Force-Triggered Thermodynamically Uphill Disulfide Reduction through Sulfur Oxidation State Control.

ABSTRACT: In addition to thermal energy, current, and light, mechanical forces activate chemical reactions, often steering reaction pathways that result in products different from those obtained under thermodynamic control. Single-molecule mechanochemistry experiments have probed how the forced activation of a single covalent bond results in accelerated scission of both homolytic and heterolytic bonds, and the ring-opening of strained mechanophores in long polymers. Due to its mechanistic simplicity, the concerted S_N2 thiol-disulfide nucleophilic substitution has been successfully used as a model system to interrogate how the nucleophilicity of an attacking organic, low-oxidation state thiol determines the force dependency of the thiol/disulfide exchange rate. Inorganic sulfur-oxyanions a

SUBMITTER: Mora M 

PROVIDER: S-EPMC12532186 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature