Molecular Bottlebrushes Featuring Brush-on-Brush Architecture
Molecular Bottlebrushes Featuring Brush-on-Brush Architecture
复制标题
具有刷上刷架构的分子洗瓶刷
DOI：
10.1021/acsmacrolett.9b00399
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发表时间：
2019-06-01
影响因子：
7.015
通讯作者：
Chen, Yongming
中科院分区：
文献类型：
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作者：
Chen, Yi;Sun, Ziyang;Chen, Yongming
通过叠氮-炔点击化学、开环聚合和原子转移自由基聚合制备了具有刷对刷（BoB）结构的分子瓶刷。采用ROP法合成了含有聚己内酯（PCL）和聚α-溴-己内酯（P（CL-Br））嵌段的二嵌段共聚物，并通过点击反应将其接枝到PCL主链上。然后通过原子转移自由基聚合（ATRP）从P（CL-Br）嵌段上接枝聚（低聚乙二醇）丙烯酸酯）（POEGA）的仲侧链，得到两亲性核/壳结构。通过原子力显微镜（AFM）对单个大分子进行成像，显示出具有明显毛状侧链的显著增厚的蠕虫状形成。有趣的是，对于具有足够长的一级和二级侧链的BoB分子瓶刷，可以沿着主链产生足够的张力，从而导致其裂解。
Molecular bottlebrushes featuring brush-on-brush (BoB) architecture were prepared by combining azide-alkyne click chemistry, ring-opening polymerization (ROP), and atom transfer radical polymerization (ATRP). Primary side chains of diblock copolymers with a poly(epsilon-caprolactone) (PCL) block and a poly alpha-bromo-epsilon-caprolactone) (P(CL-Br)) block were synthesized by ROP and then grafted onto PCL backbone by the click reaction. Then the secondary side chains of poly(oligo(ethylene glycol) acrylate) (POEGA) were grafted from the P(CL-Br) block by ATRP, yielding an amphiphilic core/shell structure. Imaging of individual macromolecules by atomic force microscopy (AFM) demonstrated dramatically thickened wormlike formation with distinct hairy side chains. Interestingly, for the BoB molecular bottlebrushes with enough long primary and secondary side chains, sufficient tension can be generated along the backbone and thus lead to its cleavage.