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.
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This work was supported by a Grants-in-Aid for Scientific Research (KAKENHI; no. 20750097), the Scientific Research for Priority Area ‘Coordination Programming’ (area 2107) and the Nanotechnology Network Project from the Ministry of Education, Culture, Sports, Science and Technology, Government of Japan.
The authors declare no competing financial interests.
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Ogi, S., Sugiyasu, K., Manna, S. et al. Living supramolecular polymerization realized through a biomimetic approach. Nature Chem 6, 188–195 (2014). https://doi.org/10.1038/nchem.1849
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