Curvature, rigidity, and pattern formation in functional polymer micelles and vesicles – From dynamic visualization to molecular simulation

Polymer micelles and vesicles form upon hydration of amphiphilic block copolymers in dilute aqueous solution. Present challenges with these self-assemblies include understanding how molecular structure and polydispersity determine nano- and mesoscopic shape and properties such as flexibility. With charged copolymers, divalent ionic ligands can rigidify polymer vesicle membranes and also induce microphase separation into domains of weak polyelectrolyte gels. In this review, we focus on the underlying physical and molecular questions concerning copolymer assembly and associated challenges and implications for nano-delivery materials. We also highlight molecular simulation techniques that can be used to investigate properties of assemblies, such as curvature, patterning, and other ionic effects in functional polymeric membranes and micelles.

► Discussion of molecular effects on mesoscopic properties in neutral assemblies.
► Discussion of microphase segregation and patterning in charged polymer membranes.
► Overview of curvature and charge effects on delivery applications.