Living supramolecular polymerization realized through a biomimetic approach
Living supramolecular polymerization realized through a biomimetic approach
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DOI：
10.1038/nchem.1849
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发表时间：
2014-03-01
期刊：
影响因子：
21.8
通讯作者：
Takeuchi, Masayuki
中科院分区：
文献类型：
--
作者：
Ogi, Soichiro;Sugiyasu, Kazunori;Takeuchi, Masayuki
聚合物化学中的各种常规反应已经转化为超分子领域，但设计活的超分子聚合仍然是一个挑战。要做到这一点，必须发生远离热力学平衡的自组织，而热力学平衡在自然界中无处不在。朊病毒感染是在生物系统中可以观察到的一个例子。在这里，我们提出了一种“人工感染”过程，在这种过程中，卟啉基单体组装成纳米颗粒，然后在纳米纤维的类似物存在下转化为纳米纤维，这种纳米纤维充当“病原体”。我们使用等地和合作模型研究了这种聚集现象，发现它是通过这两种聚集途径的微妙相互作用发生的。利用这种对发生机理的理解，我们设计了一种活性的卟啉基单体的超分子聚合。尽管聚合是非共价的，但反应动力学与传统的链生长聚合相似，并且合成的超分子聚合物具有可控的长度和窄的多分散性。
Various conventional reactions in polymer chemistry have been translated to the supramolecular domain, yet it has remained challenging to devise living supramolecular polymerization. To achieve this, self-organization occurring far from thermodynamic equilibrium-ubiquitously observed in nature-must take place. Prion infection is one example that can be observed in biological systems. Here, we present an 'artificial infection' process in which porphyrin-based monomers assemble into nanoparticles, and are then converted into nanofibres in the presence of an aliquot of the nanofibre, which acts as a 'pathogen'. We have investigated the assembly phenomenon using isodesmic and cooperative models and found that it occurs through a delicate interplay of these two aggregation pathways. Using this understanding of the mechanism taking place, we have designed a living supramolecular polymerization of the porphyrin-based monomers. Despite the fact that the polymerization is non-covalent, the reaction kinetics are analogous to that of conventional chain growth polymerization, and the supramolecular polymers were synthesized with controlled length and narrow polydispersity.