Self‐Assembled Polymer Nanoparticles from Amphiphilic Polymers with Diverse Molecular Architectures

Amphiphilic copolymers with non-AB-type molecular architectures, such as graft, star, and cyclic structures, exhibit diverse self-assembly behaviors in aqueous media that differ fundamentally from traditional AB-type block copolymers. These unique macromolecular topologies enable precise control over morphology, size, and thermoresponsive behavior of resulting nanoparticles. This chapter reviews recent progress in the design and self-assembly of amphiphilic graft, star, and cyclic copolymers, emphasizing how structural parameters—including grafting density, main-chain flexibility, arm number, and chain topology—govern the formation of micelles, vesicles, and nanodiscs. Through selected case studies and experimental insights, we demonstrate the critical role of polymer architecture in modulating packing parameters and thermodynamic stability. These findings suggest new avenues for designing advanced polymeric nanomaterials with tailored functions for biomedical and nanotechnological applications.