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Nat Chem. 2014 Mar;6(3):188-95. doi: 10.1038/nchem.1849. Epub 2014 Feb 2.

Living supramolecular polymerization realized through a biomimetic approach.

Author information

1
Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.

Abstract

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.

PMID:
24557132
DOI:
10.1038/nchem.1849
[Indexed for MEDLINE]

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