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Micrometer-sized double emulsions and antibubbles were produced and stabilized via the Pickering mechanism by colloidal interfacial layers of polymeric nanoparticles (NPs). Two types of nanoparticles, consisting either of polylactic acid (PLA) or polylactic- co -glycolic acid (PLGA), were synthesized by the antisolvent technique without requiring any surfactant. PLA nanoparticles were able to stabilize water-in-oil (W/O) emulsions only after tuning the hydrophobicity by means of a thermal treatment. A water-in-oil-in-water (W/O/W) emulsion was realized by emulsifying the previous W/O emulsion in a continuous water phase containing hydrophilic PLGA nanoparticles. Both inner and outer water phases contained a sugar capable of forming a glassy phase, while the oil was crystallizable upon freezing. Freeze drying the double emulsion allowed removing the oil and water and replacing them with air without losing the three-dimensional (3D) structure of the original emulsion owing to the sugar glassy phase. Reconstitution of the freeze-dried double emulsion in water yielded a dispersion of antibubbles, i.e., micrometric bubbles containing aqueous droplets, with the interfaces of the antibubbles being stabilized by a layer of adsorbed polymeric nanoparticles. Remarkably, it was possible to achieve controlled release of a flourescent probe (calcein) from the antibubbles through heating to 37 °C leading to bursting of the antibubbles.

The association efficiency of oxytetracycline (OTC) to pharmaceutical available, ionic oil-in-water nanoemulsions is studied. Theoretical mathematical developments allowed us to differentiate by diafiltration (DF) between thermodynamically and kinetically controlled binding of the drug to the nanoemulsions, and relate these important magnitudes to the association efficiency. The nanoemulsions have been prepared by the solvent displacement technique in the presence of cationic and anionic surfactants. The resulting nanoemulsions were stable at 4°C and 25°C for 60 days, have a size of ∼ 200 nm, showing polydispersity indexes ranging between 0.11 and 0.23, and present zeta potentials ranging between -90 and +60 mV, depending on the charge of the surfactants used. The zeta potential of the nanoemulsions influenced the interaction with OTC, having three ionic forms at different pH, namely, cationic, zwitterionic, and anionic. DF proved to be a powerful tool for the quantification of the drug association efficiency, achieving values up to 84%. Furthermore, this technique allowed obtaining different values of the drug fractions reversibly bound (11%-57%) and irreversibly bound (10%-40%) to the nanoemulsions depending on the surfactants used and pH. These findings may be useful for the development of new drug delivery systems, and as routine assays in academia and pharmaceutical industries., (© 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.)