Transient Covalent Polymers through Carbodiimide-Driven Assembly.

Autor: Saha NK; Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, OH, 45056, United States., Salvia WS; Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, OH, 45056, United States., Konkolewicz D; Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, OH, 45056, United States., Hartley CS; Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, OH, 45056, United States.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jul 29; Vol. 63 (31), pp. e202404933. Date of Electronic Publication: 2024 Jun 30.
DOI: 10.1002/anie.202404933
Abstrakt: Biochemical systems make use of out-of-equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of hours to weeks. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, temperature, pyridine concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine-tuned kinetic control in nonequilibrium polymerization systems.
(© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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