In this communication, we investigate the photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization of 2-(methylthio)ethyl methacrylate (MTEMA) using 5,10,15,20-tetraphenylporphine zinc (ZnTPP) as a photocatalyst under visible red light (λ_max = 635 nm). Interestingly, the polymerization kinetics were not affected by the presence of air as near identical polymerization kinetics were observed for non-deoxygenated and deoxygenated systems, which is attributed to the singlet oxygen quenching ability of MTEMA. In both cases, well-defined polymers were obtained with good control over the molecular weight and molecular weight distribution (MWD). Furthermore, we have demonstrated that MTEMA can undergo the polymerization-induced self-assembly (PISA) process from a poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) macromolecular chain transfer agent (macro-CTA) to yield well-defined polymeric nanoparticles of various morphologies. These nanoparticles were rapidly disassembled after exposure to visible light due to the formation of singlet oxygen by the encapsulated ZnTPP and subsequent rapid oxidation of the thioether group.

中文翻译：

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2-(甲硫基)乙基甲基丙烯酸酯：在空气存在下用于刺激响应和聚合诱导自组装的多功能单体

在本次交流中，我们研究了使用 5,10,15,20-四苯基卟啉锌 (ZnTPP) 的 2-(甲硫基)甲基丙烯酸乙酯 (MTEMA) 的光致电子/能量转移-可逆加成-断裂链转移 (PET-RAFT) 聚合作为可见红光下的光催化剂（λ _max= 635 纳米）。有趣的是，聚合动力学不受空气存在的影响，因为在非脱氧和脱氧系统中观察到几乎相同的聚合动力学，这归因于 MTEMA 的单线态氧猝灭能力。在这两种情况下，都获得了对分子量和分子量分布 (MWD) 进行良好控制的定义明确的聚合物。此外，我们已经证明 MTEMA 可以从聚（低聚（乙二醇）甲基醚甲基丙烯酸酯）（POEGMA）大分子链转移剂（macro-CTA）进行聚合诱导自组装（PISA）过程，以产生定义明确的各种形态的聚合物纳米粒子。