Supramolecular copolymerization driven by integrative self-sorting of hydrogen-bonded rosettes
| Autor: | Martin J. Hollamby, Rika Takeya, Shin-ichi Adachi, Rie Haruki, Brian R. Pauw, Hideaki Takagi, Nobutaka Shimizu, Yuichi Kitamoto, Keisuke Aratsu, Shiki Yagai |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Science
Supramolecular chemistry General Physics and Astronomy 010402 general chemistry Q1 Supramolecular polymers 01 natural sciences Article General Biochemistry Genetics and Molecular Biology Rosette (zoology) chemistry.chemical_compound Molecular recognition Copolymer QD lcsh:Science chemistry.chemical_classification Multidisciplinary 010405 organic chemistry General Chemistry Polymer 0104 chemical sciences Monomer chemistry Chemical engineering lcsh:Q Polymer synthesis Self-assembly |
| Zdroj: | Nature Communications, Vol 11, Iss 1, Pp 1-12 (2020) Nature Communications |
| ISSN: | 2041-1723 |
| DOI: | 10.1038/s41467-020-15422-6 |
| Popis: | Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function. We herein show an example of such molecular recognition-controlled kinetic assembly/disassembly processes within artificial supramolecular polymer systems using six-membered hydrogen-bonded supramolecular complexes (rosettes). Electron-rich and poor monomers are prepared that kinetically coassemble through a temperature-controlled protocol into amorphous coaggregates comprising a diverse mixture of rosettes. Over days, the electrostatic interaction between two monomers induces an integrative self-sorting of rosettes. While the electron-rich monomer inherently forms toroidal homopolymers, the additional electrostatic interaction that can also guide rosette association allows helicoidal growth of supramolecular copolymers that are comprised of an alternating array of two monomers. Upon heating, the helicoidal copolymers undergo a catastrophic transition into amorphous coaggregates via entropy-driven randomization of the monomers in the rosette. Unlike natural supramolecular polymers, artificial counterparts do not have molecular recognition processes to preorganize the supramolecular complexes before final assembly. Here, the authors show supramolecular copolymerization driven by integrative self-sorting of two different monomers into discrete six-membered supramolecular complexes (rosettes). |
| Databáze: | OpenAIRE |
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