A recent communication from our laboratory demonstrated that the presence of a small hydrophobic initiator residue (core) in water-soluble telechelic dibromo homopolymers can drive their self-assembly in aqueous solution into micelle-like nano-objects in which polymer chains adopt a folded conformation. Centered on the use of site-selective cleavable difunctional initiators, we demonstrate herein that this approach offers bottom-up and facile access to multistimuli-sensitive nanostructures for effective cargo delivery. Here, we first report the synthesis of homopolymers and copolymers encoding hydrophobicity and cleavable sites in their initiator residue in a precise sequence by single-electron transfer living radical polymerization (SET-LRP) from oligo(ethylene glycol) (macro)monomers. Employing a designed acid pH/UV light dual-cleavable initiator integrating a 2-nitroresorcinol diacetal sequence enabled on-demand middle-chain scission of the polymer chains and hence rapid/slow breakdown of the assemblies upon appropriate stimulation. Additionally, the possibility to interrogate binary co-delivery systems sequence-encoded with complimentary reactivity with combinatorial stimuli not only allows for fine-tuning the guest molecule release kinetics but also provides a mechanism to achieve control of their release behavior when different cargos are loaded.

中文翻译：

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用序列编码的疏水性引发剂对亲水性远螯聚合物的自组装和激发触发响应进行编程

我们实验室的最新消息表明，水溶性远螯二溴均聚物中存在小的疏水性引发剂残基（核心），可以促使其在水溶液中自组装成胶束状纳米物体，其中聚合物链采用折叠构象。 。集中于使用位点选择性可裂解的双官能引发剂，我们在本文中证明了该方法提供了自底向上和容易获得多刺激敏感纳米结构的途径，以实现有效的货物递送。在这里，我们首先报道了通过低聚物（乙二醇）（大分子）单体的单电子转移活性自由基聚合（SET-LRP），以精确的顺​​序合成了在其引发剂残基中编码疏水性和可裂解位点的均聚物和共聚物。使用整合了2-硝基间苯二酚二缩醛序列的设计的酸性pH / UV光双裂解引发剂，可以按需对聚合物链进行中间链断裂，因此在适当的刺激下组装快速/缓慢分解。另外，用互补刺激物以互补反应性询问序列编码的二元共递送系统的可能性不仅允许微调客体分子的释放动力学，而且还提供了一种机制，可以在装载不同货物时实现对其释放行为的控制。