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

ID: 733861.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Unexpected mechanochemical complexity in the mechanistic scenarios of disulfide bond reduction in alkaline solution
Authors:Dopieralski, Przemyslaw; Ribas-Arino, Jordi; Anjukandi, Padmesh; Krupicka, Martin; Marx, Dominik
Date of Publication (YYYY-MM-DD):2017
Title of Journal:Nature Chemistry
Journal Abbrev.:Nature Chemistry
Issue / Number:2
Start Page:164
End Page:170
Review Status:Internal review
Audience:Experts Only
Abstract / Description:The reduction of disulfides has a broad importance in chemistry, biochemistry and materials science, particularly those methods that use mechanochemical activation. Here we show, using isotensional simulations, that strikingly different mechanisms govern disulfide cleavage depending on the external force. Desolvation and resolvation processes are found to be crucial, as they have a direct impact on activation free energies. The preferred pathway at moderate forces, a bimolecular S(N)2 attack of OH-at sulfur, competes with unimolecular C-S bond rupture at about 2 nN, and the latter even becomes barrierless at greater applied forces. Moreover, our study unveils a surprisingly rich reactivity scenario that also includes the transformation of concerted S(N)2 reactions into pure bond-breaking processes at specific forces. 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.
Comment of the Author/Creator:Date: 2017, FEB 2017
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000394541900014 [ID No:1]
ISSN:1755-4330 [ID No:2]
DOI:10.1038/nchem.2632 [ID No:3]
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