A synthetic approach is developed to obtain families of luminescent lanthanide complexes and markers from a generic family of precursors built from nonadentate coordination sites. The syntheses of the precursors, based on a directed regioselective nucleophilic aromatic substitution on polyfluoropyridines, are described. Functionalisation of the synthons on the aromatic moieties allowed the introduction of labelling functions and/or the extension of the electronic delocalisation, with concomitant changes in the spectroscopic properties. The synthesis of two such families of ligands and of some of their complexes of Eu(III) and Tb(III) are described, and the photo-physical properties of the complexes were measured, revealing excellent luminescence quantum yields reaching unity in some cases. For some of these complexes, the emphasis was further put on the preparation of an N-hydroxylsuccinimide (NHS) ester as activated function for labelling. The Tb and La complexes in the NHS activated form were synthesized and fully characterized. The labelling was first demonstrated on amino functionalized polymer beads and characterized by time-resolved luminescence microscopy. In a second step, the activated Tb complex was used for the labelling of GFR44 monoclonal antibody, and was applied to the detection of carcinoembryonic antigene (CEA) within the frame of a time-resolved fluoroimmunoassay. Comparison with a commercially available kit based on a europium cryptate as energy donor confirms the efficiency of Tb to act as an energy donor with an unoptimised 35% increase of the detection efficiency.
The paramagnetic l'csonancc properties of Cl'+++ ions in AM)3 (rnby) were in/lestigated theoretically and experimenialh] in order to obtain iniormaiion. necessary for the application of this material as active material in a three-level soHd-state maser (SLSSilI). Numerically computed enrrgy lcoel«, together with their associated eigenvectors, are presented as a function of applied maqnetic field for various orientations of the maqnetic .field with respect to the crystalline symmetry axis. A. more detailed discussion is devoted to energy lcoele, eigenvectors and transition probabilities at angles 0 0 , 54.74°and 90 0 , where certain simple relations and symmetries hold. Paramagnetic spectra for signal frequencies between 5 and 24 kmc arc shown; agreement betuiocn. computed and mcosurcd resonance field8 is satisfactory.
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