RESUMEN
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.
RESUMEN
Carbodiimides and pyridines form reversible adducts that slowly deliver carbodiimide "fuels" to out-of-equilibrium reaction networks, slowing activation kinetics and elongating transient state lifetimes. More-nucleophilic pyridines give more adduct under typical conditions. This approach can be used to extend the lifetimes of transient polymer hydrogels.
RESUMEN
Competing models exist to explain the differences in the activity of zeolites and amorphous silica-aluminas. Some postulate that silica-alumina contains dilute zeolitic bridging acid sites, while others favor a pseudo-bridging silanol model. We employed a selective isotope labeling strategy to assess the existence of Si-O(H)-Al bonds using NMR-based distance measurements.