Formation of inverted hexagonal phase in SDPE as observed by solid-state (31)P NMR.

Docosahexaenoic acid (DHA), the longest and most unsaturated fatty acid commonly found in biological membranes, is known to affect various membrane properties. In a variety of cell membranes, DHA is primarily incorporated in phosphatidylethanolamines, where its function remains poorly understood. In order to understand the role of DHA in influencing membrane structure, we utilize (31)P NMR spectroscopy to study the phase behavior of 1-stearoyl-2-docosahexaenoyl-sn-glycerophosphoethanolamine (SDPE) in comparison to 1-palmitoyl-2-oleoyl-sn-glycerophosphoethanolamine (POPE) from 20 to 50 degrees C. Spectra of SDPE phospholipids show the formation of inverted hexagonal phase (H(II)) from 20 to 50 degrees C; in contrast, POPE mutilamellar dispersions exist in a lamellar liquid-crystalline phase (L(alpha)) at the same temperatures. The ability of SDPE to adopt nonbilayer phases at a physiological temperature may indicate its role in imparting negative curvature stress upon the membrane and may affect local molecular organization including the formation of lipid microdomains within biological membranes.

Molecular organization of cholesterol in polyunsaturated phospholipid membranes: a solid state 2H NMR investigation.

We compared the molecular organization of equimolar [3alpha-2H1]cholesterol in 18:0-18:1PC (1-stearoyl-2-oleoylphosphatidylcholine), 18:0-22:6PC (1-stearoyl-2-docosahexaenoylphosphatidylcholine), 18:0-20:4PC (1-stearoyl-2-arachidonylphosphatidylcholine) and 20:4-20:4PC (1,2-diarachidonylphosphatidylcholine) bilayers by solid state 2H NMR. Essentially identical quadrupolar splittings (delta v(r) = 45 +/- 1 kHz) corresponding to the same molecular orientation characterized by tilt angle alpha0 = 16 +/- 1 degrees were measured in 18:0-18:1PC, 18:0-22:6PC and 18:0-20:4PC. A profound difference in molecular interaction with dipolyunsaturated 20:4-20:4PC, in contrast, is indicated for the sterol. Specifically, the tilt angle alpha0 = 22 +/- 1 degrees (derived from delta v(r) = 37 +/- 1 kHz) is greater and its membrane intercalation is only 15 mol%.