Temperature Dependent Heterogeneous Rotational Correlation in Lipids

Abstract: Lipid structures exhibit complex and highly dynamic lateral structure; and changes in lipid density and fluidity are believed to play an essential role in membrane targeting and function. The dynamic structure of liquids on the molecular scale can exhibit complex transient density fluctuations. Here the lateral heterogeneity of lipid dynamics is explored in free standing lipid monolayers. As the temperature is lowered the probes exhibit increasingly broad and heterogeneous rotational correlation. This increase in heterogeneity appears to exhibit a critical onset, similar to those observed for glass forming fluids. We explore heterogeneous relaxation in in a single constituent lipid monolayer of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) by measuring the rotational diffusion of a fluorescent probe, 1-palmitoyl-2-[1]-sn-glycero-3-phosphocholine (NBD-PC), using wide-field time-resolved fluorescence anisotropy (TRFA). The observed relaxation exhibits a narrow, liquid-like distribution at high temperatures ({\tau} ~ 2.4 ns), consistent with previous experimental measures [1, 2]. However, as the temperature is quenched, the distribution broadens, and we observe the appearance of a long relaxation population ({\tau} ~ 16.5 ns). This supports the heterogeneity observed for lipids at high packing densities, and demonstrates that the nanoscale diffusion and reorganization in lipid structures can be significantly complex, even in the simplest amorphous architectures. Dynamical heterogeneity of this form can have a significant impact on the organization, permeability and energetics of lipid membrane structures.