Synthesis of Light‐Responsive Pyrene‐Based Polymer Nanoparticles via Polymerization‐Induced Self‐Assembly,Macromolecular Rapid Communications

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Synthesis of Light‐Responsive Pyrene‐Based Polymer Nanoparticles via Polymerization‐Induced Self‐Assembly
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2018-09-03 , DOI: 10.1002/marc.201800510
Ali Bagheri _{1,

2} , Cyrille Boyer ₂ , May Lim ₁

Affiliation

The use of an in situ, one‐pot polymerization‐induced self‐assembly method to synthesize light‐responsive pyrene‐containing nanoparticles is reported. The strategy is based on the chain extension of a hydrophilic macromolecular chain transfer agent, poly(oligo(ethylene glycol) methyl ether methacrylate), using a light‐responsive monomer, 1‐pyrenemethyl methacrylate (PyMA), via a reversible addition–fragmentation chain transfer dispersion polymerization; yielding nanoparticles of various morphologies (spherical micelles and worm‐like micelles). In this process, addition of comonomers, such as butyl methacrylate (BuMA) or methyl methacrylate (MMA), are required to obtain high PyMA monomer conversion (>80% in 24 h). The addition of comonomers reduces the π–π stacking of the pyrene moieties, which facilitates the diffusion of monomers in the nanoparticle core. The addition of BuMA (as a comonomer) offers P(PyMA‐co‐BuMA) core‐forming chains with high mobility that enables the reorganization of chains and then the evolution of morphology to form vesicles. In contrast, when MMA comonomer is used, kinetically trapped spheres are obtained; this is due to the low mobility of the core‐forming chains inhibiting in situ morphological evolution. Finally, the UV‐light‐induced dissociation of these light‐responsive nanoparticles due to the gradual cleavage of the pyrene moieties and the subsequent hydrophobic‐to‐hydrophilic transitions of the core‐forming blocks is demonstrated.

中文翻译：

通过聚合诱导的自组装合成光响应性Base基聚合物纳米粒子

据报道，使用原位单锅聚合诱导自组装方法合成了光响应性的含pyr纳米粒子。该策略基于亲水性大分子链转移剂聚（低聚乙二醇甲基丙烯酸甲酯）的扩链，该反应使用光响应性单体甲基丙烯酸1-py烯甲酯（PyMA），通过可逆加成-断裂链转移分散聚合产生各种形态的纳米颗粒（球形胶束和蠕虫状胶束）。在此过程中，需要添加共聚单体，例如甲基丙烯酸丁酯（BuMA）或甲基丙烯酸甲酯（MMA），以获得高PyMA单体转化率（在24小时内> 80％）。共聚单体的添加减少了the部分的π–π堆积，这促进了单体在纳米颗粒核中的扩散。添加BuMA（作为共聚单体）可提供P（PyMA-co -BuMA）具有高流动性的成核链，可以重组链，然后进行形态演变以形成囊泡。相反，当使用MMA共聚单体时，会获得动力学捕获的球；反之，则不会。这是由于核心形成链的低迁移率抑制了原位形态演化。最后，证明了由于the部分的逐步裂解以及随后的核心形成嵌段的疏水性至亲水性转变，这些光响应性纳米粒子在紫外线的诱导下解离。

更新日期：2018-09-03

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