Complex Emulsions by Extracting Water from Homogeneous Solutions Comprised of Aqueous Three-Phase Systems

Multiple emulsions can be obtained by binary and ternary liquid phase separation. And the use of the aqueous two-phase system provides a simple route to prepare water-in-water-in-oil (W/W/O) or water-in-water-in-water (W/W/W) multiple emulsions. It is thus expected that we can fabricate more complex emulsions by using an aqueous three-phase system. Herein, we present a simple and versatile method to generate complex emulsions based on phase separation in homogeneous droplets made up of aqueous three-phase system: poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA) and dextran (DEX) through extracting water from droplets. We examine the formation process and the effect of mass ratio of each two components in the three phase system. Emulsion droplets with five types of morphologies, i.e., binary-core/shell, core/shell-single phase Janus, ellipsoid Janus, multicore-in-matrix and single core-double shell morphologies can be formed, depending on the mass ratio of each two components and modification of PEG with Fe₃O₄ nanoparticles. We observe transition of core/shell-single phase Janus to binary-core/shell and single core-double shell to core/shell-single phase Janus geometry with prolongation of extracting time, and obtain the geometry map for the formation of different shaped droplets. Due to different affinities of PEG, PVA and DEX to certain materials, we functionalize each compartment in the complex emulsion droplets, and apply the resulting droplet for glucose sensing and the construction of antibody-mediated targeting drug delivery. This emulsion generation method is simple and the choice for the component of the aqueous three-phase system is broad, which can be further extended to generate complex emulsions from aqueous multiphase systems.