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Controlling the Structure and Length of Self‐Synthesizing Supramolecular Polymers through Nucleated Growth and Disassembly
Authors:Dr. Asish Pal  Dr. Morteza Malakoutikhah  Giulia Leonetti  Meniz Tezcan  Mathieu Colomb‐Delsuc  Dr. Van Duc Nguyen  Prof. Jasper van der Gucht  Prof. Sijbren Otto
Affiliation:1. Centre for Systems Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747?AG Groningen (The Netherlands);2. Current address: Department of Chemistry, University of Isfahan (Iran);3. Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703?HB Wageningen (The Netherlands)
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.
Keywords:block co‐fibers  dynamic covalent chemistry  nucleation and growth  self‐replication  systems chemistry
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