Rational Polyelectrolyte Design Enables Multifunctional Polyion Complex Vesicles.

Polyion complex (PIC) vesicles prepared by polyelectrolyte assembly have attracted extensive attention as distinctive carriers and nanoreactors, particularly for biological cargoes. However, the constrained regulation of their structure and functionality at this stage hinder the application of PIC vesicles. Herein, we design a new asymmetric assembly system, namely cationic-neutral-cationic triblock copolymer co-assembly with a supramolecular ionic coordination polymer. The former creates poly(ethylene oxide) (PEO) loops upon complexation, which are favorable for vesicle fabrication, while the coordination polyelectrolyte composed of metal ions and a dipicolinic acid (DPA)-based bis-ligand features well-defined functionalities depending on the incorporated metal ions. Thus, the rational combination allows controlled fabrication of PIC vesicles with a modulated structure and functionalities. Moreover, the encapsulation and release of hydrophilic dextran based on different PIC vesicles has been realized. Our design integrates the advantages of both triblock and coordination polymers, and therefore demonstrates a novel strategy for harmonious regulation of the structure and functionality of PIC vesicles. The revealed findings and achieved properties shall be inspirational for developing functional PIC vesicles and boosting their applications towards demand encapsulation and delivery.