Incorporation of hydrostatic pressure into models of hydrogen tunneling highlights a role for pressure-modulated promoting vibrations.

Biochemistry
Sam Hay, Nigel S Scrutton

Abstract

Hydrostatic pressure offers an alternative to temperature as an experimental probe of hydrogen-transfer reactions. H tunneling reactions have been shown to exhibit kinetic isotope effects (KIEs) that are sensitive to pressure, and environmentally coupled H tunneling reactions, those reactions in which H transfer is coupled to atomic fluctuations (a promoting vibration) along the reaction coordinate, often have quite temperature-dependent KIEs. We present here a theoretical treatment of the combined effect of temperature and pressure on environmentally coupled H tunneling reactions. We develop a generalized expression for the KIE, which can be used as a simple fitting function for combined experimental temperature- and pressure-dependent KIE data sets. With this expression, we are able to extract information about the pressure dependence of both the apparent tunneling distance and the frequency of the promoting vibration. The KIE expression is tested on two data sets {the reduction of chloranil by leuco crystal violet [Isaacs, N. S., Javaid, K., and Rannala, E. (1998) J. Chem. Soc., Perkin Trans. 2, 709-711] and the reduction of morphinone reductase by NADH [Hay, S., Sutcliffe, M. J., and Scrutton, N. S. (2007) Proc. Natl. Acad....Continue Reading

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Citations

Jul 20, 2010·Interdisciplinary Sciences, Computational Life Sciences·Kara E Ranaghan, Adrian J Mulholland
Feb 11, 2011·Biochemistry·Nickolay Zhadin, Robert Callender
Dec 17, 2011·Journal of the American Chemical Society·Vanja StojkovićAmnon Kohen
Feb 5, 2013·Journal of the American Chemical Society·Christopher R PudneyNigel S Scrutton
Nov 7, 2009·Journal of the American Chemical Society·Christopher R PudneyNigel S Scrutton
Jan 8, 2014·Physical Chemistry Chemical Physics : PCCP·Shaun M KandathilSam Hay
Jun 12, 2013·Annual Review of Biochemistry·Judith P Klinman, Amnon Kohen
Apr 4, 2015·Physical Chemistry Chemical Physics : PCCP·Linus O JohannissenNigel S Scrutton
Aug 24, 2016·Journal of the American Chemical Society·Alexander GeddesNigel S Scrutton
Feb 23, 2012·Nature Chemistry·Sam Hay, Nigel S Scrutton
Oct 28, 2020·Chemical Society Reviews·Agnideep DasMarine Desage-El Murr
Jan 1, 2010·Journal of Chemical Theory and Computation·Isaiah Sumner, Srinivasan S Iyengar
Oct 8, 2019·Journal of the American Chemical Society·Tianfei LiuLeif Hammarström

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