title: 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.
authors.affiliation: Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Soichiro
authors.initials: S
authors.lastname: Ogi
authors.affiliation: Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Kazunori
authors.initials: K
authors.lastname: Sugiyasu
authors.affiliation: Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Swarup
authors.initials: S
authors.lastname: Manna
authors.affiliation: Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Sadaki
authors.initials: S
authors.lastname: Samitsu
authors.affiliation: Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Masayuki
authors.initials: M
authors.lastname: Takeuchi
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D032701:Biomimetics / Q000379:methods*; D046911:Macromolecular Substances / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D058105:Polymerization
chemical_list: D046911:Macromolecular Substances