Nishimura Shin-Nosuke, Higashi Nobuyuki, Koga Tomoyuki
Department of Molecular Chemistry & Biochemistry, Faculty of Science & Engineering, Doshisha University, Kyotanabe, Kyoto, 610-0321, Japan.
Chemistry. 2017 Oct 26;23(60):15050-15058. doi: 10.1002/chem.201703655. Epub 2017 Sep 25.
Precisely incorporating a wide range of structural and functional multiblocks along a polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein, a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well-defined vinyl polymers with a narrow polydispersity is reported. Cyclic oligopeptides have been developed that contain an alkoxyamine bond in the framework. By using this type of cyclic initiator, peptide-containing multiblock copolymers are successfully synthesized by nitroxide-mediated polymerization of styrene. To demonstrate the versatility of this method, radical (co)polymerizations were carried out for different monomers (p-chlorostyrene, 4-vinylpyridine, and styrene/acrylonitrile) and by three different cyclic peptide initiators with specific amino acid sequences. The resultant multiblock copolymer is foldable through intramolecular interactions between peptide blocks. It is believed that this approach will significantly advance the field of controlled polymer synthesis for complex structures and single-chain folding.
在聚合物主链上精确引入各种结构和功能多嵌段是高分子化学中的一项重大挑战，同时也为设计高度有序的材料（包括可控聚合物折叠）提供了广阔的机遇。本文报道了一种简便通用的策略，用于制备由连续肽段和具有窄多分散性的明确乙烯基聚合物组成的功能性多嵌段共聚物。已开发出在骨架中含有烷氧基胺键的环状寡肽。通过使用这种类型的环状引发剂，通过苯乙烯的氮氧自由基介导聚合成功合成了含肽多嵌段共聚物。为了证明该方法的通用性，对不同单体（对氯苯乙烯、4-乙烯基吡啶和苯乙烯/丙烯腈）进行了自由基（共）聚合，并使用了三种具有特定氨基酸序列的不同环状肽引发剂。所得的多嵌段共聚物可通过肽段之间的分子内相互作用折叠。据信，这种方法将显著推动复杂结构和单链折叠的可控聚合物合成领域的发展。
