Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds



Akbulatov, Sergey, Tian, Yancong ORCID: 0000-0001-9075-0363, Huang, Zhen, Kucharski, Timothy J, Yang, Qing-Zheng and Boulatov, Roman ORCID: 0000-0002-7601-4279
(2017) Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds. SCIENCE, 357 (6348). 299 - 303.

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Abstract

Stretching polymer chains accelerates dissociation of a variety of internal covalent bonds, to an extent that correlates well with the force experienced by the scissile bond. Recent theory has also predicted scenarios in which applied force accelerates dissociation of unloaded bonds and kinetically strengthens strained bonds. We report here unambiguous experimental validation of this hypothesis: Detailed kinetic measurements demonstrate that stretching phosphotriesters accelerates dissociation of the unloaded phosphorus-oxygen bond orthogonal to the pulling axis, whereas stretching organosiloxanes inhibits dissociation of the aligned loaded silicon-oxygen bonds. Qualitatively, the outcome is determined by phosphoester elongation and siloxane contraction along the pulling axis in the respective rate-determining transition states. Quantitatively, the results agree with a simple mechanochemical kinetics model.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 01 Aug 2017 09:10
Last Modified: 23 Nov 2020 21:21
DOI: 10.1126/science.aan1026
Related URLs:
URI: http://livrepository.liverpool.ac.uk/id/eprint/3008703