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Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM :
Structure, thermodynamique et méthodes

Abstract : New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field.
The ACX and BCX ligands, which are acidic derivatives of modified Α- and Β-cyclodextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of triacidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity.
The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity.
To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, transmetallation constants, and the electronic relaxation rate.
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Submitted on : Thursday, August 10, 2006 - 3:38:18 PM
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Célia Bonnet. Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM :
Structure, thermodynamique et méthodes. Autre. Université Joseph-Fourier - Grenoble I, 2006. Français. ⟨tel-00089144⟩

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