This article reports molecular interaction driven aqueous assembly of supramolecularly engineered amphiphilic macromolecules to cylindrical structure. Each polymer contains a single hydrophobic trialkoxybenzamide-linked naphthalene diimide (NDI) chromophore at the chain terminal as the supramolecular structure directing unit (SSDU). Irrespective of the structure of the appended hydrophilic polymer, H-bonding promoted J-aggregation among the NDI chromophore leads to the formation of thermally stable spherical micelle (critical aggregation concentration: 0.01–0.03 mM) which reorganizes to cylindrical micelle after a few hours. The reorganization time can be regulated by pH in the case of the anionic polymer as it affects the dynamics. Isothermal titration calorimetric (ITC) studies reveal positive ΔS values for assembly of all the polymers, reflecting the self-assembly process is favored by the entropy factor similar to the elegant examples in the biological domain. In contrast, a small molecule analogue of these polymers, having a short hydrophilic wedge (instead of a water-soluble polymer), shows a reverse trend, typically expected in a process of supramolecular organization. This can be attributed to the tightly packed J-aggregation of the NDI chromophore of the SSDU that compels a close packing of the hydrophilic polymer chains in the corona, leading to the release of the surrounding water molecules and causing entropy enhancement.

中文翻译：

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两亲大分子的特定超分子相互作用调节熵有利组装。

本文报道了分子相互作用驱动的超分子工程两亲大分子至圆柱结构的水性组装。每种聚合物在链端均包含一个疏水的三烷氧基苯甲酰胺连接的萘二酰亚胺（NDI）生色团，作为超分子结构指导单元（SSDU）。无论附加的亲水性聚合物的结构如何，N结合生色团之间通过H键促进的J聚集都会导致形成热稳定的球形胶束（临界聚集浓度：0.01–0.03 mM），并在数小时后重组为圆柱形胶束。在阴离子聚合物的情况下，重组时间可以通过pH调节，因为它影响动力学。等温滴定量热法（ITC）研究显示正ΔS类似于自体领域的经典例子，熵因子有利于反映所有聚合物的组装值，反映了自组装过程。相反，这些聚合物的小分子类似物具有短的亲水性楔形物（而不是水溶性聚合物），显示出相反的趋势，通常是在超分子组织过程中预期的。这可以归因于SSDU的NDI发色团的紧密堆积的J聚集，这迫使电晕中的亲水性聚合物链紧密堆积，导致周围水分子的释放并引起熵增强。