PMID: 8962076Dec 10, 1996Paper

The change in hydrogen bond strength accompanying charge rearrangement: implications for enzymatic catalysis

Proceedings of the National Academy of Sciences of the United States of America
S O Shan, D Herschlag

Abstract

The equilibrium for formation of the intramolecular hydrogen bond (KHB) in a series of substituted salicylate monoanions was investigated as a function of delta pKa, the difference between the pKa values of the hydrogen bond donor and acceptor, in both water and dimethyl sulfoxide. The dependence of log KHB upon delta pKa is linear in both solvents, but is steeper in dimethyl sulfoxide (slope = 0.73) than in water (slope = 0.05). Thus, hydrogen bond strength can undergo substantially larger increases in nonaqueous media than aqueous solutions as the charge density on the donor or acceptor atom increases. These results support a general mechanism for enzymatic catalysis, in which hydrogen bonding to a substrate is strengthened as charge rearranges in going from the ground state to the transition state; the strengthening of the hydrogen bond would be greater in a nonaqueous enzymatic active site than in water, thus providing a rate enhancement for an enzymatic reaction relative to the solution reaction. We suggest that binding energy of an enzyme is used to fix the substrate in the low-dielectric active site, where the strengthening of the hydrogen bond in the course of a reaction is increased.

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Citations

Oct 29, 2000·Archives of Biochemistry and Biophysics·W W Cleland
Mar 29, 2001·Journal of Pharmaceutical and Biomedical Analysis·S Agatonovic-KustrinA P Yusof
Jul 27, 2001·Journal of Pharmaceutical and Biomedical Analysis·S Agatonovic-KustrinA P Yusof
Dec 31, 2010·Biochemistry·Jared B Parker, James T Stivers
Feb 17, 2011·Chemical Reviews·Sławomir Janusz Grabowski
Jan 9, 2008·Journal of the American Chemical Society·Deborah Stoner-MaPeter J Tonge
Jan 14, 2012·Journal of the American Chemical Society·Alireza ShokriSteven R Kass
Jun 5, 2012·Journal of the American Chemical Society·Alireza ShokriSteven R Kass
Mar 25, 2009·Journal of the American Chemical Society·M Ashley SpiesJerome Baudry
Apr 7, 2005·Physical Chemistry Chemical Physics : PCCP·Pedro C Gómez, Luis F Pacios
Aug 27, 2009·Proceedings of the National Academy of Sciences of the United States of America·Jason P SchwansDaniel Herschlag
Jun 27, 2013·Proceedings of the National Academy of Sciences of the United States of America·Paul A SigalaDaniel Herschlag
Oct 6, 1998·Annual Review of Biochemistry·V L Schramm
Jun 5, 2002·Annual Review of Biochemistry·Brian G Miller, Richard Wolfenden
Jan 1, 1997·Annual Review of Physical Chemistry·C L Perrin, J B Nielson
Feb 20, 2014·Journal of the American Chemical Society·Marc Nadal-FerretJosé M Lluch
Mar 8, 2014·Journal of the American Chemical Society·Matthew B NodwellStephan A Sieber
Jul 20, 2007·Proceedings of the National Academy of Sciences of the United States of America·Michael T Sykes, Michael Levitt
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Aug 23, 2016·Journal of the American Chemical Society·Yufan Wu, Steven G Boxer

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