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We introduce a theoretical framework to describe the pH-sensitive phase behavior of polyzwitterion–polyelectrolyte complex coacervates that reasonably captures the phenomenon from recent experimental observations. 

Abstract Traditionally, complex coacervation is regarded as a process whereby two oppositely charged polyelectrolytes self-assemble into spherical droplets. Here, we introduce the polyzwitterionic complex, “pZC”, formed by the liquid-liquid phase separation of a polyzwitterion and a polyelectrolyte, and elucidate a mechanism by which such complexes can assemble using theory and experimental evidence. This system exhibits orthogonal phase behavior-it remains intact in acidic conditions, but disassembles as the pH increases, a process governed by the acid-base equilibria of the constituent chains. We relate the observed phase behavior to physiological conditions within the gastrointestinal tract with a simulation of the gastroduodenal junction, and demonstrate using video microscopy the viability of polyzwitterionic coacervates as technologies for the pH-triggered release of cargo. Such a system is envisaged to tackle imminent problems of drug transport via the oral route and serve as a packaging solution to increase uptake efficiency. 

Abstract Polymer zwitterions continue to emerge as useful materials for numerous applications, ranging from hydrophilic and antifouling coatings to electronic materials interfaces. While several polymer zwitterion compositions are now well established, interest in this field of soft materials science has grown rapidly in recent years due to the introduction of new structures that diversify their chemistry and architecture. Nonetheless, at present, the variation of the chemical composition of the anionic and cationic components of zwitterionic structures remains relatively limited to a few primary examples. In this article, the versatility of 4‐vinylbenzyl sultone as a precursor to ammonium sulfonate zwitterionic monomers, which are then used in controlled free radical polymerization chemistry to afford “inverted sulfobetaine” polymer zwitterions, is highlighted. An evaluation of the solubility, interfacial activity, and solution configuration of the resultant polymers reveals the dependence of properties on the selection of tertiary amines used for nucleophilic ring‐opening of the sultone precursor, as well as useful properties comparisons across different zwitterionic compositions.