On the modulation of a high-enthalpy pretransition in binary mixtures of DMPC and DMPG by polar headgroup interaction

Employing high-sensitivity differential scanning calorimetry (DSC), we discovered a pretransition in binary mixtures of dimyristoyl phosphatidylcholine and dimyristoyl phosphatidylglycerol, the main feature of which is its extraordinarily high transition enthalpy of 6.3 Kcal/mol, nearly an order of magnitude higher than those values previously found for such transitions. Using DSC, deuterium nuclear magnetic resonance, and electron microscopy, it is shown that the energetic origin of this type of pretransition is caused by interactions between the phospholipids in their headgroup region. The most likely interaction involves the formation of a hydrogen bond between the headgroups of the two phospholipid species in the gel (L beta') phase which is disrupted at the transition to the "ripple" (P beta') phase. The finding that this large pretransition is unique for mixtures of phosphocholine and phosphoglycerol with myristoyl chains indicates a dependence of the headgroup long range order of such mixtures in the gel phase on the acyl chain length.