Model studies of force-dependent kinetics of multi-barrier reactions

Yancong Tian, Timothy J. Kucharski, Qing-Zheng Yang and Roman Boulatov ()
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Yancong Tian: University of Liverpool
Timothy J. Kucharski: University of Illinois
Qing-Zheng Yang: Technical Institute of Physics and Chemistry, Chinese Academy of Sciences
Roman Boulatov: University of Liverpool

Nature Communications, 2013, vol. 4, issue 1, 1-10

Abstract: Abstract According to transition state theory, the rate of a reaction that traverses multiple energy barriers is determined by the least stable (rate-determining) transition state. The preceding (‘inner’) energy barriers are kinetically ‘invisible’ but mechanistically significant. Here we show experimentally and computationally that the reduction rate of organic disulphides by phosphines in water, which in the absence of force proceeds by an equilibrium formation of a thiophosphonium intermediate, measured as a function of force applied on the disulphide moiety yields a usefully accurate estimate of the height of the inner barrier. We apply varying stretching force to the disulphide by incorporating it into a series of increasingly strained macrocycles. This force accelerates the reduction, even though the strain-free rate-determining step is orthogonal to the pulling direction. The observed rate–force correlation is consistent with the simplest model of force-dependent kinetics of a multi-barrier reaction.

Date: 2013
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DOI: 10.1038/ncomms3538

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