Physical studies of cell surface and cell membrane structure. Deuterium nuclear magnetic resonance studies of N-palmitoylglucosylceramide (cerebroside) head group structure.

Deuterium Fourier-transform nuclear magnetic resonance spectra of N-palmitoyl[2,3,4,6,6-2H5]glucosylceramide, N-palmitoyl[1-2H]glucosylceramide, N-palmitoyl-[5,6,6-2H3]glucosylceramide, and N-palmitoyl[6,6-2H2]-glucosylceramide have been obtained at 55.3 MHz (corresponding to a magnetic field strength of 8.5 T) for lipids as multilamellar dispersions in excess water at 90 degrees C, above the gel to liquid-crystal phase transition temperature (Tc = 82 degrees C). Spectra were also obtained for these same lipids dispersed with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine, and cholesterol, all in excess water at 90 degrees C. The results are analyzed in terms of a model in which the lipid undergoes fast axial diffusion, together with a "wobbling" of the polar head group, by mathematical methods similar to those used previously for the choline and ethanolamine head groups in phosphatidylcholines and phosphatidylethanolamines [Skarjune, R., & Oldfield, E. (1979) Biochemistry 18, 5903--5909]. However, contrary to the results obtained in the previous study, which indicated many possible conformations for the choline and ethanolamine head groups, results with labeled cerebrosides yield at most a few orientations for the glucose head group in each of the systems studied. Furthermore, where multiple solutions do occur, they fall within a narrow orientational subspace so that all solutions exhibit the same general features. We also show that the order parameter describing the head group wobble is fully determined for each system, and it indicates a rather mobile structure for the cerebroside head group, in a variety of environments. In each system studied the polar head group projects essentially straight up from the bilayer surface into the aqueous region, thereby permitting maximum hydration of the four glucose hydroxyl groups by bulk water molecules.