Living supramolecular polymerization realized through a biomimetic approach

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.

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Figure 1: Formation and transformation of supramolecular assembly of 1.
Figure 2: Kinetic and thermodynamic studies of the self-assembly behaviour of 1.
Figure 3: Kinetic studies of supramolecular polymerization initiated upon addition of H-aggregate seeds (1H-seed).
Figure 4: Living supramolecular polymerization of 1.
Figure 5: Polymer propagation from the termini of the 1H-seed seeds on a silicon substrate.

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Acknowledgements

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.

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K.S. conceived and directed the project. K.S. and S.M. initiated the project. S.O. carried out most of the experimental work. S.S. analysed the DLS results. S.O. and K.S. co-wrote the manuscript. S.O., K.S. and M.T. discussed the results and commented on the manuscript.

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Correspondence to Kazunori Sugiyasu or Masayuki Takeuchi.

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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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