Water-in-water (w/w) emulsions are particularly advantageous for biomedical-related applications, such as cell encapsulation, bioreactors, biocompatible storage, and processing of biomacromolecules. However, due to ultralow interfacial tension, generation and stabilization of uniform w/w droplets are challenging. In this work, we report a strategy of creating stable and size-controllable w/w droplets that can quickly form polyelectrolyte microcapsules (PEMCs) in a microfluidic device. A three-phase (inner, middle, outer) aqueous system was applied to create a stream of inner phase, which could be broken into droplets via a mechanical perturbation frequency, with size determined by the stream diameter and vibration frequency. The interfacial complexation is formed via electrostatic interaction of polycations of poly(diallyldimethylammoniumchloride) with polyanions of polystyrene sodium sulfate in the inner and outer phases. With addition of negatively charged silica nanoparticles, the stability, permeability, and mechanical strength of the PEMC shell could be well manipulated. Prepared PEMCs were verified by encapsulating fluorescein isothiocyanate-labeled dextran molecules and stimuli-triggered release by varying the pH value or osmotic pressure. A model enzyme, trypsin, was successfully encapsulated into PEMCs and released without impairing their catalytic activity. These results highlight its potential applications for efficient encapsulation, storage, delivery, and release of chemical, biological, pharmaceutical, and therapeutic agents.
Keywords: controlled release; interfacial complexation; mechanical perturbation; microcapsule; nanoparticle; polyelectrolyte; water-in-water droplet.