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Int. J. Mol. Sci. 2012, 13(11), 14219-14242; doi:10.3390/ijms131114219

Noncanonical Reactions of Flavoenzymes

1
Department of Biochemistry, Virginia Tech, Blacksburg, VA 24061, USA
2
Virginia Tech Center for Drug Discovery, Virginia Tech, Blacksburg, VA 24061, USA 
Received: 18 September 2012 / Revised: 17 October 2012 / Accepted: 26 October 2012 / Published: 5 November 2012
(This article belongs to the Special Issue Flavins)
View Full-Text   |   Download PDF [6846 KB, uploaded 19 June 2014]   |  

Abstract

Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates. View Full-Text
Keywords: flavoenyzmes; chorismate synthase; type II isopentenyl diphosphate/dimethylallyl diphosphate isomerase; UDP-galactopyranose mutase; alkyl-dihydroxyacetonephosphate synthase; non-redox reaction; novel function flavoenyzmes; chorismate synthase; type II isopentenyl diphosphate/dimethylallyl diphosphate isomerase; UDP-galactopyranose mutase; alkyl-dihydroxyacetonephosphate synthase; non-redox reaction; novel function
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This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Sobrado, P. Noncanonical Reactions of Flavoenzymes. Int. J. Mol. Sci. 2012, 13, 14219-14242.

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