Mechanical gating of a mechanochemical reaction cascade

Wang, J, Kouznetsova, TB, Boulatov, R ORCID: 0000-0002-7601-4279 and Craig, SL (2016) Mechanical gating of a mechanochemical reaction cascade. Nature Communications, 7 (1). 13433-.

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Official URL: https://www.nature.com/articles/ncomms13433

Abstract

Covalent polymer mechanochemistry offers promising opportunities for the control and engineering of reactivity. To date, covalent mechanochemistry has largely been limited to individual reactions, but it also presents potential for intricate reaction systems and feedback loops. Here we report a molecular architecture, in which a cyclobutane mechanophore functions as a gate to regulate the activation of a second mechanophore, dichlorocyclopropane, resulting in a mechanochemical cascade reaction. Single-molecule force spectroscopy, pulsed ultrasonication experiments and DFT-level calculations support gating and indicate that extra force of >0.5 nN needs to be applied to a polymer of gated gDCC than of free gDCC for the mechanochemical isomerization gDCC to proceed at equal rate. The gating concept provides a mechanism by which to regulate stress-responsive behaviours, such as load-strengthening and mechanochromism, in future materials designs.

Item Type:	Article
Uncontrolled Keywords:	Reaction kinetics and dynamics, Polymer chemistry
Depositing User:	Symplectic Admin
Date Deposited:	21 Nov 2016 11:47
Last Modified:	19 Jan 2023 07:25
DOI:	10.1038/ncomms13433
Open Access URL:	http://em.rdcu.be/wf/click?upn=KP7O1RED-2BlD0F9LDq...
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3004603