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 i s f o r m e d v i a e l e c t r o s t a t i c i n t e r a c t i o n o f p o l y c a t i o n s o f p o l y -(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.

We report on a simple approach for in-channel functionalization of a polydimethylsiloxane (PDMS) surface to obtain a switchable and reversible wettability change between hydrophilic and hydrophobic states. The thermally responsive polymer, poly(N-Isopropylacrylamide) (PNIPAAm), was grafted on the surface of PDMS channels by UV-induced surface grafting. PNIPAAm-grafted PDMS (PNIPAAm-g-PDMS) surface wettability can be thermally tuned to obtain water contact angles varying in the range of 24.3 to 106.1°by varying temperature at 25−38°C. By selectively modifying the functionalized area in the microfluidic channels, multiform emulsion droplets of oil-in-water (O/W), water-in-oil (W/O), oil-in-water-in-oil (O/W/O), and water-in-oil-inwater (W/O/W) could be created on-demand. Combining solid surface wettability and liquid−liquid interfacial properties, tunable generation of O/W and W/O droplet and stratified flows were enabled in the same microfluidic device with either different or the same two-phase fluidic systems, by properly heating/cooling thermal-responsive microfluidic channels and choosing suitable surfactants. Controllable creation of O/W/O and W/O/W droplets was also achieved in the same microfluidic device, by locally heating or cooling the droplet generation areas with integrated electric heaters to achieve opposite surface wettability. Hollow microcapsules were prepared using double emulsion droplets as templates in the microfluidic device with sequential hydrophobic and hydrophilic channel segments, demonstrating the strength of the proposed approach in practical applications.

Keywords: microfluidics; droplet; microcapsule; pressure-sensitive adhesive; bonding