The synthesis, lanthanide complexation, and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.
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http://dx.doi.org/10.1021/ja203378m | DOI Listing |
Inorg Chem
July 2021
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
In the process of spent fuel reprocessing, it is highly difficult to extract transplutonium elements from adjacent actinides. A deep understanding of the electronic structure of transplutonium complexes is essential for development of steady ligands for in-group separation of transplutonium actinides. In this work, we have systematically explored the potential in-group separation ability of transplutonium elements of typical quadridentate N-donor ligands (phenanthroline-derived bis-triazine, BTPhen derivatives) through quasi-relativistic density functional theory (DFT).
View Article and Find Full Text PDFInorg Chem
May 2020
Multidisciplinary Initiative Center, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
The significance of understanding the interaction between actinide(III)/lanthanide(III) (An(III)/Ln(III)) and N-donor extractants lies in the importance of efficient An/Ln separation in advanced nuclear fuel cycles and the high expectation of the application of N-donor extractants. This work reports a density functional theory study aiming at a plausible explanation of the origin of the selectivity of the ligands in An/Ln separation and an evaluation of the influence of the bridging groups of typical N-donor extractants. Five bis(triazine) N-donor ligands were considered, differing in their denticity dictated by their bridging groups and in the flexibility of these bridging groups.
View Article and Find Full Text PDFMol Neurodegener
January 2016
Université Montpellier, Montpellier, F-34095, France.
Background: Prion diseases are characterized by the accumulation in the central nervous system of an abnormally folded isoform of the prion protein, named PrP(Sc). Aggregation of PrP(Sc) into oligomers and fibrils is critically involved in the pathogenesis of prion diseases. Oligomers are supposed to be the key neurotoxic agents in prion disease, so modulation of prion aggregation pathways with small molecules can be a valuable strategy for studying prion pathogenicity and for developing new diagnostic and therapeutic approaches.
View Article and Find Full Text PDFChem Sci
August 2015
Department of Nuclear Chemistry , Czech Technical University in Prague, Břehová 7 , 115 19 Prague 1 , Czech Republic . Email:
We report the first examples of hydrophilic 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(iii) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(iii) from Eu(iii) by selective Am(iii) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(iii) from Eu(iii) in this system.
View Article and Find Full Text PDFChem Commun (Camb)
June 2015
Department of Chemistry, The University of Reading, Whiteknights, Reading RG6 6AD, UK.
Water soluble anionic and cationic bis-triazine ligands are able to suppress (mask) the extraction of corrosion and fission products such as Ni(II) and Pd(II) that are found in PUREX raffinates. Thus it is possible to separate these elements from the minor actinide Am(III). Although some masking agents have previously been developed that retard the extraction of Pd(II), this is the first time a masking agent has been developed for Ni(II).
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