Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2’:6’,2’’-terpyridine ligand: implications for actinide(III) /lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2’:6’,2’’-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III), U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UV absorption spectrophotometry, NMR studies and ESI-MS. Structures of the 1:1 complexes with Eu(III), Ce(III) and the linear uranyl (UO22+) ion were obtained by X-ray crystallographic analysis, and showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III) complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1:1 complexes with Eu(III), Ce(III) and Yb(III), while both 1:1 and 1:2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2:2 helical complexes was formed with Cu(I), with a slight preference (1.4:1) for a single directional isomer. In contrast, a 1:1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III) from Ln(III) by quadridentate N-donor ligand

Development of highly selective ligands for separations of actinides from lanthanides in the nuclear fuel cycle

This account summarizes recent work by us and others on the development of ligands for the separation of actinides from lanthanides contained in nuclear waste streams in the context of a future European strategy for nuclear waste management. The current status of actinide/lanthanide separations worldwide is briefly discussed, and the synthesis, development, and testing of different classes of heterocyclic soft N- and S-donor ligands in Europe over the last 20 years is presented. This work has led to the current benchmark ligand that displays many of the desirable qualities for industrial use. The improvement of radiolytic stability through ligand design is also discussed

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6’-bis(1,2,4-triazin-3-yl)-2,2’-bipyridine ligand dissolved in alkylated cyclohexanone Diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluent

Elasticity-mediated self-organization and colloidal interactions of solid spheres with tangential anchoring in a nematic liquid crystal

Using laser tweezers and fluorescence confocal polarizing microscopy, we study colloidal interactions of solid microspheres in the nematic bulk caused by elastic distortions around the particles with strong tangential surface anchoring. The particles aggregate into chains directed at about 30 degrees to the far field director and, at higher concentrations, form complex kinetically trapped structures. We characterize the distance and angular dependencies of the colloidal interaction forces.Comment: 6 pages, 5 figure

Von Neumann Entropy-Preserving Quantum Operations

For a given quantum state $\rho$ and two quantum operations $\Phi$ and $\Psi$, the information encoded in the quantum state $\rho$ is quantified by its von Neumann entropy $\S(\rho)$. By the famous Choi-Jamio{\l}kowski isomorphism, the quantum operation $\Phi$ can be transformed into a bipartite state, the von Neumann entropy $\S^{\mathrm{map}}(\Phi)$ of the bipartite state describes the decoherence induced by $\Phi$. In this Letter, we characterize not only the pairs $(\Phi, \rho)$ which satisfy $\S(\Phi(\rho))=\S(\rho)$, but also the pairs $(\Phi, \Psi)$ which satisfy $\S^{\mathrm{map}}(\Phi\circ\Psi) = \S^{\mathrm{map}}(\Psi)$.Comment: 7 pages, LaTeX, to appear Phys. Lett.

Highly efficient separation of actinides from lanthanides by a phenanthroline-derived bis-triazine ligand

The synthesis, lanthanide complexation, and solvent ex- traction 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, respec-tively. 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

Theory of wind accretion

A review of wind accretion in high-mass X-ray binaries is presented. We focus attention to different regimes of quasi-spherical accretion onto the neutron star: the supersonic (Bondi) accretion, which takes place when the captured matter cools down rapidly and falls supersonically toward NS magnetospghere, and subsonic (settling) accretion which occurs when plasma remains hot until it meets the magnetospheric boundary. Two regimes of accretion are separated by an X-ray luminosity of about $4\times10^{36}$ erg/s. In the subsonic case, which sets in at low luminosities, a hot quasi-spherical shell must be formed around the magnetosphere, and the actual accretion rate onto NS is determined by ability of the plasma to enter the magnetosphere due to Rayleigh-Taylor instability. We calculate the rate of plasma entry the magnetopshere and the angular momentum transfer in the shell due to turbulent viscosity appearing in the convective differentially rotating shell. We also discuss and calculate the structure of the magnetospheric boundary layer where the angular momentum between the rotating magnetosphere and the base of the differentially rotating quasi-spherical shell takes place. We show how observations of equilibrium X-ray pulsars Vela X-1 and GX 301-2 can be used to estimate dimensionless parameters of the subsonic settling accretion theory, and obtain the width of the magnetospheric boundary layer for these pulsars.Comment: LaTeX, 10 pages, 5 figures; submitted to Proc. of Int. Conf. "Physics at the Magnetspheric Boundary", Geneva, Switzerland, 25-28 June, 201

Extraction of minor actinides, lanthanides and other fission products by silica-immobilized BTBP/BTPhen ligands

Novel BTBP [bis-(1,2,4-triazin-3-yl)-2,2’-bipyridine] / BTPhen [bis-(1,2,4-triazin-3-yl)-1,10-phenanthroline] functionalized silica gels have been developed to extract minor actinides, lanthanides and other fission products. BTPhen functionalized silica gel is capable of near-quantitative removal of Am(III) in the presence of Eu(III) from aqueous HNO3, while BTBP functionalized silica gel is able to remove problematic corrosion and fission products that are found in PUREX raffinates

Hydrophilic sulfonated bis-1,2,4-triazine ligands are highly effective reagents for separating actinides(iii) from lanthanides(iii) via selective formation of aqueous actinide complexes

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. The greater ability of the tetrasulfonated ligands to retain Am(III) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(III). The selectivities for Am(III) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen