The aim of the present work was to design functionalized lipidic membranes that can selectively interact with lanthanide ions at the interface and to exploit the interaction between membranes induced by this molecular-recognition process with a view to building up self-assembled vesicles or controlling the permeability of the membrane to lanthanide ions. Amphiphilic molecules bearing a beta-diketone unit as head group were synthesized and incorporated into phospholipidic vesicles. Binding of Eu(III) ions to the amphiphilic ligand can lead to formation of a complex involving ligands of the same vesicle membrane (intravesicular complex) or of two different vesicles (intervesicular complex). The effect of Eu(III) ions on vesicle behavior was studied by complementary techniques such as fluorimetry, light scattering, and electron microscopy. The formation of an intravesicular luminescent Eu/beta-diketone ligand (1/2) complex was demonstrated. The linear increase in the binding constant with increasing concentration of ligands in the membrane revealed a cooperative effect of the ligands distributed in the vesicle membrane. The luminescence of this complex can be exploited to monitor the kinetics of complexation at the interface of the vesicles, as well as ion transport across the membrane. By encapsulation of 2,6-dipicolinic acid (DPA) as a competing ligand which forms a luminescent Eu/DPA complex, the kinetics of ion transport across the membrane could be followed. These functional vesicles were shown to be an efficient system for the selective transport of Eu(III) ions across a membrane with assistance by beta-diketone ligands.
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http://dx.doi.org/10.1002/chem.200305423 | DOI Listing |
Inorg Chem
December 2024
Department of Chemistry, Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden.
The reduction of stable trivalent lanthanide species (Ln(III)) by the excited states of organic chromophores is the basis of photocatalytic divalent lanthanide-mediated reduction reactions. While indirect evidence of the photochemical formation of the reactive Ln(II) species is abundant, direct spectroscopic evidence of their presence is scarce. Here, nine chromophores with absorptions covering the near UV and visible ranges were systematically investigated in the presence of Ln(III) ions to evaluate their ability to reduce Eu(III) upon excitation with visible light to the catalytically active Eu(II) species.
View Article and Find Full Text PDFChemistry
December 2024
University of Münster Department of Chemistry and Pharmacy: Westfalische Wilhelms-Universitat Munster Fachbereich 12 Chemie und Pharmazie, Institut für Anorganische und Analytische Chemie, Corrensstr. 28/30, 48149, Münster, GERMANY.
Two artificial imidazole-derived nucleobases, HQIm (3H-imidazo[4,5-f]quinolin-5-ol) and CaIm (imidazole-4-carboxylate), were introduced into short DNA duplexes to systematically investigate their thermal stability upon metal ion coordination. Metal-mediated base pairs are formed with the 3d metal ions CoII, NiII and ZnII, as well as with the lanthanoid ions EuIII and SmIII, which induce a thermal stabilization of up to 8 °C upon binding. The latter are the first lanthanoid-mediated base pairs involving only four donor atoms that result in a significant duplex stabilization.
View Article and Find Full Text PDFChemistryOpen
November 2024
Department of Applied Sciences, Faculty of Health and Life Sciences, Northumbria University, Newcastle upon Tyne, Tyne and Wear, NE1 8ST, UK.
Bis-1,2,4-triazine ligands are amongst the most promising soft N-donor ligands for the partitioning of trivalent actinides from trivalent lanthanides; a key separation proposed in the future reprocessing of spent nuclear fuels. In an effort to improve the extraction properties of these benchmark ligands, we propose herein a general ligand design approach that is inspired by the field of drug discovery, and we apply it to a new class of ligands in which the bidentate 3-(2-pyridyl)-1,2,4-triazine unit of the benchmark ligands is replaced by a bidentate 1,2,4-triazine-3-carboxamide unit. A series of nine novel ligands were synthesized by reactions of readily available ethyl 1,2,4-triazine-3-carboxylate building blocks with different polyamine cores and evaluated for their ability to extract and separate Am(III) and Cm(III) from Eu(III).
View Article and Find Full Text PDFInorg Chem
December 2024
Luminescent Materials Laboratory, DB, University of Verona, and INSTM, UdR Verona, Strada Le Grazie 15, Verona 37134, Italy.
Inorg Chem
December 2024
Department of Chemistry, Faculty of Science and Technology, ICFAI University Tripura, Agartala 799210, Tripura, India.
Lanthanide-based light-emitting coordination polymers (CPs) and CP gels (CPGs) have significance for applications in optical systems, image processing/multiplexing, and optical sensors. In this study, we report two new luminescent CPs (EuL-CP () and TbL-CP ()) and CPGs (EuL-gel () and TbL-gel ()) using lanthanide(III) ions (Ln(III) = Eu(III) and Tb(III)) and 4-(4-carboxyphenyl)-2,2:6,2-terpyridine ligand () capable of forming stable thermoreversible gels. Probable structures of EuL-CP () and TbL-CP () and the formations of EuL-gel () and TbL-gel () are proposed based on adequate computational studies.
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