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Sample records for tervalent lanthanide ions

  1. Contribution to the study of pseudohalides complexes of tervalent, lanthanides and actinides in solution

    International Nuclear Information System (INIS)

    Cuillerdier, Christine.

    1981-10-01

    Some complexes formed with halides or pseudohalides (iodide, cyanide, azide and thiocyanate) and tervalent lanthanides and actinides have been studied in solution. Methods like solvent extraction, polarography have been used to measure inner plus outer sphere complexation and spectroscopic methods have been chosen to study inner sphere complexes only. It has been found that inner sphere complexe of americium and neodymium with cyanide exist in aqueous solutions. Tervalent actinides form stronger inner sphere complexes with azide than lanthanide in solution. Thiocyanate complexes appear to be inner sphere and N-bonded [fr

  2. A sensitive fluorescent sensor of lanthanide ions

    CERN Document Server

    Bekiari, V; Lianos, P

    2003-01-01

    A fluorescent probe bearing a diazostilbene chromophore and a benzo-15-crown-5 ether moiety is a very efficient sensor of lanthanide ions. The ligand emits strong fluorescence only in the presence of specific ions, namely lanthanide ions, while the emission wavelength is associated with a particular ion providing high sensitivity and resolution.

  3. Lanthanide ions as spectral converters for solar cells

    NARCIS (Netherlands)

    van der Ende, B.M.; Aarts, L.; Meijerink, A.

    2009-01-01

    The use of lanthanide ions to convert photons to different, more useful, wavelengths is well-known from a wide range of applications (e.g. fluorescent tubes, lasers, white light LEDs). Recently, a new potential application has emerged: the use of lanthanide ions for spectral conversion in solar

  4. Calmodulin-lanthanide ion exchange kinetics

    International Nuclear Information System (INIS)

    Buccigross, J.; O'Donnell, C.; Nelson, D.

    1985-01-01

    A flow dialysis apparatus suitable for the study of high affinity metal binding proteins has been utilized to study calmodulin-metal exchange kinetics. Calmodulin labeled with Eu-155 and Gd-153 was dialyzed against buffer containing various competing metal ions. The rate of metal exchange was monitored by a gamma-ray scintillation detector. The kinetics of exchange are first order, and the rates fall into two categories: Ca (II) and CD (II) in one, and the lanthanides Eu (III), Gd (III), and La (III) in the other

  5. Calibration beads containing luminescent lanthanide ion complexes

    Science.gov (United States)

    The reliability of lanthanide luminescence measurements, by both flow cytometry and digital microscopy, will be enhanced by the availability of narrow-band emitting lanthanide calibration beads. These beads can also be used to characterize spectrographic instruments, including mi...

  6. Energy transfer and quenching processes of excited uranyl ion and lanthanide ions in solutions

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Tomiyasu, Hiroshi

    1995-01-01

    Deactivation processes of photoexcited uranyl ion by various lanthanide ions in aqueous solution were studied. Each lanthanide ions show different interaction with excited uranyl ion depending on its lowest excited energy level, the number of 4f electrons and the acid concentration of the solution. (author)

  7. Stability complexes of lanthanide ions with some macrocyclic polyethers

    International Nuclear Information System (INIS)

    Poluehktov, N.S.; Malinka, E.V.; Meshkova, S.B.; Bel'tyukova, S.V.; Danilkovich, M.M.

    1984-01-01

    Stability of lanthanide complexes with macrocyclic polyethers has been studied versus the number of f-electrons, spin- and orbital angular momenta of the Lu 3+ ion ground states. The following compounds were used as macrocyclic complexones: 12-crown-4 (12C4), tert-bulylbenzo-15-crown-5(BB15C5), 18-crown-6 (18C6), ditert-butylbenzo-18-crown-6(DBB18C6), dibenzo-30-crown-10 (DB30C10), cryptand [2, 2, 1] (Cr[2, 2, 1]). It is shoWn that the stability constants of the studied lanthanide complexes can be described rather satisfactorily by an expression suggested earlier that relates their values with the number of 4f-electrons and the S and L quantum numbers of the ground states of the lantharide ions

  8. Lanthanide and actinide ion phytoextraction: investigations of biosorption chemistry

    International Nuclear Information System (INIS)

    Rayson, Gary D.; Serna, Debbie D.; Moore, Jessica L.

    2009-01-01

    Investigations of the chemical interactions responsible for passive biosorption of a lanthanide (Eu (III)) and an actinide (U (VI)) metal ion is described. Spectroscopic methods for the elucidation of chemical functionalities on cultured anther cell walls from the plant Datura innoxia include metal ion luminescence measurements. These have revealed the presence of distinctly different binding environments involving one, two, and three carboxylate moieties for Eu (III) and UO 2 2+ binding and sulfonates (or sulfates) and phosphates for sequestration of Eu (III) on the uranyl ion, respectively. Additional investigations of the apparent affinities of these metals to this material have revealed the presence of both low and high affinity sites for the binding of Eu (III) with weak electrostatic attractions proposed for binding at high metal concentrations (i.e., low affinities) and surface coordination interactions responsible for higher affinities. Conversely, total uranyl ion binding revealed only a single distribution of interactions based on apparent affinities. (author)

  9. Application of lanthanide ions doped in different glasses

    International Nuclear Information System (INIS)

    Dhondiyal, Charu Chandra

    2015-01-01

    The transfer of optical excitation energy from one ion/molecule to another ion/molecule has proved to be of potential importance in industrial application as well as research. Rare earth elements (RE) although not as rare as some of them occur more prevalently then other well known material (e.g. silver, tin, tungsten) are special group of elements of the periodic table comprising lanthanide series (from lanthanum to lutetium) and actinide series (from actinium to lawrencium). Most of the actinides are highly radioactive hence their uses are limited. Fluorescence is the particular optical property of lanthanide (RE) ions. The narrow absorption and emission lines exhibited by the RE ions in crystals, glasses and solutions have always made these ions attractive as sensitive probes of solids and liquid state and also makes them useful in laser technology, CRT displays, UV to visible converters and optical communications etc. In recent years there has been a special interest to study the properties and applications of rare earth doped in glasses. Lanthanide ions in glasses play an important role, especially by retaining their emission capabilities, in the host matrix. Glass as a dielectric material plays an important role in science and industry. Its chemical, physical and particular optical properties make it suitable for applications such as opto-electronic materials, laboratory equipment, laser gain media, etc. Photoluminescence from rare earth doped glasses are of major interest in the research area of optoelectronic device applications like phosphors, display monitors, lasers and amplifiers for communication systems. Now a days, development of optical devices based on rare-earth ions doped materials is one of the interesting fields of research. Rare earth doped glasses are widely used as laser materials, optical amplifiers, optical memory devices, magneto-optical devices, medical lasers, eye safe lasers, flat panel displays, fluorescent lamps, white LED's etc

  10. Studies on mixed ligand complexes of lanthanide (III) ions

    International Nuclear Information System (INIS)

    Rajendran, G.; Usha Devi, K.G.

    2002-01-01

    As part of our research programme, we have prepared and characterized a few nitrato, thiocyanato and perchlorato complexes of lanthanide(III) ions with ligands, viz., a Schiff base derived from p-anisidine and vanillin and diphenyl sulphoxide. The complexes were characterized by the measurement of electrical conductances and magnetic susceptibilities, molecular mass and metal percentage and spectral analysis. The thermal decompositions were studied by TG and DTG techniques. The thiocyanato complexes were prepared by substitution method from nitrato complexes. p-Anisidine-vanillin (HDDA) and diphenyl sulphoxide (DPSO) are coordinated to the metal ion in unidentate fashion. All the anions were involved in coordination in these complexes. Thus they were found to have non- electrolytic behaviour with composition [Ln(HDDA) 2 (DPSO)X 3 ] where X = NO 3 ) or SCN perchlorato complexes were prepared from metal perchlorate as done in the case of nitrato complexes. They were found to have electrical conductance which corresponds to 1 : 1 electrolyte. Hence one of the perchlorate ions is outside the coordination sphere. The composition of this complex is found to be [Ln(HDDA) 3 (DPSO)(ClO 4 ) 2 ]ClO 4 . (author)

  11. Lanthanide ions as absorption spectral probes in biochemical reactions

    International Nuclear Information System (INIS)

    Misra, S.N.

    1989-01-01

    The interactions of adenine, adenosine, adenosine 5'-monophosphate, 5'-diphosphate and 5'-triphosphate with Pr(III) and Nd(III) in different stoichiometries and at varying pH levels have been investigated by electronic spectral studies. The intra 4f-4f transitions yield sharp bands which were analysed individually by Gaussian curve analysis. The energy interaction (Fsup(k),Esup(k)) spin orbit interaction (ζ4f), bonding(b), nephelauxetic (β,δ) and intensity parameters (Tsub(τ.P)) have been computed on HP-1000/45 computer using regression analyses refined by least square fit. The nature of bonding, coordination environment, outer and inner sphere coordination have been interpreted in terms of the magnitude of these parameters as compared to the lanthanide free ion. In order to supplicate the solution studies the crystalline compounds of AMP, ADP and ATP with Pr(III) and Nd(III) have been isolated and characterized by IR, 1 H and 31 P NMR studies. The infrared spectral data indicated weak interaction with the imidazole nitrogen of adenine moiety and bidentate attachment of oxygen. (author). 10 refs

  12. Development of ion imprinted polymers for the selective extraction of lanthanides from environmental samples

    International Nuclear Information System (INIS)

    Moussa, Manel

    2016-01-01

    The analysis of the lanthanide ions present at trace level in complex environmental matrices requires often a purification and preconcentration step. The solid phase extraction (SPE) is the most used sample preparation technique. To improve the selectivity of this step, Ion Imprinted Polymers (IIPs) can be used as SPE solid supports. The aim of this work was the development of IIPs for the selective extraction of lanthanide ions from environmental samples. In a first part, IIPs were prepared according to the trapping approach using 5,7-dichloroquinoline-8-ol as non-vinylated ligand. For the first time, the loss of the trapped ligand during template ion removal and sedimentation steps was demonstrated by HPLC-UV. Moreover, this loss was not repeatable, which led to a lack of repeatability of the SPE profiles. It was then demonstrated that the trapping approach is not appropriate for the IIPs synthesis. In a second part, IIPs were synthesized by chemical immobilization of methacrylic acid as vinylated monomer. The repeatability of the synthesis and the SPE protocol were confirmed. A good selectivity of the IIPs for all the lanthanide ions was obtained. IIPs were successfully used to selectively extract lanthanide ions from tap and river water. Finally, IIPs were synthesized by chemical immobilization of methacrylic acid and 4-vinylpyridine as functional monomers and either a light (Nd 3+ ) or a heavy (Er 3+ ) lanthanide ion as template. Both kinds of IIPs led to a similar selectivity for all lanthanide ions. Nevertheless, this selectivity can be modified by changing the nature and the pH of the washing solution used in the SPE protocol. (author)

  13. Magnetic Properties of linear chain compounds formed by lanthanide (III) ions and nitronyl-nitroxide radicals

    Energy Technology Data Exchange (ETDEWEB)

    Benelli, C.; Caneschi, A.; Gatteschi, D.; Pardi, L. (Florence Univ. (IT)); Rey, P. (CEA Centre d' Etudes Nucleaires de Grenoble, 38 (FR). Dept. de Recherche Fondamentale)

    1988-12-01

    The magnetic properties of novel linear chain compounds containing lanthanide (III) ions (gadolinium, europium) coupled to stable nitronyl-nitroxide radicals are reported. The metal ions and the radicals are regularly alternating along the chain. The magnetic behaviors appears to be dominated by antiferromagnetic interactions between the radicals.

  14. Magnetic Properties of linear chain compounds formed by lanthanide (III) ions and nitronyl-nitroxide radicals

    International Nuclear Information System (INIS)

    Benelli, C.; Caneschi, A.; Gatteschi, D.; Pardi, L.; Rey, P.

    1988-01-01

    The magnetic properties of novel linear chain compounds containing lanthanide (III) ions (gadolinium, europium) coupled to stable nitronyl-nitroxide radicals are reported. The metal ions and the radicals are regularly alternating along the chain. The magnetic behaviors appears to be dominated by antiferromagnetic interactions between the radicals

  15. Luminescence and host lattice structure of crystalline micro and nanoparticles co-doped with lanthanide ions

    International Nuclear Information System (INIS)

    Zurba, Nadia Khaled; Ferreira, Jose Maria da Fonte

    2012-01-01

    This article reports the investigation of crystalline micro and nanoparticles codoped with lanthanide ions, aiming at correlate their host lattice structure and chemical composition to the luminescence features. For this purpose, five phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy coupled to energy dispersive X-ray (EDX) spectroscopy, and photoluminescence (PL) spectroscopy, namely performed by their chromatic coordinates, radiance, luminance and PL emission spectra. This type of investigation concerning the optical characterization of luminescent crystalline micro and nanoparticles doped with lanthanide ions might be useful for scientific and practical applications, such as in light-emitting devices, luminescent paintings, ceramics, sensors, in nanoscience and nanotechnology. (author)

  16. Complexes of trivalent lanthanide ions with schiff base derived from vanillin and triethylenetetraamine

    International Nuclear Information System (INIS)

    Shahma, A.; Athar, M.; Ahmad, N.

    1982-01-01

    Complexes of lanthanide(III) ions with the schiff base derived from vanillin and triethylenetetraamine have been synthesised and characterised on the basis of elemental analyses, molar conductance, magnetic moment, IR and thermal analysis data. The thermograms show the elimination (OH)(OCH 3 )C 6 H 3 CH-group at low temperatures before the elimination of triethylenetetraamine part corroborating the observation made on the basis of IR spectral data. This is a clear indication of the non-coordination of the phenolic hydroxyl groups. The lanthanide ions in the complexes exhibit eight coordination numbers. (author)

  17. f-state luminescence of lanthanide and actinide ions in solution

    International Nuclear Information System (INIS)

    Beitz, J.V.

    1993-01-01

    Detailed studies of the luminescence of aquated Am 3+ are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am 3+ is confirmed to be 5 D l based on observed emission and excitation spectra. The luminescence lifetime of Am 3+ in H 2 O solution is (22 ± 3) ns and (155 ± 4) ns in D 2 O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am 3+ relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties

  18. Separation of individual lanthanides through the combined techniques of urea fractionated homogeneous precipitation and ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Umeda, K; Abrao, A

    1975-06-01

    The separation of individual lanthanides, especially Ce, Nd, Pr, Sm and La, from a rare earth chlorides concentrate by the industrial processing of monazite sand is made. To reach this goal the homogeneous fractional precipitation and ion exchange techniques were combined. Using the rare earths concentrate depleted in Cerium, fractions enriched in Nd, Pr and Sm, and one final filtrate enriched in La were obtained, by the hydrolysis of urea. The separation of individual lanthanides (Nd, Pr, Sm and La) was accomplished using two strong cationic ion exchanger columns, the second with Cu(II) as retaining ion, and EDTA-NH/sub 4/ solution buffered with acetic acid as eluant. The annoying problem of precipitation into the column during the RE elution was solved. The difficult EDTA and Cu(II) recovery was the precipitation of Cu/sub 2/S and disruption of Cu-EDTA complex by hydrolysis of thiourea. The combination of both techniques allowed the preparation of individual lanthanides as Nd, Pr and La with 99% and Sm with 90% purity.

  19. Separation of individual lanthanides through the combined techniques of urea fractionated homogeneous precipitation and ion exchange

    International Nuclear Information System (INIS)

    Umeda, K.; Abrao, A.

    1975-01-01

    The separation of individual lanthanides, especially Ce, Nd, Pr, Sm and La, from a rare earth chlorides concentrate by the industrial processing of monazite sand is made. To reach this goal the homogeneous fractional precipitation and ion exchange techniques were combined. Using the rare earths concentrate depleted in Cerium, fractions enriched in Nd, Pr and Sm, and one final filtrate enriched in La were obtained, by the hydrolysis of urea. The separation of individual lanthanides (Ns, Pr, Sm and La) was accomplished using two strong cationic ion exchanger columns, the second with Cu(II) as retaining ion, and EDTA-NH 4 solution buffered with acetic acid as eluant. The annoy problem of precipitation into the column during the RE elution was solved. The difficult EDTA and Cu(II) recovery was the precipitation of Cu 2 S and disruption of CU-EDTA complex by hydrolysis of thiourea. The combination of both techniques allowed the preparation of individual lanthanides as Nd, Pr and La with 99% and Sm with 90% purity

  20. Hydration numbers of trivalent lanthanide and actinide ions

    International Nuclear Information System (INIS)

    David, F.; Fourest, B.; Duplessis, J.

    1987-01-01

    Investigations on the structure of actinide aquo ions and determination of hydration numbers have to be studied, essentially, through radiochemical methods. They measured the transport numbers, diffusion coefficient D by the open end capillary method and ionic mobility u by electrophoresis. Both methods show a discontinuity in the transport number corresponding to the crystallographic radius of Eu 3+ or Bk 3+ ion. They deduced the volume of the actinide aquo ions, and the coordination number in the primary sphere. From calculations of the electrostriction phenomenon in the vicinity of central ion, they obtained effective volume of the water molecules and the dynamic hydration number corresponding to the second hydration sphere

  1. Techniques of laser spectroscopy in investigations of lanthanides' free atoms and ions

    International Nuclear Information System (INIS)

    Furmann, B.; Szawiola, G.; Jarosz, A.; Krzykowski, A.; Stefanska, D.; Dembczynski, J.

    2010-01-01

    Various experimental methods, used in Chair of Quantum Engineering and Metrology for determination of the hyperfine structure of electronic levels in lanthanides atoms and ions, are presented. In turn the spectroscopic methods on an atomic beam (laser induced fluorescence and laser-rf double resonance ABMR-LIRF), laser-rf double resonance in a Paul trap and spectroscopic methods in a hollow cathode discharge (optogalvanic detection and laser induced fluorescence) are presented. Each method has been characterized with its potential accuracy and domain of application. The results achieved for the atoms and the ions of lanthanum, praseodymium, neodymium and europium have been published in numerous articles (compiled in the reference list).

  2. Separation of the lanthanides on high-efficiency bonded phases and conventional ion-exchange resins

    International Nuclear Information System (INIS)

    Elchuk, S.; Cassidy, R.M.

    1979-01-01

    High-performance liquid chromatographic separations (< 20 min) of the lanthanides are illustrated for both 5- and 10-μm bonded-phase strong-acid ion exchangers. The performance of these bonded phase packings is compared with that obtained with a 13-μm styrene-divinylbenzene resin. The eluted metal ions are detected with a variable-wavelength detector after a post-column complexation reaction. The requirements and characteristics of post-column reaction for sensitive metal ion detection after separation on high-performance columns are discussed and the linearity, reproducibility, and sensitivity of the system used in the work are illustrated. The potential of on-column preconcentration for the ultratrace (pg/mL) determination of metal ions is also discussed and illustrated. 7 figures, 2 tables

  3. Charge-transfer spectra of tetravalent lanthanide ions in oxides

    NARCIS (Netherlands)

    Hoefdraad, H.E.

    The charge-transfer spectra of Ce4+, Pr4+ and Tb4+ in a number of oxides are reported. It is noted that the position of the first charge-transfer band is fixed for the metal ion in an oxygen coordination of VI, but varies in VIII coordination as a function of the host lattice. It is argued that this

  4. Crystal-field tuning of photoluminescence in two-dimensional materials with embedded lanthanide ions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ding; Chen, Weiyin; Zeng, Mengqi; Xue, Haifeng; Chen, Yunxu; Xiao, Yao; Zhang, Tao; Fu, Lei [College of Chemistry and Molecular Sciences, Institute for Advanced Studies, Wuhan University, Wuhan (China); Sang, Xiahan; Unocic, Raymond R.; Xiao, Kai [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2018-01-15

    Lanthanide (Ln) group elements have been attracting considerable attention owing to the distinct optical properties. The crystal-field surroundings of Ln ions in the host materials can determine their energy level splitting, which is of vital importance to tailor their optical properties. 2D MoS{sub 2} single crystals were utilized as the host material to embed Eu{sup 3+} and energy-level splitting was achieved for tuning its photoluminescence (PL). The high anisotropy of the 2D host materials makes them distort the degenerate orbitals of the Ln ions more efficiently than the symmetrical bulk host materials. A significant red-shift of the PL peak for Eu{sup 3+} was observed. The strategy for tailoring the energy level splitting of Ln ions by the highly designable 2D material crystal field provides a new method to extend their optical properties. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Intercalation compounds of vanadium pentoxide hydrated with metalporphyrins and lanthanide ions

    International Nuclear Information System (INIS)

    Oliveira, Herenilton Paulino

    1994-01-01

    The lamellar structure of the vanadium pentoxide matrix allows the intercalation of organic molecules, ions and conductor polymers. It is important to emphasize that the vanadium oxide matrix is an intrinsic semiconductor and presents electrochromic properties. In the beginning of this work the method of synthesis and the electrochemical and electrochromic properties were extensively explored. The effect of alkaline metal and lanthanide ions on the structure of vanadium oxide matrix was studied by X-ray and infrared spectroscopy. Moreover, the influence of those ions in the electrochemical, spectro electrochemical and magnetic properties were studied. Finally, some intercalation compounds containing porphyrins were prepared and characterized by elemental analysis, X-ray diffraction, and electronic, vibrational, Moessbauer and X-ray fluorescence spectroscopy. The electrochemical and spectro electrochemical properties were investigated. And the performance of an iron porphyrin based intercalation compound as catalyst for molecular oxygen reduction was evaluated using the rotating ring-disc electrode technique. (author)

  6. X-ray absorption and magnetic studies of trivalent lanthanide ions sorbed on pristine and phosphate-modified boehmite surfaces

    International Nuclear Information System (INIS)

    Yoon, Soh-Joung; Helmke, Philip A.; Amonette, James E.; Bleam, William F.

    2002-01-01

    The feasibility of immobilizing radionuclides on mineral surfaces was examined in the absence and the presence of phosphate anions, using trivalent lanthanide ions (Eu3+, Gd3+, and Dy3+) as chemical analogues of trivalent actinide radionuclides. The amount of the lanthanide ions (Ln3+) sorbed on boehmite (gamma-AlOOH) surfaces dramatically increased on the presence of phosphate below pH 5. The structure of the sorbed lanthanide was determined by X-ray absorption spectroscopy, magnetic susceptibility measurements, and electron paramagnetic resonance spectroscopy. We proved Dy3+ forms precipitates on boehmite surfaces in the presence of phosphate, and Gd3+ both in the presence and absence of phosphate. In the presence of phosphate, however, these rare-earth cations react to from ultrafine particles of LnPO4 surface precipitates on boehmite surfaces

  7. Ion chromatography separation of lanthanides at trace concentrations from Gd Matrix and quantification by ICP-MS

    International Nuclear Information System (INIS)

    Raut, V.V.; Jeyakumar, S.; Nagar, B.K.; Deb, S.B.; Saxena, M.K.; Tomar, B.S.

    2014-01-01

    Gadolinium compounds are mainly used as burnable poison. The presence of certain impurities is undesirable in the nuclear grade Gd compounds. Gd 2 O 3 , a most common raw material used for the preparation of nuclear grade Gd compounds. Analysis of rare earth impurities in Gd-matrices is one of the important exercises carried out to ensure the purity of Gd 2 O 3 . Determination of lanthanides at trace concentrations in lanthanide (Gd) matrix is complicated and difficult to realize. This is because the selective separation of REE's in one of the lanthanide elements is a challenging task. The present study was carried out to explore the feasibility of separating trace level lanthanides from Gd matrix by ion interaction chromatography (IIC) and to develop an analytical methodology for the determination of lanthanides by inductively coupled plasma mass spectrometry (ICP-MS). In the present investigation, the reversed phase column was dynamically modified into sulphonic acid functionalized surface by using 0.025 M n-Octane sulphonic acid (OSA). With α-HIBA eluent system, the elution order follows as Lu to La. The separations are employed with gradient elution mode. Since the sample has large excess of Gd, elution profiles with concentration gradient of HIBA were attempted. Separated fractions of Light lanthanides (LLn) and Heavy lanthanides (HLn) were collected and analyzed by ICP-MS. During MS analysis, it was observed that due to high concentration of salt (Na salt of OSA) present in the collected fractions caused difficulty in ICP-MS . Hence the experiments were carried out using another ion interacting reagent viz. 0.03 M camphor-10-sulphonic acid (CSA). Initial concentration of HIBA was kept at 0.025 M up to 15 min for the elution of HLns i.e. from Lu to Tb and it was then increased to 0.05 M to 0.3 M in 30 min. After elution of Tb, outlet of the column was switched to drain for 7 min to separate bulk Gd fraction. From 22 to 35 min effluent fraction containing Eu

  8. Synthesis and magnetic properties of CoFe2O4 spinel ferrite nanoparticles doped with lanthanide ions

    International Nuclear Information System (INIS)

    Kahn, Myrtil L.; Zhang, Z. John

    2001-01-01

    Lanthanide ions have been doped into cobalt spinel ferrites using an oil-in-water micellar method to form CoLn 0.12 Fe 1.88 O 4 nanoparticles with Ln=Ce, Sm, Eu, Gd, Dy, or Er. Doping with lanthanide ions (Ln III ) modulates the magnetic properties of cobalt spinel ferrite nanoparticles. In particular cases of Gd 3+ or Dy 3+ ions, a dramatic increase in the blocking temperature and coercivity is observed. Indeed, the introduction of only 4% of Gd 3+ ions increases the blocking temperature ∼100 K and the coercivity 60%. Initial studies on the magnetic properties of these doped nanoparticles clearly demonstrate that the relationship between the modulation of magnetic properties and the nature of doped Ln III ions is interesting but very complex. [copyright] 2001 American Institute of Physics

  9. Effect of a lanthanide ion on the micellation and self-organization of lyotropic liquid crystal systems

    International Nuclear Information System (INIS)

    Selivanova, N.M.; Osipova, V.V.; Galyametdinov, Yu.G.

    2006-01-01

    Lanthanide-containing lyotropic liquid-crystalline systems were synthesized and their phase behavior, as well as the micellar behavior of aqueous solutions of decaethylene glycol monodecyl ether in the absence and presence of a lanthanide ion, were studied. Tensimetry and conductometry were used to determine the critical micellation concentration, and the values obtained by these methods were found to be in close agreement with each other. Polarization microscopy observations showed that, in concentrated aqueous solutions, ordered lyotropic mesophases arise. The parameters of the phase transitions in the systems under study were determined. The mesophase obtained was demonstrated to have a 2D hexagonal supramolecular structure [ru

  10. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy

    International Nuclear Information System (INIS)

    Gessner, Andre

    2010-12-01

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the 5 D 0 - 7 F 0 -transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the mesopores. Lanthanide ions located here, are

  11. Influence of excitation light on the frequency upconversion of trivalent lanthanide ions

    International Nuclear Information System (INIS)

    Fu Zhenxing; Zheng Hairong; Tian Yu; Zhang Zhenglong; Cui Min

    2010-01-01

    The upconversion mechanisms of the 1 D 2 level of Tm 3+ ion under different excitation lights were analyzed. The influences of the excitation lights on the upconversion process, nonradiative relaxation from level 3 F 2 to 3 H 4 and fluorescence properties were investigated. It was shown that the one-color cw excitation could affect the profile of fluorescence, while information of the nonradiative relaxation could not be extracted. The nonradiative relaxation rate measured with the one-color pulsed excitation in crystal phase was in agreement with what was obtained in the free-standing nanometer crystal particles through the two-color pulsed excitation. The characteristics of the fluorescent emissions of Tm 3+ ions doped in various host materials were also discussed under different excitation lights. As a result of the discussion, a possible way to obtain nonradiative relaxation rate directly from a spectroscopic method in frequency domain was proposed. The study can be extended to other trivalent lanthanide ions that have upconversion through excited state absorption.

  12. Accurate determination of trace amounts of lanthanum, yttrium and all stable lanthanides in biological materials by Ion Chromatography

    International Nuclear Information System (INIS)

    Dybczynski, R.S.; Kulisa, K.; Danko, B.; Samczynski, Z.

    2007-01-01

    The analytical procedure for the isolation and preconcentration of La, Y and the lanthanides from biological materials and their determination by ion chromatography (IC) with the use of Dionex Ion Pac CS3 + CG3 column (sulfonic acid type), α-hydroxyisobutyric acid (α-HIBA) as an eluent, and PAR or Arsenazo III as color forming reagents, was elaborated. The scheme originally devised for NAA, involving microwave assisted digestion and multi step separation employing ion exchange and extraction chromatography columns was used to selectively recover REE fraction (without scandium) with 100% yield. The REE fraction was analyzed by IC at 25 and 70 o C. The run at 70 o C enabled resolution of Y and Dy peaks and as a result made possible quantitative determination of La, Y, and all lanthanides. Investigation on the mechanism of band spreading revealed that longitudinal diffusion in the stationary phase considerably contributed to the total plate height. Surprisingly, the plate height (H) calculated from Y peak was distinctly lower than H values of the adjacent lanthanides. The method was validated by analyzing several certified reference materials (CRMs). (authors)

  13. The interaction of actinide and lanthanide ions with hemoglobin and its relevance to human and environmental toxicology

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Amit, E-mail: amitk@barc.gov.in [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Ali, Manjoor [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Ningthoujam, Raghumani S. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Gaikwad, Pallavi [Department of Zoology, Savitribai Phule Pune University, Pune 411 007, Mumbai (India); Kumar, Mukesh [Solid State, Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Nath, Bimalendu B. [Department of Zoology, Savitribai Phule Pune University, Pune 411 007, Mumbai (India); Pandey, Badri N. [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2016-04-15

    Highlights: • The sites of Ln and An interaction in Hb depend upon their charge-to-ionic-radii ratio. • Th(IV), Ce(IV) and U(VI) altered structure and oxygen-binding of Hb. • Spectroscopic studies determined binding characteristics of actinides. • Metal–Hb interaction was tested in an environmentally-important aquatic midge, Chironomus. - Abstract: Due to increasing use of lanthanides/actinides in nuclear and civil applications, understanding the impact of these metal ions on human health and environment is a growing concern. Hemoglobin (Hb), which occurs in all the kingdom of living organism, is the most abundant protein in human blood. In present study, effect of lanthanides and actinides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] on the structure and function of Hb has been investigated. Results showed that these metal ions, except Ce(IV) interacted with carbonyl and amide groups of Hb, which resulted in the loss of its alpha-helix conformation. However, beyond 75 μM, these ions affected heme moiety. Metal–heme interaction was found to affect oxygen-binding of Hb, which seems to be governed by their closeness with the charge-to-ionic-radius ratio of iron(III). Consistently, Ce(IV) being closest to iron(III), exhibited a greater effect on heme. Binding constant and binding stoichiometry of Th(IV) were higher than that of U(VI). Experiments using aquatic midge Chironomus (possessing human homologous Hb) and human blood, further validated metal–Hb interaction and associated toxicity. Thus, present study provides a biochemical basis to understand the actinide/lanthanide-induced interference in heme, which may have significant implications for the medical and environmental management of lanthanides/actinides toxicity.

  14. The interaction of actinide and lanthanide ions with hemoglobin and its relevance to human and environmental toxicology

    International Nuclear Information System (INIS)

    Kumar, Amit; Ali, Manjoor; Ningthoujam, Raghumani S.; Gaikwad, Pallavi; Kumar, Mukesh; Nath, Bimalendu B.; Pandey, Badri N.

    2016-01-01

    Highlights: • The sites of Ln and An interaction in Hb depend upon their charge-to-ionic-radii ratio. • Th(IV), Ce(IV) and U(VI) altered structure and oxygen-binding of Hb. • Spectroscopic studies determined binding characteristics of actinides. • Metal–Hb interaction was tested in an environmentally-important aquatic midge, Chironomus. - Abstract: Due to increasing use of lanthanides/actinides in nuclear and civil applications, understanding the impact of these metal ions on human health and environment is a growing concern. Hemoglobin (Hb), which occurs in all the kingdom of living organism, is the most abundant protein in human blood. In present study, effect of lanthanides and actinides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] on the structure and function of Hb has been investigated. Results showed that these metal ions, except Ce(IV) interacted with carbonyl and amide groups of Hb, which resulted in the loss of its alpha-helix conformation. However, beyond 75 μM, these ions affected heme moiety. Metal–heme interaction was found to affect oxygen-binding of Hb, which seems to be governed by their closeness with the charge-to-ionic-radius ratio of iron(III). Consistently, Ce(IV) being closest to iron(III), exhibited a greater effect on heme. Binding constant and binding stoichiometry of Th(IV) were higher than that of U(VI). Experiments using aquatic midge Chironomus (possessing human homologous Hb) and human blood, further validated metal–Hb interaction and associated toxicity. Thus, present study provides a biochemical basis to understand the actinide/lanthanide-induced interference in heme, which may have significant implications for the medical and environmental management of lanthanides/actinides toxicity.

  15. Lanthanide ions doped Y2Sn2O7 nano-particles: low temperature synthesis and photoluminescence study

    International Nuclear Information System (INIS)

    Nigam, Sandeep; Sudarsan, V.; Vatsa, R.K.

    2008-01-01

    During the past decade, pyrochlore-type oxides (A 2 B 2 O 7 ) have emerged as important host matrices for lanthanide doped luminescent materials due to their higher thermal stability. Up to now, conventional solid-state reaction is the most commonly used synthetic method for preparation, of rare-earth pyrochlore oxides. This synthesis route employs a solid-state reaction of metal-oxide with appropriate rare-earth oxides at high temperature (>1200 deg C) for a long time (several days). However, in present work, Y 2 Sn 2 O 7 nanoparticles co-doped with lanthanide ions Tb 3+ and Ce 3+ were prepared based on the urea hydrolysis of Y 3+ , Sn 4+ , and Ln 3+ in ethylene glycol medium at 150 deg C followed by heating at 500, 700 and 900 deg C

  16. Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

    2015-06-15

    Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

  17. Studies on the electrochemical behavior of heavy lanthanide ions and the synthesis, characterization of heavy metal chelate complexes

    International Nuclear Information System (INIS)

    Kang, Sam Woo; Chang, Choo Hwan; Son, Byung Chan; Suh, Moo Yul; Kim, Chae Kyun

    1991-01-01

    Electrochemical behavior of some heavy lanthanide ions(Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ and Lu 3+ ) in various supporting electrolytes has been investigated by dc polarography, differential pulse polarography and cyclic voltammetry. The peak potentials and the peak currents, their dependency on the concentration and pH effects, the reversibility of the electrode reactions are described. The reduction of Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ and Lu 3+ ions in 0.1M lithium chloride solution proceeds by a three-electron change directly to the metallic state, whereas the reduction of Yb 3+ proceeds by a one-electron change followed by a two-electron change. It was found that, in differential pulse polarography and cyclic voltammetry, the peak potential, peak current and current function showed constant value in the pH range of 4.0-6.0 by varying pH and scan rates. And also the current function is found to decrease as the sweep rate is increased when the pH reaches 4.0. This fact may indicate a chemical reaction coupled with the electrochemical reaction at lower pH values(pH 3+ ion is possible to determine voltammetrically within the error of ±3.5% in the presence of other competitive lanthanide ions. (Author)

  18. Molecular engineering of lanthanide ion chelating phospholipids generating assemblies with a switched magnetic susceptibility.

    Science.gov (United States)

    Isabettini, Stéphane; Massabni, Sarah; Hodzic, Arnel; Durovic, Dzana; Kohlbrecher, Joachim; Ishikawa, Takashi; Fischer, Peter; Windhab, Erich J; Walde, Peter; Kuster, Simon

    2017-08-09

    Lanthanide ion (Ln 3+ ) chelating amphiphiles are powerful molecules for tailoring the magnetic response of polymolecular assemblies. Mixtures of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA) complexed to Ln 3+ deliver highly magnetically responsive bicelles. Their magnetic properties are readily tuned by changing the bicellar size or the magnetic susceptibility Δχ of the bilayer lipids. The former technique is intrinsically bound to the region of the phase diagram guarantying the formation of bicelles. Methods aiming towards manipulating the Δχ of the bilayer are comparatively more robust, flexible and lacking. Herein, we synthesized a new Ln 3+ chelating phospholipid using glutamic acid as a backbone: DMPE-Glu-DTPA. The chelate polyhedron was specifically engineered to alter the Δχ, whilst remaining geometrically similar to DMPE-DTPA. Planar asymmetric assemblies hundreds of nanometers in size were achieved presenting unprecedented magnetic alignments. The DMPE-Glu-DTPA/Ln 3+ complex switched the Δχ, achieving perpendicular alignment of assemblies containing Dy 3+ and parallel alignment of those containing Tm 3+ . Moreover, samples with chelated Yb 3+ were more alignable than the Tm 3+ chelating counterparts. Such a possibility has never been demonstrated for planar Ln 3+ chelating polymolecular assemblies. The physico-chemical properties of these novel assemblies were further studied by monitoring the alignment behavior at different temperatures and by including 16 mol% of cholesterol (Chol-OH) in the phospholipid bilayer. The DMPE-Glu-DTPA/Ln 3+ complex and the resulting assemblies are promising candidates for applications in numerous fields including pharmaceutical technologies, structural characterization of membrane biomolecules by NMR spectroscopy, as contrasting agents for magnetic resonance imaging, and for the development of smart optical gels.

  19. Fabrication Procedures and Birefringence Measurements for Designing Magnetically Responsive Lanthanide Ion Chelating Phospholipid Assemblies.

    Science.gov (United States)

    Isabettini, Stéphane; Baumgartner, Mirjam E; Fischer, Peter; Windhab, Erich J; Liebi, Marianne; Kuster, Simon

    2018-01-03

    Bicelles are tunable disk-like polymolecular assemblies formed from a large variety of lipid mixtures. Applications range from membrane protein structural studies by nuclear magnetic resonance (NMR) to nanotechnological developments including the formation of optically active and magnetically switchable gels. Such technologies require high control of the assembly size, magnetic response and thermal resistance. Mixtures of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and its lanthanide ion (Ln 3+ ) chelating phospholipid conjugate, 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA), assemble into highly magnetically responsive assemblies such as DMPC/DMPE-DTPA/Ln 3+ (molar ratio 4:1:1) bicelles. Introduction of cholesterol (Chol-OH) and steroid derivatives in the bilayer results in another set of assemblies offering unique physico-chemical properties. For a given lipid composition, the magnetic alignability is proportional to the bicelle size. The complexation of Ln 3+ results in unprecedented magnetic responses in terms of both magnitude and alignment direction. The thermo-reversible collapse of the disk-like structures into vesicles upon heating allows tailoring of the assemblies' dimensions by extrusion through membrane filters with defined pore sizes. The magnetically alignable bicelles are regenerated by cooling to 5 °C, resulting in assembly dimensions defined by the vesicle precursors. Herein, this fabrication procedure is explained and the magnetic alignability of the assemblies is quantified by birefringence measurements under a 5.5 T magnetic field. The birefringence signal, originating from the phospholipid bilayer, further enables monitoring of polymolecular changes occurring in the bilayer. This simple technique is complementary to NMR experiments that are commonly employed to characterize bicelles.

  20. A protocol for the refinement of NMR structures using simultaneously pseudocontact shift restraints from multiple lanthanide ions

    Energy Technology Data Exchange (ETDEWEB)

    Sala, Davide; Giachetti, Andrea; Luchinat, Claudio, E-mail: luchinat@cerm.unifi.it; Rosato, Antonio, E-mail: rosato@cerm.unifi.it [University of Florence, Magnetic Resonance Center (CERM) (Italy)

    2016-11-15

    The binding of paramagnetic metal ions to proteins produces a number of different effects on the NMR spectra of the system. In particular, when the magnetic susceptibility of the metal ion is anisotropic, pseudocontact shifts (PCSs) arise and can be easily measured. They constitute very useful restraints for the solution structure determination of metal-binding proteins. In this context, there has been great interest in the use of lanthanide(III) ions to induce PCSs in diamagnetic proteins, e.g. through the replacement native calcium(II) ions. By preparing multiple samples in each of which a different ion of the lanthanide series is introduced, it is possible to obtain multiple independent PCS datasets that can be used synergistically to generate protein structure ensembles (typically called bundles). For typical NMR-based determination of protein structure, it is necessary to perform an energetic refinement of such initial bundles to obtain final structures whose geometric quality is suitable for deposition in the PDB. This can be conveniently done by using restrained molecular dynamics simulations (rMD) in explicit solvent. However, there are no available protocols for rMD using multiple PCS datasets as part of the restraints. In this work, we extended the PCS module of the AMBER MD package to handle multiple datasets and tuned a previously developed protocol for NMR structure refinement to achieve consistent convergence with PCS restraints. Test calculations with real experimental data show that this new implementation delivers the expected improvement of protein geometry, resulting in final structures that are of suitable quality for deposition. Furthermore, we observe that also initial structures generated only with traditional restraints can be successfully refined using traditional and PCS restraints simultaneously.

  1. Structural investigation of the complexation of uranyl and lanthanide ions by CMPO-functionalized calixarenes

    International Nuclear Information System (INIS)

    Cherfa, S.

    1998-12-01

    A way to reduce the volume of nuclear wastes is to make a simultaneous extraction of actinides and lanthanides for their ulterior separation. Historically, the two first series of extractants used for the reprocessing of these wastes are the phosphine oxides and the CMPO (carbamoyl methyl phosphine oxide). In order to better know the type of complexes formed during the extraction, have been carried out structural studies concerning these two series (uranyl complexes and lanthanide nitrates). These studies have been carried out by X-ray diffraction on monocrystals. More recently, a new series of extracting molecules of lanthanides (III) and actinides (III) have been developed. It has been shown that in functionalizing an organic macrocycle of calixarene type (cyclic oligomer resulting of the poly-condensation of phenolic units) by a ligand of CMPO type, the extracting power of these molecules in terms of yield and selectivity towards the lighter lanthanides was superior to those of the CMPO alone. This study, carried out by X-ray diffraction on monocrystals of complexes formed between these ligands calix[4]arenes-CMPO (with 4 phenolic units) with uranyl and lanthanides nitrates, has allowed to define the type of the formed complexes, that is to say to establish the stoichiometry and the coordination mode (monodentate or bidentate) of the CMPO functions. These different steps of characterization have allowed too to determine the correlations existing between the complexes structures in the one hand and the selectivity and the exacerbation of the extracting power measured in liquid phase on the other hand. (O.M.)

  2. A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

    International Nuclear Information System (INIS)

    Eliseeva, Svetlana V.; Golovach, Iurii P.; Liasotskyi, Valerii S.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

    2016-01-01

    Most of the existing optical methods for Cu II detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of Cu II ions based on both visible (Tb III , Eu III ) and near-infrared (Nd III , Yb III ) emission. Quantum yields of the characteristic Ln III emission signals increases by at least two-orders of magnitude upon addition of Cu II into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu II ions does not significantly affect the energy positions of the singlet (32,260 cm −1 ) and triplet (25,640–25,970 cm −1 ) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu II to Cu I has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu II over other transition metal ions: the addition of divalent Zn II , Cd II , Pd II , Ni II , Co II or trivalent Fe III , Ga III , In III ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu II results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the

  3. A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Eliseeva, Svetlana V., E-mail: svetlana.eliseeva@cnrs-orleans.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Le Studium, Loire Valley Institute for Advanced Studies, 1 Rue Dupanloup, 45000 Orléans (France); Golovach, Iurii P.; Liasotskyi, Valerii S. [I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa (Ukraine); Antonovich, Valery P. [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine); Petoud, Stéphane, E-mail: stephane.petoud@inserm.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Meshkova, Svetlana B., E-mail: s_meshkova@ukr.net [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine)

    2016-03-15

    Most of the existing optical methods for Cu{sup II} detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a 'turn-on' lanthanide(III)-based molecular probe for the specific detection of Cu{sup II} ions based on both visible (Tb{sup III}, Eu{sup III}) and near-infrared (Nd{sup III}, Yb{sup III}) emission. Quantum yields of the characteristic Ln{sup III} emission signals increases by at least two-orders of magnitude upon addition of Cu{sup II} into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu{sup II} ions does not significantly affect the energy positions of the singlet (32,260 cm{sup −1}) and triplet (25,640–25,970 cm{sup −1}) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu{sup II} to Cu{sup I} has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu{sup II} over other transition metal ions: the addition of divalent Zn{sup II}, Cd{sup II}, Pd{sup II}, Ni{sup II}, Co{sup II} or trivalent Fe{sup III}, Ga{sup III}, In{sup III} ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu{sup II} results in a 20- to 30-times

  4. Spectrophotometric Study of Ternary Complex Forming Systems of Some Lanthanide Metal Ions with Eriochrome Cyanine R in Presence of Cetylpyridinium Bromide for Microdetermination

    Directory of Open Access Journals (Sweden)

    A. S. Dhepe

    2011-01-01

    Full Text Available Study of coordination compounds of lanthanide elements has received a great attention due to growing applications in science and technology. Number of chromogenic reagents form water soluble colored complexes with lanthanides. Eriochrome cyanine R (ECR a member of triphenylmethane type of dye has been reported to form green colored complexes with lanthanides and has been used for microdetermination of these metal ions. Addition of cationic surfactant, Cetylpyridinium bromide (CPB, a cationic surfactant sensitizes the color reactions of Gd(III, Tb(III, Dy(III, Ho(III and Lu(III with ECR. Formation of water soluble, highly colored ternary complexes with a considerable bathochromic shift of about 50 nm in presence of surfactant has been observed. Optimum reaction conditions and other analytical parameters were also evaluated. Stoichiometric ratio 1:3:3 of Ln: ECR: CPB are responsible for the observed rise in molar absorptivity and sensitivity. Beer’s law was obeyed between 0.50 to 13.00 ppm. Effective photometric range and molar absorptivity of these ternary complexes have been calculated. Effect of some common interfering ions on determination of these lanthanide metal ions was studied. A simple, rapid and highly sensitive spectrophotometeric method has been proposed for the determination of metal ions understudy.

  5. Understanding the Enhanced Magnetic Response of Aminocholesterol Doped Lanthanide-Ion-Chelating Phospholipid Bicelles.

