Raman spectroscopy, and cryo-TEM techniques. The limiting molecular areas (20 °C, pH 6.8) were observed to be 172 Å 2 for 2 and 105 Å 2 for 1, indicating a U-shaped configuration of the long polymethylene chains at the air-water interface. The larger molecular area of 2 relative to 1 at the air-water interface suggests that the alkyl chains of 2 are less ordered than those of 1 at similar pressures. The extrapolated d spacings for 1 from SAXS experiments were 32 Å in the liquid crystalline lamellar phase and 40 Å in the gel phase where the hydrocarbon chains are in their all trans configuration. The extrapolated d spacings for 2 were 27 and 33 Å in the liquid crystalline and gel phases, respectively. DSC analysis revealed phase transition temperatures of 1 and 2 in excess water at 15.3 and -23.5 °C, respectively, with observed transition enthalpies of 9.1 and 2.9 kJ/mol, respectively. These values are in good agreement with Raman spectroscopy experiments that detect alkyl melting transitions near these temperatures. Addition of 30 mol % cholesterol to both bolaamphiphile samples lowered the observed transition temperatures (1, 9.5 °C; 2, -25.1 °C) and enthalpies (1, 5.7 kJ/mol; 2, 2.5 kJ/mol), suggesting that cholesterol reduces the transition cooperativity. Extruded samples of pure 1 in buffer (30 mg/mL in 20 mM Tris, pH 8) produced vesicle structures that were variable in size (0.15-1.5 µm), with multilamellar and nonspherical morphologies apparent. Incorporation of cholesterol in the extruded samples (7:3 1/Chol), however, gave stable spherical unilamellar vesicles with a mean diameter of 857 ( 237 Å. Similar results were observed for dispersions of 2 and 7:3 2/Chol. These results suggest that stable, unilamellar monolayer membrane vesicles can be formed from bolaamphiphiles with relatively short (C16 and C20) membrane-spanning alkyl chains.

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