Physical behavior of the hydrophobic core of membranes: Properties of 1-stearoyl-2-linoleoyl-sn-glycerol

Phospholipids containing a saturated fatty acid in the primary position and an unsaturated fatty acid in the secondary position are a major structural part of biological membranes. The mixed-chain hydrophobic core of the membranes is the diacylglycerol part. To better understand the core properties of membranes we have studied the physical behavior of 1-stearoyl-2-linoleoyl-sn-glycerol (SLDG) by X-ray diffraction and differential scanning calorimetry (DSC) in the dry and hydrated states. Dry SLDG has four polymorphic phases: alpha (transition temperature, 11.6 degrees C; Delta H = 7.5 kcal/mol); sub-alpha(1) (3.0 degrees C; 0.6 kcal/mol); sub-alpha(2)(-1.0 degrees C; 0.5 kcal/mol); and beta' (16.1 degrees C; 15.4 kcal/mol). The alpha, sub-alpha(1), and sub-alpha(2) phases are metastable with a probable extended bilayer structure (d(001) approximate to 59.5 Angstrom). The chain packing of the alpha phase is hexagonal, while sub-alpha(1) and sub-alpha(2) have pseudohexagonal chain packing. The beta' phase has a tilted bilayer structure (46.9 Angstrom) with strong wide-angle diffractions, suggesting elements of orthorhombic perpendicular packing. Compared to saturated 1,2-diacylglycerols, SLDG packs much less efficiently, but, when compared to 1-stearoyl-2-oleoyl-sn-glycerol, it appears to pack somewhat more efficiently. Thus polyunsaturated linoleate chains appear to pack marginally more effectively with the saturated stearate chains than do monounsaturated chains. SLDG hydrates with 0.5 mol of H2O, which prevents the beta' phase from forming. Only one hydrated a phase (alpha(w)) and two hydrated sub-alpha (sub-alpha(w1), sub-alpha(w2)) phases are formed. These phases are similar in structure to the nonhydrated alpha phases, but the bilayer period is increased by about 2 Angstrom (d(001) approximate to 61.5 Angstrom). This causes minor changes in polymorphism, including lower melting temperatures and enthalpy. A comparison of diacylglycerols to phosphatidylcholines with the same chains shows that the addition of a strong polar group (e.g,, phosphocholine) to the free hydroxyl of the glycerol depresses chain melting and prevents the more efficient packing of the SLDG core of the bilayer.