    Science.gov (United States)

    Isabettini, Stéphane; Massabni, Sarah; Kohlbrecher, Joachim; Schuler, Lukas D; Walde, Peter; Sturm, Marina; Windhab, Erich J; Fischer, Peter; Kuster, Simon

    2017-08-29

    Cholesterol (Chol-OH) and its conjugates are powerful molecules for engineering the physicochemical and magnetic properties of phospholipid bilayers in bicelles. Introduction of aminocholesterol (3β-amino-5-cholestene, Chol-NH 2 ) in bicelles composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and the thulium-ion-chelating phospholipid 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA/Tm 3+ ) results in unprecedented high magnetic alignments by selectively tuning the magnetic susceptibility Δχ of the bilayer. However, little is known on the underlying mechanisms behind the magnetic response and, more generally, on the physicochemical forces governing a Chol-NH 2 doped DMPC bilayer. We tackled this shortcoming with a multiscale bottom-up comparative investigation of Chol-OH and Chol-NH 2 mixed with DMPC. First, simplified monolayer models on a Langmuir trough were employed to compare the two steroid molecules at various contents in DMPC. In a second step, a molecular dynamics (MD) simulation allowed for a more representative model of the bicelle bilayer while monitoring the amphiphiles and their interactions on the molecular level. In a final step, we moved away from the models and investigated the effect of temperature on the structure and magnetic alignment of Chol-NH 2 doped bicelles by SANS. The DMPC/steroid monolayer studies showed that Chol-OH induces a larger condensation effect than Chol-NH 2 at steroid contents of 16 and 20 mol %. However, this tendency was inversed at steroid contents of 10, 30, and 40 mol %. Although the MD simulation with 16 mol % steroid revealed that both compounds induce a liquid-ordered state in DMPC, the bilayer containing Chol-NH 2 was much less ordered than the analogous system containing Chol-OH. Chol-NH 2 underwent significantly more hydrogen bonding interactions with neighboring DMPC lipids than Chol-OH. It seems that, by altering the dynamics of the hydrophilic

  6. Extraction chromatography of lanthanides, ch. 8

    International Nuclear Information System (INIS)

    Siekierski, S.; Fidelis, I.

    1975-01-01

    The extraction of lanthanides by chelate formation with acidic organophosphorous extractants, by solvation of salts, and in the form of ion pairs is reviewed. The double-double effect and its significance for the lanthanide as well as the actinide separation is discussed. A short survey of the existing data on the enthalpies of lanthanide extraction and on the influence of temperature on their separation factor is given. The resolution ability of columns used for the separation of lanthanides is briefly surveyed

  7. "Plug and play" logic gates based on fluorescence switching regulated by self-assembly of nucleotide and lanthanide ions.

    Science.gov (United States)

    Pu, Fang; Ren, Jinsong; Qu, Xiaogang

    2014-06-25

    Molecular logic gates in response to chemical, biological, or optical input signals at a molecular level have received much interest over the past decade. Herein, we construct "plug and play" logic systems based on the fluorescence switching of guest molecules confined in coordination polymer nanoparticles generated from nucleotide and lanthanide ions. In the system, the addition of new modules directly enables new logic functions. PASS 0, YES, PASS 1, NOT, IMP, OR, and AND gates are successfully constructed in sequence. Moreover, different logic gates (AND, INH, and IMP) can be constructed using different guest molecules and the same input combinations. The work will be beneficial to the future logic design and expand the applications of coordination polymers.

  8. An enantiomerically pure siderophore type ligand for the diastereoselective 1 : 1 complexation of lanthanide(III ions

    Directory of Open Access Journals (Sweden)

    Markus Albrecht

    2009-12-01

    Full Text Available A facile synthesis of a highly preorganized tripodal enterobactine-type ligand 1a-H3 consisting of a chiral C3-symmetric macrocyclic peptide and three tridentate 2-amido-8-hydroxyquinoline coordinating units is presented. Complex formation with various metal ions (Al3+, Ga3+, Fe3+, La3+ and Eu3+ was investigated by spectrophotometric methods. Only in the case of La3+ and Eu3+ were well defined 1 : 1 complexes formed. On the basis of CD spectroscopy and DFT calculations the configuration at the metal centre of the La3+ complex was determined to show Λ helicity. The coordination compounds [(1aLn] presented should be prototypes for further lanthanide(III complexes with an enterobactine analogue binding situation.

  9. Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions.

    Science.gov (United States)

    Li, Xi-Li; Chen, Chun-Lai; Xiao, Hong-Ping; Wang, Ai-Ling; Liu, Cai-Ming; Zheng, Xianjun; Gao, Li-Jun; Yang, Xiao-Gang; Fang, Shao-Ming

    2013-11-21

    Reaction of the chiral ligand (-)-4,5-pinenepyridyl-2-pyrazine (L) with Ln(hfac)3·2H2O precursors [hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate, Ln = Sm(3+) (1), Eu(3+) (2), Tb(3+) (3) and Dy(3+) (4)] in methanol solution led to the formation of four noncentrosymmetric lanthanide complexes with the general formula [Ln(hfac)3L]n·H2O. The single-crystal X-ray diffraction analyses revealed that they are isostructural and take a one-dimensional (1D) chain structure based on the Ln(hfac)3L repeating units, in which the nine-coordinate Ln(3+) ions reside in a tricapped trigonal prism (TTP) environment never reported in previous 1D chain lanthanide complexes. The investigations of their photophysical properties showed that complexes 1, and 3 exhibit characteristic emissions of Sm(3+), Eu(3+) and Tb(3+) ions with respective luminescent lifetime values of 0.065, 1.066 and 0.129 ms, while complex 4 does not display any emission. The different luminescent intensities and lifetimes among them were further discussed in detail. Moreover, the magnetic properties of complexes 1-4 were assessed with a special emphasis on the Dy(3+) complex 4. Alternating-current (ac) magnetic susceptibility measurements indicated that field-induced two-step slow magnetic relaxation processes were observed in 4, indicating the single-molecule magnet (SMM) behavior of 4. In addition, the noncentrosymmetric complexes 1-4 crystallizing in the same polar point group (Cs) exhibit both ferroelectric and nonlinear optical properties at room temperature. All these features make them multifunctional crystalline molecule materials.

  10. Secret lanthanides.

    Science.gov (United States)

    Sturza, C M

    2014-09-15

    Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz.

  11. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

    Science.gov (United States)

    2016-01-01

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  12. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiu-Mei, E-mail: zhangxiumeilb@126.com; Li, Peng; Gao, Wei; Liu, Feng; Liu, Jie-Ping

    2016-12-15

    Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H{sub 2}O){sub 4}]·3H{sub 2}O (Ln=Gd (1) and Tb (2) and Dy (3), H{sub 3}TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1–3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO){sub 2} double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectively sense Pb{sup 2+} and Fe{sup 3+} ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb{sup 2+} and Fe{sup 3+} ions is exceedingly rare example. - Graphical abstract: Three Ln-MOFs were successfully synthesized using a 5-(1H-tetrazol-5-yl)isophthalic acid ligand. They displays different magnetic behavior. Especially, the Dy(III) compound slow relaxation behavior. Interestingly, the Tb(III) compound can selectively sense Pb{sup 2+} and Fe{sup 3+} ions through luminescence enhancement and quenching, respectively. - Highlights: • Three Ln-MOFs with tetrazolate dicarboxylate ligand. • Dy(III) compound displays slow relaxation behavior. • The Tb(III) compound shows highly selective luminescence sensing of the Fe{sup 3+} and Pb{sup 2+} ions.

  13. Interaction between diethylenetrithiodiacetic acid (H2T) derivatives and trivalent lanthanide ions

    International Nuclear Information System (INIS)

    Matos, J.E.X.; Melo, S.M.; Fontenele, E.M.G.

    1984-01-01

    Thiopolycarboxylic acids are a class of ligands which contain, besides carboxi-groups, sulfur atoms showing a distinct affinity towards certain solft metals. Stability constant measurements were made for metaldithiocarboxylic acid systems and performed by several authors. Some soLid complexes with 1:1 and 1:2 metal-ligand ratios were isolated and their structures determined by spectroscopic and magnetic methods. Solid complexes between some lanthanides and ethylenedithiodiacetic acid were prepared and characterized by Holanda and Giesbrecht. Investigations of the crystal structure of Zn (II), Cd (II), and Nd (III) complexes with thiodiacetic acid showed, besides coordination to carboxylic groups, the ligand being linked to the metal through the sulfur atom. (Author) [pt

  14. Solvent extraction separations of trivalent lanthanide and actinide ions using an aqueous aminomethanediphosphonic acid

    International Nuclear Information System (INIS)

    Jensen, M. P.

    1998-01-01

    The possibility of separating the trivalent lanthanides, represented by EU 3+ , and actinides, represented by Cf 3+ , using HDEHP in toluene and an aqueous phase containing N-piperidinomethane-1,1-diphosphotic acid, PMDPA, has been investigated. This modified aqueous phase offers potential advantages over the diethylenetriaminepentaacetic acid based TALSPEAK process because of the improved complexation properties of PMDPA in acidic solutions, and the ability to decompose PMDPA before disposal. Extraction experiments were conducted at 25 C in 2 M NaClO 4 between -log [H + ] 1 and 2. The studies enabled us to derive the aqueous phase speciation, the stability constants of the aqueous complexes, and the Cf/Eu separation factors. Despite the presence of an amino group in PMDPA that should favor the retention of the actinides in the aqueous phase, the Cf/Eu separation factors are near unity under the conditions studied

  15. Factors Affecting the Efficiency of Excited-States Interactions of Complexes between Some Visible Light-Emitting Lanthanide Ions and Cyclophanes Containing Spirobiindanol Phosphonates

    Directory of Open Access Journals (Sweden)

    M. S. Attia

    2007-01-01

    Full Text Available The efficiency of excited-states interactions between lanthanide ions Tb3+ and Eu3+ and some new cyclophanes (I, II, and III has been studied in different media. High luminescence quantum yield values for terbium and europium complexes in DMSO and PMMA were obtained. The photophysical properties of the green and red emissive Tb3+ and Eu3+ complexes have been elucidated, respectively.

  16. Thermodynamic study on the complexation of Trivalent actinide and lanthanide cation by N-donor ligands in homogeneous conditions; Etude thermodynamique de la complexation des ions actinide (III) et lanthanide (III) par des ligands polyazotes en milieu homogene

    Energy Technology Data Exchange (ETDEWEB)

    Miguirditchian, M

    2004-07-01

    Polydentate N-donor ligands, alone or combined with a synergic acid, may selectively extract minor actinides(III) from lanthanide(III) ions, allowing to develop separation processes of long-live radioelements. The aim of the researches carried out during this thesis was to better understand the chemical mechanisms of the complexation of f-elements by Adptz, a tridentate N-donor ligand, in homogeneous conditions. A thermodynamic approach was retained in order to estimate, from an energetic point of view, the influence of the different contributions to the reaction, and to acquire a complete set of thermodynamic data on this reaction. First, the influence of the nature of the cation on the thermodynamics was considered. The stability constants of the 1/1 complexes were systematically determined by UV-visible spectrophotometry for every lanthanide ion (except promethium) and for yttrium in a mixed solvent methanol/water in volume proportions 75/25%. The thermodynamic parameters ({delta}H{sup 0} {delta}{sup S}) of complexation were estimated by the van't Hoff method and by micro-calorimetry. The trends of the variations across the lanthanide series are compared with similar studies. The same methods were applied to the study of three actinide(III) cations: plutonium, americium and curium. The comparison of these values with those obtained for the lanthanides highlights the increase of stability of these complexes by a factor of 20 in favor of the actinide cations. This gap is explained by a more exothermic reaction and is associated, in the data interpretation, to a higher covalency of the actinide(III)-nitrogen bond. Then, the influence of the change of solvent composition on the thermodynamic of complexation was studied. The thermodynamic parameters of the complexation of europium(III) by Adptz were determined for several fractions of methanol. The stability of the complex formed increases with the percentage of methanol in the mixed solvent, owing to an

  17. Chromatographic studies of the lanthanide element separation for the americium/curium large scale separation using ion exchange resins

    International Nuclear Information System (INIS)

    Ginisty, Claude.

    1981-06-01

    The Am/Cm large scale separations, operated by chromatography with the use of ion exchange resins, are described by numerous publications. The bibliographic studies allow to retain the followed points: use of sulfonate cationic resins, development by elution with the α-hydroxyisobutyric acid, column loadings between 1 and 30% of the capacity, possibility to use no radioactive lanthanides prior to actinides for trial purposes. The optimisation of such a process is the major part of this thesis. This point is realised by introducing a new definition for the resolution, for non symmetrical elution peaks, and a measure of this dissymmetry by introducing a shape factor F. For the separation itself and for the pressure drop in the column, the influence of the following parameters are studied: composition of the elution solution (concentration and pH), column temperature (20 to 90 0 C), resin size (9 to 27 μm), rate flow of mobile phase (70 ml.cm -2 .mn -1 ), column length and diameter. Symmetrical elution peaks may be obtained, even with a 27% loading. Elution conditions may be modified during the separation process in order to have the best recovery for the two components (1,3 [fr

  18. Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles

    International Nuclear Information System (INIS)

    Uzun, Lokman; Uzek, Recep; Şenel, Serap; Say, Ridvan; Denizli, Adil

    2013-01-01

    In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Highlights: • Lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles • Direct incorporation of the fluorescent complex into polymeric backbone. • Imprinting by assistance of cupric ion coordination into nanoparticles • Evaluation of the chiral biorecognition ability of nanoparticles • Simultaneous selective separation and fluorescent monitoring

  19. Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Uzun, Lokman, E-mail: lokman@hacettepe.edu.tr [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey); Uzek, Recep; Şenel, Serap [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey); Say, Ridvan [Anadolu University, Department of Chemistry, 26470, Eskisehir (Turkey); Denizli, Adil [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey)

    2013-08-01

    In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Highlights: • Lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles • Direct incorporation of the fluorescent complex into polymeric backbone. • Imprinting by assistance of cupric ion coordination into nanoparticles • Evaluation of the chiral biorecognition ability of nanoparticles • Simultaneous selective separation and fluorescent monitoring.

  20. Selective separation of uranium and thorium from lanthanides on sulphonic ion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Hubicki, Z; Hubicka, H; Jusiak, S [Uniwersytet Marii Curie-Sklodowskiej, Lublin (Poland)

    1977-01-01

    Separation of uranium and thorium from rare earth elements was studied on sulphonic ion exchangers of various types. Ammonium acetate, ammonium salicylate, aliphatic amine acetates, metaphosphoric acid and others were used as eluants. The most effective separation was attained by using metaphosphoric acid as eluant.

  1. Electron paramagnetic resonance and neutron activation study of lanthanide ions behaviour in fluorite. Application to the geochemical study of Montroc and Burc veins (Tarn)

    International Nuclear Information System (INIS)

    Meary, Alain

    1983-01-01

    In order to obtain a better understanding of fluorite deposits, rare earth impurities have been analyzed for a large number of samples taken from cross-sections of several low temperature hydrothermal veins; two types of measurements have been used: Electron Paramagnetic Resonance (EPR) and Neutron Activation Analysis (NAA). This enabled us to measure a 'deficit of spins' relative to the total lanthanide concentration, this deficit reveals that the paramagnetic center observed by EPR is not the only mode of incorporation. For Gd no marked deficit is observed; that is the ratio of spin concentrations to total concentration [Gd 3+ ]/[Gd total ] is close to 1 in all the samples; on the other hand, the ratios [Eu 2+ ]/[Eu total ], [Ce 3- F i - ]/[Ce total ], and [Yb 3+ ]/ [Yb total ] exhibit large variations. The first result suggests that the major part of the lanthanides in the samples is incorporated in the crystal lattice and that clustering of lanthanides ions is not important. Deficit of spins observed for Ce and Nd are probably due to the dissociation of paramagnetic complexes Ce 3+ -F i - and Nd 3+ -F i - ; for Eu, it may be attributed to the oxidized state Eu 3+ . Moreover, the sign and the amplitude of the anomaly exhibited by Eu in the normalized lanthanides spectra may be correlated with the majority valence state of Eu in the crystal: a marked positive anomaly belongs to a deficit of paramagnetic divalent Eu and, inversely, if divalent Eu is the majority valence state, the Eu anomaly appears to be negative. The results obtained for the Montroc vein are consistent with a model involving discontinuous injections of hydrothermal solutions. They may be connected to variations of oxygen fugacity arising from cooling of these solutions and from precipitation of sulfides during fluorite precipitation. (author) [fr

  2. A study of the complex formation of bivalent lanthanides with tetraphenylborate-ion in organic solvents. Izuchenie kompleksoobrazovaniya dvukhvalentnykh lantanoidov s tetrafenilborat-ionom v organicheskikh rastvoritelyakh

    Energy Technology Data Exchange (ETDEWEB)

    Veleshko, I E; Mikheev, N B; Kulyukhin, S A

    1992-01-01

    Interaction of bivalent lanthanides with tetraphenylborate-ion (BPh[sub 4][sup -]) in solutions of CH[sub 3]CN and C[sub 2]H[sub 5]OH was studied by the methods of cocrystallization, conductometry and spectrophotometry.It is shown that no complexing between Ln[sup 2+] and BPh[sub 4][sup -] takes place in ethanol, wheras in CH[sub 3]CN formation of second sphere complexes of the composition [Ln(CH[sub 3]CN)[sub n

  3. Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles.

    Science.gov (United States)

    Uzun, Lokman; Uzek, Recep; Senel, Serap; Say, Ridvan; Denizli, Adil

    2013-08-01

    In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Cherfa, S

    1998-12-10

    In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

  5. Extraction of trivalent actinides and lanthanides from nitric acid solutions by ion flotation

    International Nuclear Information System (INIS)

    Mezhov, E.H.; Samatov, A.V.; Troyanovskiy, L.V.

    1992-01-01

    To determine whether the deep extraction of trivalent actinides from liquid active waste is feasible, the authors made a detailed investigation into the ion flotation of europium (as a simulator of americium) and americium from nitric acid solutions by using as an SAS precipitant either lauril phosphoric acid (LPA) to reprocess 0.1-0.7 M HNO 3 or diphosphine dioxides (PO) for 1-5 M HNO 3 . In all instances the extent of metal removal increases with floto-reagent expenditure. When the floto-reagent excess required for full precipitation is reached, the extraction of the metals under study is high, viz., 97-98% from 0.1 M HNO 3 with LPA and ∼75% from 3-3.5 M HNO 3 with PO per one flotation operation

  6. Interaction study of amino acids and the peptide aspartame with lanthanide (III) ions

    International Nuclear Information System (INIS)

    Carubelli, C.R.

    1990-01-01

    The interactions between the Nd(III) ion with the amino acids L-aspartic acid, L-glutamic acid and L-histidine and the peptide aspartame in aqueous solution were studied. The study was conducted by means of electronic spectroscopy with the Judd-Ofelt formalism for transition intensity parameters calculations. Several coordination compounds involving Nd(III), Eu(III), and Tb(III) and the ligands L-histidine and aspartame were synthesized and characterized in the solid state. Mixed compounds involving Eu(III) and Tb(III) with the same ligands were synthesized and characterized also. The characterization were achieved by chemical analysis, melting points, vibrational spectroscopy (IR) and powder X-ray diffractometry. (author)

  7. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    Among many applications of lanthanides, gadolinium complexes are used as magnetic resonance imaging (MRI) contrast agents in clinical radiology and luminescent lanthanides for bioanalysis, imaging and sensing. The chemistry of photoactive lanthanide complexes showing biological applications is of recent origin.

  8. Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

    Czech Academy of Sciences Publication Activity Database

    Lučaníková, M.; Selucký, P.; Rais, J.; Grüner, Bohumír; Kvíčalová, Magdalena

    2011-01-01

    Roč. 1, č. 1 (2011), s. 89-95 ISSN 2193-2875 R&D Projects: GA ČR GA104/09/0668; GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : Dicarbollides derivatives * TODGA * Liquid-liquid extraction * Lanthanides * Actinides Subject RIV: CA - Inorganic Chemistry

  9. Determination of 4f energy levels for trivalent lanthanide ions in YAlO{sub 3} by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

    2016-09-01

    A simple method to analyze 4f energy levels of trivalent lanthanide (Ln) ions was demonstrated by conventional X-ray photoelectron spectroscopy (XPS) measurements using Ln ions doped YAlO{sub 3} sintered polycrystalline samples. Although XPS peaks derived from Ln 4f states overlapped with the host's valence band consisting of O 2p states, the difference XPS spectra between Ln doped and non-doped samples showed only the Ln 4f peaks due to the large difference of photoionization cross sections between Ln 4f and O 2p orbitals. The difference spectra showing Ln 4f states were aligned at the valence band maximum (VBM) making use of the peaks of Al 2p inner shells, and the Ln{sup 3+} 4f energy levels referred to the VBM were determined from the Ln{sup 3+} 4f peak energies. The Ln{sup 3+} 4f energy levels obtained by this simple method were in good agreement with those previously obtained by resonant ultraviolet photoelectron spectroscopy measurements using single crystal samples. - Highlights: • Lanthanide (Ln) 4f energy in YAlO{sub 3} was studied by X-ray photoelectron spectroscopy. • The method used differences in photoionization probability between Ln 4f and O 2p. • Ln 4f states were obtained by difference spectra between Ln- and non-doped samples. • Obtained 4f energy levels agreed with those reported by a sophisticated method.

  10. Lanthanide-doped nanoparticles as the active optical medium in polymer-based devices

    NARCIS (Netherlands)

    Stouwdam, J.W.

    2004-01-01

    The luminescence of lanthanide ions in organic environment is greatly reduced compared to inorganic materials. This thesis describes the doping of the lanthanide ions in the core of inorganic nanoparticles that are soluble in organic solvents as a way to shield the lanthanide ions from the organic

  11. DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state

    Science.gov (United States)

    Hanuza, J.; Godlewska, P.; Lisiecki, R.; Ryba-Romanowski, W.; Kadłubański, P.; Lorenc, J.; Łukowiak, A.; Macalik, L.; Gerasymchuk, Yu.; Legendziewicz, J.

    2018-05-01

    The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln = Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.

  12. Engineering [Ln(DPA){sub 3}]{sup 3-} binding sites in proteins: a widely applicable method for tagging proteins with lanthanide ions

    Energy Technology Data Exchange (ETDEWEB)

    Jia Xinying; Yagi, Hiromasa; Su Xuncheng; Stanton-Cook, Mitchell; Huber, Thomas; Otting, Gottfried, E-mail: gottfried.otting@anu.edu.au [Australian National University, Research School of Chemistry (Australia)

    2011-08-15

    Paramagnetic relaxation enhancements from unpaired electrons observed in nuclear magnetic resonance (NMR) spectra present powerful long-range distance restraints. The most frequently used paramagnetic tags, however, are tethered to the protein via disulfide bonds, requiring proteins with single cysteine residues for covalent attachment. Here we present a straightforward strategy to tag proteins site-specifically with paramagnetic lanthanides without a tether and independent of cysteine residues. It relies on preferential binding of the complex between three dipicolinic acid molecules (DPA) and a lanthanide ion (Ln{sup 3+}), [Ln(DPA){sub 3}]{sup 3-}, to a pair of positively charged amino acids whose charges are not compensated by negatively charged residues nearby. This situation rarely occurs in wild-type proteins, allowing the creation of specific binding sites simply by introduction of positively charged residues that are positioned far from glutamate or aspartate residues. The concept is demonstrated with the hnRNPLL RRM1 domain. In addition, we show that histidine- and arginine-tags present binding sites for [Ln(DPA){sub 3}]{sup 3-}.

  13. Synthesis, Structure, and Magnetism of Tris(amide) {Ln[N(SiMe3)2]3}1- Complexes of the Non-Traditional +2 Lanthanide Ions.

    Science.gov (United States)

    Ryan, Austin Jack; Darago, Lucy E; Balasubramini, Sree Ganesh; Chen, Guo P; Ziller, Joseph W; Furche, Filipp; Long, Jeffrey R; Evans, William J

    2018-02-28

    A new series of Ln2+ complexes has been synthesized that overturns two previous generalizations in rare-earth metal reduction chemistry: that amide ligands do not form isolable complexes of the highly-reducing non-traditional Ln2+ ions and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR2)3 (R = SiMe3) complexes in THF under Ar with M = K or Rb in the presence of 2.2.2-cryptand (crypt) forms crystallographically-characterizable [M(crypt)][Ln(NR2)3] complexes not only for the traditional Tm2+ ion and the configurational crossover ions, Nd2+ and Dy2+, but also for the non-traditional Gd2+, Tb2+, Ho2+, and Er2+ ions. Crystallographic data as well as UV-visible, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4fn5d1 configurations for Ln2+ ions in this tris(silylamide) ligand environment. The Dy2+ complex, [K(crypt)][Dy(NR2)3], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 µB. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Extraction of lanthanides ions (III) from aqueous solution by sodium salt of the N(4-amino-benzoate)-propyl-silica gel

    International Nuclear Information System (INIS)

    Retamero, R.C.

    1991-01-01

    The silica gel 60 of specific superficial area 486 m 2 .g -1 was modified chemically with the ligand 4-amino benzoate of sodium in water-ethanol environment (l:L). The adsorptions of metallic ions were from water solutions at approximately 2 x 10 -3 M of chloride of Pr(III), Nd(III), Eu(III) and Ho(III). In these experiments we could see that the system gets the equilibrium of adsorption rapidly and that the pH of the environment has a great influence on the process of adsorption, being that the number of metal mols adsorpted in the matrix varied between 10,00 and 17,00 x 10 -5 mols. g -1 with a pH of approximately 5 for all the lanthanides, where the adsorption curves reach equilibrium. (author)

  15. Determination of the formation constant for the inclusion complex between Lanthanide ions and Dansyl chloride derivative by fluorescence spectroscopy: Theoretical and experimental investigation

    Science.gov (United States)

    Riahi, Siavash; Ganjali, Mohammad Reza; Hariri, Maryam; Abdolahzadeh, Shaghayegh; Norouzi, Parviz

    2009-09-01

    In this paper, a sensitive, easy, efficient, and suitable method for the calculation of Kf values of complexation between one derivative of Dansyl chloride [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (DMNP) and Lanthanide(III) (Ln) ions is proposed, using both spectrofluorometric and spectrophotometric methods. Determination of Kf showed that DMNP was mostly selective towards the erbium (III) ion. The validity of the method was also confirmed calculating the Stern-Volmer fluorescence quenching constants ( Ksv) that resulted in the same consequence, obtained by calculating the Kf of complexation values. In addition, the UV-vis spectroscopy was applied for the determination of Kf only for the Ln ions that had interactions with DMNP. Finally, the DFT studies were done on Er 3+ and the DMNP complex for distinguishing the active sites and estimating the pair wise interaction energy. It can be concluded that this derivative of Dansyl chloride with inherent high fluorescence intensity is a suitable reagent for the selective determination of the Er 3+ ion which can be used in constructing selective Er 3+ sensors.

  16. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

    KAUST Repository

    Wang, Feng; Han, Yu; Lim, Chinseong; Lu, Yunhao; Wang, Juan; Xu, Jun; Chen, Hongyu; Zhang, Chun; Hong, Minghui; Liu, Xiaogang

    2010-01-01

    or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal

  17. Separation of lanthanides through hydroxyapatite

    International Nuclear Information System (INIS)

    Garcia M, F.G.

    2006-01-01

    With the objective of obtaining from an independent way to each one of the lanthanides 151 Pm, 161 Tb, 166 Ho and 177 Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI 3 (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because practically these lanthanides

  18. The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes

    International Nuclear Information System (INIS)

    Sojka, Bartlomiej; Liskova, Aurelia; Kuricova, Miroslava; Banski, Mateusz; Misiewicz, Jan; Dusinska, Maria; Horvathova, Mira; Ilavska, Silvia; Szabova, Michaela; Rollerova, Eva; Podhorodecki, Artur; Tulinska, Jana

    2017-01-01

    Sodium fluoride-based β-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood (n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

  19. The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes

    Energy Technology Data Exchange (ETDEWEB)

    Sojka, Bartlomiej [Wroclaw University of Science and Technology, Department of Experimental Physics (Poland); Liskova, Aurelia; Kuricova, Miroslava [Slovak Medical University, Medical Faculty, Department of Immunology and Immunotoxicology (Slovakia); Banski, Mateusz; Misiewicz, Jan [Wroclaw University of Science and Technology, Department of Experimental Physics (Poland); Dusinska, Maria [Norwegian Institute for Air Research, Health Effects Laboratory, Department of Environmental Chemistry (Norway); Horvathova, Mira; Ilavska, Silvia; Szabova, Michaela [Slovak Medical University, Medical Faculty, Department of Immunology and Immunotoxicology (Slovakia); Rollerova, Eva [Slovak Medical University, Faculty of Public Health, Department of Toxicology (Slovakia); Podhorodecki, Artur, E-mail: artur.p.podhorodecki@pwr.edu.pl [Wroclaw University of Science and Technology, Department of Experimental Physics (Poland); Tulinska, Jana, E-mail: jana.tulinska@szu.sk [Slovak Medical University, Medical Faculty, Department of Immunology and Immunotoxicology (Slovakia)

    2017-02-15

    Sodium fluoride-based β-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood (n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

  20. Analytical chemistry of lanthanides

    International Nuclear Information System (INIS)

    Al-Sowdani, K.H.

    1986-12-01

    Candoluminescence of the lanthanides and the development of instruments for monitoring the phenomenon are described. The use of fluorescence spectroscopy, spectrofluorometry and spectrophotometry for the quantitative chemical analysis of the lanthanides is described. (U.K.)

  1. Systemic analysis of thermodynamic properties of lanthanide halides

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  2. Thermodynamics of complexation of lanthanides and some of transition metal ions by 5,5-dimethyl-cyclohexane-2-(2-hydroxyphenyl)-hydrazono-1,3-dione (DCPHD) and its derivatives

    International Nuclear Information System (INIS)

    Ramadan, A.A.T.; Abdel-Moez, M.S.; El-Shetary, B.A.; Seleim, H.S.

    1993-01-01

    Equilibrium between DCPHD, DC-4-Cl-PHD, and DC-4-Me-PHD and protons, transition, and lanthanide ions have been investigated at 30 o C by means of potentiometric titration in 75%(v/v) methanol-water mixture containing 0.10M KNO 3 as a constant ionic medium. Thermodynamic parameters(ΔG,ΔH and ΔS) referring to the formation of species HL - ,L -- ,ML +n-2 and ML 2 +n-4 (L -- denotes the ligand anion) have been determined in solutions. The solvent effects on the thermodynamic parameters of the complex formation are discussed in terms of differences in the donor ability of methanol and water solvents. The plots of thermodynamic parameters versus ionic potential (Z 2 /r) of the lanthanide elements is not linear as expected from ionic theory. The obtained curve can be resolved in an initial group (the lighter lanthanides), an intermediate group (Sm-Dy), and a final group (the heavier ones, Tb-Lu). This behavior was explained in terms of differences in the dehydration of lighter lanthanide(III) from that of heavier ones

  3. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy; Neuartige Lanthanoid-dotierte mikro- und mesoporoese Feststoffe. Charakterisierung von Ion-Wirt-Wechselwirkungen, Speziesverteilung und Lumineszenzeigenschaften mittels zeitaufgeloester Lumineszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Gessner, Andre

    2010-12-15

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the {sup 5}D{sub 0}-{sup 7}F{sub 0}-transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the

  4. The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes

    Science.gov (United States)

    Sojka, Bartlomiej; Liskova, Aurelia; Kuricova, Miroslava; Banski, Mateusz; Misiewicz, Jan; Dusinska, Maria; Horvathova, Mira; Ilavska, Silvia; Szabova, Michaela; Rollerova, Eva; Podhorodecki, Artur; Tulinska, Jana

    2017-02-01

    Sodium fluoride-based β-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

  5. Separation and estimation of lanthanides using high performance liquid chromatography

    International Nuclear Information System (INIS)

    Datta, Arpita; Sivaraman, N.; Vasudeva Rao, P.R.

    2012-01-01

    The separation efficiency of individual lanthanides depends on the stability constant of the metal-ligand complex. Therefore, stability constant data of lanthanide complexes is important in the development of high performance separation procedures. The dynamic ion exchange HPLC technique was employed at our laboratory to estimate the stability constant of lanthanides with various complexing agents. In these studies, the retention times as well as capacity factors of lanthanides and some actinides were measured as a function of CSA, complexing agent concentrations and mobile phase pH. From these studies, a correlation has been established between capacity factor of a metal ion, concentrations of ion-pairing reagent and complexing agent with the stability constant of lanthanide complex

  6. Target-Triggered Switching on and off the Luminescence of Lanthanide Coordination Polymer Nanoparticles for Selective and Sensitive Sensing of Copper Ions in Rat Brain.

    Science.gov (United States)

    Huang, Pengcheng; Wu, Fangying; Mao, Lanqun

    2015-07-07

    Copper ions (Cu(2+)) in the central nervous system play a crucial role in the physiological and pathological events, so simple, selective, and sensitive detection of cerebral Cu(2+) is of great importance. In this work, we report a facile yet effective fluorescent method for sensing of Cu(2+) in rat brain using one kind of lanthanide coordination polymer nanoparticle, adenosine monophosphate (AMP) and terbium ion (Tb(3+)), i.e., AMP-Tb, as the sensing platform. Initially, a cofactor ligand, 5-sulfosalicylic acid (SSA), as the sensitizer, was introduced into the nonluminescent AMP-Tb suspension, resulting in switching on the luminescence of AMP-Tb by the removal of coordinating water molecules and concomitant energy transfer from SSA to Tb(3+). The subsequent addition of Cu(2+) into the resulting SSA/AMP-Tb can strongly quench the fluorescence because the specific coordination interaction between SSA and Cu(2+) rendered energy transfer from SSA to Tb(3+) inefficient. The decrease ratio of the fluorescence intensities of SSA/AMP-Tb at 550 nm show a linear relationship for Cu(2+) within the concentration range from 1.5 to 24 μM with a detection limit of 300 nM. The method demonstrated here is highly selective and is free from the interference of metal ions, amino acids, and the biological species commonly existing in the brain such as dopamine, lactate, and glucose. Eventually, by combining the microdialysis technique, the present method has been successfully applied in the detection of cerebral Cu(2+) in rat brain with the basal dialysate level of 1.91 ± 0.40 μM (n = 3). This method is very promising to be used for investigating the physiological and pathological events that cerebral Cu(2+) participates in.

  7. Chelating extractants of improved selectivity. Progress report, August 1, 1978-July 31, 1979

    International Nuclear Information System (INIS)

    1979-08-01

    During the current contract period, the variation of coordination number of tervalent lanthanides observed earlier with 8-quinolinol extraction systems was exploited in the development of mixed ligand (so-called synergistic) extraction systems involving 1, 10-phenanthroline (phen) and 8-quinolinol (HOx). Using a mixture of HOx and phen significantly enhanced the difference between adjacent lanthanide ions and facilitated their separation

  8. Luminescent lanthanide reporters: new concepts for use in bioanalytical applications

    International Nuclear Information System (INIS)

    Vuojola, Johanna; Soukka, Tero

    2014-01-01

    Lanthanides represent the chemical elements from lanthanum to lutetium. They intrinsically exhibit some very exciting photophysical properties, which can be further enhanced by incorporating the lanthanide ion into organic or inorganic sensitizing structures. A very popular approach is to conjugate the lanthanide ion to an organic chromophore structure forming lanthanide chelates. Another approach, which has quickly gained interest, is to incorporate the lanthanide ions into nanoparticle structures, thus attaining improved specific activity and a large surface area for biomolecule immobilization. Lanthanide-based reporters, when properly shielded from the quenching effects of water, usually express strong luminescence emission, multiple narrow emission lines covering a wide wavelength range, and exceptionally long excited state lifetimes enabling time-gated luminescence detection. Because of these properties, lanthanide-based reporters have found widespread applications in various fields of life. This review focuses on the field of bioanalytical applications. Luminescent lanthanide reporters and assay formats utilizing these reporters pave the way for increasingly sensitive, simple, and easily automated bioanalytical applications. (topical review)

  9. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Energy Technology Data Exchange (ETDEWEB)

    Selucky, P.; Rais, J.; Lucanikova, M. [Nuclear Research Inst. plc., Rez near Prague (Czech Republic); Gruener, B.; Kvicalova, M. [Inst. of Inorganic Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Husinec-Rez near Prague (Czech Republic); Fejfarova, K. [Inst. of Physics, Academy of Sciences of the Czech Republic, Prague (Czech Republic); Cisarova, I. [Charles Univ., Prague (Czech Republic). Dept. of Chemistry

    2008-07-01

    Compounds were synthesized with the aim to develop efficient extraction agents for liquid-liquid extraction of polyvalent cations, i.e. lanthanides and actinides from high-level activity nuclear waste. Compounds of general formulation [(8-CMPO-(CH{sub 2}-CH{sub 2}O){sub 2}-1,2-C{sub 2}B{sub 9}H{sub 10})(1',2'-C{sub 2}B{sub 9}H{sub 11})-3.3'-Co(III)] with different phosphorus and nitrogen substitution (CMPO={sup 2}R,{sup 3}R P(O)-(CH{sub 2}){sub n}C(O)N{sup 1}R, {sup 1}R = t-octyl, H, Ph, {sup 2}R=Ph, n-octyl, {sup 3}R=Ph, n = 1,2)-(4a to 4e), were prepared and characterized by combination of {sup 11}B NMR, {sup 1}H high field NMR, ESI-M.S., HPLC and other techniques. Molecular structure of the sodium complex of ligand 4a ({sup 1}R = t-octyl, {sup 2}R = {sup 3}R = Ph, n = 1) was determined by single crystal X-ray diffraction analysis. Effect of several modifications in the structure of 4a-4e on the extraction properties was outlined. The study resulted in the definition of ionic ligand with enhanced extraction efficiency for 4a,b (t-octyl and H on the amidic nitrogen atom) and a better solubility of 4a and 4d ({sup 1}R = t-octyl, {sup 2}R = n-Oct, {sup 1}R=Ph, n = 1) in less polar solvents. Low polar mixtures of hydrogenated tetrapropylene (TPH) hexyl methyl ketone (HMK) can be applied as an auxiliary solvent for 4a, selected for detailed studies, replacing thus the polar and less environmentally friendly nitro-, fluoro- and chloro- solvents used in the current dicarbollide liquid-liquid extraction process. Results of the fission products separation from the simulated PUREX feed using 4a are presented inclusive procedures for Eu{sup 3+} stripping. (orig.)

  10. Synthesis and Characterization of Electroresponsive Materials with Applications In: Part I. Second Harmonic Generation. Part II. Organic-Lanthanide Ion Complexes for Electroluminescence and Optical Amplifiers.

    Science.gov (United States)

    Claude, Charles

    1995-01-01

    Materials for optical waveguides were developed from two different approaches, inorganic-organic composites and soft gel polymers. Inorganic-organic composites were developed from alkoxysilane and organically modified silanes based on nonlinear optical chromophores. Organically modified silanes based on N-((3^' -trialkoxysilyl)propyl)-4-nitroaniline were synthesized and sol-gelled with trimethoxysilane. After a densification process at 190^circC with a corona discharge, the second harmonic of the film was measured with a Nd:YAG laser with a fundamental wavelength of 1064nm, d_{33} = 13pm/V. The decay of the second harmonic was expressed by a stretched bi-exponential equation. The decay time (tau _2) was equal to 3374 hours, and was comparable to nonlinear optical systems based on epoxy/Disperse Orange 1. The processing temperature of the organically modified silane was limited to 200^circC due to the decomposition of the organic chromophore. Soft gel polymers were synthesized and characterized for the development of optical waveguides with dc-electrical field assisted phase-matching. Polymers based on 4-nitroaniline terminated poly(ethylene oxide-co-propylene oxide) were shown to exhibit second harmonic generation that were optically phase-matched in an electrical field. The optical signals were stable and reproducible. Siloxane polymers modified with 1-mercapto-4-nitrobenzene and 1-mercapto-4-methylsulfonylstilbene nonlinear optical chromophores were synthesized. The physical and the linear and nonlinear optical properties of the polymers were characterized. Waveguides were developed from the polymers which were optically phase -matched and had an efficiency of 8.1%. The siloxane polymers exhibited optical phase-matching in an applied electrical field and can be used with a semiconductor laser. Organic lanthanide ion complexes for electroluminescence and optical amplifiers were synthesized and characterized. The complexes were characterized for their thermal and

  11. Thermometric nanosize NMR-sensors for temperature determination in weakly polar non-aqueous media on the base of ion pairs of paramagnetic complexes of lanthanides(III)

    International Nuclear Information System (INIS)

    Babajlov, S.P.

    2008-01-01

    For temperature determination in solutions it is suggested that the temperature dependence of the paramagnetic lanthanide-induced shifts (LIS) in the NMR spectra on the ligand nuclei be used for [Ln(PTA) 2 (18-crown-6)] + [Ln(PTA) 4 ] - complex ion pairs formed in CCl 4 , CDCl 3 , CD 2 Cl 2 , CD 3 C 6 D 5 , and C 2 D 3 N type low-polar solvents (Ln = La, Ce, Pr, Nd, Eu; PTA is the pivalyltrifluoroacetonate anion). It was found experimentally that the [Ln(PTA) 2 (18-crown-6)] + complex cation molecules (Ln = Ce and Pr) proved most suitable for use as nanosized (∼1.1 nm) probes for temperature determinations in nonaqueous solutions. A linear dependence of the LIS on the 1 H nuclei of different groups and the difference between the LIS corresponding to the CH 2 groups of the 18-crown-6 molecules and the CH groups of the PTA anions on the reciprocal temperature (1/T) was found. The LIS of the individual signals of different groups in Ln paramagnetic complexes (relative to the signals of the diamagnetic analogs, e.g., La or Lu) may be used for temperature control in the sample, although the temperature measurement error is smaller (≤0.04 K) when the difference between the LIS of the CH 2 and CH groups is used. Due to the high thermodynamic and kinetic stability combined with small sizes of [Ln(PTA) 2 (18-crown-6)] + [Ln(PTA) 4 ] - molecules in nonaqueous solutions, these compounds may be used as thermometric NMR sensors directly in reaction media for in situ control over temperature [ru

  12. Lanthanide (III) complexes of 2-(N-salicylideneamino)-4-phenylthiazole

    International Nuclear Information System (INIS)

    Sasidharan, G.N.; Mohanan, K.; Lakshmi Prabha, A.N.

    2002-01-01

    Lanthanide(III) complexes of 2-(N-salicylideneamino)-4- phenylthiazole (HSAT) have been synthesised and characterised by elemental, analytical, thermogravimetric, molar conductance, UV- visible, IR and NMR spectral data. The ligand coordinates to the lanthanide(III) ion in a tridentate fashion without deprotonation, giving complexes of the type [Ln(HSAT) 2 (NO 3 ) 3 ] and [Ln(HSAT) 2 (H 2 0) 3 Cl 3 ]. The spectral data reveal that the ligand is bonded to the lanthanide ion through azomethine nitrogen, ring nitrogen and phenolic oxygen without deprotonation. The nitrate group acts in a bidentate fashion. The ligand and the metal complexes exhibit antibacterial and antifungal activities. (author)

  13. Application of the oscillator strength of 'hypersensitive' transitions to the investigation of complex equilibria of lanthanide ions

    International Nuclear Information System (INIS)

    Bukietynska, K.; Mondry, A.; Osmeda, E.

    1981-01-01

    Stability constants and thermodynamic parameters of Nd 3+ , Ho 3+ and Er 3+ complexes with acetates, propionates, glycolates, lactates and α-hydroxyisobutyrates were determined by a spectroscopic method based upon the measurements of the variation of oscillator strengths of 'hypersensitive' 4f-4f-transitions. The sets of βsub (n) values at 21 0 C are in a good agreement with those found potentiometrically. The stability constants of the complexes evaluated at 5 different temperatures were used for the calculation of ΔG, ΔH, ΔS values. The evaluated thermodynamic parameters are in a satisfactory agreement with those found calorimetrically. The thermodynamic parameters calculated from two independent 'hypersensitive' transitions of the Er 3+ ion are also consistent. (author)

  14. A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions

    Energy Technology Data Exchange (ETDEWEB)

    D' Aleo, Anthony; Xu, Jide; Do, King; Muller, Gilles; Raymond, Kenneth N.

    2009-04-30

    The synthesis of a cyclen derivative containing four isophthalamide groups (L{sup 1}) is described. The spectroscopic properties of the Ln(III) complexes of L{sup 1} (Ln = Gd, Tb, Yb, Eu) reveal changes of the UV/visible absorption, circular dichroism absorption, luminescence and circularly polarized luminescence properties. It is shown that at least two metal complex species are present in solution, whose relative amounts are pH dependent. When at pH > 8.0, an intense long lived emission is observed (for [L{sup 1}Tb] and [L{sup 1}Yb]) while at pH < 8.0, a weaker, shorter-lived species predominates. Unconventional Ln(III) emitters (Pr, Nd, Sm, Dy and Tm) were sensitized in basic solution, both in the visible and in the near infra-red, to measure the emission of these ions.

  15. Lanthanides in the frame of Molecular Magnetism

    Directory of Open Access Journals (Sweden)

    Gatteschi D.

    2014-07-01

    Full Text Available Molecular magnetism is producing new types of materials which cover up to date aspects of basic science together with possible applications. This article highlights recent results from the point of view of lanthanides which are now intensively used to produce single molecule magnets, single chain and single ion magnets. After a short introduction reminding the main steps of development of molecular magnetism, the basic properties of lanthanides will be covered highlighting important features which are enhanced by the electronic structure of lanthanides, like spin frustration and chirality, anisotropy and non collinear axes in zero and one dimensional materials. A paragraph of conclusions will discuss what has been done and theperspectives to be expected.

  16. Curvature of the Lanthanide Contraction: An Explanation

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, Kenneth; Wellman, Daniel; Sgarlata, Carmelo; Hill, Aru

    2009-12-21

    A number of studies have shown that for isostructural series of the lanthanides (elements La through Lu), a plot of equivalent metal-ligand bond lengths versus atomic number differs significantly from linearity and can be better fit as a quadratic equation. However, for hydrogen type wave functions, it is the inverse of the average distance of the electron from the nucleus (an estimate of size) that varies linearly with effective nuclear charge. This generates an apparent quadratic dependence of radius with atomic number. Plotting the inverse of lanthanide ion radii (the observed distance minus the ligand size) as a function of effective nuclear charge gives very good linear fits for a variety of lanthanide complexes and materials. Parameters obtained from this fit are in excellent agreement with the calculated Slater shielding constant, k.

  17. The Lanthanide Contraction Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.

    2007-04-19

    A complete, isostructural series of lanthanide complexes (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural lanthanide complexes with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependency as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published, almost complete series of lanthanide complexes. Due to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.

  18. Halogen protected cobalt bis(dicarbollide) ions with covalently bonded CMPO functions as anionic extractants for trivalent lanthanide/actinide partitioning

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Švec, Petr; Selucký, P.; Bubeníková, M.

