Three-phase interactions and interfacial transport phenomena in coacervate/oil/water systems

Complex coacervation is an associative liquid/liquid phase separation resulting in the formation of two liquid phases: a polymer-rich coacervate phase and a dilute continuous solvent phase. In the presence of a third liquid phase in the form of disperse oil droplets, the coacervate phase tends to wet the oil/water interface. This affinity has long been known and used for the formation of core/shell capsules. However, while encapsulation by simple or complex coacervation has been used empirically for decades, there is a lack of a thorough understanding of the three-phase wetting phenomena that control the formation of encapsulated, compound droplets and the role of the viscoelasticity of the biopolymers involved. In this contribution, we review and discuss the interplay of wetting phenomena and fluid viscoelasticity in coacervate/oil/water systems from the perspective of colloid chemistry and fluid dynamics, focusing on aspects of rheology, interfacial tension measurements at the coacervate/solvent interface, and on the formation and fragmentation of three-phase compound drops.