Enzymatic Rate Enhancements

Daniel M Quinn, The University of Iowa, Iowa City, Iowa, USA
R Steven Sikorski, FutureCeuticals, Momense, Illinois, USA

Published online: December 2007

DOI: 10.1002/9780470015902.a0000717.pub2

Enzymatic rate enhancements arise from the unmatched ability of enzymes to stabilize the transition states of the reactions that they catalyse. The purpose of this article is to discuss the magnitude and mechanistic origins of enzymatic rate enhancements. Selected enzymes are described that manifest a wide range of rate enhancements and corresponding catalytic strategies.

Keywords: catalytic acceleration; transition state stabilization; diffusion control; enzyme mechanisms; enzyme catalysis

Figure 1. Transition state stabilization and transition state binding in a double displacement enzyme mechanism. Free energy changes in eqn (3) that correspond to the thermodynamic cycle of Scheme 2 are shown in blue. The solid black curve plots the energetics of the enzyme reaction when [A]Km. The dashed black line shows how the free energy of the E+A state changes when [A]Km. The solid green curve plots the energetics of the nonenzymic reaction.
Figure 2. Free-energy diagram for triosephosphate isomerase catalysis.
Scheme 1.
Scheme 2.
Scheme 3.
Scheme 4.
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 Further Reading
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    Gao J, Ma S, Major DT et al. (2006) Mechanisms and free energies of enzymatic reactions. Chemical Reviews 106: 3188–3209.
    A subject of considerable current interest is the role of protein dynamics in enzyme function and the expression of enzyme catalytic power, especially as gauged through experiments that support tunneling in enzyme-catalyzed hydron transfers. The reader is referred to the following reference for an insightful review of this topic: Nagel ZD and Klinman JP (2006) Tunneling and dynamics in enzymatic hydride transfer. Chemical Reviews 106: 3095–3118.
    book Schowen RL (2006) "Chapter 29: hydrogen bonds, transition-state stabilization, and enzyme catalysis". In: Kohen A and Limbach H-H (eds) Isotope Effects in Chemistry and Biology, pp. 765–792. Boca Raton, FL: CRC Press.

Related Sub-Topics:

Enzymes: Structure and Action Mechanism
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Article Title: Enzymatic Rate Enhancements
 
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Quinn, Daniel M, and Sikorski, R Steven(Dec 2007) Enzymatic Rate Enhancements. In: eLS. John Wiley & Sons Ltd, Chichester. http://www.els.net [doi: 10.1002/9780470015902.a0000717.pub2]