    2012-01-01

    Roč. 38, č. 1 (2012), s. 103-112 ISSN 0277-5387 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * CMPR * liquid-liquid extraction * lanthanides * actinides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.813, year: 2012

  19. Separation of trivalent actinides and lanthanides from simulated high-level waste using cobalt bis(dicarbollide) ion derivate substituted with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide

    Czech Academy of Sciences Publication Activity Database

    Selucký, P.; Lučaníková, M.; Grüner, Bohumír

    2012-01-01

    Roč. 100, č. 3 (2012), s. 179-183 ISSN 0033-8230 R&D Projects: GA MŠk LC523; GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : dicarbollide * CMPO * liquid-liquid extraction * actinides * lanthanides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.373, year: 2012

  20. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  1. Coordination symmetry determination of some lanthanide complexes by x-ray diffraction

    International Nuclear Information System (INIS)

    Oliveira Paiva Santos, C. de.

    1983-01-01

    The x-ray determination of the crystal and molecular structures of three lanthanide complexes is described. The work is a contribution to the study of the coordination chemistry of lanthanide ions with organic ligands and in particular, it aims to compare the observed point symmetry of the ion environment with spectroscopic predictions. (author)

  2. Lanthanide single molecule magnets

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Jinkui; Zhang, Peng [Chinese Academy of Sciences, Changchun (China). Changchun Inst. of Applied Chemistry

    2015-10-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures - an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and explore new directions.

  3. Lanthanide single molecule magnets

    CERN Document Server

    Tang, Jinkui

    2015-01-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs, and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures – an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and...

  4. Recovery of lanthanides

    International Nuclear Information System (INIS)

    Tilley, G.L.; Doyle, W.E.

    1990-01-01

    This paper discusses a method for recovering a lanthanide and thorium from a material containing a fluorine compound and the lanthanide and thorium. It comprises a. obtaining the material from a roasted, acid-leached bastnasite ore; b. forming a mixture of the material with at least about ten weight percent of silica; c. contacting the mixture with sulfuric acid; d. heating the mixture and sulfuric acid to a temperature of at least about 150 degrees C for at least about 3 hours to cause most of the fluorine to be released as a volatile material containing silicon and fluorine; e. contacting the reacted mixture with an aqueous medium consisting essentially of water to solubilize the lanthanide and thorium while leaving an insoluble residue; and f. separating the aqueous solution of the lanthanide and thorium from the insoluble residue

  5. Lanthanide-doped luminescent nanomaterials from fundamentals to bioapplications

    CERN Document Server

    Chen, Xueyuan; Tu, Datao

    2014-01-01

    Lanthanide-Doped Luminescent Nanomaterials reviews the latest advances in the development of lanthanide-doped luminescent inorganic nanoparticles for potential bioapplications. This book covers the chemical and physical fundamentals of these nanoparticles, such as the controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in-vitro biodetection of tumor biomarkers. This book is intended for those readers who are interested in systematically understanding the materials design strategy, optical behavior of lanthanide ions, and practical bioapplications of lanthanide nanoparticles. It primarily focuses on the interdisciplinary frontiers in chemistry, physics and biological aspects of luminescent nanomaterials. All chapters were written by scientists active in this field and for a broad audience, providing both beginners and advanced researchers with comprehensive information on the ...

  6. Investigation of lanthanide ions and other paramagnetic impurities in natural fluorite by electron paramagnetic resonance: examples of application to mining exploration and geochemistry

    International Nuclear Information System (INIS)

    Chatagnon, B.

    1981-01-01

    This research thesis reports the application to geology, and more particularly to geochemistry and mining exploration, of a physical method: the electron paramagnetic resonance (EPR). After a report of a bibliographical investigation on mineralogy and geochemistry of fluorite and lanthanides, as well as on paramagnetic centres observed by physicists in synthetic fluorite, the author reports an experimental work, and describes two examples of application of EPR: firstly, the exploration of radioactive ores, and secondly, with the joint use of neutron activation analysis, the characterization of the redox status of the hydrothermal solution which is at the origin of fluorinated mineralisation

  7. Lanthanide metal-organic frameworks

    International Nuclear Information System (INIS)

    Cheng, Peng

    2015-01-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  8. Lanthanide metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Peng (ed.) [Nankai Univ., Tianjin (China). Dept. of Chemistry

    2015-03-01

    This book contains the following nine chapters: lanthanide metal-organic frameworks: syntheses, properties, and potential applications (Stephen Fordham, Xuan Wang, Mathieu Bosch, Hong-Cai Zhou); 2. chiral lanthanide metal-organic frameworks (Weisheng Liu, Xiaoliang Tang); 3. Porous lanthanide metal-organic frameworks for gas storage and separation (Bin Li, Banglin Chen); 4. Luminescent lanthanide metal-organic frameworks (Xue-Zhi Song, Shu-Yan Song, Hong-Jie Zhang); 5. Metal-organic frameworks based on lanthanide clusters (Lian Chen, Feilong Jiang, Kang Zhou, Mingyan Wu, Maochun Hong); 6. metal-organic frameworks with d-f cyanide bridges: structural diversity, bonding regime, and magnetism (Marilena Ferbinteanu, Fanica Cimpoesu, Stefania Tanase); 7. transition-lanthanide heterometal-organic frameworks: synthesis, structures, and properties (Wei Shi, Ke Liu, Peng Cheng); 8: MOFs of uranium and the actinides (Juan Su, Jiesheng Chen); 9. Nanostructured and/or nanoscale lanthanide metal-organic frameworks (Zhonghao Zhang, Zhiping Zheng).

  9. The spectroscopy and structure of some lanthanide chlorides in amide solutions

    International Nuclear Information System (INIS)

    Legendziewicz, J.; Bukietynska, K; Jezowsky-Trzebiatowska, B.

    1974-01-01

    The absorption spectra of Pr, Nd, Ho, and Er anhydrous and hydrated chlorides in formamide, methyl-, dimethyl-, and diethylformamide solutions have been investigated in the range of 8000 - 4200 cm -1 . By the Judd-Oefelt method of intensity analysis and by calculating the nepheloauxetic effect, the first coordination sphere of lanthanide ions and the approximate symmetry of amide solvates of anhydrous and hydrated lanthanide chlorides were determined. A difference between symmetry and coordination numbers for light and heavy lanthanide solvates has been found. Some considerations regarding the structure of lanthanide solvates and structure of amide molecules have been made. (B.T.)

  10. Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid

    International Nuclear Information System (INIS)

    Miller, J.H.

    1977-12-01

    This research is concerned with the solvent extraction into chloroform of the lanthanides, using 2,5-dimethyl-2-hydroxyhexanoic acid (DMHHA). This acid is the first α-hydroxy aliphatic acid to be studied as an extracting agent for the lanthanides. The chloroform-water DMHHA partition constant was determined to be 1.0 (at 0.1 M ionic strength and 25 0 C). The acid dimerizes in chloroform with a constant of 56. The light lanthanides can be extracted into chloroform by forming complexes with the DMHHA anions. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. The resultant extract is also highly aggregated. At unionized acid-to-metal ratios greater than one, extractions first occur followed by the slow precipitation of the lanthanide. At the tracer level, neodymium is extracted primarily as NdA 3 (HA) 5 and (NdA 3 ) 2 (HA)/sub q/. Very small amounts of (NdA 3 ) 2 and other metal aggregates are also present. The heavy lanthanides do not extract from solutions of DMHHA and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion the heavy lanthanides can be extracted, presumably as ion pairs. The stability constants of the light lanthanides and DMHHA were determined. The separation factors obtained from DMHHA extractions of the light lanthanides were also investigated and found to be comparable to those obtained employing normal aliphatic carboxylic acid

  11. Polymerization of lanthanide acrylonitrile complexes.

    Science.gov (United States)

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A

    2002-01-01

    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  12. Spectrally resolved confocal microscopy using lanthanide centred near-IR emission

    DEFF Research Database (Denmark)

    Liao, Zhiyu; Tropiano, Manuel; Mantulnikovs, Konstantins

    2015-01-01

    The narrow, near infrared (NIR) emission from lanthanide ions has attracted great interest, particularly with regard to developing tools for bioimaging, where the long lifetimes of lanthanide excited states can be exploited to address problems arising from autofluorescence and sample transparency...

  13. Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

    International Nuclear Information System (INIS)

    Tatsuya Suzuki

    2013-01-01

    The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution. (author)

  14. Systematic analysis of spectroscopic characteristics of the lanthanide and actinide ions with the 4f{sup N−1}5d and 5f{sup N−1}6d electronic configurations in a free state

    Energy Technology Data Exchange (ETDEWEB)

    Ma, C.-G. [College of Mathematics and Physics, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Brik, M.G., E-mail: brik@fi.tartu.ee [College of Mathematics and Physics, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Institute of Physics, University of Tartu, Riia 142, Tartu 51014 (Estonia); Institute of Physics, Jan Dlugosz University, Armii Krajowej 13/15, PL-42200 Czestochowa (Poland); Tian, Y.; Li, Q.-X. [College of Mathematics and Physics, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China)

    2014-08-01

    Highlights: • Calculated spectroscopic parameters of f{sup N−1}d configurations of the 4f and 5f ions. • Relations between the Slater parameters, spin–orbit constant, atomic number were found. • Barycenters of the electronic configuration energies were calculated. • Obtained relations reduce the number of independent terms in a free ion Hamiltonian. - Abstract: Systematic consideration of the spectroscopic properties of the f{sup N−1}d excited electronic configurations of the di-, tri- and tetravalent lanthanide and actinide ions in a free state is presented. Variations of the Hartree–Fock calculated Slater parameters for the f{sup N−1}d electron configurations, spin–orbit (SO) interaction constant ζ for the f and d electrons, and averaged values of the second, fourth and sixth powers of the 4f, 5f, 5d, 6d electrons’ radial coordinate across both series were considered; functional dependencies between the mentioned quantities were obtained. It has been shown that the Coulomb interaction parameters F{sup 2}(ff), F{sup 4}(ff), and F{sup 6}(ff) for the f{sup N−1} core increase linearly with the atomic number Z, whereas the direct and exchange Coulomb parameters F{sup 2}(fd), F{sup 4}(fd), G{sup 1}(fd), G{sup 3}(fd), G{sup 5}(fd) for the f{sup N−1}d configuration decrease linearly with Z. Since the SO interaction constant ζ{sup 1/4} is also proportional to Z, it was possible to find linear relationships between the Coulomb interaction parameters and SO constants for the f and d electrons, which effectively reduce the number of independent parameters in the free ion Hamiltonian. The constraining relations between the free ion Hamiltonian’s parameters obtained in the present paper can be used for simulations of the f–d transition spectra of these ions in various crystals.

  15. Luminescent lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.

    1999-12-13

    One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

  16. Intercalation of lanthanide trichlorides in graphite

    International Nuclear Information System (INIS)

    Stumpp, E.; Nietfeld, G.

    1979-01-01

    The reactions of the whole series of lanthanide trichlorides with graphite have been investigated. Intercalation compounds have been prepared with the chlorides of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y whereas LaCl 3 , CeCl 3 , PrCl 3 and NdCl 3 do not intercalate. The compounds were characterized by chemical and X-ray analysis. The amount of c-axis increase is consistent with the assumption that the chlorides are intercalated in form of a chloride layer sandwich resmbling the sheets in YCl 3 . The chlorides which do not intercalate crystallize in the UCl 3 structure having 3 D arrangements of ions. Obviously, these chlorides cannot form sheets between the carbon layers. The ability of AlCl 3 to volatilize lanthanide chlorides through complex formation in the gas phase can be used to increase the intercalation rate strikingly. (author)

  17. Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Tropiano, Manuel; Kenwright, Alan M.

    2017-01-01

    Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques. The photo...... and lanthanide(III) centres in these molecules inhibits the efficient sensitisation of europium. We conclude that the intramolecular collisions required for efficient Dexter energy transfer from the sensitiser to the lanthanide(III) centre can be prevented by steric congestion....

  18. Scandium, yttrium and the lanthanides

    International Nuclear Information System (INIS)

    Hart, F.A.

    1987-01-01

    This chapter on the chemistry of the coordination complexes of scandium, yttrium and the lanthanides includes sections on the nitrogen and oxygen donor ligands and complex halides of scandium, and the phosphorus and sulfur donor ligands of yttrium and the lanthanides. Complexes with the macrocylic ligands and with halides are also discussed. Sections on the NMR and electronic spectra of the lanthanides are also included. (UK)

  19. The electronic structure of the lanthanides and actinides, a comparison

    International Nuclear Information System (INIS)

    Edelstein, N.M.

    1998-01-01

    Full text: Optical spectra of the two f-element series (the lanthanides and actinides) are comparable in many respects. For the trivalent ions isolated in single crystals, both series exhibit rich, narrow line spectra. These data can be analysed in terms of a parametric model based on a free-ion Hamiltonian plus the addition of a crystal field Hamiltonian. For most systems the agreement between the calculated and experimental energy levels is quite good. In the actinide series there appears to be a correlation between the magnitude of the crystal field and the inadequacy of the fits. The early actinides exhibit multiple oxidation states for which there is no precedent in the lanthanide series. The parametric model mentioned earlier has been utilized for some tetravalent actinide systems with reasonably good results. A selective survey of results describing the similarities and differences of various lanthanide and actinide systems will be given

  20. Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Li-Mei [College of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001 (China); Liu, Jing-Xin, E-mail: jxliu411@ahut.edu.cn [College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002 (China)

    2017-01-15

    A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas (Ln(H{sub 2}O){sub 6}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·xH{sub 2}O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], (Sm(H{sub 2}O){sub 5}Cy6Q[6])·2(CdCl{sub 4})·H{sub 3}O·10H{sub 2}O (5) and (Ln(H{sub 2}O){sub 5}(NO{sub 3})@Cy6Q[6])·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl{sub 2}. Single-crystal X-ray diffraction analyses revealed that compounds 1–8 all crystallize in monoclinic space group P2{sub 1}/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1–8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO){sub 3}, Tm(NO){sub 3}, Yb(NO){sub 3} under the same conditions resulted in the compounds 9–11 with formulas Cy6Q[6]·2(CdCl{sub 4})·2H{sub 3}O·xH{sub 2}O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations. - Graphical abstract: The reaction of cyclohexanocucurbit[6]uril with lanthanide ions (La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, Ho{sup 3+}, Tm{sup 3+} and Yb{sup 3+}) under hydrochloric acid in the presence of CdCl{sub 2} resulted in eleven compounds, which demonstrate interesting lanthanide contraction effect and provide a means of separating lanthanide ions. - Highlights: • Eleven compounds of the Ln{sup 3+} with the Cy6Q[6] were synthesized and described. • Compounds 1-8 demonstrate interesting lanthanide contraction effect.

  1. Determination of the thermodynamic properties of complexation and extraction by micro-calorimetry; Determination de grandeurs thermodynamiques de complexation et d'extraction d'ions lanthanide(3) par microcalorimetrie

    Energy Technology Data Exchange (ETDEWEB)

    Charbonnel, M.Ch.; Flandin, J.L. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France)

    2000-07-01

    The CEA is currently developing the DIAMEX process, the first step in the strategy for the separation of minor actinides from high-level radioactive waste. The extractant belongs to the diamide family of molecules and is able to co-extract trivalent actinides and lanthanides. This study focuses on the thermodynamic properties ({delta}H, {delta}G, {delta}S) of lanthanide extraction by malonamide in order to better understand the mechanisms involved and to account for differences in the behavior of various diamide extractants. The main technique used is microcalorimetric titration. The Thermal Activity Monitor (TAM) microcalorimeter is a modular system with a highly stable ({+-} 0.1 mK) temperature-controlled bath containing up to four calorimetry vessel units. The sensor bulbs inserted in the reaction vessel can measure heat flows in static or dynamic conditions. Micro-calorimetry, and calorimetric titration in particular, is a fast growing field due to technical improvements in both hardware and software. In the case of an equilibrium reaction, titration allows both {delta}{sub r}G and {delta}{sub r}H (and thus {delta}{sub r}S) to be determined simultaneously. It was decided to initiate this thermochemical investigation with a homogeneous phase reaction, and the first study concerned the aqueous phase complexation of a trivalent lanthanide ion by a water-soluble diamide, tetraethyl-malonamide (TEMA: (C{sub 2}H{sub 5}){sub 2}NCO-CH{sub 2}CON(C{sub 2}H{sub 5}){sub 2}). In the test system, the heat of dilution of the diamide in water is preponderant over the heat arising from the complexation reaction; the result is a positive value corresponding to an endothermic reaction. However, the equilibration constant K and {delta} H are both very small, and cannot be calculated from the resulting Q{sub v}f(n{sub TEMA}) curves. Moreover, in aqueous phase, the reactions involved are different from those observed when neodymium(III) is extracted into an organic phase, and the

  2. Improving the SMM and luminescence properties of lanthanide complexes with LnO9 cores in the presence of ZnII: an emissive Zn2Dy single ion magnet.

    Science.gov (United States)

    Fondo, Matilde; Corredoira-Vázquez, Julio; Herrera-Lanzós, Antía; García-Deibe, Ana M; Sanmartín-Matalobos, Jesús; Herrera, Juan Manuel; Colacio, Enrique; Nuñez, Cristina

    2017-12-12

    Mononuclear complexes of stoichiometry [Ln(H 3 L)(H 2 O)(NO 3 )](NO 3 ) 2 (Ln = Tb, 1; Dy, 2, Er, 3), which crystallise with different solvates, and the heterotrinuclear compound [Zn 2 Dy(L)(NO 3 ) 3 (OH)] (4) can be obtained with the same H 3 L compartmental ligand. The single X-ray crystal structure of the mononuclear complexes shows a LnO 9 core with a muffin-like disposition while the geometry of the DyO 9 core in 4 seems to be closer to spherical capped square antiprism. The analysis of the magnetic properties of all the complexes demonstrates that the mononuclear lanthanide compounds do not show slow relaxation of the magnetization, even when the samples are diluted with a diamagnetic matrix and subjected to a dc applied field of 1000 Oe. Nevertheless, the heterotrinuclear dysprosium complex 4·3H 2 O is a field-induced single ion magnet, with an estimated U eff barrier of 59 K. The luminescence characterisation of all the metal complexes in methanol solution at 298 K also shows a notable increase in the fluorescence emission of the heterotrinuclear complex with respect to the mononuclear ones, in such a way that 4 can be defined as a fluorescent single ion magnet.

  3. Valencies of the lanthanides

    OpenAIRE

    Johnson, David A.; Nelson, Peter G.

    2018-01-01

    The valencies of the lanthanides vary more than was once thought. In addition to valencies associated with a half-full shell, there are valencies associated with a quarter- and three-quarter-full shell. This can be explained on the basis of Slater’s theory of many-electron atoms. The same theory explains the variation in complexing constants in the trivalent state (the “tetrad effect”). Valency in metallic and organometallic compounds is also discussed.

  4. A general way of analyzing EPR spectroscopy for a pair of magnetically equivalent lanthanide ions in crystal: A case study of BaY2F8:Yb3+ crystal

    Science.gov (United States)

    Liu, Honggang; Zheng, Wenchen

    2018-01-01

    Electron paramagnetic resonance (EPR) is an important tool to study the complex interactions (e.g., exchange and magnetic dipole-dipole interactions) for a pair of lanthanide (Ln) ions in crystals. How to analyze these EPR spectra and obtain the strength of each interaction is a challenge for experimentalists. In this work, a general way of calculating the EPR lines for two magnetically equivalent Ln ions is given by us to solve this problem. In order to explain their EPR spectra and obtain exchange interaction parameters Ji (i = x, y, z) between them, we deduce the analytic formulas for computing the angular dependent EPR lines for such Ln pairs under the condition of weak coupling (|Ji| ≪ hv, where v is the microwave frequency in the EPR experiment) and set up the spin-Hamiltonian energy matrix that should be diagonalized to obtain these lines if intermediate (|Ji| ˜ hv) and strong (|Ji| > hv) couplings are encountered. To verify our method, the experimental EPR spectra for the Yb3+ doped BaY2F8 crystal are considered by us and the EPR lines from the isolated Yb3+ ion and Yb3+-Yb3+ pair with distance R equal to 0.371 nm are identified clearly. Moreover, exchange interaction parameters (Jx ≈ -0.04 cm-1, Jy ≈ -0.24 cm-1, and Jz ≈ -0.1 cm-1) for such a pair are also determined by our calculations. This case study demonstrates that the theoretical method given in this work would be useful and could be applied to understand interactions between Ln ions in crystals.

  5. Tri- and tetra-substituted cyclen based lanthanide(III) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP).

    Science.gov (United States)

    Fanning, Ann-Marie; Plush, Sally E; Gunnlaugsson, Thorfinnur

    2015-05-28

    A series of tetra-substituted 'pseudo' dipeptide ligands of cyclen (1,4,7,10,-tetraazacyclododecane) and a tri-substituted 3'-pyridine ligand of cyclen, and the corresponding lanthanide(III) complexes were synthesised and characterised as metallo-ribonuclease mimics. All complexes were shown to promote hydrolysis of the phosphodiester bond of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP, τ1/2 = 5.87 × 10(3) h), a well known RNA mimic. The La(III) and Eu(III) tri-substituted 3'-pyridine lanthanide(III) complexes being the most efficient in promoting such hydrolysis at pH 7.4 and at 37 °C; with τ1/2 = 1.67 h for La(III) and 1.74 h for Eu(III). The series was developed to provide the opportunity to investigate the consequences of altering the lanthanide(III) ion, coordination ability and hydrophobicity of a metallo-cavity on the rate of hydrolysis using the model phosphodiester, HPNP, at 37 °C. To further provide information on the role that the log Ka of the metal bound water plays in phosphodiester hydrolysis the protonation constants and the metal ion stability constants of both a tri and tetra-substituted 3'pyridine complex were determined. Our results highlighted several key features for the design of lanthanide(III) ribonucelase mimics; the presence of two metal bound water molecules are vital for pH dependent rate constants for Eu(III) complexes, optimal pH activity approximating physiological pH (∼7.4) may be achieved if the log Ka values for both MLOH and ML(OH)2 species occur in this region, small changes to hydrophobicity within the metallo cavity influence the rate of hydrolysis greatly and an amide adjacent to the metal ion capable of forming hydrogen bonds with the substrate is required for achieving fast hydrolysis.

  6. Hydration of the lanthanide ions 152Eu(III), 153Gd(III) and 170Tm(III) in aqueous solutions at 298 K and similarity with the transplutonium element ions 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III)

    International Nuclear Information System (INIS)

    Ouerfelli, N.; Latrous, H.; Ammar, M.; Das, D.; Oliver, J.

    2013-01-01

    The open-end capillary method is used for the determination of ionic self-diffusion coefficients (D) for trivalent radiotracer, lanthanide and actinide ions are reported in concentrated aqueous solutions of supporting electrolytes of Gd(NO 3 ) 3 -HNO 3 or Nd(ClO 3 ) 4 -HClO 4 up to 1.5 mol.L -1 at 298.15 K and pH 2.50. The data obtained in large range of concentrations, allow deriving the limiting value D°, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. (author)

  7. Determination of stability constants of lanthanide nitrate complex formation using a solvent extraction technique

    International Nuclear Information System (INIS)

    Andersson, S.; Ekberg, C.; Liljenzin, J.O.; Nilsson, M.; Skarnemark, G.; Eberhardt, K.

    2006-01-01

    For lanthanides and actinides, nitrate complex formation is an important factor with respect to the reprocessing of nuclear fuels and in studies that treat partitioning and transmutation/conditioning. Different techniques, including microcalorimetry, various kinds of spectroscopy, ion-exchange and solvent extraction, can be used to determine stability constants of nitrate complex formation. However, it is uncommon that all lanthanides are studied at the same time, using the same experimental conditions and technique. The strengths of the complexes are different for lanthanides and actinides, a feature that may assist in the separation of the two groups. This paper deals with nitrate complex formation of lanthanides using a solvent extraction technique. Trace amounts of radioactive isotopes of lanthanides were produced at the TRIGA Mainz research reactor and at the Institutt for Energiteknikk in Kjeller, Norway (JEEP II reactor). The extraction of lanthanide ions into an organic phase consisting of 2, 6-bis-(benzoxazolyl)-4-dodecyloxylpyridine, 2-bromodecanoic acid and tert-butyl benzene as a function of nitrate ion concentration in the aqueous phase was studied in order to estimate the stability constants of nitrate complex formation. When the nitrate ion concentration is increased in the aqueous phase, the nitrate complex formation starts to compete with the extraction of metal ions. Thus the stability constants of nitrate complex formation can be estimated by measuring the decrease in extraction and successive fitting of an appropriate model. Extraction curves for La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Ho and Er were obtained and stability constants for their nitrate complex formation were estimated. Tb, Tm, Yb and Lu were also investigated, but no stability constants could be determined. The distribution ratios for the metal ions at low nitrate ion concentration were obtained at the same time, showing the effect of lanthanide contraction resulting in decreasing

  8. Thermodynamical properties of liquid lanthanides-A variational approach

    Energy Technology Data Exchange (ETDEWEB)

    Patel, H. P. [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India); Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India); Thakor, P. B., E-mail: pbthakor@rediffmail.com [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India); Sonvane, Y. A. [Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India)

    2015-06-24

    Thermodynamical properties like Entropy (S), Internal energy (E) and Helmholtz free energy (F) of liquid lanthanides using a variation principle based on the Gibbs-Bogoliubuv (GB) inequality with Percus Yevick hard sphere reference system have been reported in the present investigation. To describe electron-ion interaction we have used our newly constructed parameter free model potential along with Sarkar et al. local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermodynamical properties of liquid lanthanides.

  9. Microwave synthesis of nanostructured oxide sorbents doped with lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Mitrofanov, Andrey A., E-mail: mitrofanov-a@icloud.com; Silyavka, Elena S.; Shilovskikh, Vladimir V.; Kolonitckii, Petr D.; Sukhodolov, Nikolai G.; Selyutin, Artem A., E-mail: selutin@inbox.ru [Saint Petersburg State University, 7/9, Universitetskaya nab., St. Petersburg, 199034 (Russian Federation)

    2016-06-17

    A number of nanostructured mesoporous oxide systems based on aluminum oxide, doped with lanthanide ions have been obtained in this study. Structure and morphology of oxides obtained have been examined by X-ray diffraction analysis, thermogravimetric analysis, scanning electron microscopy. The surface area of the samples was determined by the BET method. The dependence of the adsorption of insulin on synthesized oxides from the concentration was investigated. The containing of insulin in solutions after adsorption was determined by the Bradford method. The isotherms of adsorption of insulin on resulting oxide sorbents were plotted, the dependence capacity of the sorption of insulin from the lanthanide dopant was determined.

  10. Lanthanide and actinide complexation studies with tetradentate 'N' donor ligands

    International Nuclear Information System (INIS)

    Bhattacharyya, A.; Mohapatra, M.; Mohapatra, P.K.; Rawat, N.; Tomar, B.S.; Gadly, T.; Ghosh, S.K.; Manna, D.; Ghanty, T.K.

    2014-01-01

    Because of their similar charge and chemical behaviour separation of trivalent actinides and lanthanides is an important and challenging task in nuclear fuel cycle. Soft (S,N) donor ligands show selectivity towards the trivalent actinides over the lanthanides. Out of various 'N' donor ligands studied, bis(1,2,4)triazinyl bipyridine (BTBP) and bis(1,2,4)triazinyl phenanthroline (BTPhen) were found to be most promising. In order to understand the separation behaviour of these ligands, their complexation studies with these 'f' block elements are essential. In the present work, complexation studies of various lanthanide ions (La 3+ , Eu 3+ and Er 3+ ) was studied with ethyl derivatives of BTBP (C 2 BTBP) and BTBPhen (C 2 BTPhen) and pentyl derivative of BTBP (C 5 BTBP) in acetonitrile medium using UV-Vis spectrophotometry, fluorescence spectroscopy and solution calorimetry. Computational studies were also carried out to understand the experimental results

  11. Calorimetric approach of lanthanides (3) complexation and extraction by malonamides

    International Nuclear Information System (INIS)

    Flandin, J.L.

    2001-01-01

    In the field of long lived radionuclides separation, diamides are interesting extractants because of their ability to co-extract trivalent lanthanides and actinides, which is a preliminary and essential step in high level radioactive waste reprocessing. The research carried out contributes to a better understanding of the mechanisms and the aim is the determination of thermodynamics properties (Δ r G, Δ r H et Δ r S) related to the complexation and the extraction of lanthanides(III) by malonamides. The first part of the document deals with the complexation of lanthanides(III) by an hydrosoluble diamide. The experimental results obtained by UV-visible spectrometry, TRLIF, NMR and microcalorimetric titration proved that lanthanides(III)-TEMA interactions in aqueous medium are very weak and that the complexation reaction is endothermic. The TEMA ligand still stays in the second coordination sphere of coordination of the lanthanide ion. The second part of this study focuses on the extraction of neodymium(III) nitrate by a lipophilic diamide which is an exothermic reaction. The influence of the composition of aqueous and organic phases on the thermodynamics properties Δ r G et Δ r H has been studied by microcalorimetric titration. The most influent parameter is the total concentration in extractant. As a consequence, thermodynamic values are very dependent on the organic phase organisation before and alter extraction. At the same time, this study showed the interest of the calorimetric approach for the analysis of basic reactions like diamide dilution and their organisation as oligomeric aggregates. (author)

  12. Solution chemistry of lanthanide complexes

    International Nuclear Information System (INIS)

    Brittain, H.G.

    1979-01-01

    Intermolecular energy transfer from Tb 3+ to Eu 3+ , luminescence intensity measurements, potentiometric titrations, differential absorption spectroscopy, and spectroscopic titrations were all used to study the binding of lanthanide ions by serine and threonine. At low pH (3.0 to 6.0) the complexes are mononuclear and ligand is only weakly bound. In the pH interval of 6.0 to 8.5 stronger interaction takes place between the ligand and the metal (with possible coordination of the undissociated hydroxyl group), and self-association of complexes becomes important. Above pH 8.5, base hydrolysis of the complexes leads to highly associated species in solution and shortly above this pH an insoluble precipitate is formed. It was found that energy could be transferred from Tb 3+ to Eu 3+ more efficiently among complexes prepared from racemic ligands than in complexes made from resolved ligand, but this stereoselectivity was only observed at pH values greater than 6.5 and in solutions having a 1:10 ratio of metal-to-ligand. No stereoselectivity was found in solutions having 1:5 ratios, and this observation was explained by the existence of 1:2 metal-ligand complexes existing in solutions having the higher ratio of metal-to-ligand (only 1:1 complexes are then found at lower ratios of metal-to-ligand). (author)

  13. Using lanthanide chelates and uranyl compounds for diagnostic by fluoroimmunoassays

    International Nuclear Information System (INIS)

    Santos, Elen G.; Tomiyama, Claudia S.; Kodaira, Claudia A.; Felinto, Maria C.F.C.; Lourenco, Ana V. S.; Brito, Hermi F.

    2009-01-01

    The importance of the luminescence of lanthanide ions and UO 2 2+ is related to its peculiar characteristics, e.g. long lifetime and line-like emission bands in the visible, which make these ions unique among the species that are known to luminescence. Recent developments in the field of supramolecular chemistry have allowed the design of ligands capable of encapsulating lanthanide ions, thus forming kinetically inert complexes. By introduction of chromophoric groups in these ligands, an intense luminescence of the ion can be obtained via the 'antenna effect', defined as a light conversion process involving distinct absorbing (ligand) and emitting (metal ion) components. In such a process, the quantities that contribute to the luminescence intensity are the efficiency of the absorption, the efficiency of the ligand-metal energy transfer, and the efficiency of the metal luminescence. Encapsulation of lanthanide ions with suitable ligands may therefore give rise to 'molecular devices' capable to emit strong, long-lived luminescence. Besides the intrinsic interest in their excited state properties, compounds of lanthanide ions, in particular of the Eu 3+ and Tb 3+ ions, and now UO 2 2+ are important for their potential use as luminescent labels for biological species in fluoroimmunoassays (FIAs). This is most interesting because fluorimetric labeling represents an alternative method to the use of radioactive labels, which has long been the most common way of quantifying immunoreactions. In this article we report information about luminescent materials, which gave a good signal to quantify biological molecules by TR-FIA, DELFIA , DSLFIA, RIA and FRET. (author)

  14. Lanthanide complexation in aqueous solutions

    International Nuclear Information System (INIS)

    Choppin, G.R.

    1984-01-01

    The lanthanide elements form an extended series of cations with the same charge, slightly varying radii and useful magnetic and spectroscopic properties. Their use in technology is growing rapidly as their properties are more fully explored. The lanthanides also offer scientists valuable and often unique probes for investigating a variety of chemical and physical phenomena. This review has attempted to call attention to these latter uses without trying to provide a thorough discussion of all the relevant literature. Hopefully, awareness of the more interesting facets of present studies of lanthanide complexes in aqueous solution will spur even more advances in the use of these elements. (Auth.)

  15. An NMR strategy for fragment-based ligand screening utilizing a paramagnetic lanthanide probe

    International Nuclear Information System (INIS)

    Saio, Tomohide; Ogura, Kenji; Shimizu, Kazumi; Yokochi, Masashi; Burke, Terrence R.; Inagaki, Fuyuhiko

    2011-01-01

    A nuclear magnetic resonance-based ligand screening strategy utilizing a paramagnetic lanthanide probe is presented. By fixing a paramagnetic lanthanide ion to a target protein, a pseudo-contact shift (PCS) and a paramagnetic relaxation enhancement (PRE) can be observed for both the target protein and its bound ligand. Based on PRE and PCS information, the bound ligand is then screened from the compound library and the structure of the ligand–protein complex is determined. PRE is an isotropic paramagnetic effect observed within 30 Å from the lanthanide ion, and is utilized for the ligand screening in the present study. PCS is an anisotropic paramagnetic effect providing long-range (∼40 Å) distance and angular information on the observed nuclei relative to the paramagnetic lanthanide ion, and utilized for the structure determination of the ligand–protein complex. Since a two-point anchored lanthanide-binding peptide tag is utilized for fixing the lanthanide ion to the target protein, this screening method can be generally applied to non-metal-binding proteins. The usefulness of this strategy was demonstrated in the case of the growth factor receptor-bound protein 2 (Grb2) Src homology 2 (SH2) domain and its low- and high-affinity ligands.

  16. Lanthanide Cofactors for Triphosphorylation Ribozymes

    Science.gov (United States)

    Sweeney, K. J.; Müller, U. F.

    2017-07-01

    RNA world organisms could have used trimetaphosphate as energy source for thermodynamically unfavorable RNA polymerization. Using in vitro selection we show here that Lanthanides can serve as cofactors for ribozyme-catalyzed RNA triphosphorylation.

  17. Lanthanide complexes that respond to changes in cyanide concentration in water

    International Nuclear Information System (INIS)

    Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen; Kenwright, Alan M.

    2017-01-01

    Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Lanthanide complexes that respond to changes in cyanide concentration in water

    Energy Technology Data Exchange (ETDEWEB)

    Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford (United Kingdom); Kenwright, Alan M. [Department of Chemistry, Durham University (United Kingdom)

    2017-06-26

    Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Separation of lanthanides through hydroxyapatite; Separacion de lantanidos mediante hidroxiapatita

    Energy Technology Data Exchange (ETDEWEB)

    Garcia M, F.G

    2006-07-01

    With the objective of obtaining from an independent way to each one of the lanthanides {sup 151} Pm, {sup 161} Tb, {sup 166} Ho and {sup 177} Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI{sub 3} (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because

  20. Lanthanide/Actinide Opacities

    Science.gov (United States)

    Hungerford, Aimee; Fontes, Christopher J.

    2018-06-01

    Gravitational wave observations benefit from accompanying electromagnetic signals in order to accurately determine the sky positions of the sources. The ejecta of neutron star mergers are expected to produce such electromagnetic transients, called macronovae (e.g. the recent and unprecedented observation of GW170817). Characteristics of the ejecta include large velocity gradients and the presence of heavy r-process elements, which pose significant challenges to the accurate calculation of radiative opacities and radiation transport. Opacities include a dense forest of bound-bound features arising from near-neutral lanthanide and actinide elements. Here we present an overview of current theoretical opacity determinations that are used by neutron star merger light curve modelers. We will touch on atomic physics and plasma modeling codes that are used to generate these opacities, as well as the limited body of laboratory experiments that may serve as points of validation for these complex atomic physics calculations.

  1. Quantum chemical prediction of antennae structures in lanthanide complexes

    International Nuclear Information System (INIS)

    Ottonelli, M.; Musso, G.F.; Rizzo, F.; Dellepiane, G.; Porzio, W.; Destri, S.

    2008-01-01

    In this paper the quantum chemical semiempirical procedure recently proposed by us to predict ground- and excited-state geometries of lanthanide complexes, the pseudo coordination centre method (PCC), is preliminarily compared with the semiempirical sparkle model for the calculation of lanthanide complexes (SMLC). Contrary to the SMLC method, where the rare-earth ion is replaced by a reparameterized sparkle atom, in our approach we replace it with a metal ion which is already present in the chosen semiempirical parameterization. This implies that in the optimization of the geometry of the complexes a different weight is implicitly given to the complex region including the rare-earth ion and its neighbour atoms with respect to the region of the ligands aggregate. As a consequence our approach is expected to reproduce better than the SMLC one the geometry of the ligands aggregate embedded in the complex, while the contrary happens for the coordination distances

  2. Studies on trivalent lanthanide complexes of bis-vanillin p-phenylenediamine

    International Nuclear Information System (INIS)

    Shahma, Abu; Ahmad, Naseer

    1983-01-01

    The coordination interaction of lanthanide(III) chlorides with bis-vanillin o-phenylenediamine was studied by Ansari and Ahmad (1977). It was thought fruitful to compare these with the complexes of trivalent lanthanide ions with bis-vanillin p-phenylenediamine. The newly synthesized complexes were subjected to elemental, thermogravimetric and differential thermal analyses and their melting points, magnetic susceptibilities, molar conductances determined and infrared and electronic spectra taken. (author)

  3. Use of Radioactive Ion Beams for Biomedical Research 1. in vivo labelling of monoclonal antibodies with radio-lanthanides and $^{225}$Ac

    CERN Multimedia

    2002-01-01

    % IS330 \\\\ \\\\\\begin{enumerate} \\item The aim of this study was to contribute to developments of new radiopharmaceuticals for tumour diagnosis and therapy. CERN-ISOLDE is the leading facility in the world to provide radioactive ion beams with high selectivity, purity and intensity. Radioisotope production by spallation makes available a complete range of rare earth isotopes having as complete a diversity of types and energy of radiation, of half-life, and of ionic properties as one would wish. The availability of exotic nuclei, e.g. radionuclides of rare earth elements and $^{225}$Ac, opens new possibilities for the development of radiopharmaceuticals for diagnosis and therapy.\\\\ \\\\ \\item Two approaches were followed within the experimental program. The radioactive metal ions are bound either to bio-specific ligands (monoclonal antibodies or peptides) or to unspecific low molecular weight form. The aim of the experimental program is to evaluate relationships between physico-chemical parameters of the tracer m...

  4. Synthesis, characterization and application of Lanthanide metal-ion-doped TiO2/bentonite nanocomposite for removal of Lead (II and Cadmium (II from aquatic media

    Directory of Open Access Journals (Sweden)

    Susan Samadi

    2016-07-01

    Full Text Available The efficient application of the photocatalytic activity and superficial adsorption on removing heavy metals from water, two types of sorbents, Nd-TiO2/bentonite and Ce-TiO2/bentonite nanocomposites, were synthesized by sol-gel method. The crystalline nanocomposites were obtained after heat treatment at 500 °C for 3 hours. The results of scanning electron microscopy (SEM indicates that Nd-TiO2/bentonite and Ce-TiO2/bentonite were produced on a nanoscale. The phase change of both nanocomposite from amorphous to anatase has been investigated by X- ray diffraction. Removal of lead (II and cadmium (II were studied through adsorption on these nanocomposites by letting them float in the bulk of sample for a definite time in presence and absence of light. The effective parameters in removal process were studied and optimized. The optimum pH, removal time and sorbent dosage in the absence and presence of light for Pb2+ ion were 7, 0.3 g, 15 min and for Cd2+ ion were 7, 0.4 g, 20 min, respectively. Subsequently, the effect of interfering ions in removal process was investigated at optimum conditions and no evidence of interference was observed. The study showed that reproducibility of method (n=9 is good and suitable. The results further indicated that the removal efficiency of Pb2+ ion with Nd-TiO2/bentonite in the presence of light was more than that in the absence of light. Finally, the equilibrium adsorption data fitted Freundlich and Langmuir adsorption models.

  5. Luminescence study on solvation of americium(III), curium(III) and several lanthanide(III) ions in nonaqueous and binary mixed solvents

    International Nuclear Information System (INIS)

    Kimura, T.; Nagaishi, R.; Kato, Y.; Yoshida, Z.

    2001-01-01

    The luminescence lifetimes of An(III) and Ln(III) ions [An=Am and Cm; Ln=Nd, Sm, Eu, Tb and Dy] were measured in dimethyl sulfoxide(DMSO), N,N-dimethylformamide(DMF), methanol(MeOH), water and their perdeuterated solvents. Nonradiative decay rates of the ions were in the order of H 2 O > MeOH > DMF > DMSO, indicating that O-H vibration is more effective quencher than C-H, C=O, and S=O vibrations in the solvent molecules. Maximal lifetime ratios τ D /τ H were observed for Eu(III) in H 2 O, for Sm(III) in MeOH and DMF, and for Sm(III) and Dy(III) in DMSO. The solvent composition in the first coordination sphere of Cm(III) and Ln(III) in binary mixed solvents was also studied by measuring the luminescence lifetime. Cm(III) and Ln(III) were preferentially solvated by DMSO in DMSO-H 2 O, by DMF in DMF-H 2 O, and by H 2 O in MeOH-H 2 O over the whole range of the solvent composition. The order of the preferential solvation, i.e., DMSO > DMF > H 2 O > MeOH, correlates with the relative basicity of these solvents. The Gibbs free energy of transfer of ions from water to nonaqueous solvents was further estimated from the degree of the preferential solvation. (orig.)

  6. Use of lanthanide catalysts in air electrodes

    International Nuclear Information System (INIS)

    Souza Parente, L.T. de

    1982-01-01

    A review on the lanthanide catalysts suitable for the reduction catalysis of oxygen in air electrodes is presented. The kinds of lanthanide indicated to be used as catalysts of oxygen reduction are shown. (A.R.H.) [pt

  7. Efficient Separation of Lanthanides Using Poly (Styrene-Divinyl Benzene) Aminated Anion Exchanger

    International Nuclear Information System (INIS)

    Borai, E.H.; Hassan, R.S.; El- Dessouky, M.I.; Ghonem, A.

    2008-01-01

    New chromatographic method was developed for the determination and separation of lanthanides using AS4A anionic column. The behavior of the column towards lanthanides was studied through many parameters, From the data obtained it is found that, affinity of the column toward investigated ions increase by increasing eluent concentration and it decrease retention factors. With the two investigated eluent (oxalic and citric acids), elution order for lanthanide elements was obtained in their atomic number from La to Lu. Retention times and retention orders obtained at these conditions clearly show that, lanthanides in AS4A are displaced according to anion exchange mechanism. More over separation of lanthanides using AS4A was studied using isocratic and gradient elution programs. Light and the first intermediate lanthanide elements were separated successfully by applying a gradient program containing 70% oxalic acid (100 mM) and 30% water. The problem of separation for heavy and the last intermediate lanthanide elements was solved using 100 mM alpha hydroxy isobutyric acid (α-HIBA)

  8. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry; Complexes aqueux de lanthanides (3) et actinides (3) avec les ions carbonate et sulfate. Etude thermodynamique par spectrofluorimetrie laser resolue en temps et spectrometrie de masse a ionisation electrospray

    Energy Technology Data Exchange (ETDEWEB)

    Vercouter, Th

    2005-03-15

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO{sub 3}){sub 3}{sup 3-}, is identified by solubility measurements in Na{sub 2}CO{sub 3} solutions. Then the formation constants of the complexes Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) and Eu(SO{sub 4}){sub i}{sup 3-2i} (i=1-2) are measured by TRLFS. The formation of aqueous LaSO{sub 4}{sup +} is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO{sub 3}){sub 2}{sup -} + CO{sub 3}{sup 2-} {r_reversible} Cm(CO{sub 3}){sub 3}{sup 3-} are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  9. Effect of lanthanide contraction on the mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien): Syntheses and characterizations of lanthanide complexes with a tetraelenidoantimonate ligand

    International Nuclear Information System (INIS)

    Zhao Jing; Liang Jingjing; Pan Yingli; Zhang Yong; Jia Dingxian

    2011-01-01

    Mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) (Ln=lanthanide, en=ethylenediamine, dien=diethylenetriamine, trien=triethylenetetramine) were investigated under solvothermal conditions, and novel mixed-coordinated lanthanide(III) complexes [Ln(en) 2 (dien)(η 2 -SbSe 4 )] (Ln=Ce(1a), Nd(1b)), [Ln(en) 2 (dien)(SbSe 4 )] (Ln=Sm(2a), Gd(2b), Dy(2c)), [Ln(en)(trien)(μ-η 1 ,η 2 -SbSe 4 )] ∞ (Ln=Ce(3a), Nd(3b)) and [Sm(en)(trien)(η 2 -SbSe 4 )] (4a) were prepared. Two structural types of lanthanide selenidoantimonates were obtained across the lanthanide series in both en+dien and en+trien systems. The tetrahedral anion [SbSe 4 ] 3- acts as a monodentate ligand mono-SbSe 4 , a bidentate chelating ligand η 2 -SbSe 4 or a tridentate bridging ligand μ-η 1 ,η 2 -SbSe 4 to the lanthanide(III) center depending on the Ln 3+ ions and the mixed ethylene polyamines, indicating the effect of lanthanide contraction on the structures of the lanthanide(III) selenidoantimonates. The lanthanide selenidoantimonates exhibit semiconducting properties with E g between 2.08 and 2.51 eV. - Graphical Abstract: Two structural types of lanthanide(III) selenidoantimonates are formed in both en-dien and en-trien mixed polyamines across lanthanide series, indicating the lanthanide contraction effect on the structures of the lanthanide(III) selenidoantimonates. Highlights: → Two structural types of lanthanide selenidoantimonates are prepared across the lanthanide series in both Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) systems. → The [SbSe 4 ] 3- anion acts as a mono-SbSe 4 , a η 2 -SbSe 4 or a μ-η 1 ,η 2 -SbSe 4 ligand to the Ln 3+ ions. → The soft base ligand [SbSe 4 ] 3- can be controlled to coordinate to the Ln 3+ ions with en+dien and en+trien as co-ligands.

  10. Lanthanides separation by counter - current electrophoretic using α - hydroxyisobutyric acid

    International Nuclear Information System (INIS)

    Alleluia, I.B.

