2026-04-17T03:02:58Zhttps://recercat.cat/oai/request
oai:recercat.cat:2445/1544902025-11-19T20:34:27Zcom_2072_1057col_2072_478796col_2072_478917
RECERCAT author Dopieralski, Przemyslaw author Ribas Ariño, Jordi author Anjukandi, Padmesh author Krupicka, Martin author Marx, Dominik 2020-03-31T10:20:50Z2020-03-31T10:20:50Z2016-10-242020-03-31T10:20:50Z The reduction of disulfides has broad importance in chemistry, biochemistry and materials science, in particular upon mechanochemical activation. Here, isotensional simulations disclose that strikingly different mechanisms govern disulfide cleavage depending on external force. Crucial are desolvation and resolvation processes, which directly impact on activation free energies. The preferred pathway up to moderate forces, a bimolecular SN2 attack of OH− at sulfur, competes with unimolecular C-S bond rupture at about 2 nN, while the latter even becomes barrierless beyond. Moreover, our study brings to light a surprisingly rich reactivity scenario that includes the transformation of SN2 pathways into pure bond breaking pathways at forces within the range of 1.2 to 2.2 nN. Given that these forces are easily reached in experiments, these insights will fundamentally change our understanding of mechanochemical activation in general, which is now expected to be considerably more intricate than previously thought. (c) Dopieralski, Przemyslaw et al., 2017 info:eu-repo/semantics/openAccess Polímers Reducció química Polymers Reduction (Chemistry) Unexpected mechanochemical complexity in the mechanistic scenarios of disulfide bond reduction in alkaline solution info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion