Coronal Complexation Induces Snowman‐Shaped Janus Polymersome Formation

Abstract Engineering polymersome shape is a keen area of interest because minimal variations in polymersome properties can greatly affect the performance of nanoreactors, drug delivery vehicles, and more. Although methods to transform polymersome shapes have been evolving rapidly, limitations remain in the scope of applicable polymersome compositions and adaptability to engineer a desired shape. In this work, we developed a method utilizing cationic polymer additives and coronal complexation to transform charged spherical polymersomes into asymmetric Janus polymersomes. The resulting morphologies feature a hollow polymersome compartment conjoined to a protruding bleb consisting of the complexed polymer additive, which we propose forms via a dewetting process. This methodology provides enhanced shape control through adjustments in additive composition or plasticizer content, offering additional routes to engineering novel polymersome structures.