Phospholipid acyl chain rotational dynamics are independent of headgroup structure in unilamellar vesicles containing binary mixtures of dioleoyl-phosphatidylcholine and dioleoyl-phosphatidylethanolamine.

We have examined relationships between phospholipid headgroup structure and acyl chain dynamics, and their respective roles in modulating the physical properties of biological membranes. Fluorescence lifetime and anisotropy measurements were used to assess structural changes involving the lipid acyl chains in homogeneous populations of small and large unilamellar vesicles containing binary mixtures of dioleoyl-phosphatidylcholine (PC) and dioleoyl-phosphatidylethanolamine (PE) in the liquid-crystalline (Lalpha) phase. These measurements involve three different fluorescent lipid analogs containing diphenylhexatriene (DPH) linked to either a trimethylamine moiety (i.e., TMA-DPH) or the sn-1 position of monostearoyl-phospholipids containing PC or PE headgroups (i.e., DPH-PC and DPH-PE). The average lifetimes, rotational correlation times, and order parameters associated with DPH-PC and DPH-PE are virtually identical, and are not affected by alterations in the PE content of the membrane. These results suggest that the average cross-sectional areas of the phospholipid acyl chains of DOPE and DOPC relative to the membrane normal are similar in these unilamellar vesicles. Since PC headgroups are larger than those of PE, differences in the relative orientation of the phosphocholine and phosphoethanolamine moieties relative to the membrane surface probably function to maintain optimal van der Waals contact interactions between acyl chains. On the other hand, the average lifetime associated with TMA-DPH, whose chromophoric group is near the membrane surface, increases with increasing PE content. The position of TMA-DPH relative to the membrane surface does not change, since the rotational dynamics of TMA-DPH are independent of the PE concentration. Therefore, alterations in the average lifetime of TMA-DPH results from polarity differences near the membrane surface at the level of the glycerol backbone. These results are discussed in terms of how differences in the average conformation of the glycerol backbones or phospholipid headgroups of PE and PC have the potential to regulate membrane function.