    1975-01-01

    Studies about counter-current electrophoretic separation of rare earth metal ions using α-hydroxyisobutyric acid as complexing electrolyte are discussed. La, Pr, Nd, Sm and Eu were separated and fractions with purities better than 99,9% were obtained, using neutron activation analysis. A relation between the first stability constant of the α-hydroxyisobutyrate/lanthanide complexes and their migration velocities were observed. (M.J.C.) [pt

  11. Detection of Fluorescence for Lanthanides in LiCl-KCl Molten Salt Medium

    International Nuclear Information System (INIS)

    Im, Hee Jung; Kim, Tack Jin; Song, Kyu Seok; Jee, Kwang Yong

    2007-01-01

    In the electrorefining step of the pyrochemical process, actinide ions dissolved in the LiCl-KCl eutectic salt are recovered as pure actinide metals at a cathode for a re-use as a nuclear fuel from the aspect of its nonproliferation of the nuclear fuel cycles. The lanthanide species dissolved in the LiCl-KCl eutectic salt play an important role in an effective metal purification during the electrorefining step, so it is necessary to understand the chemical and physical behaviors of lanthanides in molten salt. The in situ spectroscopic measurement system and studies according to temperature changes are essential for better understandable information. To our knowledge, the absorption studies of lanthanides at high temperatures have been reported before, but the fluorescence studies of those at high temperature are not reported yet. We will discuss here the fluorescence behaviors of lanthanides in LiCl-KCl molten salt medium according to a changing temperature

  12. Spectrophotometric, potentiometric, and gravimetric determination of lanthanides with peri-dihydroxynaphthindenone

    International Nuclear Information System (INIS)

    Hassan, S.S.M.; Mahmoud, W.H.

    1982-01-01

    Sensitive and reasonably selective methods are described for the spectrophotometric, potentiometric, and gravimetric determination of lanthanides using peri-dihydroxynaphthindenone as a novel chromogenic and precipitating reagent. The reagent forms a stable 1:2 (metal:reagent) type of complex with light lanthanides at pH 2-7 in 1:1 ethanol-water mixture. Low metal concentrations ( 4 L mol -1 cm -1 ) which obey Beer's law. Quantitative precipitation of the complexes from metal solutions of concentrations > 100 μg/mL permits both gravimetric quantitation by igniting the precipitates to the metal oxides and potentiometric titration of the excess reagent. Results with an average recovery of 98% (standard deviation 0.7%) are obtainable for 0.1 μg to 200 mg of all light lanthanides. Many foreign ions naturally occurring or frequently associated with lanthanides do not interfere or can be tolerated

  13. The kinetics of lanthanide complexation by EDTA and DTPA in lactate media.

    Science.gov (United States)

    Nash, K L; Brigham, D; Shehee, T C; Martin, A

    2012-12-28

    The interaction of trivalent lanthanide and actinide cations with polyaminopolycarboxylic acid complexing agents in lactic acid buffer systems is an important feature of the chemistry of the TALSPEAK process for the separation of trivalent actinides from lanthanides. To improve understanding of metal ion coordination chemistry in this process, the results of an investigation of the kinetics of lanthanide complexation by ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) and diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) in 0.3 M lactic acid/0.3 M ionic strength solution are reported. Progress of the reaction was monitored using the distinctive visible spectral changes attendant to lanthanide complexation by the colorimetric indicator ligand Arsenazo III, which enables the experiment but plays no mechanistic role. Under the conditions of these experiments, the reactions occur in a time regime suitable for study by stopped-flow spectrophotometric techniques. Experiments have been conducted as a function of EDTA/DTPA ligand concentration, total lactic acid concentration, and pH. The equilibrium perturbation reaction proceeds as a first order approach to equilibrium over a wide range of conditions, allowing the simultaneous determination of complex formation and dissociation rate constants. The rate of the complexation reaction has been determined for the entire lanthanide series (except Pm(3+)). The predominant pathway for lanthanide-EDTA and lanthanide-DTPA dissociation is inversely dependent on the total lactate concentration; the complex formation reaction demonstrates a direct dependence on [H(+)]. Unexpectedly, the rate of the complex formation reaction is seen in both ligand systems to be fastest for Gd(3+). Correlation of these results indicates that in 0.3 M lactate solutions the exchange of lanthanide ions between lactate complexes and the polyaminopolycarboxylate govern the process.

  14. N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Wulin [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Zheng Jun [Center of Modern Experimental Technology, Anhui University, Hefei 230039 (China); Yu Huiyou [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Wang Jianguo, E-mail: jgw@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China)

    2012-08-15

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 3} (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Sign 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.

  15. Doping Lanthanide into Perovskite Nanocrystals: Highly Improved and Expanded Optical Properties.

    Science.gov (United States)

    Pan, Gencai; Bai, Xue; Yang, Dongwen; Chen, Xu; Jing, Pengtao; Qu, Songnan; Zhang, Lijun; Zhou, Donglei; Zhu, Jinyang; Xu, Wen; Dong, Biao; Song, Hongwei

    2017-12-13

    Cesium lead halide (CsPbX 3 ) perovskite nanocrystals (NCs) have demonstrated extremely excellent optical properties and great application potentials in various optoelectronic devices. However, because of the anion exchange, it is difficult to achieve white-light and multicolor emission for practical applications. Herein, we present the successful doping of various lanthanide ions (Ce 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Er 3+ , and Yb 3+ ) into the lattices of CsPbCl 3 perovskite NCs through a modified hot-injection method. For the lanthanide ions doped perovskite NCs, high photoluminescence quantum yield (QY) and stable and widely tunable multicolor emissions spanning from visible to near-infrared (NIR) regions are successfully obtained. This work indicates that the doped perovskite NCs will inherit most of the unique optical properties of lanthanide ions and deliver them to the perovskite NC host, thus endowing the family of perovskite materials with excellent optical, electric, or magnetic properties.

  16. Transport behaviour of the lanthanide 152Eu(III), 153Gd(III) and 170Tm(III) and transplutonium element 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III) ions in aqueous solutions at 298 K

    International Nuclear Information System (INIS)

    Ouerfelli, N.

    2014-01-01

    Ionic self-diffusion coefficients (D) for trivalent radiotracers, lanthanide and actinide ions have been determined in concentrated aqueous solutions of supporting electrolytes of Gd(NO 3 ) 3 -HNO 3 or Nd(ClO 3 ) 4 -HClO 4 up to 1.5 mol L -1 at 298.15 K and pH 2.50 by the open-end capillary method. The data obtained in large range of concentrations, allow to derive the limiting value D deg, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. An empirical equation is suggested for predicting ionic hydration number with a good precision. (author)

  17. Biological toxicity of lanthanide elements on algae.

    Science.gov (United States)

    Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

    2010-08-01

    The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  18. Rapid separation of lanthanides and actinides on small particle based reverse phase supports

    Energy Technology Data Exchange (ETDEWEB)

    Datta, A.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R. [Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India)

    2010-07-01

    This paper presents the results on the use of short columns (3-5 cm long) with small particle size (1.8 {mu}m) for high performance liquid chromatographic separation of individual lanthanides and uranium from plutonium as well as uranium from thorium to achieve rapid separations i.e. separation time as short as 3.6 min for individual lanthanides, 1 min for thorium-uranium and 4.2 min for uranium from plutonium. These advantages can be exploited to significantly reduce analysis time, liquid waste generation as well as dose to operator when radioactive samples are analysed e.g. burn-up determination. In the present work, a dynamic ion-exchange chromatographic separation technique was employed using camphor-10-sulfonic acid (CSA) as the ion-pairing reagent and {alpha}-hydroxy isobutyric acid ({alpha}-HIBA) as the complexing reagent for the isolation of individual lanthanides as well as the separation of uranium from thorium. Uranium was separated from Pu(III) as well as Pu(IV) by reverse phase HPLC technique. The reverse phase HPLC was also investigated for the isolation and quantitative determination of uranium from thorium as well as lanthanide group from uranium. The dynamic ion-exchange technique using small particle support was demonstrated for measuring the concentrations of lanthanide fission products such as La, Ce, Pr, Nd and Sm in the dissolver solution of fast reactor fuel. Similarly, the assay of uranium in the dissolver solution of fast reactor was carried out using reverse phase HPLC technique. The rapid separation technique using reverse phase HPLC was also demonstrated for separation of lanthanides as a group from uranium matrix; samples of LiCl-KCl eutectic salt containing chlorides of lanthanides in uranium matrix (typically 1: 2000) were analysed. (orig.)

  19. Method of growing yttrium aluminate and/or lanthanide single crystals with perovskite structure

    International Nuclear Information System (INIS)

    Kvapil, Jiri; Perner, B.; Kvapil, Josef; Blazek, K.

    1989-01-01

    Single crystals of yttrium aluminate and/or lanthanide with perovskite structure are grown from melt in a vacuum at a pressure of gas residues of max. 0.01 Pa. The melt contains 1±0.05 gram-ions of aluminium per gram-ion of yttrium and/or lanthanides. The single crystals are then heated in a vacuum (0.01 Pa) at temperatures of 1,450 to 1,800 degC for 2 to 3 hours. (B.S.)

  20. Biosorption of lanthanides using three kinds of seaweed biomasses

    International Nuclear Information System (INIS)

    Sakamoto, Nobuo; Wang, Yudan; Gao, Lidi; Kano, Naoki; Imaizumi, Hiroshi

    2010-01-01

    In order to evaluate the efficiency of seaweed biomass as sorbent for rare earth elements (REEs), sorption experiment from aqueous solutions containing known amount of lanthanide (La, Eu or Yb) using three kinds of Ca-loaded dried seaweeds (brown algae: Sargassum hemiphyllum, green algae: Ulva pertusa and red algae: Schizymenia dubyi) in single component system was explored. Furthermore, the sorption mechanism of these elements was investigated by applying Langmuir and Freundlich isotherm equations to the data obtained. In addition, to confirm the characteristics of the seaweed biomasses, the surface morphology of the biomass before and after metal adsorption was determined by Scanning Electron Microscope (SEM). Consequently, the following matters have been mainly clarified. (1) The morphology of Sargassum hemiphyllum and Ulva pertusa surface has hardly changed even after exposing to metals. On the other hand, the change of the surface condition on Schizymenia dubyi after adsorption was observed. (2) Adsorption isotherms using the seaweed biomass can be described by Langmuir and Freundlich isotherms satisfactorily for lanthanide. These adsorption may have occurred mainly by monolayer reaction because of better-fitting for Langmuir model. (3) The seaweed biomasses could be an efficient sorbent for REEs. Particularly, Ulva pertusa is found to be a promising biosorbent for removing La. (4) Ion-exchange process is considered to be the main mechanism responsible for the sorption of lanthanide ion onto the seaweed biomass. (author)

  1. Fluorescence Spectra Studies on the Interaction between Lanthanides and Calmodulin

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The conformation of Calmodulin(CaM) induced by lanthanides has been examined using fluorescence methods.With the addition of lanthanide (Ln3+), the intrinsic fluorescence intensity of CaM without calcium ions (Apo-CaM) first increases and then decreases.Ln3+ causes the decrease of intrinsic fluorescence intensity of calcium saturated CaM (Ca2+4-CaM) only at high concentrations.At low concentrations, Ln3+ results not only in the enhancement of fluorescence intensity of Apo-CaM, but also in a blue shift of the maximum emission wavelengh of dansyl labeled calmodulin(Apo-D-CaM).The molecular mechanism of the interaction between Ln3+ and CaM has been discussed in the light of the fluorescence spectra.

  2. Advancing the scientific basis of trivalent actinide-lanthanide separations

    International Nuclear Information System (INIS)

    Nash, K.L.

    2013-01-01

    For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl - ). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

  3. Citrate-based open-quotes Talspeakclose quotes actinide-lanthanide separation process

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Toth, L.M.; Bond, W.D.

    1997-01-01

    Lanthanide elements are produced in relatively high yield by fission of 235 U. Almost all the lanthanide isotopes decay to stable nonradioactive lanthanide isotopes in a relatively short time. Consequently, it is highly advantageous to separate the relatively small actinide fraction from the relatively large quantities of lanthanide isotopes. The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. Previous work based on the use of lactic or glycolic acid has shown deleterious effects of some impurity ions such as zirconium(IV), even at concentrations on the order of 10 -4 M. Other perceived problems were the need to maintain the pH and reagent concentrations within a narrow range and a significant solubility of the organic phase at high carboxylic acid concentrations. The authors' cold experiments showed that replacing the traditional extractants glycolic or lactic acid with citric acid eliminates or greatly reduces the deleterious effects produced by impurities such as zirconium. An extensive series of batch tests was done using a wide range of reagent concentrations at different pH values, temperatures, and contact times. The results demonstrated that the citrate-based TALSPEAK can tolerate appreciable changes in pH and reagent concentrations while maintaining an adequate lanthanide extraction. Experiments using a three-stage glass mixer-settler showed a good lanthanide extraction, appropriate phase disengagement, no appreciable deleterious effects due to the presence of impurities such as zirconium, excellent pH buffering, and no significant loss of organic phase

  4. The best and the brightest: exploiting tryptophan-sensitized Tb(3+) luminescence to engineer lanthanide-binding tags.

    Science.gov (United States)

    Martin, Langdon J; Imperiali, Barbara

    2015-01-01

    Consider the lanthanide metals, comprising lanthanum through lutetium. Lanthanides form stable cations with a +3 charge, and these ions exhibit a variety of useful physical properties (long-lifetime luminescence, paramagnetism, anomalous X-ray scattering) that are amenable to studies of biomolecules. The absence of lanthanide ions in living systems means that background signals are generally a nonissue; however, to exploit the advantageous properties it is necessary to engineer a robust lanthanide-binding sequence that can be appended to any macromolecules of interest. To this end, the luminescence produced by tryptophan-sensitized Tb(3+) has been used as a selection marker for peptide sequences that avidly chelate these ions. A combinatorial split-and-pool library that uses two orthogonal linkers-one that is cleaved for selection and one that is cleaved for sequencing and characterization-has been used to develop lanthanide-binding tags (LBTs): peptides of 15-20 amino acids with low-nM affinity for Tb(3+). Further validating the success of this screen, knowledge about LBTs has enabled the introduction of a lanthanide-binding loop in place of one of the four native calcium-binding loops within the protein calcineurin B.

  5. Electronic structure of lanthanide scandates

    Science.gov (United States)

    Mizzi, Christopher A.; Koirala, Pratik; Marks, Laurence D.

    2018-02-01

    X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdSc O3,TbSc O3 , and DySc O3 . X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA +U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA +U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln 4 f ,O 2 p , and Sc 3 d states, in agreement with previous work. However, contrary to previous work the minority Ln 4 f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln 4 f electrons may play a larger role in lanthanide scandate properties than previously thought.

  6. 2. Intermetallic compounds with lanthanides

    International Nuclear Information System (INIS)

    Elemans, J.B.A.A.

    1975-01-01

    Theoretical considerations are given concerning the structures of intermetallic compounds of the lanthanides and thorium (R) on the one hand, and with Fe, Co or Ni (M) on the other. They all derive from the parent composition RM 5 with the CaCu 5 hexagonal structure. This consists of alternate layers in which the M atoms are distinguished as M 1 and M 2 . The other compounds whose structures are studied are obtained by systematic replacement of R by M, or vice versa. In the first type, every third R is replaced by two M's yielding R 2 M 17 compounds. The substitution may be truly random or structured in two ways: so that either the hexagonal structure is maintained or that it is converted into a rhombihedral one. In the second type, one M (in a M 1 position) out of every five is replaced by one R, giving rise to RM 2 compounds which form Laves phases. In the third type, the M 1 's are replaced by R's, resulting in compounds RM 3 . In the fourth type, every third M is replaced by R, yielding R 2 M 7 compounds. With M = Co and R a light lanthanide, the compounds are ferromagnets; with R yttrium, thorium, or a heavy lanthanide, they are ferrimagnets. The preparation of the compounds in an arc-melting apparatus under an Ar-atmosphere followed by annealing is described

  7. The commercial production of compounds of the lanthanides and yttrium as CRT phosphor precursors

    International Nuclear Information System (INIS)

    Kilbourn, B.T.

    1987-01-01

    The consumer acceptance of color television at the start of the 60's was triggered by the phosphor industry's discovery and production of a satisfactory red phosphor using the element europium. This element, in the middle of the lanthanide series, had until that time been an academic curiosity, prepared only in gram quantities for research. The large-scale production by the lanthanide industry, in order to meet the demand for commercial quantities of high purity europium oxide, required the introduction of new technology. Lanthanide elements other than europium, such as cerium and terbium, are also needed as the active ions for many phosphors. In addition, the inert host lattice for those emitting ions can be provided by compounds of yttrium, the element above the lanthanides in the periodic table, with comparable properties. The lanthanide industry has developed processes to produce compounds of such elements in the required quantities and purities. For commercial separation of these elements a technology known as counter-current liquid-liquid extraction has been developed. This technique, commonly called solvent extraction, is illustrated and described. The initial ore preparation steps, together with the final high purity oxide production is also mentioned

  8. Lanthanide and actinide separation studies using liquid chromatography

    International Nuclear Information System (INIS)

    Datta, Arpita; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2011-01-01

    Gradient elution procedure for isolation of individual lanthanides was studied extensively at our laboratory using monolith support. A large number of gradients were developed by varying the concentrations of CSA, α-HIBA, mobile phase pH and mobile phase flow rate. In a typical gradient run, the concentration of CSA and mobile phase flow rate were kept constant and only α-HIBA concentration was varied. Based on these studies, a binary gradient elution method was developed for the rapid separation of lanthanides, from La to Lu in about 2.8 min, with a mobile phase CSA, α-HIBA and pH being 0.03M, 0.05 to 0.15M and 3.4-3.8 respectively. The direct injection of dissolver solution from FBTR spent fuel into HPLC was investigated and the results are shown. The lanthanides present in dissolver solution were mutually separated as well as resolved from uranium and plutonium under dynamic ion exchange conditions using the monolithic column. The concentration of La, Ce, Pr, Nd and Sm were determined in the dissolver solution using a calibration plot

  9. Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

  10. Synthesis and characterization of metal soaps of lanthanides (III)

    International Nuclear Information System (INIS)

    Payolla, Filipe Boccato; Ribeiro, Sidney Jose Lima; Massbni, Antonio Carlos

    2015-01-01

    The present study describes synthesis and partial characterization of Eu"3"+, Nd"3"+, Dy"3"+, Tb"3"+ and Yb"3"+ behenate complexes. The compounds were analyzed using IR-Spectroscopy, TG-DTG, DSC, elemental analysis, XRD, luminescence and SEM. The results show the purity of the compounds. The XRD analysis and the SEM images show the high crystallinity of the complexes. TG-DTG and DSC analyses do not show a liquid crystal behavior, as occurs with other lanthanide metallic soaps. The mass loses until 1000° C show that the compounds lose ligand fragments at specific temperatures. XRD of the residues are compatible with the respective lanthanide oxides. The luminescence analysis shows that the Eu"3"+, Nd"3"+ and Tb"3"+ complexes presents appreciable emission. The Judd-Ofelt parameters obtained are compatible with the values found in the literature. It was not possible to obtain the complexes in a glass-form because it is difficult to prevent the crystallization of the complexes even using liquid nitrogen. The XDR data indicate that one of the complexes axis has 52 Å of length, agreeing with a structure containing behenate-lanthanide ion-behenate. The structures of the complexes were not fully elucidated and more analyses are necessary. The complexes presented a molar ratio of 3:1 (L:M) and were formulated as Bh_3Eu, Bh_3Nd, Bh_3Dy, Bh_3Tb e Bh_3Yb (Bh = behenate anion). (author)

  11. Behaviour of trivalent actinides and lanthanide elements in chloride solution; Comportement des lanthanides et transuraniens trivalents en milieu chlorhydrique

    Energy Technology Data Exchange (ETDEWEB)

    Marin, B [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1969-07-01

    The aim of this work is to compare the complexation in chloride solutions of trivalent lanthanides and actinides. We have first studied the solvatation of these cations without complexation. We found a difference between Am, Cm and Rare Earths (we can separate lanthanides into Light and Heavy Rare Earths). For studying the complexation we choose the technic of electrophoresis on paper after establishing a simple theory of mobilities in complex solutions. The hydrolysis of these cations was studied and compared in chloride solutions. We have then studied the complexation with the Cl{sup -} ligand in some solutions: HCl, NH{sub 4}Cl, CaCl{sub 2}, CeCl{sub 3}, LiCl. We have established that the complexation is the same in dilute HCl solutions but in concentrated solutions the trivalent actinides are more complexed. This difference is sharper in LiCl solutions. We also proposed the different models of complex in these solutions. (author) [French] Le but de ce travail est de comparer les transuraniens et lanthanides trivalents au point de vue de leur complexation en solution chlorhydrique. Nous avons ete amenes tout d'abord a etudier la solvatation de ces cations non complexes. C'est ainsi que nous pouvons constater une difference entre Am, Cm et les lanthanides. Ces derniers pouvant se separer en lanthanides legers et lanthanides lourds. Pour etudier la complexation nous avons utilise l'electrophorese sur papier apres avoir donne une theorie simple des mobilites en milieu complexant. Apres avoir etudie et compare l'hydrolyse de ces divers cations en solution chlorhydrique, nous avons etudie leur complexation avec l'ion Cl{sup -} dans dans divers milieux: HCl, NH{sub 4}Cl, CaCl{sub 2}, CeCl{sub 3}, LiCl. ous avons note qu'en solution HCl les deux series se comportent de la meme facon pour des concentrations faibles en Cl{sup -} mais que les transuraniens se complexent plus fortement dans les solutions concentrees. Cette difference s'accroit encore dans les milieux

  12. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    International Nuclear Information System (INIS)

    Billard, I.; Luetzenkirchen, K.

    2003-01-01

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  13. Lanthanides, thorium, iodine in terrestrail invertebrates

    International Nuclear Information System (INIS)

    Zhulidov, A.V.; Pokarzhevskij, A.D.; Katargin, N.V.; AN SSSR, Moscow

    1991-01-01

    It is shown that among examined terrestrial invertebrates the highest levels on lanthanide and thorium concentration are typical for animals, feeding on plant tissues - earthworms, molluscs, diploid. It is shown that there are no reasons to hope, that regularities of migration of transuranium elements and lanthanides in tropic chains are identical

  14. Scandium, yttrium and the lanthanide metals

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    The hydroxide and oxide phases that exist for scandium(III) include scandium hydroxide, which likely has both amorphous and crystalline forms, ScOOH(s), and scandium oxide. This chapter presents the data selected for the stability constants of the polymeric hydrolysis species of scandium at zero ionic strength. The behaviour of yttrium, and the lanthanide metals, in the environment is largely dependent on their solution equilibria. Hydrolysis and other complexation reactions of yttrium and the lanthanide metals are important in the disposal of nuclear waste. The trivalent lanthanide metals include lanthanum(III) through lutetium(III). A number of studies have reported a tetrad effect for the geochemical behaviour of the lanthanide series, including stability constants and distribution coefficients. The solubility of many of the lanthanide hydroxide phases has been studied at fixed ionic strength. In studying the hydrolysis of cerium(IV), a number of studies have utilised oxidation-reduction reactions in determining the relevant stability constants.

  15. Observation of divergent La3+ ion dilute effect in two series of 3-D fluorescent lanthanide-MOFs-based molecular alloys RExLa1−x–EBTC (RE3+=Eu3+ or Tb3+; EBTC4−=1,1′-ethynebenzene-3,3′,5,5′-etracarboxylate)

    International Nuclear Information System (INIS)

    Zhai, Lu; Zhang, Wen-Wei; Ren, Xiao-Ming; Zuo, Jing-Lin

    2015-01-01

    The lanthanide metal-organic frameworks (MOFs) [Ln 2 (EBTC) 1.5 (CH 3 OH) 4 ]·6H 2 O are isostructural to each other, where EBTC 4− =1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate; Ln 3+ =La 3+ , Eu 3+ and Tb 3+ ; and the corresponding MOF is abbreviated as Ln–EBTC. MOFs Eu–EBTC and Tb–EBTC emit intense red and green luminescence (visible by bare eyes), respectively. The molecular alloys of Eu x La 1−x –EBTC and Tb x La 1−x –EBTC have been successfully prepared by mixing Eu 3+ /Tb 3+ and La 3+ salts with the desired molar ratio in the starting material. Two series of Eu x La 1−x –EBTC and Tb x La 1−x –EBTC molecular alloys are isomorphic to the parent Ln–EBTC MOFs, while exhibit divergent La 3+ ion diluting effect, namely, with increasing the relative amount of La 3+ , the intensity of characteristic emission arising from Tb 3+ ion monotonely increases in Tb x La 1−x –EBTC molecular alloys, whereas that of Eu 3+ ion shows non-monotone decrease in Eu x La 1−x –EBTC molecular alloys. The possible origin is discussed for such a divergent behavior between Eu x La 1−x –EBTC and Tb x La 1−x –EBTC molecular alloys. - Graphical abstract: Two series of 3-D fluorescent lanthanide-MOFs-based molecular alloys RE x La 1−x –EBTC (RE 3+ =Eu 3+ or Tb 3+ ; EBTC 4− =1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate) have been successfully prepared by mixing Eu 3+ /Tb 3+ and La 3+ salts with the desired molar ratio in the starting material and showed photoluminescence property with divergent La 3+ ion dilute effect. - Highlights: • 3-D molecular alloys of Eu x La 1−x –EBTC and Tb x La 1−x –EBTC were prepared. • They are isomorphic to the parent Ln–EBTC MOFs. • They show photoluminescence property with divergent La 3+ ion diluting effect. • The possible origin is discussed for such a divergent behavior

  16. Far-infrared spectroscopy of lanthanide-based molecular magnetic materials

    Energy Technology Data Exchange (ETDEWEB)

    Haas, Sabrina

    2015-05-13

    This thesis demonstrates the applicability of far-infrared spectroscopy for the study of the crystal-field splitting of lanthanides in single-molecular magnetic materials. The far-infrared studies of three different kinds of single-molecular-magnetic materials, a single-ion magnet, a single-chain magnet and an exchange-coupled cluster, yielded a deeper understanding of the crystal-field splitting of the lanthanides in these materials. In addition, our results offered the opportunity to gain a deeper insight into the relaxation processes of these materials.

  17. Comparison of the thermodynamic properties and high temperature chemical behavior of lanthanide and actinide oxides

    International Nuclear Information System (INIS)

    Ackermann, R.J.; Rauh, E.G.

    1977-01-01

    The thermodynamic properties of the lanthanide and actinide oxides are examined, compared, and associated with a variety of high temperature chemical behavior. Trends are cited resulting from a number of thermodynamic and spectroscopic correlations involving solid phases, species in aqueous solution, and molecules and ions in the vapor phase. Inadequacies in the data and alternative approaches are discussed. The characterization of nonstoichiometric phases stable only at high temperatures is related to a network of heterogeneous and homogeneous equilibria. A broad perspective of similarity and dissimilarity between the lanthanides and actinides emerges and forms the basis of the projected needs for further study

  18. Two-point anchoring of a lanthanide-binding peptide to a target protein enhances the paramagnetic anisotropic effect

    International Nuclear Information System (INIS)

    Saio, Tomohide; Ogura, Kenji; Yokochi, Masashi; Kobashigawa, Yoshihiro; Inagaki, Fuyuhiko

    2009-01-01

    Paramagnetic lanthanide ions fixed in a protein frame induce several paramagnetic effects such as pseudo-contact shifts and residual dipolar couplings. These effects provide long-range distance and angular information for proteins and, therefore, are valuable in protein structural analysis. However, until recently this approach had been restricted to metal-binding proteins, but now it has become applicable to non-metalloproteins through the use of a lanthanide-binding tag. Here we report a lanthanide-binding peptide tag anchored via two points to the target proteins. Compared to conventional single-point attached tags, the two-point linked tag provides two to threefold stronger anisotropic effects. Though there is slight residual mobility of the lanthanide-binding tag, the present tag provides a higher anisotropic paramagnetic effect

  19. Introduction to molecular magnetism from transition metals to lanthanides

    CERN Document Server

    Benelli, Cristiano

    2015-01-01

    This first introduction to the rapidly growing field of molecular magnetism is written with Masters and PhD students in mind, while postdocs and other newcomers will also find it an extremely useful guide. Adopting a clear didactic approach, the authors cover the fundamental concepts, providing many examples and give an overview of the most important techniques and key applications. Although the focus is one lanthanide ions, thus reflecting the current research in the field, the principles and the methods equally apply to other systems. The result is an excellent textbook from both a scientif

  20. New strategies for the chemical separation of actinides and lanthanides

    International Nuclear Information System (INIS)

    Hudson, M.J.; Iveson, P.B.

    2002-01-01

    A general model is proposed for the effective design of ligands for partitioning. There is no doubt that the correct design of a molecule is required for the effective separation by separation of metal ions such as lanthanides(III) and actinides(III). Heterocyclic ligands with aromatic rings systems have a rich chemistry, which is only now becoming sufficiently well understood, in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with metal ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazol-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. Primary Coordination Sphere. One of the most critical features concerning whether a molecule is a suitable extraction reagent is the nature of the binding and co-ordination in the primary co-ordination sphere. This effect will be considered in depth for the selected heterocylic molecules. It will be shown how the bonding of the heterocyclic and nitrate ligands changes as the complete lanthanide series is traversed from lanthanum to lutetium. For effective solvent extraction, the ligand(s) should be able completely to occupy the primary co-ordination sphere of the metal ion to be extracted. Interactions in the secondary co-ordination sphere are of less importance. Inter-complex Hydrogen Bonding Interactions. Another feature that will be considered is the intermolecular binding between ligands when bound to the metal ion. Thus the intermolecular structures between complex molecules will be considered

  1. Lanthanide-doped luminescent ionogels

    OpenAIRE

    Lunstroot, Kyra; Driesen, Kris; Nockemann, Peter; Van Hecke, Kristof; Van Meervelt, Luc; Görller-Walrand, Christiane; Binnemans, Koen; Bellayer, Séverine; Viau, Lydie; Le Bideau, Jean; Vioux, André

    2009-01-01

    Ionogels are solid oxide host networks confining at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving anthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C6mim][Ln(tta)4], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choli...

  2. DFTB{sup +} and lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Hourahine, B [Department of Physics, SUPA, University of Strathclyde, John Anderson Building, 107 Rottenrow, Glasgow G4 0NG (United Kingdom); Aradi, B; Frauenheim, T, E-mail: benjamin.hourahine@strath.ac.u [BCCMS, Universitaet Bremen, Am Fallturm 1, 28359 Bremen (Germany)

    2010-07-01

    DFTB{sup +} is a recent general purpose implementation of density-functional based tight binding. One of the early motivators to develop this code was to investigate lanthanide impurities in nitride semiconductors, leading to a series of successful studies into structure and electrical properties of these systems. Here we describe our general framework to treat the physical effects needed for these problematic impurities within a tight-binding formalism, additionally discussing forces and stresses in DFTB. We also present an approach to evaluate the general case of Slater-Koster transforms and all of their derivatives in Cartesian coordinates. These developments are illustrated by simulating isolated Gd impurities in GaN.

  3. Lanthanide-IMAC enrichment of carbohydrates and polyols.

    Science.gov (United States)

    Schemeth, Dieter; Rainer, Matthias; Messner, Christoph B; Rode, Bernd M; Bonn, Günther K

    2014-03-01

    In this study a new type of immobilized metal ion affinity chromatography resin for the enrichment of carbohydrates and polyols was synthesized by radical polymerization reaction of vinyl phosphonic acid and 1,4-butandiole dimethacrylate using azo-bis-isobutyronitrile as radical initiator. Interaction between the chelated trivalent lanthanide ions and negatively charged hydroxyl groups of carbohydrates and polyols was observed by applying high pH values. The new method was evaluated by single standard solutions, mixtures of standards, honey and a more complex extract of Cynara scolymus. The washing step was accomplished by acetonitrile in excess volumes. Elution of enriched carbohydrates was successfully performed with deionized water. The subsequent analysis was carried out with matrix-free laser desorption/ionization-time of flight mass spectrometry involving a TiO2 -coated steel target, especially suitable for the measurement of low-molecular-weight substances. Quantitative analysis of the sugar alcohol xylitol as well as the determination of the maximal loading capacity was performed by gas chromatography in conjunction with mass spectrometric detection after chemical derivatization. In a parallel approach quantum mechanical geometry optimizations were performed in order to compare the coordination behavior of various trivalent lanthanide ions. Copyright © 2013 John Wiley & Sons, Ltd.

  4. NMR-based Enantiodifferentiation of Chiral trans-2-Phenylcyclopropane Derivatives Using a Chiral Lanthanide Shift Reagent

    International Nuclear Information System (INIS)

    Cho, Nam Sook; Kim, Hyun Sook; Song, Mi Sook

    2011-01-01

    In contrast with optical methods, there is no need to characterize the pure enantiomers. Instead, the NMR method makes use of chiral reagents that convert a mixture of enantiomers into a mixture of diastereomeric complexes. Integration of the resulting NMR spectra yields a direct measurement of enantiomeric purity as long as there is a sufficiently large difference between the chemical shifts of the two diastereoisomeric complexes to produce baseline-resolved peaks. Absolute enantiomeric configurations can also be determined using this method. Chiral lanthanide shift reagents have been used since the 1970s to form addition complexes with various compounds through interactions with electron donor sites. Lanthanide-induced, pseudo-contact shifts (LIS) are a function of the distance, r, between the nuclei under observation and the lanthanide center, and the angle, θ, between the line connecting the metal ion with the observed nucleus and the line representing the CLSR magnetic axis

  5. Synthesis and luminescent properties of PEO/lanthanide oxide nanoparticle hybrid films

    International Nuclear Information System (INIS)

    Goubard, F.; Vidal, F.; Bazzi, R.; Tillement, O.; Chevrot, C.; Teyssie, D.

    2007-01-01

    In this study, we investigate the optical properties of lanthanide oxide nanoparticles dispersed in poly(ethylene oxide) (PEO) network as thermally stable polymeric films. The aim of this work is both to keep a good optical transparency in the visible domain and to obtain luminescent materials after incorporation of nanoparticles. For this purpose, we develop luminescent nanocrystals of oxides containing terbium ion as a doping element in Gd 2 O 3 . These sub-5-nm lanthanide oxides nanoparticles have been prepared by direct oxide precipitation in high-boiling polyalcohol solutions and characterized by luminescence spectroscopy. PEO/lanthanide oxide nanohybrid films are prepared by radical polymerization of poly(ethylene glycol) methacrylate after introduction of lanthanide oxide particles. As a first result; the obtained films present interesting luminescence properties with a very low lanthanide oxide content (up to 0.29 wt%). Furthermore, these films are still transparent and keep their original mechanical properties. Prior to describe the specific applications to optical use, we report here the dynamic mechanical analysis (DMA), X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), and luminescent properties of. nanohybrid films

  6. Synthesis and luminescent properties of PEO/lanthanide oxide nanoparticle hybrid films

    Energy Technology Data Exchange (ETDEWEB)

    Goubard, F. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France)]. E-mail: fabrice.goubard@u-cergy.fr; Vidal, F. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France); Bazzi, R. [LPCML, Universite Lyon 1, 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne (France); Tillement, O. [LPCML, Universite Lyon 1, 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne (France); Nano-H, 23 rue Royal, 69001 Lyon (France); Chevrot, C. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France); Teyssie, D. [LPPI, Universite de Cergy-Pontoise, 5 Mail Gay-Lussac, Neuville-sur-Oise, 95031 Cergy-Pontoise cedex (France)

    2007-10-15

    In this study, we investigate the optical properties of lanthanide oxide nanoparticles dispersed in poly(ethylene oxide) (PEO) network as thermally stable polymeric films. The aim of this work is both to keep a good optical transparency in the visible domain and to obtain luminescent materials after incorporation of nanoparticles. For this purpose, we develop luminescent nanocrystals of oxides containing terbium ion as a doping element in Gd{sub 2}O{sub 3}. These sub-5-nm lanthanide oxides nanoparticles have been prepared by direct oxide precipitation in high-boiling polyalcohol solutions and characterized by luminescence spectroscopy. PEO/lanthanide oxide nanohybrid films are prepared by radical polymerization of poly(ethylene glycol) methacrylate after introduction of lanthanide oxide particles. As a first result; the obtained films present interesting luminescence properties with a very low lanthanide oxide content (up to 0.29 wt%). Furthermore, these films are still transparent and keep their original mechanical properties. Prior to describe the specific applications to optical use, we report here the dynamic mechanical analysis (DMA), X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), and luminescent properties of. nanohybrid films.

  7. Synthesis and luminescent spectroscopy of lanthanide complexes with dimethylpyridine-2,6-dicarboxylate (dmpc)

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M.; Hijazi, Ahmed K. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Al-Rawashdeh, Nathir A. [Department of Applied Chemical Sciences, Faculty of Arts and Sciences, Jordan University of Science and Technology, Irbid 22110 (Jordan); Department of Chemistry, United Arab Emirates University, Al Ain 15551 (United Arab Emirates); Al-Hassan, Khader A.; Al-Haj, Yaser A. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan); Ebqa' ai, Mohammad A. [Al-Qunfudah Center For Scientific Research, Umm Al-Qura University, College in Al-Qunfudah, Makkah (Saudi Arabia); Altalafha, Ammar Y. [Department of Chemistry, Faculty of Science, Yarmouk University, 1163 Irbid (Jordan)

    2015-05-15

    A series of lanthanide complexes with the general formulae [Ln(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) and [La(dmpc)(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}]NO{sub 3} were prepared by direct reaction between hydrated lanthanide(III) nitrate and dimethylpyridine-2,6-dicarboxylate (dmpc) in a 1:1 M ratio in ethylacetate–chloroform mixture. The luminescence properties of the dmpc and its Ln(III) complexes were investigated in solid state and in methanol, DMF and DMSO solutions. The Tb–dmpc, Eu–dmpc, Sm–dmpc and Dy–dmpc complexes exhibit characteristic luminescence of Tb(III), Eu(III), Sm(III) and Dy(III) ions indicating energy transfer from the dmpc to the Ln(III) ions. Scavenging activities of the dmpc and its Ln(III) complexes on DPPH{sup •} free radical were investigated in DMSO solution at a different concentrations ranges. - Highlights: • Nine new lanthanide complexes with dmpc ligand are prepared and characterized. • Ln–dmpc {Ln=Eu, Tb, Sm, Dy} complexes exhibit characteristic emissions of Ln ions. • The solvent effect on the luminescence intensity is investigated. • The antioxidant activity of the dmpc is enhanced upon complexation with lanthanide.

  8. KCeSe[sub 4]: A new solid-state lanthanide polychalcogenide

    Energy Technology Data Exchange (ETDEWEB)

    Sutorik, A C; Kanatzidis, M G [Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry and Center for Fundamental Materials Research

    1992-12-01

    Cerium and molten potassium selenide flux provide access to KCeSe[sub 4]. The structure of this novel lanthanide polychalcogenide is related to the CuAl[sub 2] structure, and Ce and Se form anionic layers with K[sup +] ions in the cavities. Each Ce[sup 3+] ion is surrounded by eight Se[sub 2][sup 2-] units in a square antiprismatic arrangement (structure shown on the right). (orig.).

  9. COMPLEXES POLYMETALLIQUES DE LANTHANIDES (III) POUR LE DEVELOPPEMENT DE NOUVEAUX MATERIAUX LUMINESCENTS

    OpenAIRE

    Marchal , Claire

    2008-01-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecularchemistry and allows the combination of their nanoscopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecu...

  10. Studies on the Interaction of a Novel 6,6''-bis(1,2,4-triazin-3-yl)- 2,2':6',2''-terpyridine Ligand with Lanthanide(III) Ions and Americium(III)

    International Nuclear Information System (INIS)

    Lewis, Frank W.; Harwood, Laurence M.; Hudson, Michael J.; Drew, Michael G.B.; Modolo, Giuseppe; Sypula, Michal; Desreux, Jean F.; Bouslimani, Nouri; Vidick, Geoffrey

    2010-01-01

    The new solvent extraction reagent 6,6''-bis(5,5,8,8-tetramethyl- 5,6,7,8-tetrahydro-1,2,4-benzo-triazin-3-yl)-2,2':6',2''-terpyridine (CyMe 4 -BTTP) has been synthesized in 4 steps from 2,2':6',2''-terpyridine. Detailed NMR and mass spectrometry studies indicate that the ligand forms 1:2 complexes with lanthanide(III) perchlorates where the aliphatic rings are conformationally constrained whereas 1:1 complexes are formed with lanthanide(III) nitrates where the aliphatic rings are conformationally mobile. An optimized structure of the 1:2 solution complex with Yb(III) was obtained from the relative magnitude of the induced paramagnetic shifts. X-ray crystallographic structures of the ligand and of its 1:1 complex with Y(III) were also obtained. In the absence of a phase-modifier, CyMe 4 -BTTP in 1-octanol showed a maximum distribution coefficient of Am(III) of 0.039 (±20%) and a maximum separation factor of Am(III) over Eu(III) of 12.0 from nitric acid solution. The metal(III) cations are extracted as the 1:1 complex from nitric acid solutions. The generally low distribution coefficients observed compared with the BTBPs arise because the 1:1 complex of CyMe 4 -BTTP is considerably less hydrophobic than the 1:2 complexes formed by the BTBPs. In M(BTTP) 3+ complexes, there is a competition between the nitrate ions and the ligand for the complexation of the metal. (authors)

  11. Increasing lanthanide luminescence by use of the RETEL effect.

    Science.gov (United States)

    Leif, Robert C; Vallarino, Lidia M; Becker, Margie C; Yang, Sean

    2006-08-01

    Luminescent lanthanide complexes produce emissions with the narrowest-known width at half maximum; however, their significant use in cytometry required an increase in luminescence intensity. The companion review, Leif et al., Cytometry 2006;69A:767-778, described a new technique for the enhancement of lanthanide luminescence, the Resonance Energy Transfer Enhanced Luminescence (RETEL) effect, which increases luminescence and is compatible with standard slide microscopy. The luminescence of the europium ion macrocyclic complex, EuMac, was increased by employing the RETEL effect. After adding the nonluminescent gadolinium ion complex of the thenoyltrifluoroacetonate (TTFA) ligand or the sodium salt of TTFA in ethanol solution, the EuMac-labeled sample was allowed to dry. Both a conventional arc lamp and a time-gated UV LED served as light sources for microscopic imaging. The emission intensity was measured with a CCD camera. Multiple time-gated images were summed with special software to permit analysis and effective presentation of the final image. With the RETEL effect, the luminescence of the EuMac-streptavidin conjugate increased at least six-fold upon drying. Nuclei of apoptotic cells were stained with DAPI and tailed with 5BrdUrd to which a EuMac-anti-5BrdU conjugate was subsequently attached. Time-gated images showed the long-lived EuMac luminescence but did not show the short-lived DAPI fluorescence. Imaging of DNA-synthesizing cells with an arc lamp showed that both S phase and apoptotic cells were labeled, and that their labeling patterns were different. The images of the luminescent EuMac and fluorescent DAPI were combined to produce a color image on a white background. This combination of simple chemistry, instrumentation, and presentation should make possible the inexpensive use of the lanthanide macrocycles, Quantum Dyes, as molecular diagnostics for cytological and histopathological microscopic imaging. (c) 2006 International Society for Analytical

  12. Selective Lanthanides Sequestration Based on a Self-Assembled Organo-silica

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, M.; Reye, C.; Corriu, R.J. P. [Univ Montpellier, Inst Charles Gerhardt Montpellier, UMR 5253, Chim Mol and Org Solide, F-34095 Montpellier 5 (France); Besson, E. [ICSM Site Marcoule, UMR 5257, Inst Chim Separat Marcoule, F-30207 Bagnols Sur Ceze (France); Van der Lee, Arie [Univ Montpellier, Inst Europeen Membranes, UMR 5635, CNRS, F-34095 Montpellier 5 (France); Besson, E.; Chollet, H. [CEA Valduc, Dept Traitement Mat Nucl, F-21120 Is Sur Tille (France); Guilard, R. [Univ Bourgogne, Inst Chim Mol, CNRS, ICMUB, UMR 5260, F-21078 Dijon (France)

    2010-07-01

    In this paper, we investigate the cation-exchange properties of a self-assembled hybrid material towards trivalent ions, lanthanides (La{sup 3+}, Eu{sup 3+}, Gd{sup 3+}, Yb{sup 3+}) and Fe{sup 3+}. The bis-zwitterionic lamellar material was prepared by sol-gel process from only 3-aminopropyltriethoxysilane (APTES), succinic anhydride, and ethylenediamine. In ethanol heated under reflux, the exchange ethylenediammonium versus Ln{sup 3+} proved to be complete by complexometry measurements and elemental analyses, one Cl{sup -} ion per one Ln(III) remaining as expected for charge balance. In aqueous solution at 20 degrees C, the material was found to be selective towards lanthanide in spite of the similarity of their ionic radii. The cation uptake depends on the nature of the salt, the difference between two lanthanides reaching up to 20% in some cases. Finally, ion-exchange reaction with FeCl{sub 3} was chosen as a probe to get more information on the material after incorporation of trivalent ions. Based on Moessbauer spectroscopic investigations on the resulting material in conjunction with the XRD analysis of materials containing trivalent ions, a structural model was proposed to describe the incorporation of trivalent ions by exchange reaction within the original zwitterionic material. (authors)

  13. Solvent extraction of lanthanide ions with 1-Phenyl-3-Methyl-4-Benzoyl-Pyrazolone-5 (HPMBP), 2. Extraction of Erbium(III), Ytterbium(III) and Lutetium(III) by HPMBP from aqueous-methanol solutions

    International Nuclear Information System (INIS)

    Czakis-Sulikowska, D.M.; Kuznik, B.; Malinowska, A.

    1990-01-01

    The solvent extraction of lanthanides(III)(Ln = Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous-50 % (ν/ν) methanol phase (K ex ), two-phase stability constants of the complexes LnL 3 (β 3 * ) and stability constants of complexes LnL 2+ , LnL 2 + , LnL 3 (β n )(Ln = Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (K a ) and the distribution constant of HPMBP (p HL ) between carbon tetrachloride and water-methanol solutions was investigated. (Authors)

  14. Lanthanide ion (III) complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate for dual biosensing of pH with chemical exchange saturation transfer (CEST) and biosensor imaging of redundant deviation in shifts (BIRDS).

