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Title: Force-induced reversal of beta-eliminations: stressed disulfide bonds in alkaline solution
Author: Dopieralski, Przemyslaw
Ribas Ariño, Jordi
Anjukandi, Padmesh
Krupicka, Martin
Marx, Dominik
Keywords: Polímers
Dinàmica molecular
Mecanismes de reacció (Química)
Molecular dynamics
Reaction mechanisms (Chemistry)
Issue Date: 4-Dec-2015
Publisher: Wiley-VCH
Abstract: Understanding the impact of tensile forces on disulfide bond cleavage is not only crucial to the breaking of cross-linkers in vulcanized materials such as strained rubber, but also to the regulation of protein activity by disulfide switches. By using ab initio simulations in the condensed phase, we investigated the response of disulfide cleavage by β-elimination to mechanical stress. We reveal that the rate- determining first step of the thermal reaction, which is the abstraction of the β- proton, is insensitive to external forces. However, forces larger than about 1 nN were found to reshape the free-energy landscape of the reaction so dramatically that a second channel is created, where the order of the reaction steps is reversed, turning β-deprotonation into a barrier-free follow-up process to C−S cleavage. This transforms a slow and force-independent process with second-order kinetics into a unimolecular reaction that is greatly accelerated by mechanical forces.
Note: Versió postprint del document publicat a:
It is part of: Angewandte Chemie-International Edition, 2015, vol. 55, num. 4, p. 1304-1308
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ISSN: 1433-7851
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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