title: Controlling the Structure and Length of Self-Synthesizing Supramolecular Polymers through Nucleated Growth and Disassembly.
abstract: Directing self-assembly processes out-of-equilibrium to yield kinetically trapped materials with well-defined dimensions remains a considerable challenge. Kinetically controlled assembly of self-synthesizing peptide-functionalized macrocycles through a nucleation-growth mechanism is reported. Spontaneous fiber formation in this system is effectively shut down as most of the material is diverted into metastable non-assembling trimeric and tetrameric macrocycles. However, upon adding seeds to this mixture, well-defined fibers with controllable lengths and narrow polydispersities are obtained. This seeded growth strategy also allows access to supramolecular triblock copolymers. The resulting noncovalent assemblies can be further stabilized through covalent capture. Taken together, these results show that self-synthesizing materials, through their interplay between dynamic covalent bonds and noncovalent interactions, are uniquely suited for out-of-equilibrium self-assembly.
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Asish
authors.initials: A
authors.lastname: Pal
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).|Current address: Department of Chemistry, University of Isfahan (Iran).
authors.forename: Morteza
authors.initials: M
authors.lastname: Malakoutikhah
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Giulia
authors.initials: G
authors.lastname: Leonetti
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Meniz
authors.initials: M
authors.lastname: Tezcan
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Mathieu
authors.initials: M
authors.lastname: Colomb-Delsuc
authors.affiliation: Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen (The Netherlands).
authors.forename: Van Duc
authors.initials: VD
authors.lastname: Nguyen
authors.affiliation: Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen (The Netherlands). jasper.vandergucht@wur.nl.
authors.forename: Jasper
authors.initials: J
authors.lastname: van der Gucht
authors.affiliation: Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands). s.otto@rug.nl.
authors.forename: Sijbren
authors.initials: S
authors.lastname: Otto
keywords: block co-fibers; dynamic covalent chemistry; nucleation and growth; self-replication; systems chemistry