Isaacman Michael J, Barron Kathryn A, Theogarajan Luke S
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 ; California Nanosystems Institute, University of California, Santa Barbara, California 93106.
J Polym Sci A Polym Chem. 2012 Jun 15;50(12):2319-2329. doi: 10.1002/pola.25989.
Amphiphilic polymers have recently garnered much attention due to their potential use in drug-delivery and other biomedical applications. A modular synthesis of these polymers is extremely desirable since it offers precise individual block characterization and increased yields. We present here for the first time a modular synthesis of poly(oxazoline)-poly(siloxane)-poly(oxazoline) block copolymers that have been clicked together using the copper-catalyzed azide-alkyne cycloaddition reaction. Various click methodologies for the synthesis of these polymers have been carefully evaluated and optimized. The approach using copper nanoparticles was found to be the most optimal among the methods evaluated. Furthermore, these results were extended to allow for a reactive Si-H group-based siloxane middle block to be successfully clicked. This enables the design of more complex amphiphilic block copolymers that have additional functionality, such as stimuli responsiveness, to be synthesized via a simple hydrosilylation reaction.
两亲性聚合物因其在药物递送和其他生物医学应用中的潜在用途，近年来备受关注。这些聚合物的模块化合成非常可取，因为它能实现精确的单个嵌段表征并提高产率。我们首次在此展示了一种聚（恶唑啉）-聚（硅氧烷）-聚（恶唑啉）嵌段共聚物的模块化合成方法，该方法利用铜催化的叠氮化物-炔烃环加成反应将它们连接在一起。已对合成这些聚合物的各种点击方法进行了仔细评估和优化。在评估的方法中，使用铜纳米颗粒的方法被发现是最理想的。此外，这些结果得到了扩展，以使基于反应性Si-H基团的硅氧烷中间嵌段能够成功连接。这使得能够设计出更复杂的两亲性嵌段共聚物，这些共聚物具有额外的功能，如刺激响应性，可通过简单的硅氢化反应合成。
