Year: 2026
Type: preprint
Abstract: The design of artificial enzyme mimics has long been guided by the paradigm of crafting static pockets for transition-state stabilization, a process reliant on stochastic molecular diffusion. These passive events impose a rate limit, and a strict criterion for substrates with suitable size and electronic matching. Inspired by biological ion pumps that drive uphill ion transport using chemical fuels, we propose that mechanical force can power an active, out-of-equilibrium catalytic pumping cycle. We herein report a solid-state mechanochemical strategy where mechanical input drives a confinement catalyst 1 ( Pd 2 L 2 ) from a closed to an open “active” state, while simultaneously pumping substrate molecules into its active site for catalytic events. This dynamic catalyst exhibits substrate size and shape recognition, and its mechano-pump mechanism is quantitatively validated by Michaelis-Menten saturation kinetics, where catalytic efficiency scales directly with the applied force. Moreover, the active-pump action overcomes inherent electrostatic repulsion, enabling cationic substrates, normally excluded from the cationic host catalysts, to be efficiently drawn in and engaged in catalytic turnover. This force-induced pumping catalysis concept is smoothly extended to photochemistry. By combining a photosensitizing unit and an active confinement catalyst, an active pumping mechano-photoredox C-H oxidation process is developed. This work establishes mechanical force not merely as a synthetic tool, but as a fundamental design parameter for catalysts, opening a pathway to life-like chemical control in which energy transduction, not just static structure, dictates function.
Source: ChemRxiv
Authors: Shi Li, Fang-Zi Liu, Xinhan Liu, Yan Liu, Jian Wang, KaKing Yan
Institution: ShanghaiTech University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7213458158