Antibodies conjugated with new highly luminescent Eu3+ and Tb3+ chelates as markers for time resolved immunoassays. Application to simultaneous determination of clenbuterol and free cortisol in horse urine.

Highly luminescent Eu(3+) and Tb(3+) complexes of 10-[4-(3-isothiocyanatopropoxy)benzoylmethyl]-1,4,7,10-tetraazacyclododecane-1,4,7 triacetic acid Eu(3+) is a subset of 1 and Tb(3+) is a subset of 1 were conjugated with a goat anti-rabbit IgG and a rabbit anti-mouse IgG, respectively, and applied as markers in a time resolved immunoassay for simultaneous quantitative determination of anabolic compounds clenbuterol (CL) and hydrocortisone (HC). The assay was performed in horse urine, using a monoclonal antibody specific to CL and a rabbit polyclonal antibody specific to the free HC. These lanthanide chelates are very stable and highly luminescent in aqueous solution and allowed to reach 10 microg L(-1) and 40 microg L(-1) sensitivities for CL and for HC, respectively. Application to the horse urine, that is a very complex matrix, has a considerable interest in the control of illegal use of these compounds.

Determination of the quadratic hyperpolarizability of trans-4-[4-(dimethylamino)styryl]pyridine and 5-dimethylamino-1,10-phenanthroline from solvatochromism of absorption and fluorescence spectra: a comparison with the electric-field-induced second-harmonic generation technique.

For fluorescent compounds, the combined use of absorption and emission solvatochromic data allows to estimate indirectly the cavity radius of the molecule in solution, a very critical parameter in the application of the solvatochromic method for the determination of the quadratic hyperpolarizability beta of dipolar molecules. For two test compounds, trans-4-[4-(dimethylamino)styryl]pyridine (DASP) and 5-dimethylamino-1,10-phenanthroline (DAPHEN), the beta values so obtained are compared with those obtained by the EFISH (Electric Field Induced Second-Harmonic generation) technique. For DAPHEN, the versatility of the method described in this work in the presence of more than one electronic transition contributing to the non-linear optical response is demonstrated.

A new polytopic bis-diazacrown-ether-polypyridine ligand and its complexes with Zn(II) salts and mononuclear and dendritic Ru(II) precursors. Synthesis, absorption spectra, redox behavior, and luminescence properties.

The new polytopic receptor 1 containing two terpyridine, one phenanthroline, and two diazacrown-ether sites has been prepared using a modular approach. Such a new species contains several pieces of information in its structure which can be processed by different metal ions to give different supramolecular inorganic architectures. Actually, reaction of 1 with Zn(CH(3)COO)(2) in methanol, and subsequent anion exchange, afforded the intramolecular ring-type [Zn(1)](2+) complex, which appears to be formed by a self-assembling reaction. A different synthetic approach, stepwise synthesis, allowed us to synthesize the two multicomponent compounds [(bpy)(2)Ru(mu-1)Ru(bpy)(2)](4+) (Ru2; bpy = 2,2'-bipyridine) and [[(bpy)(2)Ru(mu-2,3-dpp)](2)Ru(mu-1)Ru[(mu-2,3-dpp)Ru(bpy)(2)](2)](12+) (Ru6; 2,3-dpp = 2,3-bis(2-pyridyl)pyrazine). The absorption spectra and luminescence properties of 1 and [Zn(1)](2+) are dominated by pi --> pi transitions and excited states. The absorption spectra of the ruthenium compounds are dominated by ligand-centered (LC) bands in the UV region and metal-to-ligand charge-transfer (MLCT) bands in the visible. The latter compounds undergo several reversible metal-centered oxidations and ligand-centered reductions in the potential window investigated (-2.0/+2.0 V versus SCE) and exhibit MLCT luminescence in both acetonitrile fluid solution at room temperature and in butyronitrile rigid matrix at 77 K. Both the redox and photophysical properties of Ru2 and Ru6 can be assigned to specific subunits of the multicomponent structures. The data indicate that the [Ru(bpy)(2)](2+) and the dendritic [Ru[(mu-2,3-dpp)Ru(bpy)(2)](2)](6+) fragments appended to the polytopic 1ligands behave as independent components of the multicomponent arrays.

A study on the solution and gas-phase chemistry of Mn(III) and Fe(III) tetraarylporphyrin complexes by fast-atom bombardment mass spectrometry : 1: Generation of molecular signals.

Fast-atom bombardment mass spectrometry has been used to investigate the chemical behavior of Fe(III) and Mn(III) tetraarylporphyrins (TAP) in both the condensed and gas phases and to clarify the mechanisms responsible for the production of positive and negative ions. The differences in the behavior of Fe(III) and Mn(III) complexes in the positive ion mode could be correlated with those in their electronic structures and knowledge of the mechanism for the generation of negatively charged species was applied to characterize the counterion coordinated to the Mn(III)-TAP. Thus, the unprecedented, complete characterization of even complex Mn(III)-TAP was made possible.

A study on the solution and gas-phase chemistry of Mn(III) and Fe(III) tetraarylporphyrin complexes by fast-atom bombardment mass spectrometry : 2: Synthesis and characterization of molecular complexes federico maria rubino.

The chemical behavior of Fe(III) and M(III) tetraarylporphorin (TAP) complexes with N-alkylimidazoles and other suitable ligands was studied by direct reaction in the fast-atom bombardment matrix and in the gas phase. The coordination reaction occurs at the metal center and yields molecular adducts of porphyry/ligand (PL) and PL, stoichiometry. Coordinative competition between free and covalently linked ligands can be used to probe the conformation of "tailed" Mn(III)-TAP.