Monoolein forms self-assembled nanoparticles with various internally ordered nanostructures, including the lyotropic liquid crystalline inverse hexagonal and inverse bicontinuous cubic phases. This study investigated the influence of a saturated fatty acid, capric acid (decanoic acid), on the formation of different lyotropic liquid crystalline phases in monoolein-based systems. The nanoparticles were characterized by synchrotron small angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering, and zeta potential measurements. The addition of capric acid to monoolein triggered concentration dependent phase changes with the sequence evolving from an inverse primitive cubic phase to inverse double-diamond cubic, inverse hexagonal (H II ), and emulsified microemulsions. SAXS and cryo-TEM revealed the formation of both single phase and mixed phases within a nanoparticle. To understand the cytotoxicity effects of the different nanoparticles, cellular cytotoxicity and hemolysis assays were performed. Nanoparticles in emulsion and hexagonal phases were found to be less toxic than cubic phase nanoparticles. The hemolysis assays followed the same trend with cubic phase dispersions causing the highest level of hemoglobin release. In summary, this study showed that the internal lyotropic liquid crystal mesophase structure of self-assembled nanoparticles needs careful consideration in the design of drug delivery vehicles. ; Tel: +61 3 9925 4265 † Electronic supplementary information (ESI) available. See

The interactions of two 2-mm pendant oil droplets grown in the presence of an aqueous solution of poly(glycerol monomethacrylate)-stabilized polystyrene latex particles was observed using a high-speed video camera. The coalescence behavior was monitored as a function of oil type (n-dodecane versus sunflower oil) and particle size (135 versus 902 nm), as well as in the presence and absence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol)]. The damping coefficient of the coalescing n-dodecane droplets was found to increase in the presence of the latex, demonstrating particle adsorption. Coalescence times increased when the oil phase was changed from n-dodecane to sunflower oil, because of the much higher viscosity of the latter oil. In addition, increasing the adsorbed particle size from 135 to 902 nm led to longer coalescence times because of the greater distance separating the oil droplets. Coalescence times observed in the presence of the larger 902-nm particles indicated that two different modes of contact can occur prior to a coalescence event (bilayer or bridging monolayer of particles in the film). Addition of an oil-soluble surface-active cross-linker to the sunflower oil phase to react with the hydroxy groups of the particle stabilizer reduced the interfacial elasticity and ultimately prevented coalescence after cross-linking for 20 min at 25 °C. Such giant colloidosomes can remain in contact for several hours without undergoing coalescence, which demonstrates their high stability. Furthermore, coalescence is prevented even if the cross-linker is present in only one of the pendant droplets. Finally, evidence for cross-linker diffusion from one pendant droplet to another was indicated by a visible filament connecting the two droplets upon retraction.

The coalescence of two oil droplets grown at pH 10 in the presence of lightly cross-linked 260 nm diameter charge-stabilised poly(tert-butylamino)ethyl methacrylate (PTBAEMA) latexes was monitored using a high-speed video camera. Three model oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. In the absence of PPG-TDI, rapid coalescence was observed for giant PTBAEMA-stabilised Pickering oil droplets, which exhibited faster coalescence times compared to bare oil droplets. However, an increase in the damping coefficients for coalescing Pickering droplets (compared to those of bare oil droplets) indicated PTBAEMA latex particle adsorption. Addition of PPG-TDI cross-linker to oil droplets in the absence of latex particles led to a reduction in the interfacial tension confirming its surface-active nature. The oil-soluble PPG-TDI reacts with the secondary amine groups on the PTBAEMA latex, producing giant colloidosomes that remain stable to coalescence when brought into contact. This stability to coalescence was not observed for bare oil droplets in the presence of PPG-TDI, confirming that the cross-linked latex particles at the interface provide the additional stability. Finally, interactions between asymmetric n-dodecane droplets were examined. Adding oil-soluble cross-linker to only one droplet resulted in "arrested coalescence" behaviour in the presence of PTBAEMA latex particles. In this context, the droplet ageing time was found to be critical and is attributed to the relatively slow particle adsorption kinetics. Ageing times of less than 60 s led to catastrophic droplet coalescence, whereas ageing times longer than 60 s indicated cross-linker diffusion from one droplet to the other, which produced inter-cross-linked colloidosomes. Arrested coalescence was only observed for ageing times of approximately 60 s.

The interaction between a pair of millimeter-sized nanoparticle-stabilized n-dodecane droplets was analyzed using a high-speed video camera. The droplets were grown in the presence of either poly(glycerol monomethacrylate)-poly(benzyl methacrylate) (PGMA-PBzMA) diblock copolymer spheres or poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) (PGMA-PHPMA-PBzMA) triblock copolymer worms prepared by polymerization-induced self-assembly. The effect of nanoparticle morphology on droplet coalescence was analyzed by comparing 22 nm spheres to highly anisotropic worms with a mean worm width of 26 nm and comparable particle contact angle. Both morphologies lowered the interfacial tension, providing direct evidence for nanoparticle adsorption at the oil-water interface. At 0.03 w/v % copolymer, an aging time of at least 90 s was required to stabilize the n-dodecane droplets in the presence of the worms, whereas no aging was required to produce stable droplets when using the spheres, suggesting faster diffusion of the latter to the surface of the oil droplets. The enhanced stability of the sphere-coated droplets is consistent with the higher capillary pressure in this system as the planar interfaces approach. However, the more strongly adsorbing worms ultimately also confer stability. At lower copolymer concentrations (≤0.01 w/v %), worm adsorption promoted droplet stability, whereas the spheres were unable to stabilize droplets even after longer aging times. The effect of mean sphere diameter on droplet stability was also assessed while maintaining an approximately constant particle contact angle. Small spheres of either 22 or 41 nm stabilized n-dodecane droplets, whereas larger spheres of either 60 or 91 nm were unable to prevent coalescence when the two droplets were brought into contact. These observations are consistent with the greater capillary pressure stabilizing the oil-water interfaces coated with the smaller spheres. Addition of an oil-soluble polymeric diisocyanate cross-linker to either the 60 or the 91 nm spheres produced highly stable colloidosomes, thus confirming adsorption of these nanoparticles.