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ASSOCIATION CUIVRE-RADICAL PHENOXYLE: CHIMIE EN SOLUTION ET MODELES BIO-INSPIRES DE LA GALACTOSE OXYDASE

Abstract : GALACTOSE OXIDASE IS AN EXTRACELLULAR COPPER-CONTAINING ENZYME THAT CATALYSES THE OXIDATION OF PRIMARY ALCOHOLS TO THEIR CORRESPONDING ALDEHYDES WITH CONCOMITANT REDUCTION OF MOLECULAR DIOXYGEN TO HYDROGEN PEROXIDE. ITS ACTIVE SITE CONTAINS A COPPER ATOM MAGNETICALLY COUPLED TO A TYROSYL RADICAL: THIS ORIGINAL ASSOCIATION ALLOWS THE STORAGE OF TWO OXIDAZING EQUIVALENT.
WHITH SYNTHETIC COPPER COMPLEXES, WE HAVE REPRODUCED THIS ASSOCIATION AND EXTENSED IT TO MORE COMPLEX STRUCTURES WHICH CAN CONTAIN THREE AND FOUR OXIDAZING EQUIVALENTS.
FIRST, WE HAVE PREPARED THE PRECURSOR COPPER COMPLEXES FROM SEVERAL LIGANDS. THE PHENOXYL COPPER(II) COMPLEXES HAVE BEEN OBTAINED BY ONE- ELECTRON OXYDATION. OUR RESUTS DEMONSTRATE THAT THE LIGAND STRUCTURE INFLUENCES THE GEOMETRY ARROUND THE METAL CENTER AND ALSO THE STABILITY OF THE RADICAL SPECIES.
IN A SECOND PART, WE HAVE INVESTIGATED THE SOLUTION CHEMISTRY OF THE LIGAND UNDER VARIOUS COPPER AND DIOXYGEN STATUS IN ORDER TO MIMIC AND UNDERSTAND THE MATURATION OF GALACTOSE OXIDASE ; 19 FLUORINE NMR SPECTROSCOPY PROVED TO BE A POWERFUL TOOL IN THIS STUDY: 19F LABELING HAS BEEN REALIZED BY INCORPORATED A
F ATOM IN A QUINOLIN OR A F ATOM AND A CF3 GROUP IN A PHENOL.
IN THE LAST PART, THE SYNTHESIS OF BIO-INSPIRED COMPLEXES WHICH CAN CONTAIN THREE AND FOUR OXIDAZING EQUIVALENT HAVE BEEN INVESTIGATED: THE FIRST BRIDGING PHENOXYL COPPER COMPLEXES HAVE BEEN OBTAINED AND CHARACTERIZED.
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https://tel.archives-ouvertes.fr/tel-00011247
Contributor : Fabien Michel <>
Submitted on : Tuesday, December 20, 2005 - 5:47:14 PM
Last modification on : Friday, November 6, 2020 - 3:48:48 AM
Long-term archiving on: : Tuesday, April 6, 2010 - 4:32:30 PM

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  • HAL Id : tel-00011247, version 1

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Fabien Michel. ASSOCIATION CUIVRE-RADICAL PHENOXYLE: CHIMIE EN SOLUTION ET MODELES BIO-INSPIRES DE LA GALACTOSE OXYDASE. Autre. Université Joseph-Fourier - Grenoble I, 2005. Français. ⟨tel-00011247⟩

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