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J Am Chem Soc. 2011 Apr 20;133(15):5683-5. doi: 10.1021/ja111457h. Epub 2011 Mar 24.

Kinetic challenges facing oxalate, malonate, acetoacetate, and oxaloacetate decarboxylases.

Author information

1
Department of Biochemistry and Biophysics, University of North Carolina, Chapel Hill, North Carolina 27599-7260, United States. water@med.unc.edu

Abstract

To compare the powers of the corresponding enzymes as catalysts, the rates of uncatalyzed decarboxylation of several aliphatic acids (oxalate, malonate, acetoacetate, and oxaloacetate) were determined at elevated temperatures and extrapolated to 25 °C. In the extreme case of oxalate, the rate of the uncatalyzed reaction at pH 4.2 was 1.1 × 10(-12) s(-1), implying a 2.5 × 10(13)-fold rate enhancement by oxalate decarboxylase. Whereas the enzymatic decarboxylation of oxalate requires O(2) and Mn(II), the uncatalyzed reaction is unaffected by the presence of these cofactors and appears to proceed by heterolytic elimination of CO(2).

PMID:
21434608
PMCID:
PMC3077560
DOI:
10.1021/ja111457h
[Indexed for MEDLINE]
Free PMC Article

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