Supramolecular interactions between catalytic species allow rational control over reaction kinetics

Abstract

The non-covalent interactions between two phase-transfer catalysts allow tuning of reaction kinetics from bimolecular, to pseudo 0th order, to sigmoidal. Kinetic models and DFT calculations are used to obtain detailed insight in the system.

Supramolecular copolymerization through self-correction of non-polymerizable transient intermediates

“…Although traditional studies of self-sorting focus on the nal equilibrium products, the kinetically controlled steady state intermediates with tunable structure and life-time could also play leading roles, if a meticulous design is considered. Moreover, endeavors should be made to couple various strategies including selfsorting, chemical fuel-driven assembly, 8-14 and catassembly, [48][49][50][51] together with other constitution elements especially the feedback loops, [52][53][54][55][56][57][58] to construct interaction networks that nally evolve into complex assembly systems, as shown by living beings. With the continuous inux of energy and matter that regulates the evolution process, new structures, patterns, functions, and even 'new chemistry' could emerge from sufficiently complex assembly systems.…”

Urea-Functionalized Heterocycles: Structure, Hydrogen Bonding and Applications

“…Catalytic effect was due to a synergism between naphthyridine 35e and K2CO3, so for efficient autoregulation, the concentration of the salt should also be kept constant [135]. Further investigations showed that, while simple UPys had no catalytic effect on Michael additions, the ester functionalized derivative 92 was also able to act as a phasetransfer agent for K 2 CO 3 (similarly to the naphthyridine derivative 35e) and, thus, to catalyze Michael additions in CDCl 3 [136].…”

Cation recognition controlled by protonation or chemical reduction: a computational study

“…1 NCIs also facilitate dynamic interactions between reactive molecules, resulting in a single regulatory control typical of living systems. [2][3][4] In addition, macromolecular interactions inside a cell are managed by: (i) localizing the reactive compounds within the same subcellular compartment and (ii) keeping the reactive structures close to proteins, lipids or DNA via NCIs. 5 NCIs involving cationic species occur in side-chain interactions of proteins, 6,7 ion channels, [8][9][10] catalysis, 11,12 and antibody binding sites.…”