School of Chemistry and Biochemistry , Georgia Institute of Technology , 901 Atlantic Drive NW , Atlanta , Georgia 30332 , United States.
J Am Chem Soc. 2019 Jan 30;141(4):1446-1451. doi: 10.1021/jacs.8b12154. Epub 2019 Jan 18.
A new approach to radical ring-opening polymerization is presented that employs a new thionolactone monomer to generate polymers with thioester-containing backbones. The use of a thiocarbonyl acceptor overcomes longstanding reactivity problems in the field to give complete ring-opening and quantitative incorporation into a variety of acrylate polymers. The resulting copolymers readily degrade under hydrolytic conditions, in addition to cysteine-mediated degradation through transthioesterification. The strategy is compatible with reversible addition-fragmentation chain transfer (RAFT) polymerization and permits the synthesis of block polymers for the preparation of well-defined macromolecular structures.
提出了一种新的自由基开环聚合方法，该方法采用新型硫代内酯单体生成含硫酯骨架的聚合物。使用硫羰基受体克服了该领域长期存在的反应性问题，可完全开环并定量掺入各种丙烯酸酯聚合物中。所得共聚物在水解条件下容易降解，此外还可以通过 trans 硫酯交换进行半胱氨酸介导的降解。该策略与可逆加成-断裂链转移（RAFT）聚合兼容，并允许合成嵌段聚合物以制备具有明确结构的大分子结构。