    Science.gov (United States)

    Huang, Yuegao; Coman, Daniel; Ali, Meser M; Hyder, Fahmeed

    2015-01-01

    Relaxivity-based magnetic resonance of phosphonated ligands chelated with gadolinium (Gd(3+)) shows promise for pH imaging. However instead of monitoring the paramagnetic effect of lanthanide complexes on the relaxivity of water protons, biosensor (or molecular) imaging with magnetic resonance is also possible by detecting either the nonexchangeable or the exchangeable protons on the lanthanide complexes themselves. The nonexchangeable protons (e.g. -CHx, where 3 ≥ x ≥ 1) are detected using a three-dimensional chemical shift imaging method called biosensor imaging of redundant deviation in shifts (BIRDS), whereas the exchangeable protons (e.g. -OH or -NHy , where 2 ≥ y ≥ 1) are measured with chemical exchange saturation transfer (CEST) contrast. Here we tested the feasibility of BIRDS and CEST for pH imaging of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (DOTA-4AmP(8-)) chelated with thulium (Tm(3+) ) and ytterbium (Yb(3+)). BIRDS and CEST experiments show that both complexes are responsive to pH and temperature changes. Higher pH and temperature sensitivities are obtained with BIRDS for either complex when using the chemical shift difference between two proton resonances vs using the chemical shift of a single proton resonance, thereby eliminating the need to use water resonance as reference. While CEST contrast for both agents is linearly dependent on pH within a relatively large range (i.e. 6.3-7.9), much stronger CEST contrast is obtained with YbDOTA-4AmP(5-) than with TmDOTA-4AmP(5-). In addition, we demonstrate the prospect of using BIRDS to calibrate CEST as new platform for quantitative pH imaging. Copyright © 2014 John Wiley & Sons, Ltd.

  15. Thermodynamic properties of britholites CaxLay(SiO4)6-u(PO4)uOt, study of the properties of diffusion and fixation of lanthanide and trans-uranian ions in britholites: application in the field of luminescent materials and of storage of nuclear wastes

    International Nuclear Information System (INIS)

    El Ouenzerfi, R.

    2003-02-01

    This work deals in particular with the synthesis and the characterization of the apatitic oxy-silico-phosphates. In a first part is studied the quaternary system: CaO-La 2 O 3 -SiO 2 P 2 O 5 in order to determine the range in which the pure phospho-silicated apatites exist. Then, the obtained phases have been identified and characterized by chemical analysis methods, electron microprobe analysis, X-ray diffraction, infrared and Raman spectroscopies. The study of the uranium solubilization and diffusion in apatitic matrices has been carried out from the determination of the substitution limit, of the oxidation degree and of the diffusion coefficient of uranium in a phospho-silicated apatite. In a second part, the luminescence properties of the Eu 3+ and Ce 3+ ions in phospho-silicated apatites have been studied. This work allows to have a wider vision of the oxy-silico-phosphated apatites and of their synthesis conditions. The study of the physical and chemical properties of britholites doped with actinides or lanthanides ions will be useful to the study of the optical properties of these matrices. (O.M.)

  16. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    Science.gov (United States)

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  17. Investigation of the photoluminescence properties of composite optical resins containing high lanthanide content

    International Nuclear Information System (INIS)

    Wang Dongmei; Wang Fuxiang; Peng Weixian

    2012-01-01

    Novel composite optical resins with high lanthanide content have been synthesized through a free radical copolymerization of methacrylic acid (MA), styrene (St) and Eu(DBM) 3 ·H 2 O nanocrystals. We characterized the structure, the thermal properties, dimensions and photoluminescence properties of Eu(DBM) 3 ·H 2 O nanocrystals. Our results indicated that the diameters of the Eu(DBM) 3 ·H 2 O nanocrystals were within the range of 30 to 300 nm. These materials exhibited characteristic europium ion luminescence. The europium-bearing nanocrystals and were then incorporated into the copolymer systems of MA/St and luminescence functional optical resins with high lanthanide content (50 wt%) were obtained. The combination of these particles and optical resins is facile because the diameter of Eu(DBM) 3 ·H 2 O is decreased. These copolymer-based optical resins not only possess good transparency and mechanical performance, but also exhibit an intense narrow band emission of lanthanide complexes and longer fluorescence lifetimes under UV excitation at room temperature. - Highlights: ► Novel composite optical resins with high lanthanide content have been synthesized. ► The Eu(DBM) 3 ·H 2 O nanocrystals were within the range of 30 to 300 nm. ► Fluorescent resins with high lanthanide content (50 wt%) were obtained. ► Resins exhibit intense emission of lanthanide and longer fluorescence lifetimes. ► Variety properties of Eu(DBM) 3 ·H 2 O nanocrystals were characterized.

  18. Lanthanides in molecular magnetism: old tools in a new field.

    Science.gov (United States)

    Sorace, Lorenzo; Benelli, Cristiano; Gatteschi, Dante

    2011-06-01

    In this tutorial review we discuss some basic aspects concerning the magnetic properties of rare-earth ions, which are currently the subject of a renovated interest in the field of molecular magnetism, after the discovery that slow relaxation of the magnetization at liquid nitrogen temperature can occur in mononuclear complexes of these ions. Focusing on Dy(III) derivatives a tutorial discussion is given of the relation of the crystal field parameters, which determine the anisotropy of these systems and consequently their interesting magnetic properties, with the geometry of the coordination sphere around the lanthanide centre and with the pattern of f orbitals. The problem of systems of low point symmetry is also addressed by showing how detailed single crystal investigation, coupled to more sophisticated calculation procedures, is an absolute necessity to obtain meaningful structure-property relationships in these systems.

  19. Luminescence properties of isomeric and tautomeric lanthanide pyridinedicarboxylates

    International Nuclear Information System (INIS)

    Puntus, L.N.; Zolin, V.F.; Babushkina, T.A.; Kutuza, I.B.

    2004-01-01

    The luminescence and PMR spectra of europium salts of six isomers of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, and 3,5-pyridinedicarboxylic acids (PDA) had been studied. The distribution of the effective charge in the nearest surroundings of the Eu 3+ ion in these salts was evaluated from Stark splittings of electronic transitions. The values of relative integral intensities of electronic transitions 5 D 0 - 7 F J (J=0-4) in the luminescence spectra were reported. Compounds investigated were divided into three subgroups taking into account the details of the structure of the ligands and details of the luminescence spectra. The ligand coordination manners as well as the strength of interaction between lanthanide ion and ligands were confirmed by data of the PMR and IR spectroscopy

  20. Complexes of light lanthanides with 2,4-dimethoxybenzoic acid

    Directory of Open Access Journals (Sweden)

    WIESLAWA FERENC

    2000-01-01

    Full Text Available The complexes of light lanthanides with 2,4-dimethoxybenzoic acid of the formula: Ln(C9H9O43·nH2O where Ln = La(III, Ce(III, Pr(III, Nd(III, Sm(III, Eu(III, Gd(IIII, and n = 3 for La(III, Gd(III, n = 2 for Sm(III, Eu(III, and n = 0 for Ce(III, Pr(III, Nd(III have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric studies and X-ray diffraction measurements. The complexes have colours typical for Ln3+ ions (La, Ce, Eu, Gd-white, Sm-cream, Pr-green, Nd-violet. The carboxylate group in these complexes is a symmetrical, bidentate, chelating ligand. They are crystalline compounds characterized by various symmetry. On heating in air to 1273 K the 2,4-dimethoxybenzoates of the light lanthanides decompose in various ways. The hydrated complexes decompose in two or three steps while those of anhydrous ones only in one or two. The trihydrate of lanthanum 2,4-dimethoxybenzoate first dehydrates to form the anhydrous salt, which then decomposes to La2O3via the intermediate formation of La2O2CO3. The hydrates of Sm(III, Eu(III, Gd(III decompose in two stages. First, they dehydrate forming the anhydrous salts, which then decompose directly to the oxides of the respective metals. The anhydrous complexes of Ce(III, Pr(III decompose in one step, while that of Nd(III in two. The solubilities of the 2,4-dimethoxybenzoates of the light lanthanides in water and ethanol at 293 K are in the order of: 10-3 mol dm-3 and 10-4-10-3 mol dm-3, respectively.

  1. Calorimetric approach of lanthanides (3) complexation and extraction by malonamides; Approche calorimetrique de la complexation et de l'extraction des lanthanides (3) par les malonamides

    Energy Technology Data Exchange (ETDEWEB)

    Flandin, J.L

    2001-07-01

    In the field of long lived radionuclides separation, diamides are interesting extractants because of their ability to co-extract trivalent lanthanides and actinides, which is a preliminary and essential step in high level radioactive waste reprocessing. The research carried out contributes to a better understanding of the mechanisms and the aim is the determination of thermodynamics properties ({delta}{sub r}G, {delta}{sub r}H et {delta}{sub r}S) related to the complexation and the extraction of lanthanides(III) by malonamides. The first part of the document deals with the complexation of lanthanides(III) by an hydrosoluble diamide. The experimental results obtained by UV-visible spectrometry, TRLIF, NMR and microcalorimetric titration proved that lanthanides(III)-TEMA interactions in aqueous medium are very weak and that the complexation reaction is endothermic. The TEMA ligand still stays in the second coordination sphere of coordination of the lanthanide ion. The second part of this study focuses on the extraction of neodymium(III) nitrate by a lipophilic diamide which is an exothermic reaction. The influence of the composition of aqueous and organic phases on the thermodynamics properties {delta}{sub r}G et {delta}{sub r}H has been studied by microcalorimetric titration. The most influent parameter is the total concentration in extractant. As a consequence, thermodynamic values are very dependent on the organic phase organisation before and alter extraction. At the same time, this study showed the interest of the calorimetric approach for the analysis of basic reactions like diamide dilution and their organisation as oligomeric aggregates. (author)

  2. Nonaqueous method for dissolving lanthanide and actinide metals

    International Nuclear Information System (INIS)

    Crisler, L.R.

    1975-01-01

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol

  3. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry

    International Nuclear Information System (INIS)

    Vercouter, Th.

    2005-03-01

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO 3 ) 3 3- , is identified by solubility measurements in Na 2 CO 3 solutions. Then the formation constants of the complexes Eu(CO 3 ) i 3-2i (i=1-3) and Eu(SO 4 ) i 3-2i (i=1-2) are measured by TRLFS. The formation of aqueous LaSO 4 + is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO 3 ) 2 - + CO 3 2- ↔ Cm(CO 3 ) 3 3- are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  4. Lanthanide-Doped Ceria Nanoparticles as Backside Coaters to Improve Silicon Solar Cell Efficiency.

    Science.gov (United States)

    Hajjiah, Ali; Samir, Effat; Shehata, Nader; Salah, Mohamed

    2018-05-23

    This paper introduces lanthanide-doped ceria nanoparticles as silicon solar cell back-side coaters, showing their influence on the solar cell efficiency. Ceria nanoparticles can be synthesized to have formed oxygen vacancies (O-vacancies), which are associated with converting cerium ions from the Ce 4+ state ions to the Ce 3+ ones. These O-vacancies follow the rule of improving silicon solar cell conductivity through a hopping mechanism. Besides, under near-ultra violet (near-UV) excitation, the reduced trivalent cerium Ce 3+ ions are directly responsible for down converting the un-absorbed UV wavelengths to a resultant green photo-luminescence emission at ~520 nm, which is absorbed through the silicon solar cell’s active layer. Adding lanthanide elements such as Neodymium “Nd” as ceria nanoparticle dopants helps in forming extra oxygen vacancies (O-vacancies), followed by an increase in the number of Ce 4+ to Ce 3+ ion reductions, thus enhancing the conductivity and photoluminescence down conversion mechanisms. After introducing lanthanide-doped ceria nanoparticles on a silicon solar cell surface, a promising enhancement in the behavior of the solar cell current-voltage curve is observed, and the efficiency is improved by about 25% of its initial value due to the mutual impact of improving both electric conductivity and optical conversions.

  5. New Lanthanide Alkynylamidinates and Diiminophosphinates

    Directory of Open Access Journals (Sweden)

    Farid M. Sroor

    2015-11-01

    Full Text Available This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl, in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O. Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate complexes, [Ph–C≡C–C(NCy2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho. The products were isolated in moderate to high yields (61%–89% as brightly colored, crystalline solids. The chloro-functional neodymium(III bis(cyclopropylethynylamidinate complex [{c-C3H5–C≡C–C(NiPr2}2Ln(µ-Cl(THF]2 (8 was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr2] in THF and structurally characterized. A new monomeric Ce(III-diiminophosphinate complex, [Ph2P(NSiMe32]2Ce(µ-Cl2Li(THF2 (9, has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe32]. Structurally, this complex resembles the well-known “ate” complexes (C5Me52Ln(µ-Cl2Li(THF2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III dichloride did not lead to an isolable cerium(IV species.

  6. NMR study of structure of lanthanide complexes in solution

    International Nuclear Information System (INIS)

    Choppin, G.R.

    1976-01-01

    The diagnostic value PMR studies of diamagnetic lanthanide complexes to define the nature of the species in the lanthanide-pyruvate system is discussed. The use of NMR spectra of both diamagnetic and paramagnetic lanthanide complexes to obtain detailed structural information is reviewed

  7. Slow magnetic relaxation in carbonato-bridged dinuclear lanthanide(III) complexes with 2,3-quinoxalinediolate ligands.

    Science.gov (United States)

    Vallejo, Julia; Cano, Joan; Castro, Isabel; Julve, Miguel; Lloret, Francesc; Fabelo, Oscar; Cañadillas-Delgado, Laura; Pardo, Emilio

    2012-08-11

    The coordination chemistry of the 2,3-quinoxalinediolate ligand with different lanthanide(III) ions in basic media in air affords a new family of carbonato-bridged M(2)(III) compounds (M = Pr, Gd and Dy), the Dy(2)(III) analogue exhibiting slow magnetic relaxation behaviour typical of single-molecule magnets.

  8. Bis(pentamethylene)urea complexes of the lanthanide nitrates: synthesis, characterization, properties

    International Nuclear Information System (INIS)

    Souza, H.K.S. de; Pedrosa, A.M.G.; Marinho, E.P.M.; Batista, M.K.S.; Melo, D.M.A.; Zinner, K.; Zinner, L.B.; Zukerman-Schpector, J.; Vicentini, G.

    2003-01-01

    Lanthanide nitrate complexes of bis(pentamethylene)urea (BPMU) with general formula Ln(NO 3 ) 3 3BPMU, where Ln: La, Nd, Sm, Eu, Ho and Er have been prepared and characterized based on CHN elemental analyses, lanthanide titration with EDTA, molar conductivity, spectroscopic data and thermal studies. The infrared spectra show that ligands (BPMU) are bonded through the carbonyl oxygen, nitrate counter-ions are bidentate linked to the central ions. The structure of the neodymium complex was determined. The crystal is monoclinic, P2 1/c ,Z=4, with the following parameters: a=10.148(1) A, b=21.879(2), c=19.154(2) A, β=104.11(1) deg., V=4124.3(7) A 3 . The polyhedron is a distorted tricapped trigonal prism, coordination number nine

  9. Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3)

    International Nuclear Information System (INIS)

    Philippini, V.

    2007-12-01

    Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An 3+ and Ln 3+ cations. The study of the solubility of double carbonates (AlkLn(CO 3 ) 2 ,xH 2 O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO 3 ) 4 5- whereas the heaviest (Eu and Dy) form Ln(CO 3 ) 3 3- in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO 3 ) 4 5- while Dy to Lu form Ln(CO 3 ) 3 3- . Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO 3 ) 3 3- complex, specially with Cs + . Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)

  10. Lanthanide ions induce hydrolysis of hemoglobin-bound 2,3-diphosphoglycerate (2,3-DPG), conformational changes of globin and bidirectional changes of 2,3-DPG-hemoglobin's oxygen affinity.

    Science.gov (United States)

    Cheng, Y; Lin, H; Xue, D; Li, R; Wang, K

    2001-02-14

    The changes in structure and function of 2,3-diphosphoglycerate-hemoglobin (2,3-DPG-Hb) induced by Ln(3+) binding were studied by spectroscopic methods. The binding of lanthanide cations to 2,3-DPG is prior to that to Hb. Ln(3+) binding causes the hydrolysis of either one from the two phosphomonoester bonds in 2,3-DPG non-specifically. The results using the ultrafiltration method indicate that Ln(3+) binding sites for Hb can be classified into three categories: i.e. positive cooperative sites (N(I)), non-cooperative strong sites (N(S)) and non-cooperative weak sites (N(W)) with binding constants in decreasing order: K(I)>K(S)>K(W). The total number of binding sites amounts to about 65 per Hb tetramer. Information on reaction kinetics was obtained from the change of intrinsic fluorescence in Hb monitored by stopped-flow fluorometry. Fluctuation of fluorescence dependent on Ln(3+) concentration and temperature was observed and can be attributed to the successive conformational changes induced by Ln(3+) binding. The results also reveal the bidirectional changes of the oxygen affinity of Hb in the dependence on Ln(3+) concentration. At the range of [Ln(3+)]/[Hb]<2, the marked increase of oxygen affinity (P(50) decrease) with the Ln(3+) concentration can be attributed to the hydrolysis of 2,3-DPG, while the slight rebound of oxygen affinity in higher Ln(3+) concentration can be interpreted by the transition to the T-state of the Hb tetramer induced by Ln(3+) binding. This was indicated by the changes in secondary structure characterized by the decrease of alpha-helix content.

  11. Synthesis, characterization and luminescent properties of lanthanide complexes with an unsymmetrical tripodal ligand

    Energy Technology Data Exchange (ETDEWEB)

    Yan Zhenzhong [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Tang Yu [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)], E-mail: tangyu@lzu.edu.cn; Liu Weisheng; Tan Minyu [State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2008-09-15

    Solid complexes of lanthanide nitrates with a new unsymmetrical tripodal ligand, bis[(2'-benzylaminoformyl)phenoxyl)ethyl](ethyl)amine (L) have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Sm(III), Eu(III), Tb(III) and Dy(III) nitrate complexes in solid state were also investigated. Under the excitation of UV light, these complexes exhibited characteristic emission of central metal ions.

  12. Structure of the X-ray photoelectron spectra of fluorides and oxides of lanthanides connected with the dynamic effect

    International Nuclear Information System (INIS)

    Teterin, Yu.A.; Teterin, A.Yu.; Lebedev, A.M.; Utkin, I.O.; Nikitin, A.S.

    1998-01-01

    Impact of dynamic effect on the fine structure of the X-ray electron spectra of the lanthanide oxides and fluorides is considered. Significant complication of the Ln4p-electrons occurs due to interaction of configurations of the basic single-hole and additional two-hole finite states of the 4p 5 4d 10 4f n ↔ 4p 6 4d 8 4f n+1 type. Impact of the atoms nature of the nearest surrounding of the lanthanides ions on the parameters of such fine structure is evaluated [ru

  13. Optimization of the radio lanthanides separation device

    International Nuclear Information System (INIS)

    Vera T, A. L.

    2009-01-01

    At present, cancer is a major cause of mortality in our country, therefore, its prevention, diagnosis and treatment are vital to health systems. The cancer treatment and other diseases, from monoclonal antibodies, peptides, or amino macro aggregates marked with beta particle emitting radionuclides, is a highly promising field. The radioactive lanthanides: Pm, Tb, Ho, and Lu are beta emitters, which possess nuclear and chemical properties, which have shown their feasibility as radioisotopes of radiotherapeutic use. However, these radioisotopes are not available commercially in this connection, the Research Laboratory of Radioactive Materials of the National Institute of Nuclear Research, has developed the methodology of production of these radioisotopes and based on this work is designed, constructed and installed the radio lanthanides separation device for the radioisotopes production routinely. This device is part of the cell, , which has and auxiliary air service, an extraction system and is protected with a 10 cm of lead shielding. The radio lanthanides separation device is manual and easy to handle. The main function of this equipment is the radio lanthanides separation from extractive chromatography through packed columns with a commercial resin (Ln SPS) and coated on the top and bottom by fiberglass. The radio lanthanides separation device comprises a main carrousel where the separation columns and elution containers are mounted. It also has a system of open irradiation vials, carrier samples for columns and glassware. This paper presents a detailed description of the radio lanthanides separation device and its management, which allows the radioisotopes production Pm, Tb, Ho, and Lu from the separation of its parents Nd, Dy, Gd, and Yb respectively. (Author)

  14. Syntheses, structures, photoluminescence and photocatalysis of 2D layered lanthanide-carboxylates with 2, 2′-dithiodibenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Ling; Zhong, Jie-Cen; Qiu, Xing-Tai; Sun, Yan-Qiong, E-mail: sunyq@fzu.edu.cn; Chen, Yi-Ping

    2017-02-15

    Two series of lanthanide-carboxylates, [Ln(2,2′-dtba)(2,2′-Hdtba)(EtOH)]{sub n} (I:Ln=Eu(1a), Dy(1b)) and [Ln(2,2′-dtba)(2,2′-Hdtba)(4,4′-bpy){sub 0.5}]{sub n} (II:Ln=Eu(2a), Dy(2b), Tb(2c) 2,2′-H{sub 2}dtba=2,2′-dithiodibenzoic acid, 4,4′-bpy=4,4′-bipyridine) have been synthesized under hydrothermal conditions. Interestingly, the H{sub 2}dtba organic ligand was generated by in situ S–S reaction of 2-mercaptobenzoic acid. Compounds I and II possess different 2D layered structures based on similar 1D [Ln(2,2′-dtba)]{sup +} chains. Photoluminescence studies reveal that compounds I and II exhibit strong lanthanide characteristic emission bands. Remarkably, Compounds 1b and 2a both exhibit good photocatalytic activity for degradation of Rhodamine-B (Rh-B) under the simulated sunlight irradiation. - Graphical abstract: Two series of lanthanide-carboxylates have been in situ synthesized under hydrothermal conditions. The lanthanide-carboxylates exhibit strong lanthanide characteristic emission bands and good photocatalytic activity for degradation of Rhodamine-B. - Highlights: • 2D layered lanthanide-carboxylates with 2,2′-dithiodibenzoic acid. • In situ S–S reaction of 2-mercaptobenzoic acid under hydrothermal condition. • The Emission spectra of I and II exhibit the characteristic transition of lanthanide ions. • Compounds 1b and 2a exhibit good photocatalytic activity for degradation of Rhodamine-B.

  15. Perturbing Tandem Energy Transfer in Luminescent Heterobinuclear Lanthanide Coordination Polymer Nanoparticles Enables Real-Time Monitoring of Release of the Anthrax Biomarker from Bacterial Spores.

    Science.gov (United States)

    Gao, Nan; Zhang, Yunfang; Huang, Pengcheng; Xiang, Zhehao; Wu, Fang-Ying; Mao, Lanqun

    2018-06-05

    Lanthanide-based luminescent sensors have been widely used for the detection of the anthrax biomarker dipicolinic acid (DPA). However, mainly based on DPA sensitization to the lanthanide core, most of them failed to realize robust detection of DPA in bacterial spores. We proposed a new strategy for reliable detection of DPA by perturbing a tandem energy transfer in heterobinuclear lanthanide coordination polymer nanoparticles simply constructed by two kinds of lanthanide ions, Tb 3+ and Eu 3+ , and guanosine 5'-monophosphate. This smart luminescent probe was demonstrated to exhibit highly sensitive and selective visual luminescence color change upon exposure to DPA, enabling accurate detection of DPA in complex biosystems such as bacterial spores. DPA release from bacterial spores on physiological germination was also successfully monitored in real time by confocal imaging. This probe is thus expected to be a powerful tool for efficient detection of bacterial spores in responding to anthrax threats.

  16. Gamma ray induced decomposition of lanthanide nitrates

    International Nuclear Information System (INIS)

    Joshi, N.G.; Garg, A.N.

    1992-01-01

    Gamma ray induced decomposition of the lanthanide nitrates, Ln(NO 3 ) 3 .xH 2 O where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm and Yb has been studied at different absorbed doses up to 600 kGy. G(NO 2 - ) values depend on the absorbed dose and the nature of the outer cation. It has been observed that those lanthanides which exhibit variable valency (Ce and Eu) show lower G-values. An attempt has been made to correlate thermal and radiolytic decomposition processes. (author). 20 refs., 3 figs., 1 tab

  17. Factors in the complexation of lanthanides

    International Nuclear Information System (INIS)

    Choppin, G.R.

    1976-01-01

    The lanthanide cations are classified as hard acids and thus will coordinate strongly with oxygen and fluorine donor atoms. The electrostatic model is applied to lanthanide complexes with the dielectric constant as a parameter; the plot of ΔG vs sum of ionic radii confirm the ionic nature of the bonding. The enthalpy and entropy changes are shown to compensate each other to produce an almost linear variation in the free energy of complexation. Outer-sphere and inner-sphere complexation is discussed

  18. Extraction characteristics of trivalent lanthanides and actinides in mixtures of dinonylnaphthalenesulfonic acid and carboxylic acids

    International Nuclear Information System (INIS)

    West, M.H.

    1983-03-01

    Dinonylnaphthalenesulfonic acid (HDNNS) has been shown to be an effective liquid cation exchanger for the extraction of metal ions. This extractant has proven to be successful in the extraction of trivalent lanthanides and actinides in the pH range of 2.0 to 3.0, although it shows little selectivity for individual ions because of its strong acid character. In an effort to improve the selectivity of HDNNS between trivalent lanthanides and actinides, carboxylic acids were added to the organic phase and the effects on the extraction characteristics of HDNNS were investigated. Three carboxylic acids - nonanoic, cyclohexanecarboxylic, and cyclohexanebutyric - were studied with the following metals: Am(III), Cm(III), Ce(III), Eu(III), and Tm(III). The distributions of the metal ions were studied holding the HDNNS concentration constant while varying the carboxylic acid concentrations over a range of 1.0 x 10 -5 M to 1.0 M. Results indicated that the greatest enhancement of the extraction occurred at a carboxylic acid concentration of 1.0 x 10 -2 M with negative effects occurring at 0.5 M and 1.0 M. The effects on the extraction of the trivalent lanthanides and actinides were interpreted in terms of the structural differences of the carboxylic acids, the effect of the carboxylic acids on the HDNNS extraction mechanism, and the ionic properties of the metals studied

  19. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

    KAUST Repository

    Wang, Feng

    2010-02-25

    Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase, modifying electronic properties, modulating magnetism as well as tuning emission properties. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF 4 nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF 4 upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels to volumetric three-dimensional displays. © 2010 Macmillan Publishers Limited. All rights reserved.

  20. The geochemistry and mobility of the lanthanides in marine sediments

    International Nuclear Information System (INIS)

    Elderfield, H.

    1988-07-01

    A study has been made to evaluate lanthanide mobility in sediments directly by measuring concentrations of 10 lanthanide elements in sediments and pore waters. Due to the very low concentrations of the lanthanides in sea water relative to marine sediments, evidence of lanthanide mobilization is usually difficult to detect from studies of solid-phase geochemistry. Results show that the lanthanides can be extremely mobile. Concentrations in pore waters up to 100 times sea water concentrations have been measured. The conclusions are tentative but the present data suggest that the lanthanides are mobilized during oxidation of organic-rich sediments and are relocated in part in association with secondary Fe-rich phases. The behaviour of Ce is, predictably, somewhat different from the other lanthanides and may be more mobile as a consequence of its redox chemistry. (author)

  1. Analytical scheme for group separation of the lanthanides from biological materials before their determination by Neutron Activation Analysis

    International Nuclear Information System (INIS)

    Danko, B.; Samczynski, Z.; Dybczynski, R.

    2006-01-01

    The analytical procedure for the selective and quantitative isolation of the lanthanides as a group from biological materials has been developed on the basis of experiments with radio-tracers. Ion exchange and extraction column chromatography were used for the isolation of elements of interest from matrix and the other trace elements prior to irradiation in a nuclear reactor. The method enables quantitative separation of the lanthanide fraction, free from highly activating macro components, as well as from other trace elements including uranium, which can be the source of serious errors due to uranium 235 U fission reaction (n,f). In order to minimize the potential spectrometric interferences lanthanide fraction after neutron irradiation was divided into two sub-fractions, taking advantage of the different anion exchange affinities of individual lanthanide complexes with EDTA to strongly basic anion exchanger. The effective microwave digestion procedures for ca 500 mg biological samples was elaborated and the new, original method for checking the yield of the entire analytical procedure - including mineralization of the sample - was applied. Neutron activation analysis (NAA) of BCR 670 Aquatic Plant ? one of the only two CRMs of biological origin available on the market, which offers the certified values for all lanthanides was used for verification of performance of the proposed analytical scheme. (authors)

  2. Studies of Lanthanide Transport in Metallic Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinsuo; Taylor, Christopher

    2018-04-02

    Metallic nuclear fuels were tested in fast reactor programs and performed well. However, metallic fuels have shown the phenomenon of FCCI that are due to deleterious reactions between lanthanide fission products and cladding material. As the burnup is increased, lanthanide fission products that contact with the cladding could react with cladding constituents such as iron and chrome. These reactions produce higher-melting intermetallic compounds and low-melting alloys, and weaken the mechanical integrity. The lanthanide interaction with clad in metallic fuels is recognized as a long-term, high-burnup cause of the clad failures. Therefore, one of the key concerns of using metallic fuels is the redistribution of lanthanide fission products and migration to the fuel surface. It is believed that lanthanide migration is in part due to the thermal gradient between the center and the fuel-cladding interface, but also largely in part due to the low solubility of lanthanides within the uranium-based metal fuel. PIE of EBR-II fuels shows that lanthanides precipitate directly and do not dissolve to an appreciable extent in the fuel matrix. Based on the PIE data from EBR-II, a recent study recommended a so-called “liquid-like” transport mechanism for lanthanides and certain other species. The liquid-like transport model readily accounts for redistribution of Ln, noble metal fission products, and cladding components in the fuel matrix. According to the novel mechanism, fission products can transport as solutes in liquid metals, such as liquid cesium or liquid cesium–sodium, and on pore surfaces and fracture surfaces for metals near their melting temperatures. Transport in such solutions is expected to be much more rapid than solid-state diffusion. The mechanism could explain the Ln migration to the fuel slug peripheral surface and their deposition with a sludge-like form. Lanthanides have high solubility in liquid cesium but have low solubility in liquid sodium. As a

  3. Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

    Science.gov (United States)

    Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2014-12-21

    The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

  4. Characterizing the magnetic susceptibility tensor of lanthanide-containing polymethylated-DOTA complexes

    Energy Technology Data Exchange (ETDEWEB)

    Strickland, Madeleine [National Institutes of Health, Laboratory of Molecular Biophysics, Biochemistry and Biophysics Center, National Heart, Lung, and Blood Institute (United States); Schwieters, Charles D. [National Institutes of Health, Office of Intramural Research, Center for Information Technology (United States); Göbl, Christoph [Technische Universität München, Department of Chemistry (Germany); Opina, Ana C. L. [National Institutes of Health, Imaging Probe Development Center, National Heart, Lung, and Blood Institute (United States); Strub, Marie-Paule [National Institutes of Health, Laboratory of Molecular Biophysics, Biochemistry and Biophysics Center, National Heart, Lung, and Blood Institute (United States); Swenson, Rolf E.; Vasalatiy, Olga [National Institutes of Health, Imaging Probe Development Center, National Heart, Lung, and Blood Institute (United States); Tjandra, Nico, E-mail: tjandran@nhlbi.nih.gov [National Institutes of Health, Laboratory of Molecular Biophysics, Biochemistry and Biophysics Center, National Heart, Lung, and Blood Institute (United States)

    2016-10-15

    Lanthanide complexes based on the DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) cage are commonly used as phase contrast agents in magnetic resonance imaging, but can also be utilized in structural NMR applications due to their ability to induce either paramagnetic relaxation enhancement or a pseudocontact shift (PCS) depending on the choice of the lanthanide. The size and sign of the PCS for any given atom is determined by its coordinates relative to the metal center, and the characteristics of the lanthanide’s magnetic susceptibility tensor. Using a polymethylated DOTA tag (Ln-M8-SPy) conjugated to ubiquitin, we calculated the position of the metal center and characterized the susceptibility tensor for a number of lanthanides (dysprosium, thulium, and ytterbium) under a range of pH and temperature conditions. We found that there was a difference in temperature sensitivity for each of the complexes studied, which depended on the size of the lanthanide ion as well as the isomeric state of the cage. Using {sup 17}O-NMR, we confirmed that the temperature sensitivity of the compounds was enhanced by the presence of an apically bound water molecule. Since amide-containing lanthanide complexes are known to be pH sensitive and can be used as probes of physiological pH, we also investigated the effect of pH on the Ln-M8-SPy susceptibility tensor, but we found that the changes in this pH range (5.0–7.4) were not significant.

  5. Characterizing the magnetic susceptibility tensor of lanthanide-containing polymethylated-DOTA complexes

    International Nuclear Information System (INIS)

    Strickland, Madeleine; Schwieters, Charles D.; Göbl, Christoph; Opina, Ana C. L.; Strub, Marie-Paule; Swenson, Rolf E.; Vasalatiy, Olga; Tjandra, Nico

    2016-01-01

    Lanthanide complexes based on the DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) cage are commonly used as phase contrast agents in magnetic resonance imaging, but can also be utilized in structural NMR applications due to their ability to induce either paramagnetic relaxation enhancement or a pseudocontact shift (PCS) depending on the choice of the lanthanide. The size and sign of the PCS for any given atom is determined by its coordinates relative to the metal center, and the characteristics of the lanthanide’s magnetic susceptibility tensor. Using a polymethylated DOTA tag (Ln-M8-SPy) conjugated to ubiquitin, we calculated the position of the metal center and characterized the susceptibility tensor for a number of lanthanides (dysprosium, thulium, and ytterbium) under a range of pH and temperature conditions. We found that there was a difference in temperature sensitivity for each of the complexes studied, which depended on the size of the lanthanide ion as well as the isomeric state of the cage. Using "1"7O-NMR, we confirmed that the temperature sensitivity of the compounds was enhanced by the presence of an apically bound water molecule. Since amide-containing lanthanide complexes are known to be pH sensitive and can be used as probes of physiological pH, we also investigated the effect of pH on the Ln-M8-SPy susceptibility tensor, but we found that the changes in this pH range (5.0–7.4) were not significant.

  6. Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

    Energy Technology Data Exchange (ETDEWEB)

    Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

    2013-03-01

    The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

  7. Pressure-induced polyamorphism in lanthanide-solute metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liangliang; Li, Renfeng; Liu, Haozhe [Harbin Institute of Technology, Harbin (China); Center for High Pressure Science Technology Advanced Research, Changchun (China); Wang, Luhong [Harbin Institute of Technology, Harbin (China); Qu, Dongdong [School of Mechanical and Mining Engineering, The University of Queensland, Brisbane, QLD (Australia); Zhao, Haiyan [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States); Center for Advanced Energy Studies, University of Idaho, Idaho Falls, ID (United States); Chapman, Karena W.; Chupas, Peter J. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL (United States)

    2017-06-15

    The electronic structure inheritance of lanthanide-solvent atoms in lanthanide-based metallic glasses has been proposed. Is a polyamorphism possible in lanthanide-solute metallic glasses? So far, polyamorphic phase transitions in metallic glass containing lanthanide have been observed only in lanthanide-solvent metallic glasses. Here, a pressure-induced transition between two distinct amorphous states, accompanied by a 7% volume collapse at ambient pressure, was observed in La{sub 43.4}Pr{sub 18.6}Al{sub 14}Cu{sub 24} metallic glass, with low lanthanide content, by using in situ X-ray total scattering method. The transformation also indicated by changes in short range and medium range order. Thus, it is proposed that the lanthanide-solute metallic glasses also inherit 4f electronic transition from pure lanthanide element in polyamorphic transition. This discovery offers a supplement to research on lanthanide-based metallic glasses, which further provides a new perspective of the polyamorphic transformation in metallic glasses containing lanthanide element. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Polymetallic lanthanide (III) complexes for the design of new luminescent materials

    International Nuclear Information System (INIS)

    Marchal, C.

    2008-09-01

    The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecular chemistry and allows the combination of their nano-scopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecular lanthanide complexes quite challenging. In order to better understand the factors determining the assembly of lanthanide-based polymetallic arrays, we designed two different types of organic ligands, which favor, in one case, formation of infinite polymetallic complexes (coordination polymers), and in the case the assembly of discrete polymetallic architectures. Thus, we show that the use of flexible and multi-dentate picolinate-derivative ligands enables the formation of infinite and luminescent infinite frameworks which display very interesting luminescent properties. Geometry of the ligand has a great influence on the final network architecture. Particularly, implementation of four picolinate units within a tetrapodal ligand results in the controlled assembly of 1-D coordination polymers. Conversely to favor the controlled assembly of discrete polymetallic arrays we use dissymmetric ligands which displays low denticity. Complexation studies of a tridentate 8- hydroxyquinoline-derivative ligand as well as a tetradentate ligand possessing an oxazoline ring are presented. (author)

  9. An optical authentication system based on imaging of excitation-selected lanthanide luminescence.

    Science.gov (United States)

    Carro-Temboury, Miguel R; Arppe, Riikka; Vosch, Tom; Sørensen, Thomas Just

    2018-01-01

    Secure data encryption relies heavily on one-way functions, and copy protection relies on features that are difficult to reproduce. We present an optical authentication system based on lanthanide luminescence from physical one-way functions or physical unclonable functions (PUFs). They cannot be reproduced and thus enable unbreakable encryption. Further, PUFs will prevent counterfeiting if tags with unique PUFs are grafted onto products. We have developed an authentication system that comprises a hardware reader, image analysis, and authentication software and physical keys that we demonstrate as an anticounterfeiting system. The physical keys are PUFs made from random patterns of taggants in polymer films on glass that can be imaged following selected excitation of particular lanthanide(III) ions doped into the individual taggants. This form of excitation-selected imaging ensures that by using at least two lanthanide(III) ion dopants, the random patterns cannot be copied, because the excitation selection will fail when using any other emitter. With the developed reader and software, the random patterns are read and digitized, which allows a digital pattern to be stored. This digital pattern or digital key can be used to authenticate the physical key in anticounterfeiting or to encrypt any message. The PUF key was produced with a staggering nominal encoding capacity of 7 3600 . Although the encoding capacity of the realized authentication system reduces to 6 × 10 104 , it is more than sufficient to completely preclude counterfeiting of products.

  10. Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence.

    Science.gov (United States)

    Zhang, Kun; Xie, Xiaoji; Li, Hongyu; Gao, Jiaxin; Nie, Li; Pan, Yue; Xie, Juan; Tian, Dan; Liu, Wenlong; Fan, Quli; Su, Haiquan; Huang, Ling; Huang, Wei

    2017-09-01

    Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H 2 sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide-oxalate MOFs that are highly water stable, with so far the highest room-temperature proton conductivity (3.42 × 10 -3 S cm -1 ) under 100% relative humidity (RH) among lanthanide-based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition-metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider-range applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Actinide-lanthanide separation by bipyridyl-based ligands. DFT calculations and experimental results

    International Nuclear Information System (INIS)

    Borisova, Nataliya E.; Eroshkina, Elizaveta A.; Korotkov, Leonid A.; Ustynyuk, Yuri A.; Alyapyshev, Mikhail Yu.; Eliseev, Ivan I.; Babain, Vasily A.

    2011-01-01

    In order to gain insights into effect of substituents on selectivity of Am/Eu separation, the synthesis and extractions tests were undertaken on the series of bipyridyl-based ligands (amides of 2,2'-bipyridyl-6,6'-dicarboxylic acid: L Ph - N,N'-diethyl-N,N'-diphenyl amide; L Bu2 - tetrabutyl amide; L Oct2 - tetraoctyl amide; L 3FPh - N,N'-diethyl-N,N'-bis-(3-fluorophenyl) amide; as well as N,N'-diethyl-N,N'-diphenyl amide of 4,4'-dibrom-2,2'-bipyridyl-6,6'-dicarboxylic acid and N,N'-diethyl-N,N'-diphenyl amide of 4,4'-dinitro-2,2'-bipyridyl-6,6'-dicarboxylic acid) as well as structure and stability of their complexes with lanthanides and actinides were studied. The extraction tests were performed for Am, lanthanide series and transition metals in polar diluents in presence of chlorinated cobalt dicarbolide and have shown high distribution coefficients for Am. Also was found that the type of substituents on amidic nitrogen exerts great influence on the extraction of light lanthanides. For understanding of the nature of this effect we made QC-calculations at DFT level, binding constants determination and X-Ray structure determination of the complexes. The UV/VIS titration performed show that the composition of all complexes of the amides with lanthanides in solution is 1:1. In spite of the binding constants are high (lgβ about 6-7 in acetonitrile solution), lanthanide ions have binding constants with the same order of magnitude for dialkyl substituted extractants. The X-Ray structures of the complexes of bipyridyl-based amides show the composition of 1:1 and the coordination number of the ions being 10. The DFT optimized structures of the compounds are in good agreement with that obtained by X-Ray. The gas phase affinity of the amides to lanthanides shows strong correlation with the distribution ratios. We can infer that the bipyridyl-based amides form complexes with metal nitrates which have similar structure in solid and gas phases and in solution, and the DFT

  12. 1,3-thiazole as suitable antenna ligand for lanthanide photoluminescence in [LnCl{sub 3}(thz){sub 4}].0.5thz, Ln = Sm, Eu, Gd, Tb, Dy

    Energy Technology Data Exchange (ETDEWEB)

    Dannenbauer, Nicole; Mueller-Buschbaum, Klaus [Wuerzburg Univ. (Germany). Inst. for Inorganic Chemistry; Kuzmanoski, Ana; Feldmann, Claus [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. for Inorganic Chemistry

    2014-02-15

    The series of luminescent monomeric lanthanide thiazole complexes [LnCl{sub 3}(thz){sub 4}].0.5thz (Ln = Sm, Eu, Gd, Tb, Dy; thz = 1,3-thiazole) has been synthesised and characterised by powder and single-crystal X-ray diffraction, IR and photoluminescence spectroscopy, DTA/TG as well as elemental analysis. The colourless compounds exhibit photoluminescence in the visible region with varying quantum efficiencies up to QY = 48 % for [LnCl{sub 3}(thz){sub 4}].0.5thz. Both, the lanthanide ions as well as the thiazole ligand contribute to the luminescence. Excitation can be achieved via intra-4f transitions and by exciting the ligand, emission is observed mainly from the lanthanide ions again by 4f transitions. Thiazole can transfer energy to the lanthanide ions, which further feeds the lanthanide emission by an efficient antenna effect even at room temperature. The lanthanide ions show pentagonal-bipyramidal coordination by three chloride anions and four N atoms of 1,3-thiazole, which leads to a strong {sup 5}D{sub 0} → {sup 7}F{sub 4} transition for europium. Significant differences arise as compared to thiophene complexes because no sulphur atom is involved in the metal coordination, as the thiazole ligand is solely coordinated via its nitrogen function. (orig.)

  13. Tuning the sensitivity of lanthanide-activated NIR nanothermometers in the biological windows.

    Science.gov (United States)

    Cortelletti, P; Skripka, A; Facciotti, C; Pedroni, M; Caputo, G; Pinna, N; Quintanilla, M; Benayas, A; Vetrone, F; Speghini, A

    2018-02-01

    Lanthanide-activated SrF 2 nanoparticles with a multishell architecture were investigated as optical thermometers in the biological windows. A ratiometric approach based on the relative changes in the intensities of different lanthanide (Nd 3+ and Yb 3+ ) NIR emissions was applied to investigate the thermometric properties of the nanoparticles. It was found that an appropriate doping with Er 3+ ions can increase the thermometric properties of the Nd 3+ -Yb 3+ coupled systems. In addition, a core containing Yb 3+ and Tm 3+ can generate light in the visible and UV regions upon near-infrared (NIR) laser excitation at 980 nm. The multishell structure combined with the rational choice of dopants proves to be particularly important to control and enhance the performance of nanoparticles as NIR nanothermometers.

  14. Separation process for lanthanides based on solvation properties of non ionic surfactants

    International Nuclear Information System (INIS)

    Draye, M.; Favre-Reguillon, A.; Foos, J.; Cote, G.

    2004-01-01

    In the present study, cloud-point extraction is used with a lipophilic chelating agent (8-hydroxyquinoline) to extract and separate lanthanum (III) and gadolinium (III) from an aqueous solution. The methodology used is based on the formation of lanthanide (III) organic complexes that are soluble in a micellar phase of non-ionic surfactant. The lanthanide (III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud-point temperature. The cloud-point temperature, the structure of the lipophilic part of the nonionic surfactant and the chelating agent - metal molar ratio are identified as factors determining the extraction efficiency and selectivity. With Triton X-114, high selectivity and decontamination factor for Gd(III) is observed indicating that micelle mediated extraction involving cloud-point extraction is promising for the specific separation of actinide ions from nuclear waste solution. (authors)

  15. Selective chelation and extraction of lanthanides and actinides with supercritical fluids

    International Nuclear Information System (INIS)

    Brauer, R.D.; Carleson, T.E.; Harrington, J.D.; Jean, F.; Jiang, H.; Lin, Y.; Wai, C.M.

    1994-01-01

    This report is made up of three independent papers: (1) Supercritical Fluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) Supercritical Fluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest

  16. High-performance separation and supercritical extraction of lanthanides and actinides

    International Nuclear Information System (INIS)

    Datta, Arpita; Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2010-01-01

    Extensive studies were carried out at Chemistry Group, IGCAR for the rapid separation of individual lanthanides and actinides using dynamic ion-exchange chromatographic technique. The atom percent fission was determined from the concentrations of the lanthanide fission products, uranium and plutonium contents of dissolver solution. These advantages were exploited to significantly reduce analysis time, liquid waste generation as well as dose to operator. Supercritical fluid extraction (SFE) of actinides from waste matrices was studied in detail at our laboratory using modified supercritical carbon dioxide (Sc-CO 2 ). Complete extraction and recovery of uranium, plutonium and americium from various matrices was achieved using Sc-CO 2 modified with suitable ligands. The technique was demonstrated for the recovery of plutonium from actual waste received from different laboratories. (author)

  17. Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

    Science.gov (United States)

    Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

    2012-01-16

    Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

  18. Lanthanide - actinide separation: a challenge in the back end of nuclear fuel cycle

    International Nuclear Information System (INIS)

    Mohapatra, P.K.

