Well-defined core–shell nanoparticles with a phthalimide core are synthesized using reversible addition–fragmentation chain transfer (RAFT)-mediated dispersion polymerization-induced self-assembly (PISA) of a novel vinyl benzyl phthalimide monomer, namely (2-(4-vinylbenzyl)iso-indoline-1,3-dione) (VBzPHT). Diblock copolymers consisting of poly(poly(ethylene glycol) methyl ether methacrylate)-block-(2-(4-vinylbenzyl)iso-indoline-1,3-dione) (PEGMA₁₅-b-PVBzPHT_n) self-assemble into nanoparticles during polymerization in methanol at 70 °C, when using poly(methyl ether methacrylate)-macro RAFT agent (macro-CTA, DP = 15, M_n = 7600 g mol⁻¹, Đ = 1.14) and 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator. While maintaining a constant chain length of the solvophilic macro-CTA agent, we show that varying the solvophobic PVBzPHT block length (DP = 15–200) under concentrated conditions (15 wt%) achieves self-assembled structures of increasing size. These nanoparticles, ranging from 95 to 389 nm in hydrodynamic diameter, are assessed using both dynamic light scattering and dry state transmission electron microscopy. Finally, we investigate hydrazine-responsive deprotection of phthalimide bearing amphiphilic (PEGMA₁₅-b-PVBzPHT_n) block copolymers, leading to the formation of poly(poly(ethylene glycol) methyl ether methacrylate)-block-vinyl benzyl amine (PEGMA₁₅-b-(PVBzNH₂)_n). This increased solvophilicity leads to complex aggregated assemblies in situ. The insights of this study offer guidelines to the preparation of well-defined nanoparticles through PISA, with unique post-synthetic responsiveness amenable to applications in drug delivery and biocatalysis.

中文翻译：

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聚合诱导的(2-(4-乙烯基苄基)异二氢吲哚-1,3-二酮)自组装用于合成肼响应性嵌段共聚物纳米颗粒

使用新型乙烯基苄基邻苯二甲酰亚胺单体（即（2-（4-乙烯基苄基)异二氢吲哚-1,3-二酮) ( VBzPHT )。由聚(聚(乙二醇)甲醚甲基丙烯酸酯)-嵌段-(2-(4-乙烯基苄基)异-二氢吲哚-1,3-二酮) ( PEGMA ₁₅ - b -PVBzPHT _n )组成的二嵌段共聚物自组装成纳米颗粒70 °C 甲醇聚合过程中，使用聚（甲基_醚甲基丙烯酸酯）-macro RAFT 试剂（macro-CTA，DP = 15，Mn = 7600 g mol ⁻¹，Đ = 1.14）和 2,2′-偶氮双(异丁腈)(AIBN)作为引发剂。在保持亲溶剂性大 CTA 剂链长恒定的同时，我们发现在浓缩条件 (15 wt%) 下改变疏溶剂性PVBzPHT嵌段长度 (DP = 15–200) 可实现尺寸不断增加的自组装结构。这些纳米颗粒的流体动力学直径范围为 95 至 389 nm，使用动态光散射和干态透射电子显微镜进行评估。最后，我们研究了邻苯二甲酰亚胺两亲性 ( PEGMA ₁₅ - b -PVBzPHT _n ) 嵌段共聚物的肼响应脱保护，导致形成聚(聚(乙二醇)甲醚甲基丙烯酸酯)-嵌段-乙烯基苄胺 ( PEGMA ₁₅ - b- (PVBzNH ₂ ) _n )。这种增加的亲溶剂性导致了复杂的原位聚集组装体。这项研究的见解为通过 PISA 制备明确的纳米颗粒提供了指导，该纳米颗粒具有独特的合成后响应性，适合药物输送和生物催化中的应用。