Wavelength-dependent photoreactions present an opportunity to achieve chemoselectivity of functional groups that otherwise demonstrate similar reactivity under traditional thermal conditions. Relying on this concept, we demonstrate that a difunctional iniferter with two thiocarbonylthio groups can be divergently photoactivated to prepare polymeric nanoparticles via polymerization-induced self-assembly (PISA). A hydrophilic poly(oligoethylene glycol methacrylate) macroiniferter was synthesized via selective activation of one thiocarbonylthio moiety with green light. The resulting green-light-active ω-end was then further chain extended with benzyl methacrylate to obtain well-defined nanoparticles by PISA without activation of the blue-light-active α-end iniferter. The obtained nanoparticles could then be used as nanoparticle-iniferters (nanoiniferters) by chain extending from the corona with N,N-dimethylacrylamide via blue-light-mediated photoiniferter polymerization. This approach leverages the wavelength-dependent photolysis of thiocarbonylthio moieties to both synthesize and modify well-defined polymer nanoparticles.

中文翻译：

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发散光离子聚合物聚合诱导的自组装


波长依赖性光反应为实现官能团的化学选择性提供了机会，否则在传统热条件下表现出相似的反应性。依靠这个概念，我们证明了具有两个硫代羰基硫基的双官能化脱毛剂可以通过聚合诱导自组装 （PISA） 进行发散光活化以制备聚合物纳米颗粒。通过用绿光选择性活化一个硫代羰基硫代基团，合成了亲水性聚（聚甲基丙烯酸聚乙二醇酯）大分子脱硫剂。然后用甲基丙烯酸苄酯进一步延伸所得的绿光活性 ω 端，以通过 PISA 获得定义明确的纳米颗粒，而无需激活蓝光活性 α 端干扰物。然后，获得的纳米颗粒可以通过蓝光介导的光离子干扰物聚合从电晕中伸出的链与 N，N-二甲基丙烯酰胺用作纳米粒子干扰物（nanoiniferter）。这种方法利用硫代羰基硫代基团的波长依赖性光解来合成和修饰定义明确的聚合物纳米颗粒。