Topology-directed multi-tunable self-assembly of linear and tadpole-shaped amorphous-responsive-crystalline terpolymers

Abstract

Chain architecture can play a crucial role in topology-directed self-assembly (TDSA). To gain insight into the unique properties originating from linear–cyclic conjugates, ABC linear terpolymer (LTP) and (c-AB)C tadpole-shaped terpolymer (TTP) comprising amorphous polystyrene (A), dual-responsive poly(2-(dimethylamino)ethyl methacrylate) (B) and crystallizable poly(ε-caprolactone) (C) segments were designed. Although the LTP only showed a single phase transition in aqueous solution, TTP solutions could exhibit UCST and LCST dual phase transitions due to more confined aggregation behaviors. Core–shell–corona spheres (for the LTP) and multicompartment lamellae (for the TTP) were initially prepared by self-assembly at ambient temperature, followed by thermo/pH-induced self-assembly to transform into abundant nano-objects involving compound micelles, branched micelles, micellar clusters, vesicles, and lamellae. The LTP and TTP assemblies exhibited significantly different orders of morphological transformation and nano-object shapes, revealing a pronounced topology effect. This study affords a promising platform to construct multi-tunable TDSA systems.