Emulsion-Templated Poly(N-Isopropylacrylamide) Shells Formed by Thermo-Enhanced Interfacial Complexation

The encapsulation of fragile biomacromolecules is crucial in many biotechnological applications but remains challenging. Interfacial complexation (IC) in water-in-oil emulsions proves to be an efficient process for the formation of protective polymer layers at the surface of capsule-precursor water droplets. In this work, the enhancement of conventional IC by introducing thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) strands in the interfacial polymer layer is described. Surfactant-polymer IC is implemented in water-in-fluorocarbon oil emulsions between a water-soluble poly(L-lysine)-g-poly(N-isopropylacrylamide) cationic copolymer (PLL-g-PNIPAM) and an oil-soluble anionic surfactant. Fluorescence imaging demonstrates that the thermal collapse transition of PNIPAM strands, triggered by gentle heating, induces an enrichment of the polymer layer initially formed by IC. Spontaneous co-precipitation of nanoparticles initially dispersed in the aqueous cores—with no specific treatment—is also achieved upon PNIPAM transition. This process is leveraged to irreversibly segregate these nanoparticles in the interfacial polymer layer, resulting in gel-like mixed shells. Thermo-enhancement of conventional IC is thus a promising approach for the straightforward formation, strengthening, and functionalization of capsule shells. As implemented in mild conditions, thermo-enhanced IC is additionally compatible with the encapsulation of proteins, opening new opportunities for delivery systems of biomacromolecules.