Xiao Yue, Li Hui, Zhang Bohan, Cheng Zehong, Li Yang, Tan Xuyu, Zhang Ke
Institute of Chemical Biology and Nanomedicine, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.
Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, United States.
Macromolecules. 2018 Apr 24;51(8):2899-2905. doi: 10.1021/acs.macromol.8b00208. Epub 2018 Apr 3.
We have synthesized a series of stimuli-responsive brush polymers by grafting azide-terminated side chains onto a self-immolative, alkyne-bearing poly(benzyl ether) backbone, which is prepared by anionic polymerization of quinone methide-based monomers. Upon exposure to a decapping reagent (Pd(0) or F), these brush polymers undergo an irreversible degradation cascade from head to tail to yield individual side chains. It is observed that several factors affect the depolymerization kinetics, including solvent polarity, type of counterion, the rate of the decapping chemistry, and interestingly, the rigidity of the side chains.
我们通过将叠氮基封端的侧链接枝到一种自牺牲性的、含炔基的聚（苄基醚）主链上，合成了一系列刺激响应性刷状聚合物，该主链由基于醌甲基化物的单体通过阴离子聚合制备。暴露于去封端试剂（Pd(0)或F）时，这些刷状聚合物会发生从头部到尾部的不可逆降解级联反应，从而产生单个侧链。据观察，有几个因素会影响解聚动力学，包括溶剂极性、抗衡离子类型、去封端化学的速率，有趣的是，还有侧链的刚性。
