Fan Jingwei, Borguet Yannick P, Su Lu, Nguyen Tan P, Wang Hai, He Xun, Zou Jiong, Wooley Karen L
Departments of Chemistry, Chemical Engineering, Materials Science and Engineering, and Laboratory for Synthetic-Biologic Interactions, Texas A&M University, P.O. Box 30012, 3255 TAMU, College Station, Texas 77842, United States.
ACS Macro Lett. 2017 Sep 19;6(9):1031-1035. doi: 10.1021/acsmacrolett.7b00603. Epub 2017 Sep 8.
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 -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 N 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--poly(β-benzyl-l-aspartate)) (P(NB--PBLA)). Highly efficient postpolymerization modification was achieved by aminolysis of PBLA side chains for facile installment of functional moieties onto the molecular brushes.
通过“接枝贯穿”合成策略制备了具有多肽作为侧链的明确分子刷，并对刷状分子结构进行二维控制。通过整合N-羧基酸酐开环聚合（NCA ROP）和开环易位聚合（ROMP），以可控方式独立构建了所需长度的多肽侧链和聚降冰片烯刷状主链。利用N流加速的NCA ROP制备了从降冰片烯基伯胺引发的不同长度的多肽大分子单体，然后通过ROMP使这些大分子单体聚合。发现需要二氯甲烷和离子液体的混合物作为溶剂体系，以构建具有从聚降冰片烯主链发出的密集接枝肽链的分子刷聚合物，即聚（降冰片烯-聚（β-苄基-L-天冬氨酸））（P（NB-PBLA））。通过PBLA侧链的氨解实现了高效的后聚合修饰，以便将功能部分轻松安装到分子刷上。
