Tucker Bryan S, Coughlin McKenzie L, Figg C Adrian, Sumerlin Brent S
George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.
ACS Macro Lett. 2017 Apr 18;6(4):452-457. doi: 10.1021/acsmacrolett.7b00140. Epub 2017 Apr 4.
We report a new strategy toward polymer-protein conjugates using a grafting-from method that employs photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Initial screening of reaction conditions showed rapid polymerization of acrylamides under high dilution in water using eosin Y as a photocatalyst in the presence of a tertiary amine. A lysozyme-modified chain transfer agent allowed the same conditions to be utilized for grafting-from polymerizations, and we further demonstrated the broad scope of this technique by polymerizing acrylic and styrenic monomers. Finally, retention of the RAFT end group was suggested by successful chain extension with -isopropylacrylamide from the polymer-protein conjugates to form block copolymer-protein conjugates. This strategy should expand the capabilities of grafting-from proteins with RAFT polymerization under mild conditions to afford diverse functional materials.
我们报道了一种利用“接枝自”方法制备聚合物-蛋白质共轭物的新策略,该方法采用光诱导电子/能量转移-可逆加成-断裂链转移(PET-RAFT)聚合反应。反应条件的初步筛选表明,在水中高稀释度下,以曙红Y作为光催化剂,在叔胺存在的情况下,丙烯酰胺能快速聚合。一种溶菌酶修饰的链转移剂使得相同的条件可用于“接枝自”聚合反应,并且我们通过聚合丙烯酸和苯乙烯类单体进一步证明了该技术的广泛适用性。最后,通过用聚(N-异丙基丙烯酰胺)从聚合物-蛋白质共轭物成功进行链延伸以形成嵌段共聚物-蛋白质共轭物,表明了RAFT端基得以保留。该策略应能扩展在温和条件下通过RAFT聚合对蛋白质进行“接枝自”反应的能力,从而提供多种功能材料。