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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 715711.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Force-Induced Reversal of β-Eliminations: Stressed Disulfide Bonds in Alkaline Solution
Authors:Dopieralski, Przemyslaw; Ribas-Arino, Jordi; Anjukandi, Padmesh; Krupicka, Martin; Marx, Dominik
Language:English
Date of Publication (YYYY-MM-DD):2016
Title of Journal:Angewandte Chemie-International Edition
Journal Abbrev.:Angew. Chem. Int. Ed.
Volume:55
Issue / Number:4
Start Page:1304
End Page:1308
Review Status:Internal review
Audience:Experts Only
Abstract / Description: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 beta-elimination to mechanical stress. We reveal that the rate-determining first step of the thermal reaction, which is the abstraction of the beta-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 beta-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.
Comment of the Author/Creator:Date: 2016, JAN 22 2016
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Dopieralski,P.; Ribas-Arino,J.; Anjukandi,P.; Marx,D.] Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany.
Identifiers:ISI:000369852200011 [ID No:1]
ISSN:1433-7851 [ID No:2]
DOI:10.1002/anie.201508005 [ID No:3]
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