Abstract Heterografted amphiphilic molecular brushes are highly grafted macromolecules with both hydrophilic and hydrophobic side chains attached to the backbone. These macromolecules display a unique combination of properties and can self-assemble in solution to form stable structures at very low concentration. Herein, we report a straightforward and robust methodology to access such macromolecules from precursors carrying xanthate side groups. Iterative aminolysis of a fraction of the xanthates and telomerization from the resulting thiols allow preparing heterografted molecular brushes with adjustable backbone dimensions, compositions, and grafting densities, which is exemplified with polymethacrylate hydrophobic grafts and poly(methacrylic acid), poly(acrylic acid) and poly(N-isopropylacrylamide) hydrophilic grafts. Yet, the molecular brushes display relatively high dispersities, which makes this approach not suited to synthesize well-defined heterografted molecular brushes. Nonetheless, the heterografted molecular brushes self-assemble in aqueous solution to form stable core-shell micelles, as observed by dynamic light scattering, with radii of gyration ranging from 30 to more than 100 nm, and critical micellar concentrations as low as 0.3 mg/mL.

中文翻译：

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调聚制备的两亲异质接枝分子刷的合成与自组装

摘要 异质接枝两亲分子刷是高度接枝的大分子，亲水和疏水侧链都连接到主链上。这些大分子显示出独特的特性组合，并且可以在溶液中自组装以在非常低的浓度下形成稳定的结构。在此，我们报告了一种直接且稳健的方法，可从带有黄原酸侧基的前体中获取此类大分子。一部分黄原酸酯的迭代氨解和来自所得硫醇的调聚允许制备具有可调节骨架尺寸、组成和接枝密度的异质接枝分子刷，例如聚甲基丙烯酸酯疏水接枝物和聚（甲基丙烯酸）、聚（丙烯酸）和聚（N-异丙基丙烯酰胺）亲水接枝物。然而，分子刷表现出相对较高的分散性，这使得这种方法不适合合成定义明确的异质接枝分子刷。尽管如此，异质接枝分子刷在水溶液中自组装形成稳定的核壳胶束，如通过动态光散射观察到的，旋转半径范围从 30 到超过 100 nm，临界胶束浓度低至 0.3 mg/毫升。