    2015-01-01

    Due to their similar size and chemical state, separation of trivalent lanthanide and actinide ions has always been a challenging topic of research. Of late, the growing concern for the radioactive waste management in the back end of the nuclear fuel cycle has led to the possibility of transmuting the long-lived transuranides in high flux reactors. This necessitates the development of processes for the separation of lanthanides and actinides in acidic/low pH media. In view of the high absorption cross section of few lanthanides, their presence in relatively large proportion (10-100 times) impedes the transmutation process. Processes such as the TRAMEX and TALSPEAK have been used for the separation of lanthanides from trivalent actinides. Of late soft donor ligands containing S and N donor atoms have been used for the selective extraction of trivalent actinide ions. The commercially available S-donor compound, CYANEX 301 (bis(2,4,4-trimethylpentyl) dithiophosphinic acid) has been used to yield separation factor (S.F.) values in the excess of 6000. Synergistic extraction with N-donor ligands such as 2,2'-bipyridyl and 1,10-phenanthroline have yielded S.F. values close to 40,000. N-donor ligands such as BTP (bis-triazinylpyridine), BTBP (bis-triazinylbipyridyl) and BTPhen (bis-triazinyl-phenanthroline) have been particularly effective from relatively acidic feed conditions. The present lecture will give a brief outline of the separation processes and experimental results of studies carried out using various S and N donor ligands. Use of room temperature ionic liquids for more favorable separations will be highlighted. Liquid membrane separation results for application to back end nuclear fuel cycle will also be discussed. (author)

  19. Design and synthesis of some polyaminopolycarboxylic acids and the structural influence of their anions on the separation of actinides and lanthanides

    International Nuclear Information System (INIS)

    Tse, P.K.

    1983-01-01

    Investigation of some methods for the preparation of four polyaminopolycarboxylic acids: thiobis(ethylenenitrilo)-N,N,N',N'-tetraacetic acid, N,N-bis(2-aminoethyl)aniline-N',N',N'',N''-tetraacetic acid, bis(3-aminopropyl)ether-N,N,N',N'-tetraacetic acid and N,N-bis[N',N'-dicarboxymethyl-3-aminopropyl]-N-methylammonioacetate are reported. The coordinating properties of their anions with regard to lanthanide ions have been examined. Polyaminopolycarboxylates form 1:1 chelate species with trivalent lanthanide ions in aqueous media. The stability constants of their metal chelate species depend upon the size of the chelating rings formed, the basicity of the middle atom in the chain, and the number of coordination points between anion and metal cation. Tracer level 241 Am- 155 Eu cation-exchange experiments explore how the relative magnitude of the chelate stability constants affects the separation of members of the lanthanide and actinide series

  20. Lanthanide doped strontium-barium cesium halide scintillators

    Science.gov (United States)

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  1. Ultrasmall lanthanide oxide nanoparticles for biomedical imaging and therapy

    CERN Document Server

    Lee, Gang Ho

    2014-01-01

    Most books discuss general and broad topics regarding molecular imagings. However, Ultrasmall Lanthanide Oxide Nanoparticles for Biomedical Imaging and Therapy, will mainly focus on lanthanide oxide nanoparticles for molecular imaging and therapeutics. Multi-modal imaging capabilities will discussed, along with up-converting FI by using lanthanide oxide nanoparticles. The synthesis will cover polyol synthesis of lanthanide oxide nanoparticles, Surface coatings with biocompatible and hydrophilic ligands will be discussed and TEM images and dynamic light scattering (DLS) patterns will be

  2. Giant exchange interaction in mixed lanthanides

    Science.gov (United States)

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

    2016-01-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470

  3. Diagnostic study about lanthanides (rare earths)

    International Nuclear Information System (INIS)

    Ribeiro, G.F.

    1985-01-01

    The world situation of rare earths (lanthanides) is evaluated, and a comparison of the Brazilian situation in respect to other countries is established, concerning the following aspects: geology of mineral deposits; main sources, uses, reserves and production; their consumption, prices and state-of-art of geological researches and industrial processes for physical and chemical separation / concentration of these elements. (C.L.B.) [pt

  4. Analysis of the shift of zero-phonon lines for f–d luminescence of lanthanides in relation to the Dorenbos model

    International Nuclear Information System (INIS)

    Zych, Aleksander; Ogieglo, Joanna; Ronda, Cees; Mello Donegá, Celso de; Meijerink, Andries

    2013-01-01

    The Dorenbos relation is an empirical model that relates the position of the lowest fd level of any lanthanide ion with that of Ce 3+ in the same host lattice. The relation is widely used to estimate the energy of fd levels of trivalent lanthanide ions in a given host lattice based on the peak position of the lowest fd level of at least one of the lanthanide ions in that host. The energy of fd levels is determined from peak maxima in excitation and emission spectra. In this work we use the position of zero-phonon lines (ZPLs) as input to investigate the accuracy of the Dorenbos relation. To this end, the ZPL positions of the fd bands for trivalent lanthanide ions in four different host lattices (CaF 2 , Y 3 Al 5 O 12 , LiYF 4 , and YPO 4 ) were obtained and used as input in the Dorenbos relation. The results are compared to those obtained through the standard procedure using band maxima. The data indicate that the ZPL approach gives more accurate estimates for the position of the lowest fd level with standard deviations that are 2–3 times smaller than those obtained for band maxima. The results confirm the concept of the Dorenbos model (constant energy difference between the fd levels of lanthanides) and show that the accuracy is even better than previously reported. The main cause for the larger deviation from positions of band maxima is related to a larger inaccuracy in determining band maxima compared to ZPLs. - Highlights: ► Zero-phonon lines were measured for the lanthanide series in different hosts. ► Values for the Dorenbos relation were revised for the zero-phonon line approach. ► Revised values are based on multiple materials where zero-phonon lines are observed.

  5. Effective core potential methods for the lanthanides

    International Nuclear Information System (INIS)

    Cundari, T.R.; Stevens, W.J.

    1993-01-01

    In this paper a complete set of effective core potentials (ECPs) and valence basis sets for the lanthanides (Ce to Lu) are derived. These ECPs are consistent not only within the lanthanide series, but also with the third-row transition metals which bracket them. A 46-electron core was chosen to provide the best compromise between computational savings and chemical accuracy. Thus, the 5s and 5p are included as ''outer'' core while all lower energy atomic orbitals (AOs) are replaced with the ECP. Generator states were chosen from the most chemically relevant +3 and +2 oxidation states. The results of atomic calculations indicate that the greatest error vs highly accurate numerical potential/large, even-tempered basis set calculations results from replacement of the large, even-tempered basis sets with more compact representations. However, the agreement among atomic calculations remains excellent with both basis set sizes, for a variety of spin and oxidation states, with a significant savings in time for the optimized valence basis set. It is expected that the compact representation of the ECPs and valence basis sets will eventually encourage their use by computational chemists to further explore the bonding and reactivity of lanthanide complexes

  6. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    International Nuclear Information System (INIS)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox) 0.5 (H 2 O)] n ·2n(H 2 O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H 2 sfpip)(ox)(H 2 O) 4 ] n ·2n(H 2 O) (Ln=Nd (8) Sm (9)), [H 2 ox=oxalic acid, H 3 sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H 3 sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox 2− anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

  7. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-15

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox){sub 0.5}(H{sub 2}O)]{sub n}·2n(H{sub 2}O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H{sub 2}sfpip)(ox)(H{sub 2}O){sub 4}]{sub n}·2n(H{sub 2}O) (Ln=Nd (8) Sm (9)), [H{sub 2}ox=oxalic acid, H{sub 3}sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H{sub 3}sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox{sup 2−} anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

  8. Application of multi-step excitation schemes for detection of actinides and lanthanides in solutions by luminescence/chemiluminescence laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Izosimov, I. [Joint Institute for Nuclear Research, Joliot Curie 6, Dubna 141980 (Russian Federation)

    2016-07-01

    The use of laser radiation with tunable wavelength allows the selective excitation of actinide/lanthanide species with subsequent registration of luminescence/chemiluminescence for their detection. This work is devoted to applications of the time-resolved laser-induced luminescence spectroscopy and time-resolved laser-induced chemiluminescence spectroscopy for the detection of lanthanides and actinides. Results of the experiments on U, Eu, and Sm detection by TRLIF (Time Resolved Laser Induced Fluorescence) method in blood plasma and urine are presented. Data on luminol chemiluminescence in solutions containing Sm(III), U(IV), and Pu(IV) are analyzed. It is shown that appropriate selectivity of lanthanide/actinide detection can be reached when chemiluminescence is initiated by transitions within 4f- or 5f-electron shell of lanthanide/actinide ions corresponding to the visible spectral range. In this case chemiluminescence of chemiluminogen (luminol) arises when the ion of f element is excited by multi-quantum absorption of visible light. The multi-photon scheme of chemiluminescence excitation makes chemiluminescence not only a highly sensitive but also a highly selective tool for the detection of lanthanide/actinide species in solutions. (author)

  9. Unexpected magnetism, and transport properties in mixed lanthanide compound

    Science.gov (United States)

    Pathak, Arjun; Gschneidner, Karl, Jr.; Pecharsky, Vitalij; Ames Laboratory Team

    For intelligent materials design it is desirable to have compounds which have multiple functionalities such as a large magnetoresistance, ferromagnetic and ferrimagnetic states, and field-induced first-order metamagnetic transitions. Here, we discuss one such example where we have combined two lanthanide elements Pr and Er in Pr0.6Er0.4Al2. This compound exhibits multiple functionalities in magnetic fields between 1 and 40 kOe. It undergoes only a trivial ferrimagnetism to paramagnetism transition in a zero magnetic field, but Pr0.6Er0.4Al2 exhibits a large positive magnetoresistance (MR) for H >=40 kOe, a small but non negligible negative MR for H field cooling from the paramagnetic state. These phenomena are attributed to the competition between single-ion anisotropies of Pr and Er ions coupled with the opposite nearest-neighbor and next-nearest-neighbor exchange interactions. This work was supported by the US Department of Energy, Office of Basic Energy Science, Division of Material Sciences and Engineering. The research was performed at the Ames Laboratory. The Ames Laboratory is operated by Iowa State University for the US D.

  10. Lanthanide-containing polymer microspheres by multiple-stage dispersion polymerization for highly multiplexed bioassays.

    Science.gov (United States)

    Abdelrahman, Ahmed I; Dai, Sheng; Thickett, Stuart C; Ornatsky, Olga; Bandura, Dmitry; Baranov, Vladimir; Winnik, Mitchell A

    2009-10-28

    We describe the synthesis and characterization of metal-encoded polystyrene microspheres by multiple-stage dispersion polymerization with diameters on the order of 2 mum and a very narrow size distribution. Different lanthanides were loaded into these microspheres through the addition of a mixture of lanthanide salts (LnCl(3)) and excess acrylic acid (AA) or acetoacetylethyl methacrylate (AAEM) dissolved in ethanol to the reaction after about 10% conversion of styrene, that is, well after the particle nucleation stage was complete. Individual microspheres contain ca. 10(6)-10(8) chelated lanthanide ions, of either a single element or a mixture of elements. These microspheres were characterized one-by-one utilizing a novel mass cytometer with an inductively coupled plasma (ICP) ionization source and time-of-flight (TOF) mass spectrometry detection. Microspheres containing a range of different metals at different levels of concentration were synthesized to meet the requirements of binary encoding and enumeration encoding protocols. With four different metals at five levels of concentration, we could achieve a variability of 624, and the strategy we report should allow one to obtain much larger variability. To demonstrate the usefulness of element-encoded beads for highly multiplexed immunoassays, we carried out a proof-of-principle model bioassay involving conjugation of mouse IgG to the surface of La and Tm containing particles and its detection by an antimouse IgG bearing a metal-chelating polymer with Pr.

  11. Advances in lanthanide-based luminescent peptide probes for monitoring the activity of kinase and phosphatase.

    Science.gov (United States)

    Pazos, Elena; Vázquez, M Eugenio

    2014-02-01

    Signaling pathways based on protein phosphorylation and dephosphorylation play critical roles in the orchestration of complex biochemical events and form the core of most signaling pathways in cells (i.e. cell cycle regulation, cell motility, apoptosis, etc.). The understanding of these complex signaling networks is based largely on the biochemical study of their components, i.e. kinases and phosphatases. The development of luminescent sensors for monitoring kinase and phosphatase activity is therefore an active field of research. Examples in the literature usually rely on the modulation of the fluorescence emission of organic fluorophores. However, given the exceptional photophysical properties of lanthanide ions, there is an increased interest in their application as emissive species for monitoring kinase and phosphatase activity. This review summarizes the advances in the development of lanthanide-based luminescent peptide sensors as tools for the study of kinases and phosphatases and provides a critical description of current examples and synthetic approaches to understand these lanthanide-based luminescent peptide sensors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Some aspects of synergistic extraction of actinides and lanthanides from mixed aqueous-organic media

    International Nuclear Information System (INIS)

    Shukla, J.P.; Subramanian, M.S.

    1981-01-01

    Various aspects of the synergistic extraction and separation of actinides and lanthanides from mixed aqueous-organic solutions (polar media) have been reviewed. Notable recent developments as well as its current status in solvent extraction systems where the aqueous acidic phase contains an organic solvent which is completely miscible with water, are presented briefly. In general, extraction increases in the presence of an organic component. The less polar the additive, the higher is the tendency to form neutral metal complexes which ultimately brings about an increase in the extraction. In a polar media, synergism has mostly been observed, though antagonism is not uncommon. An attempt has been made to classify the factors that play an important role in polar phase extractions. Also, their influence particularly on the extractability of actinides and lanthanides is discussed. The discussion is limited to the factors affecting the extraction equilibria, effect of dielectric constant of the polar medium, solvation of the extracting agent and to the composition and stability of the metal complex in the organic phase. Hydroxyl (OHsup(-)) bearing organic additives, e.g. alcohols, and solvents not containing the hydroxyl group such as acetone, dimethylsulphoxide, tetrahydrofuran, amides and acetonitrile etc. are the two major classes of organic additives considered in these studies. Generally, synergistic effect in extraction of the ion-association (TBP, TOPO, sulphoxides etc.) or anion exchange (amines etc.) type is relatively more pronounced compared to other extractions. A tabular summary concerning extraction of actinides and lanthanides from polar media is appended for ready reference. (author)

  13. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    Science.gov (United States)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- anions as linkers to bridge the adjacent layers. Compounds 8-9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1-7 to 8-9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1-9 were also investigated.

  14. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    International Nuclear Information System (INIS)

    Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

    2015-01-01

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2 1 helical chains. While the Nd(III) ions are bridged through μ 2 -HIDC 2− and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2 1 helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2 1 helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature

  15. Homodinuclear lanthanide complexes of phenylthiopropionic acid: Synthesis, characterization, cytotoxicity, DNA cleavage, and antimicrobial activity

    Science.gov (United States)

    Shiju, C.; Arish, D.; Kumaresan, S.

    2013-03-01

    Lanthanide complexes of La(III), Pr(III), Nd(III), Sm(III), and Ho(III) with phenylthiopropionic acid were synthesized and characterized by elemental analysis, mass, IR, electronic spectra, molar conductance, TGA, and powder XRD. The results show that the lanthanide complexes are homodinuclear in nature. The two lanthanide ions are bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles are consistent with the proposed formulations. Powder XRD studies show that all the complexes are amorphous in nature. Antimicrobial studies indicate that these complexes exhibit more activity than the ligand itself. The DNA cleavage activity of the ligand and its complexes were assayed on Escherichia coli DNA using gel electrophoresis in the presence of H2O2. The result shows that the Pr(III) and Nd(III) complexes have completely cleaved the DNA. The anticancer activities of the complexes have also been studied towards human cervical cancer cell line (HeLa) and colon cancer cells (HCT116) and it was found that the La(III) and Nd(III) complexes are more active than the corresponding Pr(III), Sm(III), Ho(III) complexes, and the free ligand on both the cancer cells.

  16. Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

    Science.gov (United States)

    Burek, Katja; Eidner, Sascha; Kuke, Stefanie; Kumke, Michael U.

    2018-02-01

    The luminescence of Lanthanide(III) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(III) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K ≤ T ≤ 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M ≤ I ≤ 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.

  17. Self-assembled coordination nanoparticles from nucleotides and lanthanide ions with doped-boronic acid-fluorescein for detection of cyanide in the presence of Cu2+ in water.

    Science.gov (United States)

    Kulchat, Sirinan; Chaicham, Anusak; Ekgasit, Sanong; Tumcharern, Gamolwan; Tuntulani, Thawatchai; Tomapatanaget, Boosayarat

    2012-01-30

    The sensor molecule, F-oBOH, containing boronic acid-linked hydrazide and fluorescein moieties was synthesized. For anion sensing applications, F-oBOH was studied in aqueous media. Unfortunately, F-oBOH was found to be hydrolyzed in water. Therefore, a new strategy was developed to prevent the hydrolysis of F-oBOH by applying self-assembly coordination nanoparticles network (F-oBOH-AMP/Gd(3+) CNPs). Interestingly, the nanoparticles network displayed the enhancement of fluorescent signal after adding Cu(2+) following by CN(-). The network, therefore, possessed a high selectivity for detection of CN(-) compared to other competitive anions in the presence of Cu(2+). Cyanide ion could promote the Cu(2+) binding to F-oBOH incorporated in AMP/Gd(3+) CNPs to give the opened-ring form of spirolactam resulting in the fourfold of fluorescence enhancement compared to Cu(2+) complexation without CN(-). Additionally, the log K value of F-oBOH-AMP/Gd(3+) CNPs⊂Cu(2+) toward CN(-) was 3.97 and the detection limits obtained from naked-eye and spectrofluorometry detections were 20μM and 4.03μM, respectively. The proposed method was demonstrated to detect CN(-) in drinking water with high accuracy. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Stability constants of mixed ligand complexes of lanthanide(III) and yttrium(III) with complexone and substituted salicylic acids

    International Nuclear Information System (INIS)

    Kolhe, Vishnu; Dwivedi, K.

    1996-01-01

    Salicylic acid and substituted salicylic acids are potential antimicrobial agents. Binary complexes of salicylic acid and its substituted derivatives with lanthanide(III) and yttrium(III) metal ions have been reported. There are reports on the ternary metal complexing equilibria with some lanthanide(III) and yttrium(III) metal ions involving aminopolycarboxylic acid as one ligand and salicylic acid (SA) and other related compounds as the second ligands. Ethylene glycol bis(2-aminoethylether)- N, N, N', N'-tetraacetic acid (EGTA) is an important member of aminopolycarboxylic acid and finds many applications in medicine and biology. Recently, few ternary complexes have been reported using EGTA as ligand. In view of biological importance of simple and mixed ligand complexes EGTA, SA and DNSA (3,5-dinitrosalicylic acid), a systematic study has been undertaken for the determination of stability constant and the results are reported. (author). 6 refs., 1 fig., 2 tabs

  19. Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

    International Nuclear Information System (INIS)

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

    2014-01-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln 2 (Hpdc) 2 (C 2 O 4 )(H 2 O) 4 ] n ·2nH 2 O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H 3 pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H 3 pdc was decomposed into (ox) 2− with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2 1 /c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H 3 pdc was decomposed into (ox) 2− with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence

  20. Synthetic Smectite Colloids: Characterization of Nanoparticles after Co-Precipitation in the Presence of Lanthanides and Tetravalent Elements (Zr, Th

    Directory of Open Access Journals (Sweden)

    Muriel Bouby

    2015-09-01

    Full Text Available The magnesian smectite hectorite is a corrosion product frequently detected in nuclear waste glass alteration experiments. The structural incorporation of a single trivalent lanthanide was previously demonstrated. Hectorite was presently synthesized, for the first time, in the presence of several lanthanides (La, Eu, Yb following a multi-step synthesis protocol. The smallest-sized particles (nanoparticles, NPs were isolated by centrifugation and analyzed by asymmetrical flow field-flow fractionation (AsFlFFF coupled to ICP-MS, in order to obtain information on the elemental composition and distribution as a function of the size. Nanoparticles can be separated from the bulk smectite phase. The particles are able to accommodate even the larger-sized lanthanides such as La, however, with lower efficiency. We, therefore, assume that the incorporation proceeds by substitution for octahedral Mg accompanied by a concomitant lattice strain that increases with the size of the lanthanides. The presence of a mixture does not seem to affect the incorporation extent of any specific element. Furthermore, syntheses were performed where in addition the tetravalent zirconium or thorium elements were admixed, as this oxidation state may prevail for many actinide ions in a nuclear waste repository. The results show that they can be incorporated as well.

  1. Experimental solubility measurements of lanthanides in liquid alkalis

    Science.gov (United States)

    Isler, Jeremy; Zhang, Jinsuo; Mariani, Robert; Unal, Cetin

    2017-11-01

    In metallic nuclear fuel, lanthanide fission products play a crucial role in the fuel burnup-limiting phenomena of fuel cladding-chemical interaction (FCCI). The lanthanides have been hypothesized to transport by a 'liquid-like' mechanism out of the metallic fuel to the fuel peripheral to cause FCCI. By liquid fission product cesium and liquid bond sodium, the lanthanides are transported to the peripheral of the fuel through the porosity of the fuel. This work investigates the interaction between the lanthanides and the alkali metals by experimentally measuring the solubility of lanthanides within liquid sodium, and neodymium in liquid cesium and mixtures of cesium and sodium. The temperature dependence of the solubility is experimentally determined within an inert environment. In addition, the dependence of the solubility on the alkali metal concentration in liquid mixtures of cesium and sodium was examined. In quantifying the solubility, the fundamental understanding of this transport mechanism can be better determined.

  2. Magneto, spectral and thermal studies of lanthanum and lanthanide(3) bromide and nitrate complexes of 2,2'bipyridine mono N-oxide

    International Nuclear Information System (INIS)

    Agarwal, R.K.

    1988-01-01

    Lanthanide(3) bromide and nitrate complexes of 2,2'-bipyridine mono N-oxide (BipyNO) having the composition Ln(BipyNO) 3 Br 3 and Ln(BipyNO) 2 (NO 3 ) 3 (Ln=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Yb) have been prepared and characterized by means of conductance, molecular weight, magnetic and spectral studies. The ligand acts as a bidentate O,N-chelating agent. The coordination number nine or ten for lanthanide ions has been assigned to these complexes. 3 tabs., 25 refs. (author)

  3. Separation device of radio lanthanides (DISER)

    International Nuclear Information System (INIS)

    Vera T, A.L.; Monroy G, F.; Vazquez M, J.C.; Jimenez B, F.

    2008-01-01

    At the present time the cancer is one of the main causes of mortality in our country, therefore, its prevention, diagnostic and treatment is of vital importance for those health systems. The treatment of the cancer and other illnesses, starting from monoclonal antibodies, peptides, macro aggregates or marked aminoacids with beta particles emitting radioisotopes, it is an extremely promising field. The radioactive lanthanides: Promethium 149, Terbium 161, Holmium 166 and Lutetium 177 are beta emitting (β), which possess nuclear and chemical properties that have shown their feasibility like radioisotopes of radiotherapeutic use. However, these radioisotopes are not commercially available; to this respect, the Radioactive Materials Research Laboratory (LIMR) of the National Institute of Nuclear Research (ININ), it has developed the methodology of production of these radioisotopes and based on these works, there is designed, built and mounted the Radio lanthanides Separation Device (DISER) able to carry out the radioisotopes production in a routine way. This device is content in a cell that has an auxiliary air service, an extraction system and it is protected with a lead armor-plating of 10 cm. The DISER it is manual and easy of managing. The main function of this equipment is the radio lanthanides separation starting from the extractive chromatography by means of packed columns with a commercial resin (LnSPS) and recovered in the superior and inferior part by fiber glass. The DISER is composed by a main carrousel where the separation columns and the elution recipients are mounted. Also counts with an opening system of irradiation vials, port samples for columns and glass material. The present work presents a detailed description of the DISER, as well as its handling that allows to produce the radioisotopes Promethium-149, Terbium-161, Holmium-166 and Lutetium-177 starting from the separation of its parent elements Neodymium-149, Gadolinium-161, Dysprosium-166 and

  4. Versatile lanthanide-azide complexes with azide/carboxylate/hydroxy mixed bridged chain exhibiting magnetic and luminescent properties

    International Nuclear Information System (INIS)

    Wang Haichao; Xue Min; Guo Qian; Zhao Jiongpeng; Liu Fuchen; Ribas, Joan

    2012-01-01

    Two new lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb for 1 and Tb for 2, isonic=isonicotinate), were obtained in hydrothermal condition. X-ray diffraction analysis indicated the two complexes are isomorphic chain structure in which the Ln III ions are mixed bridged by the azide anions, hydroxyl anions and carboxylate groups of the isonicotinate ligands. Further studies indicated weak antiferromagnetic interactions between the Ln III ions in 1 and 2, and complex 2 exhibit green sensitized Luminescent character of Tb III ion. - Graphical abstract: Two new 1D lanthanide-azide complexes, [Ln 2 (N 3 )(isonic) 2 (OH) 3 (Hisonic)(H 2 O)] n (Ln=Yb III for 1 and Tb III for 2, isonic=isonicotinate), were synthesized by hydrothermal reaction and exhibit interesting magnetism and fluorescence properties. Highlights: ► The research provided a new method for synthesizing lanthanide-azide complexes. ► The complexes have an interesting azide/hydroxyl/carboxylate mixed bridged1D chain structure. ► The antiferromagnetic coupling between the complexes and 2 displays green luminescence.

  5. Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

    Science.gov (United States)

    Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

    2017-08-07

    Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH 3 OH)(H 2 O) 2 ](CH 3 OH) 2 } n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO 3 ) 3 ·xH 2 O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH 2 ) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp 2- and dippH - display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg -1 K -1 for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters

  6. On dependence of stability of lanthanide(3) complexes with coloured ligands on the element nature

    International Nuclear Information System (INIS)

    Poluehktov, N.S.; Meshkova, S.B.; Rusakova, N.V.

    1984-01-01

    The change in the colour intensity of Ln(3) complexes with coloured ligands (methyl thymol blue, glycine cresol red, stilbazo, glycine thymol blue, methyl ortanyl S, ortanyl B, phthalexone S, semiphthalexone S, cresolphtalexone, sulfarsazen) in the natural series of lanthanoids is considered. A correlation equation is suggested that permits to describe the relative colour intensity (quenching molar coefficients, stability constants) of complexes in the series of lanthanide(3) ions versus the number of f-electrons, spin and orbital quantum numbers of the ground states. Using the ratio obtained it is possible to calculate the values of appropriate functions of complexes of elements for which such data are not available

  7. Dependence of stability of lanthanide(3) complexes with coloured ligands on the element nature

    Energy Technology Data Exchange (ETDEWEB)

    Poluehktov, N S; Meshkova, S B; Rusakova, N V [AN Ukrainskoj SSR, Odessa. Fiziko-Khimicheskij Inst.

    1984-07-01

    The change in the colour intensity of Ln(3) complexes with coloured ligands (methyl thymol blue, glycine cresol red, stilbazo, glycine thymol blue, methyl ortanyl S, ortanyl B, phthalexone S, semiphthalexone S, cresolphtalexone, sulfarsazen) in the natural series of lanthanoids is considered. A correlation equation is suggested that permits to describe the relative colour intensity (quenching molar coefficients, stability constants) of complexes in the series of lanthanide(3) ions versus the number of f-electrons, spin and orbital quantum numbers of the ground states. Using the ratio obtained it is possible to calculate the values of appropriate functions of complexes of elements for which such data are not available.

  8. Advanced Extraction Methods for Actinide/Lanthanide Separations

    International Nuclear Information System (INIS)

    Scott, M.J.

    2005-01-01

    The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

  9. Advanced Extraction Methods for Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.

    2005-12-01

    The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

  10. Thermal decomposition of lanthanide and actinide tetrafluorides

    International Nuclear Information System (INIS)

    Gibson, J.K.; Haire, R.G.

    1988-01-01

    The thermal stabilities of several lanthanide/actinide tetrafluorides have been studied using mass spectrometry to monitor the gaseous decomposition products, and powder X-ray diffraction (XRD) to identify solid products. The tetrafluorides, TbF 4 , CmF 4 , and AmF 4 , have been found to thermally decompose to their respective solid trifluorides with accompanying release of fluorine, while cerium tetrafluoride has been found to be significantly more thermally stable and to congruently sublime as CeF 4 prior to appreciable decomposition. The results of these studies are discussed in relation to other relevant experimental studies and the thermodynamics of the decomposition processes. 9 refs., 3 figs

  11. Analysis and separation of lanthanide elements

    International Nuclear Information System (INIS)

    Almeida Pimentel, E. de.

    1973-01-01

    Improvements of rare earth separation by the combined use of acetic and critic acid were studied and analytical methods for determining some of the lanthanides were tryed out. Separations of the R.E. studied were favorable when citric acid (solution A) and acetic acid (solution B) were used in the proportion of 10:1 at pH=4,00. Neutron activation, spectro-photometric, polarographic, volumetric and gravimetric procedures allowed the determination of 8 R.E.; samarium, neodymium, praseodymium, lanthanum, cerium, holmium, erbium and europium

  12. Structure and Magnetic Properties of Lanthanide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Dickerson, James Henry [Vanderbilt Univ., Nashville, TN (United States)

    2014-06-01

    We have had considerable success on this project, particularly in the understanding of the relationship between nanostructure and magnetic properties in lanthanide nanocrystals. We also have successfully facilitated the doctoral degrees of Dr. Suseela Somarajan, in the Department of Physics and Astronomy, and Dr. Melissa Harrison, in the Materials Science Program. The following passages summarize the various accomplishments that were featured in 9 publications that were generated based on support from this grant. We thank the Department of Energy for their generous support of our research efforts in this area of materials science, magnetism, and electron microscopy.

  13. Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

    International Nuclear Information System (INIS)

    Cornehl, H.H.; Hornung, G.; Schwarz, H.

    1996-01-01

    The gas-phase reactivity of the fluorinated hydrocarbons CF 4 , CHF 3 , CH 3 F, C 2 F 6 , 1,1-C 2 H 4 F 2 , and C 6 F 6 with the lanthanide cations Ce + , Pr + , Sm + , Ho + , Tm + , and Yb + and the reactivity of C 6 H 5 F with all lanthanide cations Ln + (Ln = La-Lu, with the exception of Pm + ) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane, hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a 'harpoon'-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln + RF. The most reactive lanthanides La + , Ce + , Gd + , and Tb + and also the formal closed-shell species Lu + exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm + and Yb + the formation of neutral LnF 3 is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs

  14. Investigations for the influence of geochemical parameters on the sorption and desorption of lanthanides and uranium onto opalinus clay as potential host rock for a repository

    International Nuclear Information System (INIS)

    Moeser, Christina

    2010-01-01

    The development of a disposal in deep geological formations for radioactive waste is a very important task for the future. The safety assessment for more than a hundred thousand years needs a full understanding of all processes of interaction between the radioactive waste and the surrounded formations. This work contributes to this understanding. The interaction between lanthanides (homologues of the actinides americium, curium and berkelium) / uranium and the host rock opalinus clay under influence of organic substances (NOM) have been analyzed and discussed. The complex system was split into 3 binary basic systems with the following interactions - Interactions between lanthanides / uranium and NOM - Interactions between lanthanides / uranium and the opalinus clay - Interactions between NOM and opalinus clay All binary systems can be influenced by geological parameters like pH, ion strength and competing cations. The sorption / desorption of the lanthanides onto the opalinus clay is analyzed via inductively coupled plasma mass spectrometry. For the investigation of the complexation behavior of metals with NOM we used capillary electrophoresis coupled with inductively coupled plasma mass spectrometry. Under these conditions the chosen model organic humic acid affected the sorption of the lanthanides onto opalinus clay favorably. The smaller organic compounds, which dominate in the composition of the clay organics, remobilized the metals after sorption onto clay and the sorption can be inhibited by NOM. Due to the reduced metal sorption onto Opalinus clay by NOM, a migration through the clay may be possible.

  15. Thermodynamics of complexation of lanthanides with 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl) pyridine

    Energy Technology Data Exchange (ETDEWEB)

    Rawat, N.; Bhattacharyya, A.; Tomar, B.S. [Bhabha Atomic Research Centre, Trombay, Mumbai (India). Radiochemistry Div.; Ghosh, S.K.; Gadly, T. [Bhabha Atomic Research Centre, Trombay, Mumbai (India). Bioorganic Div.

    2011-07-01

    Solvent extraction studies on separation of trivalent actinides from lanthanides using 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl) pyridines have shown promising results with respect to separation factor and efficiency in acidic medium. In order to understand their complexation behavior, the stability constant (log {beta}) of trivalent lanthanides (La, Nd, Eu, Tb, Ho, Tm, Lu) with 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine (ethyl-BTP) have been determined in methanol medium (ionic strength 0.01 M) using spectrophotometric titrations. The stoichiometry of the complexes is found to vary with the ionic size of lanthanide ion. The variation in log {beta} across the lanthanide series is attributed to variation in solvation characteristics of the metal ion. Comparison of log {beta} for Ln(III)-ethyl-BTP complexes with other alkyl derivatives showed increase in the stability with increasing length of the alkyl group due to hydrophobic interaction. In the case of Eu(III), the speciation was also corroborated by time resolved fluorescence spectroscopy. The thermodynamic parameters ({delta} G, {delta} H, {delta} S) for complexation of Eu(III) with ethyl-BTP, were determined by microcalorimetry, which revealed strong metal ion-ligand interaction with the reactions driven mainly by enthalpy. (orig.)

  16. Spectral studies of Lanthanide interactions with membrane surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Karukstis, K.K.; Kao, M.Y.; Savin, D.A.; Bittker, R.A.; Kaphengst, K.J.; Emetarom, C.M.; Naito, N.R.; Takamoto, D.Y. [Harvey Mudd College, Claremont, CA (United States)

    1995-03-23

    We have monitored the interactions of the series of trivalent lanthanide cations with the thylakoid membrane surface of spinach chloroplasts using two complementary spectral techniques. Measurements of the fluorescence emission of the extrinsic probe 2-p-toluidinonaphthalene-6-sulfonate (TNS) and the absorbance of the intrinsic chromophore chlorophyll provide two sensitive means of characterizing the dependence of the cation-membrane interaction on the nature of the cation. In these systems, added lanthanide cations adsorb onto the membrane surface to neutralize exposed segments of membrane-embedded protein complexes. The lanthanide-induced charge neutralization increases the proximity of added TNS anion to the membrane surface as evidenced by variations in the TNS fluorescence level and wavelength of maximum emission. Our results reveal a strong dependence of TNS fluorescence parameters on both lanthanide size and total orbital angular momentum L value. Lanthanides with greater charge density (small size and/or low L value) enhance the TNS fluorescence level to a greater extent. A possible origin for the lanthanide-dependent TNS fluorescence levels is suggested in terms of a heterogeneity in the number and type of TNS binding sites. The data are consistent with the proposal that larger lanthanides with smaller enthalpies of hydration induce more significant membrane appression. 59 refs., 9 figs., 2 tabs.

  17. Supercritical fluid extraction of lanthanides and actinides from solid materials with a fluorinated β-diketone

    International Nuclear Information System (INIS)

    Lin, Y.; Brauer, R.D.; Laintz, K.E.; Wai, C.M.

    1993-01-01

    Direct extraction of metal ions by supercritical carbon dioxide is highly inefficient because of the charge neutralization requirement and the weak solute-solvent interactions. One suggested approach of extracting metal ions by supercritical carbon dioxide is to convert the charged species into metal chelates using a chelating agent in the fluid phase. This paper describes a method of extracting lanthanide and uranyl ions from a solid material by supercritical carbon dioxide containing a fluorinated beta-diketone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione(FOD). Potential applications of this SFE method for separating the f-block elements from environmental samples are discussed. 13 refs., 2 tabs

  18. Lanthanide light for biology and medical diagnosis

    International Nuclear Information System (INIS)

    Bünzli, Jean-Claude G.

    2016-01-01

    Optical imaging emerges as a vital component of the various techniques needed to meet the stringent requirements of modern bioanalysis and bioimaging. Lanthanide luminescent bioprobes (LLBs) have greatly contributed to this field during the past 35 years because they have definite advantages such as little or no photobleaching and, thanks to time-gated detection, high sensitivity. The review summarizes the numerous tools offered by LLBs under their various forms, coordination compounds, nanoparticles, upconverting nanoparticles and their bioconjugates. It then focuses on biosensing, including point-of-care analysis, and then on both in vitro and in vivo bioimaging with visible and NIR light. The last section compares the performances of LLBs versus those of other commonly used bioprobes (organic dyes, quantum dots, and transition metal complexes). It is concluded that although LLBs will not replace all of existing bioprobes, they add invaluable new specific technologies to the biologist and medical doctor toolboxes. A good deal of improvements are achieved through nanotechnologies, which demonstrates that progresses in biosciences depend on the intersection of different disciplines, photophysics, chemistry, biochemistry, nanotechnology, and materials science. - Highlights: • Lanthanide luminescent bioprobes (LLBs) are indispensable tools in biosciences. • The tools provided by LLBs are summarized. • Main trends in biosensing and point-of-care analysis are presented. • Issues regarding optical bioimaging with visible and NIR light are described. • Characteristics of LLBs, including nanoparticles, are compared to other bioprobes.

  19. Lanthanide light for biology and medical diagnosis

    Energy Technology Data Exchange (ETDEWEB)

    Bünzli, Jean-Claude G., E-mail: jean-claude.bunzli@epfl.ch [Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 35002 (China); Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland)

    2016-02-15

    Optical imaging emerges as a vital component of the various techniques needed to meet the stringent requirements of modern bioanalysis and bioimaging. Lanthanide luminescent bioprobes (LLBs) have greatly contributed to this field during the past 35 years because they have definite advantages such as little or no photobleaching and, thanks to time-gated detection, high sensitivity. The review summarizes the numerous tools offered by LLBs under their various forms, coordination compounds, nanoparticles, upconverting nanoparticles and their bioconjugates. It then focuses on biosensing, including point-of-care analysis, and then on both in vitro and in vivo bioimaging with visible and NIR light. The last section compares the performances of LLBs versus those of other commonly used bioprobes (organic dyes, quantum dots, and transition metal complexes). It is concluded that although LLBs will not replace all of existing bioprobes, they add invaluable new specific technologies to the biologist and medical doctor toolboxes. A good deal of improvements are achieved through nanotechnologies, which demonstrates that progresses in biosciences depend on the intersection of different disciplines, photophysics, chemistry, biochemistry, nanotechnology, and materials science. - Highlights: • Lanthanide luminescent bioprobes (LLBs) are indispensable tools in biosciences. • The tools provided by LLBs are summarized. • Main trends in biosensing and point-of-care analysis are presented. • Issues regarding optical bioimaging with visible and NIR light are described. • Characteristics of LLBs, including nanoparticles, are compared to other bioprobes.

  20. Highly Luminescent Lanthanide Complexes of 1 Hydroxy-2-pyridinones

    Energy Technology Data Exchange (ETDEWEB)

    University of California, Berkeley; Lawrence National Laboratory; Raymond, Kenneth; Moore, Evan G.; Xu, Jide; Jocher, Christoph J.; Castro-Rodriguez, Ingrid; Raymond, Kenneth N.

    2007-11-01

    The synthesis, X-ray structure, stability, and photophysical properties of several trivalent lanthanide complexes formed from two differing bis-bidentate ligands incorporating either alkyl or alkyl ether linkages and featuring the 1-hydroxy-2-pyridinone (1,2-HOPO) chelate group in complex with Eu(III), Sm(III) and Gd(III) are reported. The Eu(III) complexes are among some of the best examples, pairing highly efficient emission ({Phi}{sub tot}{sup Eu} {approx} 21.5%) with high stability (pEu {approx} 18.6) in aqueous solution, and are excellent candidates for use in biological assays. A comparison of the observed behavior of the complexes with differing backbone linkages shows remarkable similarities, both in stability and photophysical properties. Low temperature photophysical measurements for a Gd(III) complex were also used to gain insight into the electronic structure, and were found to agree with corresponding TD-DFT calculations for a model complex. A comparison of the high resolution Eu(III) emission spectra in solution and from single crystals also revealed a more symmetric coordination geometry about the metal ion in solution due to dynamic rotation of the observed solid state structure.

  1. Efficiency of crystalline laser materials based on lanthanides

    International Nuclear Information System (INIS)

    Synek, M.

    1990-01-01

    Lanthanide-based laser-crystal efficiency has been investigated, using the laser-active ions Dy 2+ and Nd 3+ as significant illustrations. Authors' calculations, and various approaches by other authors, are reviewed. In specific examples of treatment, the analytical self-consistent field(SCF) expansion method has been used to calculate accurate ab initio wave functions and energy levels for a number of excited states of Nd 3+ and Dy 2+ , which were investigated for the first time. General group-theoretical principles were considered and the formulae for crystal-field parameters were obtained. The Racah quantum numbers were included in these calculations, in fact showing sizeable energy effects. Oscillator strengths, calculated from the SCF wave functions, revealed which orbitals can be neglected without influencing the transition probability at the fourth significant figure. The relationship to the spectral character of the pumping device was considered. The efficiency parameters (mechanical, economic, and energetic) have to be considered as supplementing the related threshold energy parameter. It would be conceivable to predict the applicability of competing laser systems to a specific task, based on integrated energy pictures. (author). 32 refs., 2 tabs

  2. Lanthanide complexes of 2-aminoacetophenone and 2-acetylaminoacetophenone 2-thenoylhydrazone

    International Nuclear Information System (INIS)

    Singh, Praveen K.; Singh, B.

    1998-01-01

    The reaction of lanthanide chlorides with 2-aminoacetophenone-2-thenoyl- hydrazone and 2-acetylaminoacetophenone-2-thenoylhydrazone yield complexes of the type [Ln(aath) 2 Cl 2 (H 2 )O]Cl and [Ln(acaath) 2 Cl 2 ]Cl. These complexes have been characterized by molar conductance, magnetic susceptibility, TGA, DTA and various spectroscopic techniques such as mass, IR, NMR, UV - visible and emission spectra. Mass spectral data indicate the aath complexes to be monomeric. Thermal stability of the complexes and presence of one water molecule in aath complex is indicated by TGA and DTA studies. Electronic spectra of Pr(III) and Nd(III) complexes show the coordination number to be nine and eight around the metal ions in the aath and acaath complexes, respectively. This has also been inferred from the spectral features of the hypersensitive transition in the Nd(III) complexes. The lowering in coordination number from aath to acaath complexes may be attributed to increase in chelate ring size and/or steric/inductive effect of methyl group. Emission spectral studies of the [Eu(aath) 2 Cl 2 (H 2 O)]Cl and [Eu(acaath) 2 Cl 2 ]Cl suggest tricapped trigonal prismatic (D 3h ) and square antiprismatic (D 4d ) geometry, respectively. (author)

  3. Diphenyl-phosphinyl-morpholide (DPPM) lanthanide trifluoroacetate adducts

    International Nuclear Information System (INIS)

    Carvalho, L.R.F. de; Kim, D.J.

    1984-01-01

    Preparation and properties of adducts of lanthanide salts and diphenyl-phosphinyl-morpholide (DPPM) have been described in the literature. Addition compounds containing lanthanide nitrates, isothiocyanates, perchlorates, chlorides, bromides with DPPM have been obtained. In this article, the preparation and characterization of the addition compounds of lanthanide trifluoroacetates (TFA) with DPPM are reported. The compounds of general formula Ln (TFA) 3 . 3DPPM, Ln= La-Lu, Y were characterized by elemental analysis, melting ranges, infrared spectra, absorption and emission visible spectra, X-ray powder patterns. (Author) [pt

  4. Lanthanide-doped upconverting phosphors for bioassay and therapy

    Science.gov (United States)

    Guo, Huichen; Sun, Shiqi

    2012-10-01

    Lanthanide-doped fluorescent materials have gained increasing attention in recent years due to their unique luminescence properties which have led to their use in wide-ranging fields including those of biological applications. Aside from being used as agents for in vivo imaging, lanthanide-doped fluorescent materials also present many advantages for use in bioassays and therapy. In this review, we summarize the applications of lanthanide-doped up-converting phosphors (UCPs) in protein and gene detection, as well as in photodynamic and gene therapy in recent years, and outline their future potential in biological applications. The current report could serve as a reference for researchers in relevant fields.

  5. Static and dynamic modelling of lanthanide and actinide cations in solution

    International Nuclear Information System (INIS)

    Marjolin, A.

    2012-01-01

    We propose a theoretical approach, based on both quantum analyses (energy decomposition analysis and topological analysis of the chemical bond) and classical molecular dynamics, for the study of f-element complexes. First, we introduce the different QM methods adapted to the study of f-elements and use them for geometry optimization and interaction energy calculations of the model system [M-(OH 2 )] m+ where M is a lanthanide or actinide cation. We then perform energy decomposition analysis to quantify the physical nature of the metal-ligand interaction in terms of the different contributions. Furthermore, the different energy contributions will be used as reference curves for the parameterization of the polarizable force fields AMOEBA and SIBFA. Next, starting from the optimized geometries, we establish the reference diabatic dissociation curves at high level of theory so as to take into account the multi-reference nature of the systems. These dissociation curves will also be used for parameterization of the AMOEBA potential. We then propose a three step validation protocol as well as a first application, it being the computation of Gibbs hydration free energies for the f-element cations. We also propose an extension of the SIBFA force field to trivalent lanthanide ions and tetravalent actinide ions. Last, we use the topological analysis approaches of ELF and NCI to investigate the nature of the different interactions in Gadolinium(III) model and real systems. The aim of the whole study was to develop and apply different theoretical approaches so as to be able to discriminate between lanthanide and actinide cations. Indeed, despite their similar chemical behavior, they still feature a selective character that we wish to be able to both explain and predict. (author) [fr

  6. Observation of divergent La{sup 3+} ion dilute effect in two series of 3-D fluorescent lanthanide-MOFs-based molecular alloys RE{sub x}La{sub 1−x}–EBTC (RE{sup 3+}=Eu{sup 3+} or Tb{sup 3+}; EBTC{sup 4−}=1,1′-ethynebenzene-3,3′,5,5′-etracarboxylate)

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Lu [State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing Tech University, Nanjing 210009 (China); State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Zhang, Wen-Wei, E-mail: wwzhang@nju.edu.cn [State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Ren, Xiao-Ming, E-mail: xmren@njtech.edu.cn [State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing Tech University, Nanjing 210009 (China); Zuo, Jing-Lin [State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)

    2015-10-15

    The lanthanide metal-organic frameworks (MOFs) [Ln{sub 2}(EBTC){sub 1.5}(CH{sub 3}OH){sub 4}]·6H{sub 2}O are isostructural to each other, where EBTC{sup 4−}=1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate; Ln{sup 3+}=La{sup 3+}, Eu{sup 3+} and Tb{sup 3+}; and the corresponding MOF is abbreviated as Ln–EBTC. MOFs Eu–EBTC and Tb–EBTC emit intense red and green luminescence (visible by bare eyes), respectively. The molecular alloys of Eu{sub x}La{sub 1−x}–EBTC and Tb{sub x}La{sub 1−x}–EBTC have been successfully prepared by mixing Eu{sup 3+}/Tb{sup 3+} and La{sup 3+} salts with the desired molar ratio in the starting material. Two series of Eu{sub x}La{sub 1−x}–EBTC and Tb{sub x}La{sub 1−x}–EBTC molecular alloys are isomorphic to the parent Ln–EBTC MOFs, while exhibit divergent La{sup 3+} ion diluting effect, namely, with increasing the relative amount of La{sup 3+}, the intensity of characteristic emission arising from Tb{sup 3+} ion monotonely increases in Tb{sub x}La{sub 1−x}–EBTC molecular alloys, whereas that of Eu{sup 3+} ion shows non-monotone decrease in Eu{sub x}La{sub 1−x}–EBTC molecular alloys. The possible origin is discussed for such a divergent behavior between Eu{sub x}La{sub 1−x}–EBTC and Tb{sub x}La{sub 1−x}–EBTC molecular alloys. - Graphical abstract: Two series of 3-D fluorescent lanthanide-MOFs-based molecular alloys RE{sub x}La{sub 1−x}–EBTC (RE{sup 3+}=Eu{sup 3+} or Tb{sup 3+}; EBTC{sup 4−}=1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate) have been successfully prepared by mixing Eu{sup 3+}/Tb{sup 3+} and La{sup 3+} salts with the desired molar ratio in the starting material and showed photoluminescence property with divergent La{sup 3+} ion dilute effect. - Highlights: • 3-D molecular alloys of Eu{sub x}La{sub 1−x}–EBTC and Tb{sub x}La{sub 1−x}–EBTC were prepared. • They are isomorphic to the parent Ln–EBTC MOFs. • They show photoluminescence property with divergent La

  7. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  8. Assembly and luminescence properties of lanthanide-polyoxometalates/polyethyleneimine/SiO{sub 2} particles with core–shell structure

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail: junwang924@yahoo.com.cn; Fan, Shaohua; Zhao, Weiqian; Zhang, Hongyan

    2013-01-01

    In this paper, two lanthanide-polyoxometalate (LnW{sub 10}) complexes were bonded on the surface of the polyethyleneimine (PEI)-modified silica nanoparticles with different sizes, resulting in the formation of LnW{sub 10}/PEI/SiO{sub 2} particles. The hybrid core–shell particles were characterized by infrared, luminescent spectra, scanning electronic microscope, and transmission electronic microscope. The particles obtained exhibit the fine spherical core–shell structure and the excellent luminescence properties. The luminescence spectra studies revealed that the formation of LnW{sub 10}/PEI/SiO{sub 2} particles and the size of particle have an influence on the luminescence properties of lanthanide ions. - Highlights: ► SiO{sub 2}/polyethyleneimine (PEI) shows the chemisorption for Ln-polyoxometalates (LnW{sub 10}). ► The core-shell LnW{sub 10}/PEI/SiO{sub 2} nanoparticles with different sizes were fabricated. ► The hybrid particles exhibit the excellent luminescence properties. ► The sizes of particles affect the luminescence properties of lanthanide ions.

