Intramolecular excimer kinetics of fluorescent dipyrenyl lipids: 2. DOPE/DOPC membranes.

The intramolecular dynamics of the excimer-forming dipyrenyl lipids (DipynPE) of different chain lengths (n) in fully hydrated dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC) binary mixtures was investigated by the use of frequency-domain fluorescence intensity dcay technique. Using a 3-state model (see companion paper), the extent of aggregation and rotational rate of the two covalently attached pyrene moieties in DipynPE were estimated from the frequency-domain data. At 1 degrees C, the rotational rate and aggregation for Dipy4PE and Dipy10PE were insensitive to DOPE% of the lipid bilayer. At 27 degrees C, the rotational rate decreased, whereas the aggregation increased steadily for Dipy10PE as the DOPE% of the bilayer increased from 0 to 80. However, an abrupt increase in the rotational rate and a decrease in the aggregation for Dipy10PE were detected as the DOPE% reached 100, at which point the membranes are in the inverted hexagonal (HII) phase. No similar changes were found for Dipy4PE. These results indicate that the presence of PE with large intrinsic-curvature increases the lateral stress at the region near the center of the bilayer, and that this stress can be relieved as the membranes enter the highly curved HII phase.