Stereochemistry and size of sugar head groups determine structure and phase behavior of glycolipid membranes: densitometric, calorimetric, and X-ray studies.

The role carbohydrate moieties play in determining the structure and energetics of glycolipid model membranes has been investigated by small- and wide-angle X-ray scattering, differential scanning densitometry (DSD), and differential scanning microcalorimetry (DSC). The dependence of a variety of thermodynamic and structural parameters on the stereochemistry of the OH groups in the pyranose ring and on the size of the sugar head group has been studied by using an homologous series of synthetic stereochemically uniform glyceroglycolipids having glucose, galactose, mannose, maltose, or trimaltose head groups and saturated ether-linked alkyl chains with 10, 12, 14, 16, or 18 carbon atoms per chain. The combined structural and thermodynamic data indicate that stereochemical changes of a single OH group in the pyranose ring can cause dramatic alterations in the stability and in the nature of the phase transitions of the membranes. The second equally important determinant of lipid interactions in the membrane is the size of the head group. A comparison of lipids with glucose, maltose, or trimaltose head groups and identical hydrophobic moieties has shown that increasing the size of the neutral carbohydrate head group strongly favors the bilayer-forming tendency of the glycolipids. These experimental results provide a verification of the geometric model advanced by Israelachvili et al. (1980) [Israelachvili, J. N., Marcelja, S., & Horn, R. G. (1980) Q. Rev. Biophys. 13, 121-200] to explain the preferences lipids exhibit for certain structures. Generally galactose head groups confer highest stability on the multilamellar model membranes as judged on the basis of the chain-melting transition. This is an interesting aspect in view of the fact that galactose moieties are frequently observed in membranes of thermophilic organisms. Glucose head groups provide lower stability but increase the number of stable intermediate structures that the corresponding lipids can adopt. Galactolipids do not even assume a stable intermediate L alpha phase for lipids with short chain length but perform only Lc----HII transitions in the first heating. The C2 isomer, mannose, modifies the phase preference in such a manner that only L beta----HII changes can occur. Maltose and trimaltose head groups prevent the adoption of the HII phase and permit only L beta----L alpha phase changes. The DSD studies resulted in a quantitative estimate for the volume change associated with the L alpha----HII transition of 14-Glc. The value of delta v = 0.005 mL/g supports the view that the volume difference between L alpha and HII is minute.(ABSTRACT TRUNCATED AT 400 WORDS)

Effect of lipid admixtures on the L-dipalmitoylphosphatidylcholine subtransition.

The effect of lipid admixtures on the properties of the L-dipalmitoylphosphatidylcholine (L-DPPC) subtransition is investigated by using high-sensitivity differential scanning calorimetry. The four admixtures used are D-DPPC, L-dipalmitoylphosphatidylethanolamine (L-DPPE), cholesterol, and palmitic acid. In all cases the subtransition decreases in enthalpy until disappearance with increase of the admixture concentrations. About 5-7 mol% of D-DPPC or palmitic acid are sufficient for abolishment (without position shifts) of the subtransition, while, on addition of L-DPPE or cholesterol, it persists up to about 20 mol% of the admixture and its disappearance is accompanied by a slight shift to higher temperatures. These data are tentatively interpreted in terms of lateral mixing of L-DPPC and admixture as indicating compound formation with D-DPPC and palmitic acid, and clustering of L-DPPE and cholesterol.