Journal ArticleDOI
Understanding enzyme-catalyzed proton abstraction from carbon acids: Details of stepwise mechanisms for β-elimination reactions
John A. Gerlt,Paul G. Gassman +1 more
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Gerlt et al. as mentioned in this paper showed that the enzyme-catalyzed abstraction of a proton from a carbon adjacent to a carbonyl/carboxylic acid group (α-proton of a carbon acid) requires that the pKa of the aproton be decreased such that it is equal to (± 2-3 pK a units) or las than that of the protonated active site basic catalyst.Abstract:
The observed rates of enzyme-catalyzed abstraction of a proton from a carbon adjacent to a carbonyl/carboxylic acid group (α-proton of a carbon acid) require that the pKa of the a-proton be decreased such that it is equal to (±2-3 pK a units) or las than that of the protonated active site basic catalyst. This can be accomplished by concerted general acid-general base catalysis: Gerlt, J. A.; Kozarich, J. W.; Kenyon, G. L.; Gassman, P. G. J. Am. Chem. Soc. 1991, 113, 9667read more
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Understanding the rates of certain enzyme-catalyzed reactions: Proton abstraction from carbon acids, acyl transfer reactions, and displacement reactions of phosphodiesters
John A. Gerlt,Paul G. Gassman +1 more
TL;DR: This paper proposes that one (or more) general acid catalyst positioned adjacent to the carbonyl or phosphoryl oxygens of the substrate is primarily responsible for reducing both delta G zero and delta G++int from the values that characterize nonenzymatic reactions.
Journal ArticleDOI
Mechanisms and free energies of enzymatic reactions.
TL;DR: Each enzyme has its unique characteristics, and enzymes use all possible means to achieve the ultimate objective of reducing the free energy of activation, as demonstrated in the experiments and computational results reviewed in this article.
Journal ArticleDOI
The Enolase Superfamily: A General Strategy for Enzyme-Catalyzed Abstraction of the α-Protons of Carboxylic Acids†
Patricia C. Babbitt,Miriam S. Hasson,Miriam S. Hasson,Joseph E. Wedekind,Joseph E. Wedekind,David R. J. Palmer,William C. Barrett,George H. Reed,Ivan Rayment,Dagmar Ringe,George L. Kenyon,John A. Gerlt +11 more
TL;DR: A superfamily of enzymes related by their ability to catalyze the abstraction of the alpha-proton of a carboxylic acid to form an enolic intermediate is discovered, and the established and deduced structure-function relationships in the superfamily allow the prediction that other apparent members of the family for which no catalytic functions have yet been assigned will also perform chemistry involving abstraction of their alpha-protons.
Journal ArticleDOI
Controlled racemization of optically active organic compounds: Prospects for asymmetric transformation
Eelco J. Ebbers,Gerry J.A. Ariaans,Joannes P.M. Houbiers,Alle Bruggink,Alle Bruggink,Binne Zwanenburg +5 more
Journal ArticleDOI
The architecture of parallel β-helices and related folds
TL;DR: Three-dimensional structures have been determined of a large number of proteins characterized by a repetitive fold where each of the repeats (coils) supplies a strand to one or more parallel β-sheets, which suggests that coils can be added or removed by duplication or deletion of the DNA corresponding to oneor more coils and explains how homologous proteins can have different numbers of coils.
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