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(ε-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.

中文翻译：

---

用于pH引导的0D–3D纳米物体制造的非线性晶体-非晶响应三元共聚物的合理设计

尽管在高分子自组装方面取得了重要进展，但是使用制备好的聚合物来获得0D–3D纳米材料仍然具有挑战性。为了应对这一挑战并阐明拓扑相关的特性，a线性嵌段聚合物（TLBP）及其星形类似物包含聚（ε-己内酯），聚苯乙烯和聚（丙烯酸）链段被设计。与带有两个未锁定聚苯乙烯链段的星形三元共聚物相比，具有环状聚苯乙烯嵌段的TLBP可以表现出更高的熔融温度，pH转换时2D纳米结构的稳定性增强以及更丰富的纳米颗粒形态，从而显示出显着的环化效果。随着水与DMF比例的增加，自组装过程中发生了0D到1D到2D的形态转变。TLBP组件不同于星形组合中具有混合核心的芯冠电晕胶束，其多室胶束是基本的建筑图案。由于两亲性，结晶，氢键和静电相互作用之间的内在平衡，共聚物组件受到引人入胜的pH引导的圆柱体-血小板-纳米片-囊泡-球（对于星形）和树突状囊-球形-囊泡-纳米片-ta-胶束簇（对于TLBP）的转变。复杂大分子体系结构的合理设计提供了对拓扑效应的新见解，并且体系结构，结晶和依赖于刺激的分层自组装系统可以充当实现尺寸可调的纳米对象的强大平台。