Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
RIKEN , SPring-8 Center, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan.
J Am Chem Soc. 2017 May 31;139(21):7164-7167. doi: 10.1021/jacs.7b03152. Epub 2017 May 19.
Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.
两亲性无规嵌段共聚物在水中的正交自组装和分子内交联提供了一种在单链聚合物和纳米聚集体中定制具有良好定义的隔室和结构域的方法。对于具有双隔室的单链聚合物，通过活性自由基聚合（LRP）和后功能化合成了一种带有亲水性聚（乙二醇）（PEG）和疏水性十二烷基、苄基和烯烃侧基的两亲性无规嵌段共聚物；十二烷基和苄基单元被引入不同的嵌段段中，而 PEG 侧基则沿链统计连接。该共聚物通过疏水十二烷基和苄基侧基在水中的正交自组装，然后进行分子内交联，自折叠形成带有双但不同的疏水纳米隔室的单链聚合物。带有氯端基的单链交联聚合物可用作 LRP 的球形大分子引发剂，提供包含亲水性纳米颗粒和疏水性聚合物尾巴的两亲性蝌蚪大分子；因此，蝌蚪在水中自组装成多隔室聚集体。
