Interest in triggered depolymerization is growing, driven by needs in sustainable plastics, self-healing materials, controlled release, and sensory amplification. For many triggered depolymerization reactions, the rate-limiting step does not directly involve the stimulus, and therefore, depolymerization kinetics exhibit only weak or no correlation to the concentration and reactivity of the stimulus. However, for many applications, a direct relationship between the stimulus and the depolymerization kinetics is desired. Here we designed, synthesized, and studied a polymer in which a nucleophile-induced chain scission (NICS) mechanism competes with the chain unzipping pathway. We find that the choice of the chain end functionality and the character of the nucleophile determines which of these is the predominant pathway. The NICS pathway was found to be dependent on the stimulus concentration, in contrast to the chain unzipping mechanism. We demonstrate transferability of these molecular-scale, structure–property relationships to nanoscale materials by formulating the polymers into host nanoparticles.

中文翻译：

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具有竞争解聚途径的聚合物：解链与断链

在可持续塑料、自愈材料、控释和感官放大的需求的推动下，对触发解聚的兴趣正在增长。对于许多触发的解聚反应，限速步骤不直接涉及刺激，因此，解聚动力学与刺激的浓度和反应性仅表现出微弱的相关性或没有相关性。然而，对于许多应用，需要刺激和解聚动力学之间的直接关系。在这里，我们设计、合成和研究了一种聚合物，其中亲核试剂诱导的断链 (NICS) 机制与链解链途径竞争。我们发现，链端功能的选择和亲核试剂的特性决定了其中哪一个是主要途径。与链解链机制相反，发现 NICS 途径依赖于刺激浓度。我们通过将聚合物配制成主体纳米颗粒，证明了这些分子尺度、结构-性质关系与纳米尺度材料的可转移性。