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Trends Biochem Sci. 2006 May;31(5):276-83. Epub 2006 Apr 5.

To be or not to be an oxidase: challenging the oxygen reactivity of flavoenzymes.

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Department of Genetics and Microbiology, University of Pavia, via Ferrata 1, Pavia 27100, Italy.


Flavin-dependent enzymes catalyse a wide range of reactions and, thereby, facilitate a variety of cellular processes. Among the properties that equip flavoenzymes with this chemical versatility is their reactivity towards oxygen, which shows huge variation among flavoproteins. A survey of known 3D structures of flavin-dependent oxidases and dehydrogenases and the correlation with their functional properties indicates that there are no structural rules that enable prediction of whether or how a flavoenzyme reacts with oxygen. Combinations of subtle factors such as dipole pre-organization, charge distribution, dynamics and solvation in the active centre determine the balance of interactions that control oxygen reactivity. The chemical basis of oxygen reactivity remains a puzzling problem and represents one of the challenging questions in modern flavoenzymology.

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