Abstract In this paper, we examined self-assembly of amphiphilic homopolymers bearing the double brush side chains of a hydrophilic PEG and various hydrophobic units including butyl, octyl, dodecyl, octadecyl, and oleyl groups in water. Analyzed by size exclusion chromatography coupled with multiangle laser light scattering, those homopolymers formed uniform micelles, unimer micelles, and large aggregates like rod micelles in water; the morphology depended on the hydrophobic side chains and changed at a certain threshold degree of polymerization (DPth). The homopolymer comprising butyl groups folded into compact micelles via intramolecular association in water, independent of molecular weight. In contrast, the homopolymer carrying octyl groups formed either uniform micelles via multichain association ( DPth). The homopolymers carrying dodecyl, octadecyl, and oleyl groups exclusively undergo multichain association in water but form either uniform micelles ( DPth). Uniquely, those DPth values decreased with increasing the hydrophobicity of the pendants; more hydrophobic homopolymers tend to form large aggregates at shorter polymer chains. Additionally, those homopolymers with broad molecular weight distribution induced chain length-dependent self-sorting to simultaneously produce uniform micelles and large aggregates in water.

中文翻译：

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由悬垂设计和链长引发的水中两亲性均聚物自组装的形态转变

摘要 在本文中，我们研究了带有亲水性 PEG 的双刷侧链和各种疏水性单元（包括丁基、辛基、十二烷基、十八烷基和油基）在水中的两亲均聚物的自组装。通过尺寸排阻色谱结合多角度激光散射分析，这些均聚物在水中形成均匀胶束、单聚体胶束和棒状胶束等大聚集体；形态取决于疏水侧链，并在一定的聚合度阈值 (DPth) 下发生变化。包含丁基的均聚物通过水中的分子内缔合折叠成紧密的胶束，与分子量无关。相比之下，带有辛基的均聚物通过多链缔合 (DPth) 形成均匀的胶束。带有十二烷基的均聚物，十八烷基和油基在水中只经历多链缔合，但形成均匀的胶束（DPth）。独特的是，这些 DPth 值随着悬垂物疏水性的增加而降低；更疏水的均聚物倾向于在较短的聚合物链上形成大的聚集体。此外，那些具有宽分子量分布的均聚物会诱导依赖于链长的自分选，从而在水中同时产生均匀的胶束和大的聚集体。