Responsive Janus and Cerberus emulsions via temperature-induced phase separation in aqueous polymer mixtures

Complex aqueous emulsions represent a promising material platform for the encapsulation of cells, pharmaceuticals, or nutrients, for the fabrication of structured particles, as well as for mimicking the barrier-free compartmentalization of biomolecules found in living cells. Herein, we report a novel, simple, and scalable method of creating multicomponent aqueous droplets with highly uniform internal droplet morphologies that can be controllably altered after emulsification by making use of a thermal phase separation approach. Specifically, temperature-induced phase separation inside as-formed emulsion droplets comprising aqueous mixtures of two or more hydrophilic polymers allows for the generation of Janus and Cerberus emulsion droplets with adjustable internal morphologies that are solely controlled by a balance of interfacial tensions. We demonstrate our approach by applying both, microfluidic and scalable batch production, and present a detailed model study with predictive capabilities that enables fine-tuning and dynamically altering the droplet morphology as a function of types, molecular weights, and hydrophilicities of the polymers as well as the surfactant hydrophilic-lipophilic balance. The ability to rationally design complex aqueous emulsion droplets with previously unattainable dynamic control over their morphologies after emulsification entails the potential to design new responsive soft materials with implications for a variety of applications beyond encapsulation, including the design of complex adaptive and self-regulating materials, e.g. for chemical and biological sensing applications.