McClelland Kevin P, Clemons Tristan D, Stupp Samuel I, Weiss Emily A
Simpson Querrey Institute, Northwestern University, 303 East Superior Street, Chicago, Illinois 60611, United States.
ACS Macro Lett. 2020 Jan 21;9(1):7-13. doi: 10.1021/acsmacrolett.9b00891. Epub 2019 Dec 11.
This Letter describes the use of CdSe quantum dots (QDs) as photocatalysts for photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of a series of aqueous acrylamides and acrylates. The high colloidal solubility and photostability of these QDs allowed polymerization to occur with high efficiency (>90% conversion in 2.5 h), low dispersity (PDI < 1.1), and ultralow catalyst loading (<0.5 ppm). The use of protein concentrators enabled the removal of the photocatalyst from the polymer and monomer with tolerable metal contamination (8.41 ug/g). These isolated QDs could be recycled for four separate polymerizations without a significant decrease in efficiency. By changing the pore size of the protein concentrators, the QDs and polymer could be separated from the remaining monomer, allowing for the synthesis of block copolymers using a single batch of QDs with minimal purification steps and demonstrating the fidelity of chain ends.
本信函描述了将CdSe量子点(QDs)用作光催化剂,用于一系列丙烯酰胺和丙烯酸酯在水中的光致电子转移可逆加成-断裂链转移(PET-RAFT)聚合反应。这些量子点具有高胶体溶解度和光稳定性,使得聚合反应能够高效进行(2.5小时内转化率>90%)、分散度低(PDI<1.1)且催化剂负载量超低(<0.5 ppm)。使用蛋白质浓缩器能够从聚合物和单体中去除光催化剂,且金属污染可耐受(8.41微克/克)。这些分离出的量子点可循环用于四次单独的聚合反应,而效率无显著降低。通过改变蛋白质浓缩器的孔径,量子点和聚合物可与剩余单体分离,从而使用一批量子点以最少的纯化步骤合成嵌段共聚物,并证明链端的保真度。