Abstract Microsized giant vesicles supporting a hindered amine on their shells were obtained by the photopolymerization-induced self-assembly of amphiphilic diblock copolymers using the photo nitroxide mediated living radical polymerization (photo NMP) technique. The diblock copolymer consisting of hydrophilic poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate) (PTPMA) and hydrophobic poly(methyl methacrylate-random-2,2,6,6-tetramethyl-4-piperidyl methacrylate), P(MMA-r-TPMA) produced various morphologies depending on the stirring speed during the photo NMP-induced self-assembly, block lengths of the copolymer, and hydrophobicity of the P(MMA-r-TPMA) block chain. A 300-rpm stirring speed during the polymerization provided worm-like vesicles with a long axis of over 100 μm along with small spherical vesicles with a 3-μm diameter. As the stirring speed increased to 600 rpm, the worm-like vesicles changed into spherical vesicles. A further increase in the stirring speed to 900 rpm produced much smaller spherical vesicles. The extension of the block chains also reduced the size of the vesicles. An increase in the hydrophobicity of the hydrophobic block chain varied the morphology of the vesicles. While PTPMA-b-P(MMA-r-TPMA) provided spherical vesicles, PTPMA-b-P(n-propyl methacrylate (PrMA)-r-TPMA) produced deformed vesicles accompanied by a size increase. On the other hand, PTPMA-b-P(n-butyl methacrylate (BuMA)-r-TPMA) produced much smaller vesicles. Furthermore, PTPMA-b-P(MMA-r-BuMA-r-TPMA) (MMA/BuMA = 0.487/0.513) provided a morphology similar to that formed by PTPMA-b-P(PrMA-r-TPMA) due to the negligible difference in the hydrophobic energy between Pr and Me0.487/Bu0.513. These observations indicated that the morphology of the vesicles was controlled by manipulating the hydrophobic energy of the hydrophobic block chain. GRAPHICAL ABSTRACT

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通过光活性自由基聚合诱导自组装制备在壳上负载受阻胺的巨型囊泡

摘要 使用光氮氧介导的活性自由基聚合 (photo NMP) 技术，通过光聚合诱导的两亲性二嵌段共聚物自组装，获得了在其壳上负载受阻胺的微型巨泡。由亲水性聚（2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯）（PTPMA）和疏水性聚（甲基丙烯酸甲酯-无规-2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯）组成的二嵌段共聚物, P(MMA-r-TPMA) 根据光 NMP 诱导的自组装过程中的搅拌速度、共聚物的嵌段长度和 P(MMA-r-TPMA) 嵌段链的疏水性产生各种形态。聚合过程中以 300 rpm 的搅拌速度提供长轴超过 100 μm 的蠕虫状囊泡以及直径为 3 μm 的小球形囊泡。随着搅拌速度增加到 600 rpm，蠕虫状囊泡变为球形囊泡。将搅拌速度进一步提高到 900 rpm 会产生更小的球形囊泡。区块链的延伸也减小了囊泡的大小。疏水性嵌段链疏水性的增加改变了囊泡的形态。虽然 PTPMA-bP(MMA-r-TPMA) 提供了球形囊泡，但 PTPMA-bP(甲基丙烯酸正丙酯 (PrMA)-r-TPMA) 产生了变形的囊泡，伴随着尺寸的增加。另一方面，PTPMA-bP（甲基丙烯酸正丁酯（BuMA）-r-TPMA）产生小得多的囊泡。此外，PTPMA-bP(MMA-r-BuMA-r-TPMA) (MMA/BuMA = 0.487/0.513) 提供了与 PTPMA-bP(PrMA-r-TPMA) 形成的形态相似的形态，因为在Pr 和 Me0.487/Bu0.513 之间的疏水能。这些观察表明囊泡的形态是通过操纵疏水嵌段链的疏水能量来控制的。图形概要