Interactions of Pluronic block copolymers with lipid monolayers studied by epi-fluorescence microscopy and by adsorption experiments.

The interactions of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers, i.e. Pluronics F87, F88 and F127, with monolayers composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) were investigated with different monolayer techniques. Surface pressure-area isotherms were recorded of co-spread Pluronic/lipid mixtures with different Pluronic content to determine the influence of the polymers on the monolayer phase transitions. The squeeze-out pressure of the polymers upon film compression was dependent on the PPO block length. The monolayer compression experiments were coupled with fluorescence microscopy to visualize the phase separation into polymer-rich and lipid-rich domains and to monitor morphological changes of the lipid domains in the monolayer. Extensive phase separation was observed in the coexistence region between liquid-expanded (LE) and liquid-condensed (LC) lipid phases, where pure polymer domains coexisting with round LE-domains containing polymer, and polymer-free LC-domains were seen. We also investigated the adsorption of Pluronics to a lipid monolayer after injecting a polymer solution underneath a pre-formed lipid monolayer by following the change in pressure at constant area. The results show that polymer adsorption is a superposition of two individual processes with different kinetics. Pluronics with a higher hydrophobicity and with a smaller molecular weight adsorb faster and the type and phase state of the lipid determines the surface pressure where no further Pluronic molecules adsorb to the interface. This critical surface pressure depends on the PPO block length, whereas the strength of the interaction with the lipids is determined by the relative PEO content. This indicates that also interactions between the PEO blocks and the lipid headgroup region are occurring. The interactions with the unsaturated lipid POPC in the liquid-expanded phase turn out to be stronger than for lipids in the liquid-condensed phase, where the polymers are excluded.