Cationic gel-phase liposomes with "decorated" anionic SPIO nanoparticles: morphology, colloidal, and bilayer properties.

The assembly and complexation of oppositely charged colloids are important phenomena in many natural and synthetic processes. Liposome-nanoparticle assemblies (LNAs) represent an interesting hybrid system that combines "soft" and "hard" colloidal materials. This work describes the formation and characterization of gel-phase LNAs formed by the binding of anionic superparamagnetic iron oxide (SPIO) nanoparticles to cationic dipalmitoylphosphatidylcholine (DPPC)/dipalmitoyltrimethylammonium propane (DPTAP) liposomes. Particles were examined with hydrodynamic diameters below (16 nm) and above (30 nm) the cutoff reported for supported lipid bilayer formation. LNA formation with 16 nm particles was entropically driven and particles bound individually to yield "decorated" structures. In this case, increasing nanoparticle concentration yielded colloidal LNA aggregates and eventual charge inversion. In contrast, LNA formation with 30 nm particles was enthalpically driven, and the nanoparticles aggregated at the bilayer interface. These aggregates led to significant LNA aggregation and large bilayer sheets due to liposome rupture despite minimal charge screening of the liposome surface. In this case SLBs were present, but these structures were not dominant. Differences in LNA structure were also revealed through the lipid phase transition behavior. This work infers size-dependent nanoparticle binding and LNA formation mechanisms that can be used to tailor colloidal and bilayer properties. Analogies are made to polyelectrolyte patch charge heterogeneities and DNA complexation with cationic liposomes.