  9. Upconversion studies in rare earth ions-doped lanthanide materials

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... studied samples in order to get the visible upconversion emission on 976 nm excitation. References. [1] F Azuel, Chem. Rev. 104, 139 (2004). [2] W M Yen, S Shionoya and H Yamamoto (eds), Practical applications of phosphors (CRC. Press, Taylor and Francis Group, 2006). [3] F Wang and X Liu, Chem.

  10. Fragment molecular orbital method for studying lanthanide interactions with proteins

    Energy Technology Data Exchange (ETDEWEB)

    Tsushima, Satoru [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Komeiji, Y. [National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Mochizuki, Y. [Rikkyo Univ., Tokyo (Japan)

    2017-06-01

    The binding affinity of the calcium-binding protein calmodulin towards Eu{sup 3+} was studied as a model for lanthanide protein interactions in the large family of ''EF-hand'' calcium-binding proteins.

  11. Recovery of uranium and the lanthanides from phosphate rock

    Energy Technology Data Exchange (ETDEWEB)

    Habashi, F; Awadalla, F T; Zailaf, M

    1986-06-01

    A process is proposed for the treatment of phosphate rock for the recovery of uranium and lanthanides. The process assures the production of phosphatic fertilisers without polluting the environment with radioactive material.

  12. DNA base pair resolution measurements using resonance energy transfer efficiency in lanthanide doped nanoparticles.

    Directory of Open Access Journals (Sweden)

    Aleksandra Delplanque

    Full Text Available Lanthanide-doped nanoparticles are of considerable interest for biodetection and bioimaging techniques thanks to their unique chemical and optical properties. As a sensitive luminescence material, they can be used as (bio probes in Förster Resonance Energy Transfer (FRET where trivalent lanthanide ions (La3+ act as energy donors. In this paper we present an efficient method to transfer ultrasmall (ca. 8 nm NaYF4 nanoparticles dispersed in organic solvent to an aqueous solution via oxidation of the oleic acid ligand. Nanoparticles were then functionalized with single strand DNA oligomers (ssDNA by inducing covalent bonds between surface carboxylic groups and a 5' amine modified-ssDNA. Hybridization with the 5' fluorophore (Cy5 modified complementary ssDNA strand demonstrated the specificity of binding and allowed the fine control over the distance between Eu3+ ions doped nanoparticle and the fluorophore by varying the number of the dsDNA base pairs. First, our results confirmed nonradiative resonance energy transfer and demonstrate the dependence of its efficiency on the distance between the donor (Eu3+ and the acceptor (Cy5 with sensitivity at a nanometre scale.

  13. DNA base pair resolution measurements using resonance energy transfer efficiency in lanthanide doped nanoparticles.

    Science.gov (United States)

    Delplanque, Aleksandra; Wawrzynczyk, Dominika; Jaworski, Pawel; Matczyszyn, Katarzyna; Pawlik, Krzysztof; Buckle, Malcolm; Nyk, Marcin; Nogues, Claude; Samoc, Marek

    2015-01-01

    Lanthanide-doped nanoparticles are of considerable interest for biodetection and bioimaging techniques thanks to their unique chemical and optical properties. As a sensitive luminescence material, they can be used as (bio) probes in Förster Resonance Energy Transfer (FRET) where trivalent lanthanide ions (La3+) act as energy donors. In this paper we present an efficient method to transfer ultrasmall (ca. 8 nm) NaYF4 nanoparticles dispersed in organic solvent to an aqueous solution via oxidation of the oleic acid ligand. Nanoparticles were then functionalized with single strand DNA oligomers (ssDNA) by inducing covalent bonds between surface carboxylic groups and a 5' amine modified-ssDNA. Hybridization with the 5' fluorophore (Cy5) modified complementary ssDNA strand demonstrated the specificity of binding and allowed the fine control over the distance between Eu3+ ions doped nanoparticle and the fluorophore by varying the number of the dsDNA base pairs. First, our results confirmed nonradiative resonance energy transfer and demonstrate the dependence of its efficiency on the distance between the donor (Eu3+) and the acceptor (Cy5) with sensitivity at a nanometre scale.

  14. Double liquid membrane system for the removal of actinides and lanthanides from acidic nuclear wastes

    International Nuclear Information System (INIS)

    Chiarizia, R.; Danesi, P.R.

    1985-01-01

    Supported liquid membranes (SLM), consisting of an organic solution of n-octyl-(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl-phosphate (TBP) in decalin are able to perform selective separation and concentration of actinide and lanthanide ions from aqueous nitrate feed solutions and synthetic nuclear wastes. In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of nitric acid which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO 3 from the strip solution. In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HNO 3 concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion. 15 refs., 10 figs., 1 tab

  15. Syntheses, structures and luminescence properties of lanthanide coordination polymers with helical character

    International Nuclear Information System (INIS)

    Zhou Ruisha; Cui Xiaobing; Song Jiangfeng; Xu Xiaoyu; Xu Jiqing; Wang Tiegang

    2008-01-01

    A series of lanthanide coordination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4), H 2 ip=isophthalic acid, im=imidazole] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been synthesized and characterized by elemental analyses, infrared (IR), ultraviolet-visible-near infrared (UV-Vis-NIR) and single-crystal X-ray diffraction analyses. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 features a 2-D network making of two different kinds of quadruple-helical chains. Compounds 2 and 3 present the characteristic emissions of Pr(III) and Nd(III) ions in NIR region, respectively. Compound 4 shows sensitized luminescence of Dy(III) ions in visible region. - Graphical abstract: A series of lanthanide coodination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4)] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been reported. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 displays a 2-D network making of two kinds of quadruple-helical chains. Display Omitted

  16. Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

    International Nuclear Information System (INIS)

    Thuery, P.

    2009-01-01

    Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H 4 L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO 2 ) 2 Ln 2 (L) 2 (C 2 O 4 )] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N 4 O 4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO 2 ) 2 (C 2 O 4 )] 2+ di-cations, resulting in the formation of a 3D framework. In [(UO 2 ) 4 Gd 2 (L) 2 (C 2 O 4 ) 3 (H 2 O) 6 ].2H 2 O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO 2 ) 2 Gd(L)(C 2 O 4 )(OH)].H 2 O (4) is a 2D assembly in which cationic {[(UO 2 ) 2 (C 2 O 4 )(OH)] + } n chains are linked to one another by the [Gd(L)] - groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

  17. Polysulfide coordination clusters of the lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Ying-Zhao; Bestgen, Sebastian; Gamer, Michael T.; Roesky, Peter W. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Konchenko, Sergey N. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk (Russian Federation); Novosibirsk State University (Russian Federation)

    2017-10-16

    The reaction of [(DippForm){sub 2}Ln(thf){sub 2}] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm){sub 3}Ln{sub 3}S{sub 12}] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln{sub n}S{sub x}) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S{sub 8} with divalent lanthanides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Energy level schemes of f{sup N} electronic configurations for the di-, tri-, and tetravalent lanthanides and actinides in a free state

    Energy Technology Data Exchange (ETDEWEB)

    Ma, C.-G. [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Brik, M.G., E-mail: mikhail.brik@ut.ee [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Institute of Physics, University of Tartu, Ravila 14C, Tartu 50411 (Estonia); Institute of Physics, Jan Dlugosz University, Armii Krajowej 13/15, PL-42200 Czestochowa (Poland); Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland); Liu, D.-X.; Feng, B.; Tian, Ya [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Suchocki, A. [Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland)

    2016-02-15

    The energy level diagrams are theoretically constructed for the di-, tri-, tetravalent lanthanide and actinide ions, using the Hartree–Fock calculated parameters of the Coulomb and spin–orbit interactions within f{sup N} (N=1…13) electron configurations. These diagrams are analogous to Dieke's diagram, which was obtained experimentally. They can be used for an analysis of the optical spectra of all considered groups of ions in various environments. Systematic variation of some prominent energy levels (especially those ones with a potential for emission transitions) along the isoelectronic 4f/5f ions is considered. - Highlights: • Energy level schemes for di-, tri, tetravalent lanthanides/actinides are calculated. • Systematic variation of the characteristic energy levels across the series is considered. • Potentially interesting emission transitions are identified.

  19. Tetraphenylborate as a non - coordinating anion in hexamethyphosphoramine (HMPA) and tetramethylurea (TMU) lanthanide complexes

    International Nuclear Information System (INIS)

    Kuya, M.K.; Serra, O.A.

    1979-01-01

    The synthesis of the HMPA and TMU complexes of rare earth ions using tetraphenylborate, a non-coordinating anion, as a precipitating agent is reported. The compounds obtained conform to the general formula LnL 6 (B PHI 4 ) 3 (Ln=Ce-Lu,Y, whe L=HMPA and Ln=nd, Sm,Eu,Er,Y when L=TMU). The characterization by conductance, infrared and visible measurements is consistent with the lack of donor capacity of tetraphenylborate ion, and with a coordination number six in a nearly octahedral site symmetry for both type of compounds. The TMU complexes seem to be more stable than the corresponding HMPA ones, indicating that the steric factor can be more important than the donor capacity of the ligands in this type of lanthanide compounds. (author) [pt

  20. Luminescent hybrid materials functionalized with lanthanide ethylenodiaminotetraacetate complexes containing β-diketonate as antenna ligands

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Franklin P.; Costa, Israel F.; Espínola, José Geraldo P.; Faustino, Wagner M.; Moura, Jandeilson L. [Departamento de Química-Universidade Federal da Paraíba, 58051-970 João Pessoa, PB (Brazil); Brito, Hermi F.; Paolini, Tiago B. [Departamento de Química Fundamental-Instituto de Química da Universidade de São Paulo, 05508-900 São Paulo, SP (Brazil); Felinto, Maria Cláudia F.C. [Instituto de Pesquisas energéticas e Nucleares-IPEN, 05508-900 São Paulo, SP (Brazil); Teotonio, Ercules E.S., E-mail: teotonioees@quimica.ufpb.br [Departamento de Química-Universidade Federal da Paraíba, 58051-970 João Pessoa, PB (Brazil)

    2016-02-15

    Three organic–inorganic hybrid materials based on silica gel functionalized with (3-aminopropyl)trimethoxysilane (APTS), [3-(2-aminoetilamino)-propil]-trimetoxissilano (DAPTS) and 3-[2-(2-aminoetilamino)etilamino] propiltrimetoxysilane (TAPTS) and subsequently modified with EDTA derivative were prepared by nonhomogeneous route and were then characterized. The resulting materials named SilXN-EDTA (X=1 for APTS, 2 for DAPTS and 3 for TAPTS) were used to obtain new lanthanide Ln{sup 3+}-β-diketonate (Ln{sup 3+}=Eu{sup 3+}, Gd{sup 3+} and Tb{sup 3+}) complexes covalently linked to the functionalized silica gel surfaces (named SilXN-EDTALn-dik, dik=tta, dbm, bzac and acac). The photophysical properties of the new luminescent materials were investigated and compared with those with similar system presenting water molecules coordinated to the lanthanide ions, SilXN-EDTALn-H{sub 2}O. The SilXN-EDTAEu-dik and SilXN-EDTATb-dik systems displayed characteristic red and green luminescence when excited by UV radiation. Furthermore, the quantitative results showed that the emission quantum efficiency (η), experimental intensity parameters Ω{sub 2} and Ω{sub 4}, and Einstein's emission coefficient (A{sub 0J}) of the SilXN-EDTAEu-dik materials were largely dependent on the ligands. Based on the luminescence data, the most efficient intramolecular energy transfer processes were found to the SilXN-EDTAEu-dik (dik: tta and dbm) and SilXN-EDTATb-acac materials, which exhibited more pure emission colors. These materials are promising red and green phosphors, respectively. - Highlights: • New highly luminescent hybrid materials containing lanthanide-EDTA complexes. • The effect of three silylanting agent on the adsorption and luminescent properties has been studied. • The luminescence sensitizing by different β-diketonate ligands have been investigated.

  1. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

  2. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    International Nuclear Information System (INIS)

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-01-01

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg"2"+ detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb"3"+ from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg"2"+ into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg"2"+. As a kind of Hg"2"+ nanosensor, the probe exhibited excellent selectivity for Hg"2"+ and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg"2"+ in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg"2"+ was achieved based on time-resolved spectroscopy.

  3. Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

    Science.gov (United States)

    Hackett, Timothy A.; Baldwin, D. J.; Paudyal, D.

    2017-11-01

    Theoretical understanding of interactions between localized and mobile electrons and the crystal environment in light lanthanides is important because of their key role in much needed magnetic anisotropy in permanent magnet materials that have a great impact in automobile and wind turbine applications. We report electronic, magnetic, and magnetocrystalline properties of these basic light lanthanide elements studied from advanced density functional theory (DFT) calculations. We find that the inclusion of onsite 4f electron correlation and spin orbit coupling within the full-potential band structure is needed to understand the unique magnetocrystalline properties of these light lanthanides. The onsite electron correlation, spin orbit coupling, and full potential for the asphericity of charge densities must be taken into account for the proper treatment of 4f states. We find the variation of total energy as a function of lattice constants that indicate multiple structural phases in Ce contrasting to a single stable structure obtained in other light lanthanides. The 4f orbital magnetic moments are partially quenched as a result of crystalline electric field splitting that leads to magnetocrystalline anisotropy. The charge density plots have similar asphericity and environment in Pr and Nd indicating similar magnetic anisotropy. However, Ce and Sm show completely different asphericity and environment as both orbital moments are significantly quenched. In addition, the Fermi surface structures exemplified in Nd indicate structural stability and unravel a cause of anisotropy. The calculated magnetocrystalline anisotropy energy (MAE) reveals competing c-axis and in-plane anisotropies, and also predicts possibilities of unusual structural deformations in light lanthanides. The uniaxial magnetic anisotropy is obtained in the double hexagonal closed pack structures of the most of the light lanthanides, however, the anisotropy is reduced or turned to planar in the low symmetry

  4. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min, E-mail: xiejm391@sohu.com

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 3}TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H{sub 3}TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  5. Trends in metallo-organic chemistry of scandium, yttrium, and the lanthanides

    International Nuclear Information System (INIS)

    Singh, A.

    1994-01-01

    Several interesting aspects of the metallo-organic chemistry of group 3 and the lanthanides have been highlighted, which include: (a) the chemistry of a few notable organolanthanide compounds, alkoxo and aryloxo derivatives derived from sterically demanding ligands, (b) new trends in the chemistry of lanthanide heterometallic alkoxides, (c) an account of zero valent organometallics of yttrium and the lanthanides, and (d) aspects of agostic interactions in the lanthanide metallo-organic compounds. (author). 49 refs

  6. Measurement of isotopic composition of lanthanides in reprocessing process solutions by high-performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC/ICP-MS)

    International Nuclear Information System (INIS)

    Okano, Masanori; Jitsukata, Shu; Kuno, Takehiko; Yamada, Keiji

    2011-01-01

    Isotopic compositions of fission products in process solutions and wastes in a reprocessing plant are valuable to proceed safety study of the solutions and research/development concerning treatment/disposal of the wastes. The amount of neodymium-148 is a reliable indication to evaluate irradiation history. The isotopic compositions of samarium and gadolinium in high radioactive wastes are referred to as essential data to evaluate environmental impact in geological repositories. However, pretreatment of analysis must be done with complicated chemical separation such as solvent extraction and ion exchange. The actual measurement data of isotopic compositions of lanthanides comparable to the one of actinides in spent fuel reprocessing process has not been obtained enough. Rapid and high sensitive analytical technique based on high-performance liquid chromatography (HPLC) with an inductively coupled plasma mass spectrometry (ICP-MS) has been developed for the measurement of isotopic compositions of lanthanides in spent fuel reprocessing solutions. HPLC/ICP-MS measurement system was customized for a glove-box to be applied to the radioactive solutions. The cation exchange chromatographic columns (Shim-pack IC-C1) and injection valve (20μL) were located inside of the glove-box except the chromatographic pump. The elements of lanthanide group were separated by a gradient program of HPLC with α-hydroxyisobutyric acid. Isotopic compositions of lanthanides in eluate was sequentially analyzed by a quadruple ICP-MS. Optimization of parameter of HPLC and ICP-MS measurement system was examined with standard solutions containing 14 lanthanide elements. The elements of lanthanides were separated by HPLC and detected by ICP-MS within 25 minutes. The detection limits of Nd-146, Sm-147 and Gd-157 were 0.37 μg L -1 , 0.69 μg L -1 and 0.47 μg L -1 , respectively. The analytical precision of the above three isotopes was better than 10% for standard solutions of 100 μg L -1 with

  7. Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3); Mise en evidence d'un changement de stoechiometrie du complexe carbonate limite au sein de la serie des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V

    2007-12-15

    Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An{sup 3+} and Ln{sup 3+} cations. The study of the solubility of double carbonates (AlkLn(CO{sub 3}){sub 2},xH{sub 2}O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO{sub 3}){sub 4}{sup 5-} whereas the heaviest (Eu and Dy) form Ln(CO{sub 3}){sub 3}{sup 3-} in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO{sub 3}){sub 4}{sup 5-} while Dy to Lu form Ln(CO{sub 3}){sub 3}{sup 3-}. Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO{sub 3}){sub 3}{sup 3-} complex, specially with Cs{sup +}. Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)

  8. Synthesis and characterization of lanthanide based nanomaterials for radiation detection and biomedical applications

    Science.gov (United States)

    Yao, Mingzhen

    2011-12-01

    Lanthanide based nanomaterials have shown a great potential in various areas such as luminescence imaging, luminescent labels, and detection of cellular functions. Due to the f-f transitions of the metal ion, luminescence of lanthanide ions is characterized by sharp and narrow emissions. In this dissertation lanthanide based nanoparticles such as Ce3+, Eu3+ and other lanthanide ions doped LaF3 were synthesized, their characterization, encapsulation and embedding into hybrid matrix were investigated and some of their biomedical and radiological applications were studied. DMSO is a common solvent which has been used widely for biological applications. LaF3:Ce nanoparticles were synthesized in DMSO and it was found that their fluorescent emission originates from the metal-to-ligand charge-transfer excited states. After conjugation with PpIX and then encapsulation within PLGA, the particles show efficient uptake by cancer cells and great cytotoxicity, which is promising for applications in cancer treatments. However, the emission of Eu3+ in DMSO is totally different from LaF3:Ce, very strong characteristic luminescence is observed but no emissions from metal-to-ligand charge-transfer excited states as observed in LaF3:Ce in DMSO. Besides, it is very interesting to see that the coupling of Eu 3+ with O-H oscillations after water was introduced has an opposite effect on emission peaks at 617 nm and its shoulder peak at 613 nm. As a result, the intensity ratio of these two emissions has a nearly perfect linear dependence on increasing water concentration in Eu-DMSO, which provides a very convenient and valuable method for water determination in DMSO. Ce3+ has been well known as an emitter for radiation detection due to its very short decay lifetime. However, its emission range limited the environment in which the detection system works. Whereas, Quantum dots have high luminescence quantum efficiency but their low stopping power results in very weak scintillation

  9. Sparkle/PM7 Lanthanide Parameters for the Modeling of Complexes and Materials.

    Science.gov (United States)

    Dutra, José Diogo L; Filho, Manoel A M; Rocha, Gerd B; Freire, Ricardo O; Simas, Alfredo M; Stewart, James J P

    2013-08-13

    The recently published Parametric Method number 7, PM7, is the first semiempirical method to be successfully tested by modeling crystal structures and heats of formation of solids. PM7 is thus also capable of producing results of useful accuracy for materials science, and constitutes a great improvement over its predecessor, PM6. In this article, we present Sparkle Model parameters to be used with PM7 that allow the prediction of geometries of metal complexes and materials which contain lanthanide trications. Accordingly, we considered the geometries of 224 high-quality crystallographic structures of complexes for the parameterization set and 395 more for the validation of the parameterization for the whole lanthanide series, from La(III) to Lu(III). The average unsigned error for Sparkle/PM7 for the distances between the metal ion and its coordinating atoms is 0.063Å for all lanthanides, ranging from a minimum of 0.052Å for Tb(III) to 0.088Å for Ce(III), comparable to the equivalent errors in the distances predicted by PM7 for other metals. These distance deviations follow a gamma distribution within a 95% level of confidence, signifying that they appear to be random around a mean, confirming that Sparkle/PM7 is a well-tempered method. We conclude by carrying out a Sparkle/PM7 full geometry optimization of two spatial groups of the same thulium-containing metal organic framework, with unit cells accommodating 376 atoms, of which 16 are Tm(III) cations; the optimized geometries were in good agreement with the crystallographic ones. These results emphasize the capability of the use of the Sparkle Model for the prediction of geometries of compounds containing lanthanide trications within the PM7 semiempirical model, as well as the usefulness of such semiempirical calculations for materials modeling. Sparkle/PM7 is available in the software package MOPAC2012, at no cost for academics and can be obtained from http://openmopac.net.

  10. Design and synthesis of macrocyclic ligands and their complexes of lanthanides and actinides

    International Nuclear Information System (INIS)

    Alexander, V.

    1995-01-01

    A review article which covers the various design and synthetic strategies developed to synthesize macrocyclic complexes of lanthanides and actinides, their structural features, quantitative studies on the stabilities of these complexes, their applications, and the structure-reactivity principle would be an asset for those who are actively engaged in this area of research. This review is also purported to give a comprehensive view of the current status of this area of research to the beginners and to highlight the application of this chemical research to emerging nonchemical applications to lure the potential workers. The coordination template effect provides a general strategy for the synthesis of a wide variety of discrete metal complexes. The principal conceptual and experimental development that have established and exploited this strategy are briefly outlined. A brief review of the coordination template effect and subsequent developments in the design of macrocyclic complexes of alkali, alkaline earth, and transition metal ions is presented as an essential basis for the rational design of new macrocyclic complexes of lanthanides and actinides. The exciting aspect of this chemistry is that in the majority of cases the molecules meet the design criteria very well. It is evident that in an increasing number of cases the driving force behind the synthetic effort is the desire to create a molecule which will enable the user to make specific applications. 506 refs

  11. High gradient magnetic separation of upconverting lanthanide nanophosphors based on their intrinsic paramagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Arppe, Riikka, E-mail: riikka.arppe@utu.fi; Salovaara, Oskari; Mattsson, Leena; Lahtinen, Satu; Valta, Timo; Riuttamaeki, Terhi; Soukka, Tero [University of Turku, Department of Biotechnology (Finland)

    2013-09-15

    Photon upconverting nanophosphors (UCNPs) have the unique luminescent property of converting low-energy infrared light into visible emission which can be widely utilized in nanoreporter and imaging applications. For the use as reporters in these applications, the UCNPs must undergo a series of surface modification and bioconjugation reactions. Efficient purification methods are required to remove the excess reagents and biomolecules from the nanophosphor solution after each step to yield highly responsive reporters for sensitive bioanalytical assays. However, as the particle size of the UCNPs approaches the size of biomolecules, the handling of these reporters becomes cumbersome with traditional purification methods such as centrifugation. Here we introduce a novel approach for purification of bioconjugated 32-nm NaYF{sub 4}: Yb{sup 3+}, Er{sup 3+}-nanophosphors from excess unbound biomolecules utilizing high gradient magnetic separation (HGMS)-system constructed from permanent super magnets which produce magnetic gradients in a magnetizable steel wool matrix amplifying the magnetic field. The non-magnetic biomolecules flowed straight through the magnetized HGMS-column while the UCNPs were eluted only after the magnetic field was removed. In the UCNPs the luminescent centers, i.e., lanthanide-ion dopants are responsible for the strong upconversion luminescence, but in addition they are also paramagnetic. In this study we have shown that the presence of these weakly paramagnetic luminescent lanthanides actually also enables the use of HGMS to capture the UCNPs without incorporating additional optically inactive magnetic core into them.

  12. Development and Testing of an Americium/Lanthanide Separation Flowsheet Using Sodium Bismuthate

    Energy Technology Data Exchange (ETDEWEB)

    Jack Law; Bruce Mincher; Troy Garn; Mitchell Greenhalgh; Nicholas Schmitt; Veronica Rutledge

    2014-04-01

    The separation of Am from the lanthanides and curium is a key step in proposed advanced fuel cycle scenarios. The partitioning and transmutation of Am is desirable to minimize the long-term heat load of material interred in a future high-level waste repository. A separation process amenable to process scale-up remains elusive. Given only subtle chemistry differences within and between the ions of the trivalent actinide and lanthanide series this separation is challenging ; however, higher oxidation states of americium can be prepared using sodium bismuthate and separated via solvent extraction using diamylamylphosphonate (DAAP) extraction. Among the other trivalent metals only Ce is also oxidized and extracted. Due to the long-term instability of Am(VI) , the loaded organic phase is readily selectively stripped to partition the actinide to a new acidic aqueous phase. Batch extraction distribution ratio measurements were used to design a flowsheet to accomplish this separation. Additionally, crossflow filtration was investigated as a method to filter the bismuthate solids from the feed solution prior to extraction. Results of the filtration studies, flowsheet development work and flowsheet performance testing using a centrifugal contactor are detailed.

  13. Examination of competitive lanthanide sorption onto smectites and its significance in the management of radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Galunin, Evgeny [Departament de Quimica Analitica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Alba, Maria D. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Cientificas - Universidad de Sevilla, Av. Americo Vespucio 49, 41092 Sevilla (Spain); Santos, Maria J. [Departamento de Quimica, Universidade Estadual de Londrina, Londrina, PR 86051-990 (Brazil); Abrao, Taufik [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Cientificas - Universidad de Sevilla, Av. Americo Vespucio 49, 41092 Sevilla (Spain); Vidal, Miquel, E-mail: miquel.vidal@ub.edu [Departament de Quimica Analitica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

    2011-02-28

    The competitive effect of La and Lu (analogues of radionuclides appearing in radioactive waste) in the sorption in four smectites was examined. Sorption and desorption distribution coefficients (K{sub d}; K{sub d,des}), and desorption rates (R{sub des}) were determined from batch tests in two media: deionized water and, to consider the influence of cement leachates, 0.02 mol L{sup -1} Ca. The competitive effect was lower when high-affinity sites were available, as in the water medium at the lowest range of initial lanthanide concentration, with high K{sub d} for La and for Lu (5-63 x 10{sup 4} L kg{sup -1}). Lower K{sub d} was measured at higher initial concentrations and in the Ca medium, where Lu showed a stronger competitive effect. This was confirmed by fitting the sorption data to a two-solute Langmuir isotherm. The desorption data indicated that sorption was virtually irreversible for the scenarios with high sorption, with an excellent correlation between K{sub d} and K{sub d,des} (R{sup 2} around 0.9 for the two lanthanides). Assuming that radioactive waste is a mixture of radionuclides, and that Ca ions will be provided by the cement leachates, this would reduce the retention capacity of clay engineered barriers.

  14. Synthesis and study on complexes of some lanthanides to L-isoleucine

    International Nuclear Information System (INIS)

    Le Minh Tuan; Pham Minh Tuan; Tran The Dinh

    2007-01-01

    The formation of lanthanide (La, Pr and Nd) complexes with L-isoleucine have been studied as a function of pH values. The titrations were performed at 25 o C, and the ionic strength of the medium was maintained at 0.10 M by using potassium nitrate. The formation curves of their complexes (n-p[L]) were obtained by means of the titration data. Then the stability constants were determined in relation to these curves. The complexes were synthesized in the mixture of water-ethanol. The coordination of the complexes were determined by elements analysis, 13 C-NMR, 1 H-NMR and IR methods. These complexes are formulated as Ln(HIle) 3 .(NO 3 ) 3 .3H 2 O; (Ln: La, Pr and Nd,; L-Ile: L-isoleucine). Comparison of the IR, 13 C-NMR and 1 H-NMR spectra of the ligand with those of their complexes shows that isoleucine acts as a bidentate ligand bonding the lanthanide ions through the amino and carboxylate groups. (author)

  15. High gradient magnetic separation of upconverting lanthanide nanophosphors based on their intrinsic paramagnetism

    International Nuclear Information System (INIS)

    Arppe, Riikka; Salovaara, Oskari; Mattsson, Leena; Lahtinen, Satu; Valta, Timo; Riuttamäki, Terhi; Soukka, Tero

    2013-01-01

    Photon upconverting nanophosphors (UCNPs) have the unique luminescent property of converting low-energy infrared light into visible emission which can be widely utilized in nanoreporter and imaging applications. For the use as reporters in these applications, the UCNPs must undergo a series of surface modification and bioconjugation reactions. Efficient purification methods are required to remove the excess reagents and biomolecules from the nanophosphor solution after each step to yield highly responsive reporters for sensitive bioanalytical assays. However, as the particle size of the UCNPs approaches the size of biomolecules, the handling of these reporters becomes cumbersome with traditional purification methods such as centrifugation. Here we introduce a novel approach for purification of bioconjugated 32-nm NaYF 4 : Yb 3+ , Er 3+ -nanophosphors from excess unbound biomolecules utilizing high gradient magnetic separation (HGMS)-system constructed from permanent super magnets which produce magnetic gradients in a magnetizable steel wool matrix amplifying the magnetic field. The non-magnetic biomolecules flowed straight through the magnetized HGMS-column while the UCNPs were eluted only after the magnetic field was removed. In the UCNPs the luminescent centers, i.e., lanthanide-ion dopants are responsible for the strong upconversion luminescence, but in addition they are also paramagnetic. In this study we have shown that the presence of these weakly paramagnetic luminescent lanthanides actually also enables the use of HGMS to capture the UCNPs without incorporating additional optically inactive magnetic core into them

  16. Synthesis, structures, and luminescent properties of lanthanide complexes with triphenylphospine oxide

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yan; Xu, Shan; Wang, Xin; Li, Yue-Xue; Jin, Qiong-Hua [Department of Chemistry, Capital Normal University, Beijing (China); Liu, Min [The College of Materials Science and Engineering, Beijing University of Technology (China); Xin, Xiu-Lan [School of Food and Chemical Engineering, Beijing Technology and Business University (China)

    2017-07-03

    Seven lanthanide complexes [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}] (1-3) (OPPh{sub 3} = triphenylphosphine oxide, Ln = Nd, Sm, Gd), [Dy(OPPh{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}) (4), [Ln(OPPh{sub 3}){sub 3}(NO{sub 3}){sub 3}]{sub 2} (5-7) (Ln = Pr, Eu, Gd) were synthesized by the reactions of different lanthanide salts and OPPh{sub 3} ligand in the air. These complexes were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR and fluorescence spectra. Structure analysis shows that complexes 1-4 are mononuclear complexes formed by OPPh{sub 3} ligands and nitrates. The asymmetric units of complexes 5-7 consist of two crystallographic-separate molecules. Complex 1 is self-assembled to construct a 2D layer-structure of (4,4) net topology by hydrogen bond interactions. The other complexes show a 1D chain-like structure that was assembled by OPPh{sub 3} ligands and nitrate ions through C-H..O interactions. Solid emission spectra of compounds 4 and 6 are assigned to the characteristic fluorescence of Tb{sup 3+} (λ{sub em} = 480, 574 nm) and Eu{sup 3+} (λ{sub em} = 552, 593, 619, 668 nm). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties

    Directory of Open Access Journals (Sweden)

    Stephan R. Mathis

    2018-01-01

    Full Text Available Four anthracene-based lanthanide metal-organic framework structures (MOFs were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC in dimethylformamide (DMF under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i {{[Ln2(ADC3(DMF4·DMF]}n, Ln = Eu (1 and Tb (2} and (ii {{[Ln2(ADC3(DMF2(OH22·2DMF·H2O]}n, Ln = Er (3 and Tm (4}. The metal centers exist in various coordination environments; nine coordinate in (i, while seven and eight coordinate in (ii. The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.

  18. Synthesis, structure and luminescence properties of lanthanide complex with a new tetrapodal ligand featuring salicylamide arms

    International Nuclear Information System (INIS)

    Song Xueqin; Wen Xiaoguang; Liu Weisheng; Wang Daqi

    2010-01-01

    A new tetrapodal ligand 1,1,1-tetrakis{[(2'-(2-furfurylaminoformyl))phenoxyl]methyl}methane (L) has been prepared and their coordination chemistry with Ln III ions has been investigated. The structure of {[Ln 4 L 3 (NO 3 ) 12 ].H 2 O} ∞ (Ln=Nd, Eu)] shows the binodal 4,3-connected three-dimensional interpenetration coordination polymers with topology of a (8 6 ) 3 (8 3 ) 4 notation. [DyL(NO 3 ) 3 (H 2 O) 2 ].0.5CH 3 OH and [ErL(NO 3 ) 3 (H 2 O) (CH 3 OH)].CH 3 COCH 3 is a 1:1 mononuclear complex with interesting supramolecular features. The structure of [NdL(H 2 O) 6 ].3ClO 4 .3H 2 O is a 2:1 mononuclear complex which further self-assembled through hydrogen bond to form a three-dimensional supramolecular structures. The result presented here indicates that both subtle variation of the terminal group and counter anions can be applied in the modulation of the overall molecular structures of lanthanide complex of salicylamide derivatives due to the structure specialties of this type of ligand. The luminescence properties of the Eu III complex are also studied in detail. - Grapical Abstract: We present here a series of zero- to three-dimensional lanthanide coordination structures and luminescence properties of Eu(III) complex of a new tetrapodal ligand.

  19. Predictive thermodynamic models for liquid--liquid extraction of single, binary and ternary lanthanides and actinides

    International Nuclear Information System (INIS)

    Hoh, Y.C.

    1977-03-01

    Chemically based thermodynamic models to predict the distribution coefficients and the separation factors for the liquid--liquid extraction of lanthanides-organophosphorus compounds were developed by assuming that the quotient of the activity coefficients of each species varies slightly with its concentrations, by using aqueous lanthanide or actinide complexes stoichiometric stability constants expressed as its degrees of formation, by making use of the extraction mechanism and the equilibrium constant for the extraction reaction. For a single component system, the thermodynamic model equations which predict the distribution coefficients, are dependent on the free organic concentration, the equilibrated ligand and hydrogen ion concentrations, the degree of formation, and on the extraction mechanism. For a binary component system, the thermodynamic model equation which predicts the separation factors is the same for all cases. This model equation is dependent on the degrees of formation of each species in their binary system and can be used in a ternary component system to predict the separation factors for the solutes relative to each other

  20. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  1. Stability constants of the Europium complexes with the chloride ions

    International Nuclear Information System (INIS)

    Jimenez R, M.; Solache R, M.; Rojas H, A.

    2000-01-01

    The stability constants of lanthanides complexes with chloride ions which were determined at the same ionic force but in different media, are significantly different. It does not exist a systematic study over these stability constants. The purpose of this work is to determine the stability constants of the europium complexes with chloride ions at 303 K, by the solvents extraction method. (Author)

  2. High performance separation of lanthanides and actinides

    International Nuclear Information System (INIS)

    Sivaraman, N.; Vasudeva Rao, P.R.

    2011-01-01

    The major advantage of High Performance Liquid Chromatography (HPLC) is its ability to provide rapid and high performance separations. It is evident from Van Deemter curve for particle size versus resolution that packing materials with particle sizes less than 2 μm provide better resolution for high speed separations and resolving complex mixtures compared to 5 μm based supports. In the recent past, chromatographic support material using monolith has been studied extensively at our laboratory. Monolith column consists of single piece of porous, rigid material containing mesopores and micropores, which provide fast analyte mass transfer. Monolith support provides significantly higher separation efficiency than particle-packed columns. A clear advantage of monolith is that it could be operated at higher flow rates but with lower back pressure. Higher operating flow rate results in higher column permeability, which drastically reduces analysis time and provides high separation efficiency. The above developed fast separation methods were applied to assay the lanthanides and actinides from the dissolver solutions of nuclear reactor fuels

  3. Carbon-based magnetic nanocomposites in solid phase dispersion for the preconcentration some of lanthanides, followed by their quantitation via ICP-OES

    International Nuclear Information System (INIS)

    Tajabadi, F.; Sovizi, M.R.; Yamini, Y.

    2013-01-01

    We report on a method for the extraction of the lanthanide ions La(III), Sm(III), Nd(III) and Pr(III) using a carbon-ferrite magnetic nanocomposite as a new adsorbent, and their determination via flow injection ICP-OES. The lanthanide ions were converted into their complexes with 4-(2-pyridylazo)resorcinol, and these were adsorbed onto the nanocomposite. Fractional factorial design and central composite design were applied to optimize the extraction efficiencies to result in preconcentration factors in the range of 141-246. Linear calibration plots were obtained, the limits of detection (at S/N = 3) are between 0. 5 and 10 μg L -1 , and the intra-day precisions (n = 3) range from 3.1 to 12.8 %. The method was successfully applied to a certified reference material. (author)

  4. Radical-lanthanide ferromagnetic interaction in a T bIII bis-phthalocyaninato complex

    Science.gov (United States)

    Komijani, Dorsa; Ghirri, Alberto; Bonizzoni, Claudio; Klyatskaya, Svetlana; Moreno-Pineda, Eufemio; Ruben, Mario; Soncini, Alessandro; Affronte, Marco; Hill, Stephen

    2018-02-01

    Recent studies have highlighted the importance of organic ligands in the field of molecular spintronics, via which delocalized electron-spin density can mediate magnetic coupling to otherwise localized 4 f moments of lanthanide ions, which show tremendous potential for single-molecule device applications. To this end, high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is employed to study a neutral terbium bis-phthalocyaninato metalorganic complex, [TbPc2 ] 0, with the aim of understanding the magnetic interaction between the Ising-like moment of the lanthanide ion and the unpaired spin density on the coordinating organic radical ligand. The measurements were performed on a previously unknown [TbPc2 ] 0 structural phase crystallizing in the Pnma space group. EPR measurements on powder samples of [TbPc2 ] 0 reveal an anisotropic spectrum, which is attributed to the spin-1/2 radical coupled weakly to the EPR-silent T bIII ion. Extensive double-axis rotation studies on a single crystal reveal two independent spin-1/2 signals with differently oriented (albeit identical) uniaxial g -tensors, in complete agreement with x-ray structural studies that indicate two molecular orientations within the unit cell. The easy-axis nature of the radical EPR spectra thus reflects the coupling to the Ising-like T bIII moment. This is corroborated by studies of the isostructural [YPc2 ] 0 analog (where Y is nonmagnetic yttrium), which gives a completely isotropic radical EPR signal. The experimental results for the terbium complex are well explained on the basis of an effective model that introduces a weak ferromagnetic Heisenberg coupling between an isotropic spin-1/2 and an anisotropic spin-orbital moment, J =6 , that mimics the known, strong easy-axis Tb ⋯P c2 crystal-field interaction.

  5. Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

    Energy Technology Data Exchange (ETDEWEB)

    Akhila Maheswari, M.; Subramanian, M.S. [Department of Chemistry, Indian Institute of Technology, Chennai (India)

    2005-02-15

    A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using {sup 13}C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physico-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg{sup -1} for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO{sub 3} medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t{sub 1/2} values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30{mu}gL{sup -1}. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

  6. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

    International Nuclear Information System (INIS)

    Riviere, Ch.

    2000-01-01

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  7. Synthesis and characterization of lanthanide picrate complexes with 4-picoline-N-oxide (4-pic N O)

    International Nuclear Information System (INIS)

    Silva, E.M. da.

    1991-01-01

    The lanthanide picrate complexes with 4-picoline-N-oxide were obtained from ethanolic solutions of the hydrated lanthanide picrate and the ligand. The lanthanide content was determined by complexometric titration with EDTA. Carbon, Nitrogen and Hydrogen were determined by microanalytical procedures. Chemical analysis of the lanthanide picrate complexes are also presented. (author)

  8. Preparation, characterization and thermal behaviour study of 4-dimethyl amino benzal pyruvate of lanthanides (III) and yttrium (III) in solid state

    International Nuclear Information System (INIS)

    Miyano, M.H.

    1990-01-01

    Solid state compounds involving Ln and DMBP, where Ln trivalent lanthanides (except promethium) and yttrium; DMBP 4-dimethyl amino benzylidene pyruvate, were prepared by addition of ligand to the corresponding metal ions chlorides, both in aqueous solution. The precipitates were washed with distilled water and dried at 40 0 C in a forced circulation oven. Complexometry with EDTA, thermogravimetry (TG), differential thermal analysis (DTA), infra-red absorption and X-ray diffraction have been used in the study of these compounds. (author)

  9. Determination of stability constants of lanthanide complexes with tetracycline

    International Nuclear Information System (INIS)

    Saiki, Mitiko

    1975-01-01

    The stability constants of complexes compounds formed with tetracycline and lanthanides elements were determined for all lanthanides except promethium. The experimental procedure used was solvent extraction of the lanthanides labelled with their radioactive isotopes. It was shown that the formed complexes are mononuclear and that no hydroxo complexes or negatively charged complexes are formed in the experimental conditions of this work. Four methods of calculation were used for all complexes studied: the method of the average number of ligands, the method of limiting value, the method of two parameters and the method of weighted least squares. A comparison was made of the graphical methods with the method of least squares, showing the convenience of preceding least squares calculation by the graphical methods, in order to verify eventual mistakes of numerical data. It was shown the advantage of using radioisotopes of the elements for such a study, specially if the solvent extraction technique is used to-get the experimental data. (author)

  10. 'Americium(III)/trivalent lanthanides' separation using organothiophosphinic acids

    International Nuclear Information System (INIS)

    Hill, C.; Madic, C.; Baron, P.; Ozawa, Masaki; Tanaka, Yasumasa.

    1997-01-01

    The present paper describes the extraction of neodymium and other lanthanides by saponified Cyanex 301 acid. The saponification of commercial Cyanex 301 acid favoured the extraction of macro concentrations of neodymium from sodium nitrate aqueous solutions (pH eq ∼ 4). The amount of lanthanide extracted in the organic phase always reached the third of the initial concentration of saponified Cyanex 301 acid, which assumed a cation exchange mechanism to occur during the extraction. No nitrate anion took part in the complex formation. This paper also compares the abilities of purified Cyanex 301, Cyanex 302 and Cyanex 272 acids to extract and separate 241 Am(III) from 152 Eu(III). Very high separation factors S.F. Am/Eu were observed in the case of purified Cyanex 301 acid. Finally some studies are presented herein using tri-n-butylphosphate (TBP) as a synergistic extractant with Cyanex 301 acid to separate actinides from trivalent lanthanide. (author)

  11. Separation of lanthanides using micro solvent extraction system

    International Nuclear Information System (INIS)

    Nishihama, S.; Tajiri, Y.; Yoshizuka, K.

    2006-01-01

    A micro solvent extraction system for the separation of lanthanides has been investigated. The micro flow channel is fabricated on a poly(methyl methacrylate) (PMMA) plate, and solvent extraction progresses by feeding aqueous and organic solutions into the channel simultaneously. The extraction equilibrium is quickly achieved, without any mechanical mixing, when a narrow channel (100 μm width and 100 μm depth) is used. The results of solvent extraction from the Pr/Nd and Pr/Sm binary solutions revealed that both lanthanides are firstly extracted together, and then, the lighter lanthanide extracted in the organic solution alternatively exchanges to the heavier one in the aqueous solution to achieve the extraction equilibrium. The phase separation of the aqueous and organic phases after extraction can also be successively achieved by contriving the cross section of the flow channel, and the extractive separation of Pr/Sm is demonstrated. (authors)

  12. From Antenna to Assay: Lessons Learned in Lanthanide Luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Evan; Samuel, Amanda; Raymond, Kenneth

    2008-09-25

    Ligand-sensitized luminescent lanthanide(III) complexes are of considerable current interest due to their unique photophysical properties (micro- to millisecond lifetimes, characteristic and narrow emission bands, and large Stokes shifts), which make them well suited to serve as labels in fluorescence-based bioassays. The long-lived Ln(III) emission can be temporally resolved from scattered light and background fluorescence, resulting in vastly enhanced measurement sensitivity. One of the challenges in this field is the design of sensitizing ligands that provide highly emissive Ln(III) complexes that also possess sufficient stability and aqueous solubility required for practical applications. In this account we give an overview of some of the general properties of the trivalent lanthanides and follow with a summary of advances made in our laboratory in the development of highly luminescent Tb(III) and Eu(III) complexes for applications in biotechnology. A focus of our research has been the optimization of these compounds as potential commercial agents for use in Homogeneous Time Resolved Fluorescence (HTRF) technology, the requirements and current use of which will be briefly discussed. Our approach involves developing high-stability octadentate Tb(III) and Eu(III) complexes that rely on all-oxygen donor atoms as well as using multi-chromophore chelates to increase molar absorptivity compared to earlier examples that utilize a single pendant antenna chromophore. We have found that ligands based on 2-hydroxyisophthalamide (IAM) provide exceptionally emissive Tb(III) complexes with quantum yield values up to ca. 60%. Solution thermodynamic studies have indicated that these complexes are stable at the nanomolar concentrations required for commercial assays. Through synthetic modification of the IAM-chromophore, in conjunction with time-dependent density functional theory (TD-DFT) calculations, we have developed a method to predict absorption and emission properties of

  13. Determination of the knight shift in liquid alloys of silver with lanthanides by stroboscopic observation of perturbed angular correlations according to the reaction 109Ag(p,n)109Cd

    International Nuclear Information System (INIS)

    Gundelfinger, F.

