Abstract
S-S-Stretch! A series of increasingly strained macrocyclic disulfides investigated experimentally and by high-level DFT calculations reveals that the kinetics of thiol/disulfide exchange are independent of the restoring force in the disulfide moiety. This finding is consistent with the SN2 mechanism of thiol/disulfide exchange and lends insight into the acceleration of disulfide reduction upon stretching of certain proteins.
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