LAUSR

Despite important advances in macromolecular self-assembly, it remains challenging to achieve 0D–3D nanomaterials using an as-prepared polymer. To address this challenge and elucidate topology-related properties, a tadpole-linear block polymer (TLBP) and its starlike analogue comprising poly(e-caprolactone), polystyrene and poly(acrylic acid) segments are designed. Compared with a star terpolymer bearing two unlocked polystyrene segments, the TLBP with a cyclic polystyrene block can exhibit elevated melting temperature, enhanced stability of 2D nanostructures upon pH switch and more abundant nanoparticle morphologies, revealing a pronounced cyclization effect. With the increase of the ratio of water to DMF, 0D-to-1D-to-2D morphological transitions occurred during self-assembly. Different from core–corona micelles with a mixed core in star assemblies, TLBP assemblies had multicompartment micelles as fundamental building motifs. Owing to the intrinsic balances among amphipathy, crystallization, hydrogen bonding and electrostatic interactions, copolymer assemblies are subjected to intriguing pH-guided cylinder-platelet-nanosheet-vesicle-sphere (for star) and dendritic vesicle-spherical vesicle-platelet-nanosheet-tadpole-micelle cluster (for TLBP) transitions. Rational design of complex macromolecular architecture affords new insight into the topology effect, and architecture, crystallization and stimulus-dependent hierarchical self-assembly systems may act as a robust platform to achieve dimension-tunable nano-objects.