The self-assembly of amphiphilic oligomers/polymers is a versatile and promising approach for creating nonspherical polymeric nanoparticles. Discrete amphiphilic oligomers/polymers with molecularly defined structures are ideal candidates for fabricating smart nanoparticles and for achieving a deeper understanding of structure-controlled self-assembly. Herein, discrete and disperse amphiphilic homopolymers of PAZO_nTEG_2n, with hydrophobic azobenzene are designed and synthesized as the main chains tethered with hydrophilic tetraethylene glycol monomethyl ether (TEG) units, to accurately investigate the impact of dispersity on their self-assembly in solution. The discrete-PAZO₈TEG₁₆ in DMF/water and in THF/water results in the formation of 2D lamellae, while the dispersed counterpart prefers to self-assemble into spherical micelles. The significant difference is due to their distinction between interior structures of assembly. Furthermore, photoisomerization of azobenzene triggers dissociation/reassembly for discrete polymeric nanoparticles but no obvious change for the dispersed counterparts under irradiation with UV/vis light. This work reveals the influence of dispersity on the self-assembly of amphiphilic polymers and stimuli-responsive properties of their nanomaterials, which is desirable for universal applicability in fabricating smart 2D lamellas.

中文翻译：

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分散性对含主链偶氮苯的两亲均聚物自组装的影响

两亲低聚物/聚合物的自组装是一种用于制造非球形聚合物纳米颗粒的通用且有前景的方法。具有分子定义结构的离散两亲低聚物/聚合物是制造智能纳米粒子和更深入地了解结构控制自组装的理想候选者。在此，设计并合成了 PAZO _n TEG _2n的离散和分散的两亲均聚物，以疏水性偶氮苯为主链，与亲水性四甘醇单甲醚 (TEG) 单元相连，以准确研究分散性对其在溶液中自组装的影响. 分立式 PAZO ₈ TEG ₁₆在 DMF/水和 THF/水中导致二维薄片的形成，而分散的对应物更喜欢自组装成球形胶束。显着差异是由于它们在装配的内部结构之间的区别。此外，偶氮苯的光异构化引发离散聚合物纳米粒子的解离/重新组装，但在紫外/可见光照射下分散的对应物没有明显变化。这项工作揭示了分散性对两亲聚合物的自组装及其纳米材料的刺激响应特性的影响，这对于制造智能二维薄片的普遍适用性是可取的。