Laboratorium für Organische Chemie, Department of Chemistry and Applied biosciences, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2020 Aug 17;59(34):14656-14663. doi: 10.1002/anie.202006273. Epub 2020 Jul 15.
We report the synthesis of monomers for atom-transfer radical polymerization (ATRP) and a reversible addition-fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT-containing polymers are suitable for rapid amide-forming ligations for both post-polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star-shaped block copolymers. In addition, we applied post-polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT-containing copolymer. Cellular assays revealed that the polymer-antibiotic conjugate is biocompatible and provides efficient light-controlled release of the antibiotic on demand.
我们报告了用于原子转移自由基聚合（ATRP）和可逆加成-断裂链转移（RAFT）试剂的单体的合成，这些单体带有三氟硼酸亚胺（TIMs），在聚合后定量转化为三氟甲磺酸酰基钾（KAT）。所得含 KAT 的聚合物适合于聚合后修饰和聚合物偶联的快速酰胺形成连接。聚合物偶联反应迅速，即使在环境温度下的稀（微摩尔）水性条件下也是如此，从而能够合成各种线性和星形嵌段共聚物。此外，我们将聚合后修饰应用于将光笼闭的环状抗生素（短杆菌肽 S）共价连接到含 KAT 的共聚物的侧链上。细胞实验表明，聚合物-抗生素缀合物具有生物相容性，并能够按需提供高效的光控抗生素释放。
