Well-defined molecular brushes bearing polypeptides as side chains were prepared by a "grafting through" synthetic strategy with two-dimensional control over the brush molecular architectures. By integrating N-carboxyanhydride ring-opening polymerizations (NCA ROPs) and ring-opening metathesis polymerizations (ROMPs), desirable segment lengths of polypeptide side chains and polynorbornene brush backbones were independently constructed in controlled manners. The N2 flow accelerated NCA ROP was utilized to prepare polypeptide macromonomers with different lengths initiated from a norbornene-based primary amine, and those macromonomers were then polymerized via ROMP. It was found that a mixture of dichloromethane and an ionic liquid were required as the solvent system to allow for construction of molecular brush polymers having densely-grafted peptide chains emanating from a polynorbornene backbone, poly(norbornene-graft-poly(β-benzyl-l-aspartate)) (P(NB-g-PBLA)). Highly efficient postpolymerization modification was achieved by aminolysis of PBLA side chains for facile installment of functional moieties onto the molecular brushes.

中文翻译：

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通过N-羧甲基开环聚合和开环易位聚合的二维控制的多肽分子刷的二维合成。

通过“嫁接”合成策略对刷分子结构进行二维控制，制备了带有多肽作为侧链的明确定义的分子刷。通过整合N-羧基酐开环聚合（NCA ROP）和开环复分解聚合（ROMP），多肽侧链和聚降冰片烯刷骨架的理想链段长度可以受控方式独立构建。利用N2流动加速的NCA ROP制备基于降冰片烯基伯胺的不同长度的多肽大分子单体，然后通过ROMP聚合这些大分子单体。已发现需要使用二氯甲烷和离子液体的混合物作为溶剂体系，以构建具有由聚降冰片烯骨架，聚降冰片烯-接枝-聚（β-苄基- L-天冬氨酸））（P（NB-g-PBLA））。通过将PBLA侧链进行氨解以实现将功能性部分轻松安装到分子刷上，可以实现高效的后聚合修饰。