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  • Coordination chemistry  (1)
  • Gadolinium  (1)
  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1911-1918 
    ISSN: 1434-1948
    Schlagwort(e): Macrocycles ; Photochemistry ; Fluorescence spectroscopy ; Coordination chemistry ; Zinc ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The macrocyclic ligands L2 and L3, containing a triethylenetetraamine and a tetraethylenepentaamine moiety linked to the methyl groups of 2,9-dimethyl-1,10-phenanthroline, bind H+ and Zn2+ ions giving rise to modulation of the fluorescence emission intensity. The equilibrium constants and the enthalpy changes for ligand protonation were determined by means of pH-metric and microcalorimetric methods in 0.1 M Me4NCl solutions at 298.1±0.1 K. Also the stability constants of the Zn2+ complexes were determined under the same experimental conditions. L2 forms only mononuclear complexes, while L3 also forms dizinc(II) species. The phenanthroline group has fluorescence emission properties, but interaction with the lone pairs of benzylic nitrogen atoms produces an efficient quenching of the emission. Such a quenching effect can be avoided by deactivation of the benzylic nitrogen atoms by means of protonation or Zn2+ complexation. Hence, L2 and L3 behave as chemosensor for H+ and Zn2+, the photochemical properties of the ligands being modulated by the formation of different protonated and complexed species. In the case of L3, the fluorescence emission is also controlled by the metal to ligand molar ratio, because of the formation of an emissive binuclear complex.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    ISSN: 1434-1948
    Schlagwort(e): Gadolinium complexes ; Gadolinium ; Magnetic Resonance Imaging (MRI) ; Contrast agents ; Polyamino-polycarboxylic ligands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Equilibrium data on the interaction of DTMA [(DTMA = DOTA tetrakis(methylammide)] with Gd3+ in aqueous solution, properties of the complexes formed in the pH range 0.6-11.8, water proton relaxation rate enhancement, and the crystal structure analysis of the [Gd(DTMA)H2O]3+ complex are reported. In the crystal structure the metal ion is bound to the nitrogen atoms of the tetraazamacrocyclic moiety, to the amidic oxygen atoms, and to an oxygen atom of a water molecule. The nine donors are located at the vertices of a distorted square antiprism, which is capped by the coordinated water oxygen atom in the axial position. In solution [Gd(DTMA)]3+ is not very stable [logKML = 12.8(1)] and gives rise to the formation of [Gd(DTMA)OH]2+ [pKa = 7.9(1)] and [Gd(HDTMA)]4+ [logK(ML+H) = 3.4(1)]. The proton solvent relaxivity of aqueous complex solutions assumes a constant value in the pH range 3-8, increasing at higher and lower pH. For pH 〉 3 the data are in good agreement with a previous study on the same compound. For pH 〈 3 a new interpretation is presented, based on the formation of [Gd(HDTMA)]4+ and the release of Gd3+.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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