    1975-01-01

    In liquid alloys of the composition Agsub(1-x)Rsub(x) (0 109 Ag(p,n) 109 Cd* induced by 10 MeV protons. In first appoximation, the values found for the relative change of knight shift prove to be proportional to the negative z-component of the 4f-shell spin of the respective lanthanide metals. The major part of the knight shift is produced by the spin polarization of the conduction electrons due to coupling to the spins of the lanthanide ions. The possible coupling mechanisms are discussed. (orig./GSC) [de

  14. Electrospray mass spectrometry for actinides and lanthanide speciation

    International Nuclear Information System (INIS)

    Moulin, C.; Amekraz, B.; Colette, S.; Doizi, D.; Jacopin, C.; Lamouroux, C.; Plancque, G.

    2006-01-01

    Electrospray mass spectrometry (ES-MS) is a new speciation technique that has the great interest to be able to probe the element, the ligand and the complex in order to reach the speciation. This paper will focus on the use of ES-MS for the speciation of actinides/lanthanides on several systems of interest in various fields such as the interaction between DTPA (decorporant) and europium, HEBP and uranium, BTP (new extracting agent) and lanthanides with comparison with known chemistry as well as whenever possible with other speciation techniques

  15. SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

    Science.gov (United States)

    Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

    1962-08-14

    A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

  16. Characterization and thermogravimetric analysis of lanthanide hexafluoroacetylacetone chelates.

    Science.gov (United States)

    Shahbazi, Shayan; Stratz, S Adam; Auxier, John D; Hanson, Daniel E; Marsh, Matthew L; Hall, Howard L

    2017-01-01

    This work reports the thermodynamic characterizations of organometallic species as a vehicle for the rapid separation of volatile nuclear fission products via gas chromatography due to differences in adsorption enthalpy. Because adsorption and sublimation thermodynamics are linearly correlated, there is considerable motivation to determine sublimation enthalpies. A method of isothermal thermogravimetric analysis, TGA-MS and melting point analysis are employed on thirteen lanthanide 1,1,1,5,5,5-hexafluoroacetylacetone complexes to determine sublimation enthalpies. An empirical correlation is used to estimate adsorption enthalpies of lanthanide complexes on a quartz column from the sublimation data. Additionally, four chelates are characterized by SC-XRD, elemental analysis, FTIR and NMR.

  17. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    -molecule magnets (SMMs). Starting from the archetype SMM Mn12 we present the details of the mechanisms governing the relaxation of the magnetization of these systems. In Chapter 2 we present our work on the coordination chemistry of lanthanides with a new Schiff-base ligand, H3L [(E)-3-((2-hydroxyphenyl...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  18. Lanthanide recognition: A Ho3+ potentiometric membrane sensor as a probe for determination of terazosin

    International Nuclear Information System (INIS)

    Ganjali, Mohammad Reza; Shams, Haniyeh; Faridbod, Farnoush; Hajiaghababaei, Leila; Norouzi, Parviz

    2009-01-01

    In this study, complexation of N'-(1-pyridin-2-ylmethylene)-2-furohydrazide (NFH) with some metal ions was investigated by conductometry and spectroscopy. Then, a Ho 3+ potentiometric membrane sensor was prepared based on the highly selective complexation between this ionophore and Ho 3+ . These new ionophores are more selective than the previously reported ones. In this work, for the first time, the proposed sensor was applied in indirect determination of the terazocine in its pharmaceutical formulation. The interest in constructing lanthanide sensors arises because they have similar ionic radii to calcium, but a higher charge density, which allows them to be used as probes to find the interactions between Ca 2+ and biologically important molecules.

  19. Application of lanthanide complexes for the purification of di-isobutyl-sulfoxide

    International Nuclear Information System (INIS)

    Osorio, V.K.L.; Martinez, S.A.Q.; Silva, R.M.X. da

    1984-01-01

    A new procedure for the purification of sulfoxides based on the selective precipitation of their complexes with class (a) metallic ions is reported. A commercial sample of di-isobutylsulfoxide containing about 5 - 10% of the corresponding sulfone was purified by precipitation with lanthanide perchlorates from alcoholic solutions. The recovery of the sulfoxide from the solid complex was accomplished by dissolving the complex in water and extracting the sulfoxide with chloroform. Alternatively the aqueous solution of the complex was passed successively through columns containing strongly acidic cation-exchanger resin in the H-cycle and strongly basic anionic-exchanger in the OH-cycle. T.L.C. homogeneous sulfoxide was obtained simply by evaporation of the solvent at reduced pressure. (Author) [pt

  20. Yttrium and lanthanide nitrate complexes of N,N1-bis(4-antipyryl methylidene) ethylenediamine

    International Nuclear Information System (INIS)

    Joseph, Siby; Radhakrishnan, P.K.

    1998-01-01

    Complexes of yttrium and lanthanide nitrates with a Schiff base, N, N 1 -bis(4-antipyrylmethylidene)ethylenediamine (BAME) having the general formula [Ln(BAME) 2 (NO 3 )](NO 3 ) 2 , where Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er have been synthesised and characterised by elemental analyses, molar conductance in non-aqueous solvents, electronic, infrared and proton NMR spectra. BAME acts as a neutral bidentate ligand coordinating through both azomethine nitrogen atoms. One of the nitrate groups is coordinated in a bidentate manner. A coordination number of six may be assigned to the metal ion in these complexes. The covalency parameters evaluated from the solid state electronic spectra suggest weak covalent character of the metal-ligand bond. (author)

  1. Synthesis, characterization and anticancer activities of two lanthanide(III) complexes with a nicotinohydrazone ligand

    Science.gov (United States)

    Xu, Zhou-Qin; Mao, Xian-Jie; Jia, Lei; Xu, Jun; Zhu, Tao-Feng; Cai, Hong-Xin; Bie, Hong-Yan; Chen, Ru-Hua; Ma, Tie-liang

    2015-12-01

    Two isostructural acylhydrazone based complexes, namely [Ce(penh)2(H2O)4](NO3)3·4H2O (1) and [Sm(penh)2(NO3)2](NO3)·C2H5OH (2) (penh = 2-acetylpyridine nicotinohydrazone), have been obtained and characterized by physico-chemical and spectroscopic methods. The ten-coordinated lanthanide metal ion in each complex is surrounded by two independent tridentate neutral acylhydrazones with two ON2 donor sets. The other four coordination oxygen atoms are from four water molecules and two bidentate nitrate anions for complexes 1 and 2, respectively, thus giving distorted bicapped square antiprism geometry. Both complexes have excellent antitumor activity towards human pancreatic cancer (PATU8988), human colorectal cancer (lovo) and human gastric cancer(SGC7901) cell line. Furthermore, the cell apoptosis of complex 1 is detected by AnnexinV/PI flow cytometry.

  2. Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals

    Science.gov (United States)

    Sun, Qi; Mundoor, Haridas; Ribot, Josep; Singh, Vivek; Smalyukh, Ivan; Nagpal, Prashant

    2014-03-01

    Upconversion of infrared radiation into visible light has been investigated for applications in biological imaging and photovoltaics. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb3+) , and slow rate of energy transfer (to Er3+ states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increases the rate of resonant energy transfer from Yb3+ to Er3+ ions by 6 fold. While we do observe strong metal mediated quenching (14 fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared, and hence enhances the nanocrystal UPL. This strong columbic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

  3. Study of interactions between lanthanides/actinides and humic substances by a steric exclusion chromatographic method

    International Nuclear Information System (INIS)

    Moulin, V.

    1986-01-01

    The knowledge of cation-humic matter interactions has a great importance in order to have a better understanding of the contribution of these substances to the possible transport of radioactive elements in the geosphere via groundwaters. The method chosen to study the formation of soluble species between lanthanides/actinides ions and humic acids from different origins is a chromatographic technique of gel filtration. This dynamic equilibrium method is based on the separation of the formed complex and the free cation by the porous packing gel. Different elements have been studied by this method: UO 2 2+ , Eu 3+ , Th 4+ and global interaction constants have been calculated. The application to transuranic elements is undertaken. (orig.)

  4. Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals.

    Science.gov (United States)

    Sun, Qi-C; Mundoor, Haridas; Ribot, Josep C; Singh, Vivek; Smalyukh, Ivan I; Nagpal, Prashant

    2014-01-08

    Upconversion of infrared radiation into visible light has been investigated for applications in photovoltaics and biological imaging. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb(3+)), and slow rate of energy transfer (to Er(3+) states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increase the rate of resonant energy transfer from Yb(3+) to Er(3+) ions by 6 fold. While we do observe strong metal mediated quenching (14-fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared and hence enhances the nanocrystal UPL. This strong Coulombic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

  5. Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

    Science.gov (United States)

    Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

    2015-09-08

    Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement.

  6. Lanthanide ion (III) complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (DOTA-4AmP8−) for dual biosensing of pH with CEST (chemical exchange saturation transfer) and BIRDS (biosensor imaging of redundant deviation in shifts)

    Science.gov (United States)

    Huang, Yuegao; Coman, Daniel; Ali, Meser M.; Hyder, Fahmeed

    2014-01-01

    Relaxivity based magnetic resonance of phosphonated ligands chelated with gadolinium (Gd3+) shows promise for pH imaging. However instead of monitoring the paramagnetic effect of lanthanide complexes on the relaxivity of water protons, biosensor (or molecular) imaging with magnetic resonance is also possible by detecting either the non-exchangeable or the exchangeable protons on the lanthanide complexes themselves. The non-exchangeable protons (e.g., –CHx, where 3≥x≥1) are detected using a three-dimensional chemical shift imaging method called Biosensor Imaging of Redundant Deviation in Shifts (BIRDS), whereas the exchangeable protons (e.g., –OH or –NHy, where 2≥y≥1) are measured with Chemical Exchange Saturation Transfer (CEST) contrast. Here we tested the feasibility of BIRDS and CEST for pH imaging of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (DOTA-4AmP8−) chelated with thulium (Tm3+) and ytterbium (Yb3+). BIRDS and CEST experiments show that both complexes are responsive to pH and temperature changes. Higher pH and temperature sensitivities are obtained with BIRDS for either complex when using the chemical shift difference between two proton resonances vs. using the chemical shift of a single proton resonance, thereby eliminating the need to use water resonance as reference. While CEST contrast for both agents is linearly dependent on pH within a relatively large range (i.e., 6.3-7.9), much stronger CEST contrast is obtained with YbDOTA-4AmP5− than with TmDOTA-4AmP5−. In addition, we demonstrate the prospect of using BIRDS to calibrate CEST as new platform for quantitative pH imaging. PMID:24801742

  7. Three phenoxo-bridged dinuclear lanthanide complexes. Syntheses, crystal structures, and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhi-Chao; Dai, Rui-Peng; Yang, En-Cui [College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Tianjin Normal University (China); Dong, Hui-Ming; Zhao, Xiao-Jun [College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Tianjin Normal University (China); Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin (China)

    2018-03-15

    Three dinuclear lanthanide complexes [Ln{sub 2}(H{sub 2}L){sub 2}(NO{sub 3}){sub 4}] [Ln = Dy (1), Tb (2), and Gd (3)] [H{sub 3}L = 2-hydroxyimino-N'-[(2-hydroxy-3-methoxyphenyl)methylidene]- propanohydrazone] were solvothermally synthesized by varying differently anisotropic rare earth ions. Single-crystal structural analyses demonstrate that all the three complexes are crystallographically isostructural with two centrosymmetric Ln{sup III} ions aggregated by a pair of monodeprotonated H{sub 2}L{sup -} anions. Weak intramolecular antiferromagnetic interactions with different strength were mediated by a pair of phenoxo bridges due to superexchange and/or single-ion anisotropy. Additionally, the Dy{sup III}-based entity shows the strongest anisotropy exhibits field-induced single-molecule magnetic behavior with two thermally activated relaxation processes. In contrast, 3 with isotropic Gd{sup III} ion has a significant cryogenic magnetocaloric effect with the maximum entropy change of 25.7 J.kg{sup -1}.K{sup -1} at 2.0 K and 70.0 kOe. (copyright 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    International Nuclear Information System (INIS)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E.; Chan, Benny C.; Lill, Daniel T. de

    2015-01-01

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C 6 H 2 O 5 )(C 6 H 3 O 5 )(H 2 O)] n (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted

  9. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E. [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States); Chan, Benny C. [Department of Chemistry, The College of New Jersey, 2000 Pennington Road, Ewing, NJ 08628 (United States); Lill, Daniel T. de, E-mail: ddelill@fau.edu [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States)

    2015-05-15

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.

  10. A novel strategy for phosphopeptide enrichment using lanthanide phosphate co-precipitation.

    Science.gov (United States)

    Mirza, Munazza Raza; Rainer, Matthias; Güzel, Yüksel; Choudhary, Iqbal M; Bonn, Günther K

    2012-08-01

    Reversible phosphorylation of proteins is a common theme in the regulation of important cellular functions such as growth, metabolism, and differentiation. The comprehensive understanding of biological processes requires the characterization of protein phosphorylation at the molecular level. Although, the number of cellular phosphoproteins is relatively high, the phosphorylated residues themselves are generally of low abundance due to the sub-stoichiometric nature. However, low abundance of phosphopeptides and low degree of phosphorylation typically necessitates isolation and concentration of phosphopeptides prior to mass spectrometric analysis. In this study, we used trivalent lanthanide ions (LaCl(3), CeCl(3), EuCl(3), TbCl(3), HoCl(3), ErCl(3), and TmCl(3)) for phosphopeptide enrichment and cleaning-up. Due to their low solubility product, lanthanide ions form stable complexes with the phosphate groups of phosphopeptides and precipitate out of solution. In a further step, non-phosphorylated compounds can easily be removed by simple centrifugation and washing before mass spectrometric analysis using Matrix-assisted laser desorption/ionisation-time of flight. The precipitation method was applied for the isolation of phosphopeptides from standard proteins such as ovalbumin, α-casein, and β-casein. High enrichment of phosphopeptides could also be achieved for real samples such as fresh milk and egg white. The technology presented here represents an excellent and highly selective tool for phosphopeptide recovery; it is easily applicable and shows several advantages as compared with standard approaches such as TiO(2) or IMAC.

  11. Methods for Generating Highly Magnetically Responsive Lanthanide-Chelating Phospholipid Polymolecular Assemblies.

    Science.gov (United States)

    Isabettini, Stéphane; Baumgartner, Mirjam E; Reckey, Pernille Q; Kohlbrecher, Joachim; Ishikawa, Takashi; Fischer, Peter; Windhab, Erich J; Kuster, Simon

    2017-06-27

    Mixtures of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and its lanthanide ion (Ln 3+ ) chelating phospholipid conjugate, 1,2-dimyristoyl-sn-glycero-3-phospho-ethanolamine-diethylene triaminepentaacetate (DMPE-DTPA), assemble into highly magnetically responsive polymolecular assemblies such as DMPC/DMPE-DTPA/Ln 3+ (molar ratio 4:1:1) bicelles. Their geometry and magnetic alignability is enhanced by introducing cholesterol into the bilayer in DMPC/Cholesterol/DMPE-DTPA/Ln 3+ (molar ratio 16:4:5:5). However, the reported fabrication procedures remain tedious and limit the generation of highly magnetically alignable species. Herein, a simplified procedure where freeze thawing cycles and extrusion are replaced by gentle heating and cooling cycles for the hydration of the dry lipid film was developed. Heating above the phase transition temperature T m of the lipids composing the bilayer before cooling back below the T m was essential to guarantee successful formation of the polymolecular assemblies composed of DMPC/DMPE-DTPA/Ln 3+ (molar ratio 4:1:1). Planar polymolecular assemblies in the size range of hundreds of nanometers are achieved and deliver unprecedented gains in magnetic response. The proposed heating and cooling procedure further allowed to regenerate the highly magnetically alignable DMPC/Cholesterol/DMPE-DTPA/Ln 3+ (molar ratio 16:4:5:5) species after storage for one month frozen at -18 °C. The simplicity and viability of the proposed fabrication procedure offers a new set of highly magnetically responsive lanthanide ion chelating phospholipid polymolecular assemblies as building blocks for the smart soft materials of tomorrow.

  12. On the suitability of lanthanides as actinide analogs

    International Nuclear Information System (INIS)

    Raymond, Kenneth; Szigethy, Geza

    2008-01-01

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

  13. Filled buckyballs: recent developments from the endohedral metallofullerenes of lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Edelmann, F T [Magdeburg Univ. (Germany). Chemisches Inst.

    1995-05-15

    Metal-containing fullerenes - an intensively studied area of research. Recent developments in the field of endohedral metallofullerenes of lanthanides and the perspectives these results provide for the future are discussed herein. An additional theme is the specific incorporation of metal salts in carbon nanotubes, relatives of fullerenes, which Green et al. reported recently. (orig.)

  14. Lanthanide Lewis acid-mediated enantioselective conjugate radical additions.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar

    2002-08-22

    [reaction: see text] Lanthanide triflates along with proline-derived ligands have been found to be efficient catalysts for enantioselective conjugate addition of nucleophilic radicals to enoates. N-Acyl oxazolidinones, when used as achiral additives, gave meaningful enhancements in the ees for the product.

  15. Lanthanide(III) Complexes with Tridentate Schiff Base Ligand ...

    African Journals Online (AJOL)

    Lanthanide complexes, hydrazino, antioxidant activity, X-ray structure. 1. Introduction ... measured using a Johnson Matthey scientific magnetic suscepti- bility balance. 2.1. .... of the ligand and that the nitrogen atom supporting this proton is not involved in the ... 4f-electrons are not involved in the coordination. These facts.

  16. Influencing fatty acid composition of yeasts by lanthanides

    Czech Academy of Sciences Publication Activity Database

    Kolouchová, I.; Sigler, Karel; Zimola, M.; Řezanka, Tomáš; Matatková, O.; Masák, J.

    2016-01-01

    Roč. 32, č. 8 (2016), s. 126 ISSN 0959-3993 R&D Projects: GA ČR GA14-00227S Institutional support: RVO:61388971 Keywords : Fatty acids * Lanthanides * Microbial lipids Subject RIV: EE - Microbiology, Virology Impact factor: 1.658, year: 2016

  17. Synthetic approaches to lanthanide complexes with tetrapyrrole type ligands

    International Nuclear Information System (INIS)

    Pushkarev, V E; Tomilova, L G; Tomilov, Yu V

    2008-01-01

    Approaches to the synthesis of single-, double- and triple-decker complexes of lanthanides with phthalocyanines and their analogues known to date are considered. Examples of preparation of sandwich-type complexes based on other metals of the Periodic system are given.

  18. Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays

    Energy Technology Data Exchange (ETDEWEB)

    Anstey, Mitchell R. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Fruetel, Julia A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Hayden, Carl C. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Buckley, Heather L. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Arnold, John [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2013-09-01

    Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

  19. Sol–gel preparation of selected lanthanide aluminium garnets

    Czech Academy of Sciences Publication Activity Database

    Dubnikova, N.; Garskaite, E.; Pinkas, J.; Bezdička, Petr; Beganskiene, A.; Kareiva, A.

    2010-01-01

    Roč. 55, č. 2 (2010), s. 213-219 ISSN 0928-0707 Institutional research plan: CEZ:AV0Z40320502 Keywords : lanthanide aluminium garnets * sol-gel processing Subject RIV: CA - Inorganic Chemistry Impact factor: 1.525, year: 2010

  20. Addition compounds of yttrium and lanthanide perrhenates with tetramethylene sulphoxide

    International Nuclear Information System (INIS)

    Umeda, K.

    1977-01-01

    Adducts of lanthanide perrhenates with tetramethylene sulfoxide are prepared and characterized. The compounds having as general formula Ln(Re04) 3 .7.5 TMSO(ln=La-Lu and Y) are characterized by elemental analysis, infrared spectra, molar conductance measurements, x-ray powder patterns, differential scanning calorimetry curves, melting temperature range measurements and thermogravimetric analysis [pt

  1. Studies of lanthanide complexes by a combination of spectroscopic methods

    Czech Academy of Sciences Publication Activity Database

    Krupová, Monika; Bouř, Petr; Andrushchenko, Valery

    2015-01-01

    Roč. 22, č. 1 (2015), s. 44 ISSN 1211-5894. [Discussions in Structural Molecular Biology. Annual Meeting of the Czech Society for Structural Biology /13./. 19.03.2015-21.03.2015, Nové Hrady] Institutional support: RVO:61388963 Keywords : lanthanide complexes * chirality sensing * chirality amplification * spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry

  2. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Riviere, Ch

    2000-10-05

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  3. r-PROCESS LANTHANIDE PRODUCTION AND HEATING RATES IN KILONOVAE

    Energy Technology Data Exchange (ETDEWEB)

    Lippuner, Jonas; Roberts, Luke F., E-mail: jlippuner@tapir.caltech.edu [TAPIR, Walter Burke Institute for Theoretical Physics, California Institute of Technology, MC 350-17, 1200 E California Boulevard, Pasadena CA 91125 (United States)

    2015-12-20

    r-process nucleosynthesis in material ejected during neutron star mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients depend on the composition of the ejecta, which determines the local heating rate from nuclear decays and the opacity. Kasen et al. and Tanaka and Hotokezaka pointed out that lanthanides can drastically increase the opacity in these outflows. We use the new general-purpose nuclear reaction network SkyNet to carry out a parameter study of r-process nucleosynthesis for a range of initial electron fractions Y{sub e}, initial specific entropies s, and expansion timescales τ. We find that the ejecta is lanthanide-free for Y{sub e} ≳ 0.22−0.30, depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Y{sub e} lead to reduced heating rates, due to individual nuclides dominating the heating. We calculate approximate light curves with a simplified gray radiative transport scheme. The light curves peak at about a day (week) in the lanthanide-free (-rich) cases. The heating rate does not change much as the ejecta becomes lanthanide-free with increasing Y{sub e}, but the light-curve peak becomes about an order of magnitude brighter because it peaks much earlier when the heating rate is larger. We also provide parametric fits for the heating rates between 0.1 and 100 days, and we provide a simple fit in Y{sub e}, s, and τ to estimate whether or not the ejecta is lanthanide-rich.

  4. r-PROCESS LANTHANIDE PRODUCTION AND HEATING RATES IN KILONOVAE

    International Nuclear Information System (INIS)

    Lippuner, Jonas; Roberts, Luke F.

    2015-01-01

    r-process nucleosynthesis in material ejected during neutron star mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients depend on the composition of the ejecta, which determines the local heating rate from nuclear decays and the opacity. Kasen et al. and Tanaka and Hotokezaka pointed out that lanthanides can drastically increase the opacity in these outflows. We use the new general-purpose nuclear reaction network SkyNet to carry out a parameter study of r-process nucleosynthesis for a range of initial electron fractions Y e , initial specific entropies s, and expansion timescales τ. We find that the ejecta is lanthanide-free for Y e ≳ 0.22−0.30, depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Y e lead to reduced heating rates, due to individual nuclides dominating the heating. We calculate approximate light curves with a simplified gray radiative transport scheme. The light curves peak at about a day (week) in the lanthanide-free (-rich) cases. The heating rate does not change much as the ejecta becomes lanthanide-free with increasing Y e , but the light-curve peak becomes about an order of magnitude brighter because it peaks much earlier when the heating rate is larger. We also provide parametric fits for the heating rates between 0.1 and 100 days, and we provide a simple fit in Y e , s, and τ to estimate whether or not the ejecta is lanthanide-rich

  5. Lanthanide co-ordination frameworks: Opportunities and diversity

    International Nuclear Information System (INIS)

    Hill, Robert J.; Long, De-Liang; Hubberstey, Peter; Schroeder, Martin; Champness, Neil R.

    2005-01-01

    Significant successes have been made over recent years in preparing co-ordination framework polymers that show macroscopic material properties, but in the vast majority of cases this has been achieved with d-block metal-based systems. Lanthanide co-ordination frameworks also offer attractive properties in terms of their potential applications as luminescent, non-linear optical and porous materials. However, lanthanide-based systems have been far less studied to date than their d-block counterparts. One possible reason for this is that the co-ordination spheres of lanthanide cations are more difficult to control and, in the absence of design strategies for lanthanide co-ordination frameworks, it is significantly more difficult to target materials with specific properties. However, this article highlights some of the exciting possibilities that have emerged from the earliest investigations in this field with new topological families of compounds being discovered from relatively simple framework components, including unusual eight, seven and five-connected framework systems. Our own research, as well as others, is leading to a much greater appreciation of the factors that control framework formation and the resultant observed topologies of these polymers. As this understanding develops targeting particular framework types will become more straightforward and the development of designed polyfunctional materials more accessible. Thus, it can be seen that lanthanide co-ordination frameworks have the potential to open up previously unexplored directions for materials chemistry. This article focuses on the underlying concepts for the construction of these enticing and potentially highly important materials

  6. Highly efficient separation materials created by computational approach. For the separation of lanthanides and actinides

    International Nuclear Information System (INIS)

    Goto, Masahiro; Uezu, Kazuya; Aoshima, Atsushi; Koma, Yoshikazu

    2002-05-01

    In this study, efficient separation materials have been created by the computational approach. Based on the computational calculation, novel organophosphorus extractants, which have two functional moieties in the molecular structure, were developed for the recycle system of transuranium elements using liquid-liquid extraction. Furthermore, molecularly imprinted resins were prepared by the surface-imprint polymerization technique. Thorough this research project, we obtained two principal results: 1) design of novel extractants by computational approach, and 2) preparation of highly selective resins by the molecular imprinting technique. The synthesized extractants showed extremely high extractability to rare earth metals compared to those of commercially available extractants. The results of extraction equilibrium suggested that the structural effect of extractants is one of the key factors to enhance the selectivity and extractability in rare earth extractions. Furthermore, a computational analysis was carried out to evaluate the extraction properties for the extraction of rare earth metals by the synthesized extractants. The computer simulation was shown to be very useful for designing new extractants. The new concept to connect some functional moieties with a spacer is very useful and is a promising method to develop novel extractants for the treatment of nuclear fuel. In the second part, we proposed a novel molecular imprinting technique (surface template polymerization) for the separation of lanthanides and actinides. A surface-templated resin is prepared by an emulsion polymerization using an ion-binding (host) monomer, a resin matrix-forming monomer and the target Nd(III) metal ion. A host monomer which has amphiphilic nature forms a complex with a metal ion at the interface, and the complex remains as it is. After the matrix is polymerized, the coordination structure is 'imprinted' at the resin interface. Adsorption of Nd(III) and La(III) ions onto the

  7. Synthesis, structure and photoluminescence of novel lanthanide (Tb(III), Gd(III)) complexes with 6-diphenylamine carbonyl 2-pyridine carboxylate

    International Nuclear Information System (INIS)

    An Baoli; Gong Menglian; Cheah, Kok-Wai; Wong, Wai-Kwok; Zhang Jiming

    2004-01-01

    A novel organic ligand, 6-diphenylamine carbonyl 2-pyridine carboxylic acid (HDPAP), and the corresponding lanthanide complexes, tris(6-diphenylamine carbonyl 2-pyridine carboxylato) terbium(III) (Tb-DPAP) and tris(6-diphenylamine carbonyl 2-pyridine carboxylato) gadolinium(III) (Gd-DPAP) have been designed and synthesized. The crystal structure and photoluminescence of Tb-DPAP and Gd-DPAP have been studied. The results showed that the lanthanide complexes have electroneutral structures, and the solid terbium complex emits characteristic green fluorescence of Tb(III) ions at room temperature while the gadolinium complex emits the DPAP ligand phosphorescence. The lowest triplet level of DPAP ligand was calculated from the phosphorescence spectrum of Gd-DPAP in N,N-dimethyl formamide (DMF) dilute solution determined at 77 K, and the energy transfer mechanisms in the lanthanide complexes were discussed. The lifetimes of the 5 D 4 levels of Tb 3+ ions in the terbium complex were examined using time-resolved spectroscopy, and the values are 0.0153±0.0001 ms for solid Tb(DPAP) 3 ·11.5H 2 O and 0.074±0.007 ms for 2.5x10 -5 mol/l Tb-DPAP ethanol solution

  8. Effect of applied hydrostatic pressure on the quenching kinetics, and electronic and molecular structure of eight and nine-coordinate lanthanide complexes in solution

    International Nuclear Information System (INIS)

    Maupin, C.L.; Riehl, J.P.

    1998-01-01

    Full text: Applied hydrostatic pressure may be used as a probe of the reaction mechanism for various solution reactions involving lanthanide ions. In this work we report on the use of high pressure to probe the mechanism of enantioselective quenching between racemic luminescent lanthanide complexes containing Dy(III) Tb(III) and Eu(III), and optically active transition metal complexes as quenchers. Diastereomeric rate constants are obtained from a biexponential fit of the luminescence decay. Particular attention will be given to solvation effects on the measured diastereomeric rate constants. The source of chirality is ascribed to a enantioselective rearrangement step within a bimolecular 'encounter' complex yielding a intermolecular geometry in which the energy transfer is efficient. The effect of high pressure on the molecular and electronic structure of these complexes will also be discussed

  9. Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

    Science.gov (United States)

    Mathis Ii, Stephan R; Golafale, Saki T; Bacsa, John; Steiner, Alexander; Ingram, Conrad W; Doty, F Patrick; Auden, Elizabeth; Hattar, Khalid

    2017-01-03

    Ultra large pore isostructural metal organic frameworks (MOFs) which exhibit both photoluminescence and scintillation properties, were synthesized from trans-4,4'-stilbenedicarboxylic acid (H 2 L) and trivalent lanthanide (Ln) metal salts under solvothermal conditions (Ln = Er 3+ (1) and Tm 3+ (2)). This new class of mesoporous materials is a non-interpenetrating network that features ultra-large diamond shaped pores of dimensions with approximate cross-sectional dimensions of 28 Å × 12 Å. The fully deprotonated ligand, L, is isolated and rigidified as it serves as the organic linker component of the MOF structure. Its low density unit cells possess asymmetric units with two crystallographically independent Ln 3+ ions in seven coordinate arrangements. A distinct feature of the structure is the bis-bidentate carboxylate groups. They serve as a ligand that coordinates two Ln(iii) ions while each L connects four Ln(iii) ions yielding an exceptionally large diamond-shaped rectangular network. The structure exhibits ligand-based photoluminescence with increased lifetime compared to free stilbene molecules on exposure to UV radiation, and also exhibits strong scintillation characteristics, comprising of both prompt and delayed radioluminescence features, on exposure to ionizing radiation.

  10. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    International Nuclear Information System (INIS)

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-01

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln 2 (phen) 2 (SO 4 ) 3 (H 2 O) 2 ] n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)] n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO 4 2− anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of 5 D 0 → 7 F J (J=0–4) of the Eu(III)

  11. Stability constants of the Europium complexes with the chloride ions; Constantes de estabilidad de los complejos del europio con los iones cloruro

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez R, M.; Solache R, M.; Rojas H, A. [Instituto Nacional de Investigaciones Nucleares, Departamento de Quimica, A.P. 18-1027, C.P. 11801 Mexico D.F. (Mexico)

    2000-07-01

    The stability constants of lanthanides complexes with chloride ions which were determined at the same ionic force but in different media, are significantly different. It does not exist a systematic study over these stability constants. The purpose of this work is to determine the stability constants of the europium complexes with chloride ions at 303 K, by the solvents extraction method. (Author)

  12. Formation constants of lanthanide(III)- aminopolycarboxylate- ATP mixed ligand complexes and their systematics

    International Nuclear Information System (INIS)

    Verma, Sangeeta; Limaye, S.N.; Saxena, M.C.

    1993-01-01

    Formation constants (log Ksub(MAL)sup(MA), log Ksub(ML)sup(M) and log Ksub(ML)sup(ML) of mixed ligand lanthanide(III) complexes of the type [Ln(III).A.ATP[ 2 , where LN(III)=La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ or Dy 3+ ' A=NTA(nitrilotriacetate) or HEDTA (2-hydroxyethylethylenediamine triacetate) and ATP=adenosine 5'-triphosphate (L), and of the binary [Ln(III).ATP[ and [Ln(III).(ATP) 2 [ complexes have been determined by potentiometric pH titrations using the Irving-Rossotti approach at three temperatures 20, 30 and 40 degC and at a fixed ionic strength, I=0.2 mol dm -3 (NAclO 4 ). The solution stabilities (log Ksub(MAL)sup(MA) values) are influenced by the electrostatic effect involved in ternary complexation and increase with temperature. The enthalpy factor (ΔH) has been found to be small but unfavourable and the entropy factor (ΔS) large and favourable. The log Ksub(MAL)sup(MA) values lie in the order NTA>HEDTA with respect to A and La 3+ 3+ 3+ 3+ 3+ 3+ >Gd 3+ 3+ 3+ with respect to lanthanides. Tetrad effect is present in the formation constant values; its magnitude has been found to lie in the sequence f 7 >f 3 -f 4 ≅ f 10 -f 11 for the Ln(III) ions. Systematics in the formation constant values has been further studied by evaluating changes in the inter-electronic repulsion Racah parameters, extra stabilisation of specific 4f 9 -configurations and nephelauxetic ratio using experimental values of the formation constants. (author). 24 refs., 2 figs., 3 tabs

  13. Structural and thermodynamic aspects of aqueous solution of trivalent lanthanides complexation by hydrophobic compounds of tartaric acid, by gluconic acid and related molecules. Outlook for liquid-liquid extraction of these cations

    International Nuclear Information System (INIS)

    Giroux, Sebastien

    1999-01-01

    This work deals with the complexation of lanthanide(III) ions by different molecules and with the synthesis of hydrophobic molecules able to extract them of an aqueous solution. Its aim is to describe the systems obtained by the determination of the formation constants of the species and by the description of their structure. The aim of this work is also to obtain a selective complexation of lanthanides(III) towards actinides(III), because this aim presents a great interest in the reprocessing of radioactive wastes. The complexation studies have been followed by potentiometry, NMR, UV-visible spectroscopy and circular dichroism. The first mixtures studied are the couples: lanthanide(III)-gluconic acid (LH). The complexes system they formed has been described and the structures have been specified; a strong complexation has been revealed. The MLH -2 specie induces a selectivity between the lanthanides(III) equivalent to those obtained with EDTA and its uncharged character allows to consider the use of gluconic acid as extractant. The use of ligands as glucosaminic acid or glucamine slows the beginning of the complexation until pH= 6-7. The neutral specie MLH -2 is formed too. In order to use the complexing properties of gluconic acid and its selective character towards lanthanides(III), the synthesis of molecules derived containing a long alkyl chain with a hydrophobic character has been carried out for using them as extracting agents. An original method of the preparation of tartramides is presented. This preparation consists of an amidation of one of the carboxylic functions of the tartaric acid by a fatty amine. These molecules, surface-active, complex the lanthanides(III) and extract them in an organic phase using the tri-n-butyl phosphate as co-extractant. (O.M.)

  14. Highly Luminescent, Water-Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates.

    Science.gov (United States)

    Kalyakina, Alena S; Utochnikova, Valentina V; Bushmarinov, Ivan S; Ananyev, Ivan V; Eremenko, Igor L; Volz, Daniel; Rönicke, Franziska; Schepers, Ute; Van Deun, Rik; Trigub, Alexander L; Zubavichus, Yan V; Kuzmina, Natalia P; Bräse, Stefan

    2015-12-01

    Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on Eu(III) and Tb(III) complexes as visible emitters and Nd(III) , Er(III) , and Yb(III) complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X-ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X-ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5 Eu0.5 (pfb)3 (H2 O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)(-) →Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, Kenneth M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a “hard” anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized.

  16. Organometallic complex chemistry of plutonium and selected lanthanides

    International Nuclear Information System (INIS)

    Seemann, U.

    1987-01-01

    This study deals with the metallo-organic chemistry of plutonium and also with that of some lanthanides. For plutonium, the conversion of Cs 2 PuCl 6 with four equivalents KCp is investigated. In the series Sm, Gd, Dy and Er, compounds of the type Cp 2 LnX and the base adducts with acetonitrile are analysed. The ligand X passes the series Cl, N 3 , NCS and NCO. Both, the thermal and the vibrational spectroscopic behaviour is investigated. In addition, the effect of a changed ligand sphere on the optical spectrum is discussed. The adduct-free compounds are described by a ternary reaction not yet known from literature. For the first time, force constant calculations are carried out on metallo-organic compounds of lanthanides. With the exception of Cp 2 LnCl compounds, all compouds are presented for the first time in the framework of this study. (orig.) [de

  17. Optical Properties of Lanthanides in Condensed Phase, Theory and Applications

    Directory of Open Access Journals (Sweden)

    Renata Reisfeld

    2015-04-01

    Full Text Available The basic theories of electronic levels and transition probabilities of lanthanides are summarized. Their interpretation allows practical preparation of new materials having application in lighting, solar energy utilization, optoelectronics, biological sensors, active waveguides and highly sensitive bioassays for in vitro detection in medical applications. The ways by which the weak fluorescence arising from electronic transition within the four f-configurations can be intensified will be discussed. This includes the intermixing of the four f-states with ligands of the host matrix, excitation to higher d-electronic states. Additional intensification of luminescence by plasmonic interaction with gold, silver and copper nanoparticles will be discussed. A short history of the time development of the research and the names of the scientists who made the major contribution of our understanding of lanthanides spectroscopy are presented.

  18. Medium temperature reaction between lanthanide and actinide carbides and hydrogen

    International Nuclear Information System (INIS)

    Dean, G.; Lorenzelli, R.; Pascard, R.

    1964-01-01

    Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C 1-x , H 2x ). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [fr

  19. Synthesis and investigation of uranylphosphates, uranylarsenanes, and uranylvanadates of lanthanides

    International Nuclear Information System (INIS)

    Chernorukov, N.G.; Knyazev, A.V.; Barch, S.V.; Feoktisova, S.V.; Suleymanov, E.V.

    2000-01-01

    Currently compounds A k (B V UO 6 ) k-m (OH) m .nH 2 O (A k - Y, La-Lu, B V -P, As, V) are of interest as the possible mineral-like forms of linkage in an environment of uranium and radioactive isotopes of lanthanides of an artificial origin, as modeling systems for study of similar compounds of six-valence neptunium and plutonium, and as objects, suitable for allocation and division lanthanides and actinides. In order to determine a role of water molecules in the formation of the crystal structure of inorganic hydrates and processes of dehydration uranium minerals with the general formula A k (B V UO 6 ) k-m (OH) m .nH 2 O and their synthetic analogues (A k - one-, two- and three-valent elements, B V -elements of the fifth group of Periodic system) are rather convenient objects. (authors)

  20. Crystal structure study of new lanthanide silicates with silico-carnotite structure

    International Nuclear Information System (INIS)

    Piccinelli, F.; Lausi, A.; Speghini, A.; Bettinelli, M.

    2012-01-01

    The crystal structures of new rare earth-based silicate compounds (Ca 3 Eu 2 Si 3 O 12 , Ca 3 Gd 2 Si 3 O 12 , Ca 3 Dy 2 Si 3 O 12 , Ca 3 Er 2 Si 3 O 12 and Ca 3 Lu 2 Si 3 O 12 ) have been determined using powder X-ray diffraction. From Rietveld refinement calculations on the collected powder patterns we observe a different distribution of the rare earth ions on the three available crystal sites characterized by different coordination numbers, depending on the ionic radius of the rare earth ion. The reasons of the instability of the silico-carnotite structure for lanthanide ions larger than Eu 3+ have been deduced. In addition, in order to detect crystal phase transitions, the powder patterns of Ca 3 Eu 2 Si 3 O 12 and Ca 3 Sm 2 Si 3 O 12 samples have been collected as a function of the temperature (RT-1000 °C range), but no phase transitions have been observed. - Graphical abstract: Synchrotron X-ray diffraction allows us the accurate determination of the RE 3+ ions distribution on the three available crystal sites of the silico-carnotite structure. Highlights: ► The structure of the Ca 3 M 2 Si 3 O 12 (M=Eu, Gd, Dy, Er and Lu) was determined. ► Different distribution of RE 3+ ions on the three available crystal sites was observed. ► The instability of the silico-carnotite structure for RE=La→Sm was discussed.

  1. Synthesis and characterization of metal soaps of lanthanides (III); Sintese e caracterizacao de saboes metalicos de lantanidios (III)

    Energy Technology Data Exchange (ETDEWEB)

    Payolla, Filipe Boccato; Ribeiro, Sidney Jose Lima; Massbni, Antonio Carlos [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Araraquara, SP (Brazil). Instituto de Quimica; Centro Universitario de Araraquara (UNIARA), Araraquara, SP (Brazil)

    2015-07-01

    The present study describes synthesis and partial characterization of Eu{sup 3+}, Nd{sup 3+}, Dy{sup 3+}, Tb{sup 3+} and Yb{sup 3+} behenate complexes. The compounds were analyzed using IR-Spectroscopy, TG-DTG, DSC, elemental analysis, XRD, luminescence and SEM. The results show the purity of the compounds. The XRD analysis and the SEM images show the high crystallinity of the complexes. TG-DTG and DSC analyses do not show a liquid crystal behavior, as occurs with other lanthanide metallic soaps. The mass loses until 1000° C show that the compounds lose ligand fragments at specific temperatures. XRD of the residues are compatible with the respective lanthanide oxides. The luminescence analysis shows that the Eu{sup 3+}, Nd{sup 3+} and Tb{sup 3+} complexes presents appreciable emission. The Judd-Ofelt parameters obtained are compatible with the values found in the literature. It was not possible to obtain the complexes in a glass-form because it is difficult to prevent the crystallization of the complexes even using liquid nitrogen. The XDR data indicate that one of the complexes axis has 52 Å of length, agreeing with a structure containing behenate-lanthanide ion-behenate. The structures of the complexes were not fully elucidated and more analyses are necessary. The complexes presented a molar ratio of 3:1 (L:M) and were formulated as Bh{sub 3}Eu, Bh{sub 3}Nd, Bh{sub 3}Dy, Bh{sub 3}Tb e Bh{sub 3}Yb (Bh = behenate anion). (author)

  2. Organometallic compounds of the lanthanides, actinides and early transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Cardin, D J [Trinity Coll., Dublin (Ireland); Cotton, S A [Stanground School, Peterborough (UK); Green, M [Bristol Univ. (UK); Labinger, J A [Atlantic Richfield Co., Los Angeles, CA (USA); eds.

    1985-01-01

    This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided.

  3. Magnetic dipole moments of odd-odd lanthanides

    International Nuclear Information System (INIS)

    Sharma, S.D.; Gandhi, R.

    1988-01-01

    Magnetic dipole moments of odd-odd lanthanides. Collective model of odd-odd nuclei is applied to predict the magnetic dipole moments, (μ) of odd-odd lanthanides. A simplified version of expression for μ based on diagonalisation of Hamiltonian (subsequent use of eigenvectors to compute μ) is developed for cases of ground state as well as excited states using no configuration mixing and is applied to the cases of odd-odd lanthanides. The formulae applied to the eleven (11) cases of ground states show significant improvement over the results obtained using shell model. Configuration mixing and coriolis coupling is expected to cause further improvement in the results. On comparing the earlier work in this direction the present analysis has clarified that in the expression μ the projection factors have different signs for the case I=Ωp - Ωn and I=Ωn - Ωp, and sign of μ is negative in general in the second case while it is positive in all others of spin projection alignments. Although the general expression holds for excited states as well but in lanthanide region, the experimental reports of magnetic dipole moments of excite states (band heads of higher rational sequences) are not available except in case of five (5) neutron resonance states which cannot be handled on the basis of the present approach with no configuration mixing. Although in the present discussion, the model could not be applied to excited states but the systematics of change in its magnitude with increasing spin at higher rational states is very well understood. The particle part supressed under faster rotation of the nuclear core and thus finally at higher spin I, the value μ is given by μ=g c I (same as in case of even-even nuclei). These systematics are to be verified whenever enough data for higher excited states are available. (author). 11 refs

  4. Analytical applications of superacid dissolution of actinide and lanthanide substrates

    International Nuclear Information System (INIS)

    Avens, L.R.; Eller, P.G.; Asprey, L.B.; Abney, K.D.; Kinkead, S.A.

    1987-01-01

    The superacid system HF/SbF 5 is extraordinarily effective for total dissolution of actinide and lanthanide ceramic oxides, fluorides, and metals. Optical or gamma spectroscopy can be used directly on the solutions. Evaporation of the HF/SbF 5 solvent under vacuum leaves a residue which is easily dissolved by ordinary mineral acids. The resulting aqueous solutions are readily amenable to conventional analytical methods

  5. Photoluminescence and Coordination Behaviour of Lanthanide Complexes of Tris (Aminomethyl)Ethane-5-Oxine in Aqueous Solution.

    Science.gov (United States)

    Akbar, Rifat; Baral, Minati; Kanungo, B K

    2017-01-01

    Photophysical properties of a multidentate tripodal ligand, 5,5'-(2-(((8-hydroxyquinolin-5-yl) methylamino)methyl)-2-methylpropane-1,3-diyl) bis (azanediyl)bis (methylene)diquinolin-8-ol, (TAME5OX), with La 3+ and Er 3+ ions have been examined for photonics applications. The change in behavior in electronic spectra of these complexes reveals the use of TAME5OX as a sensitive optical pH based sensor to detect Ln 3+ ions whereas indication of strong green fluorescence allows simultaneous sensing within the visible region in competitive medium. The intense fluorescence intermittently gets quenched under acidic and basic conditions due to photoinduced intramolecular electron transfer from the excited 8-hydroxyquinoline (8-HQ) moiety to the metal ion. This renders these compounds the OFF-ON-OFF type of pH-dependent fluorescent sensor. The thermodynamic stability and coordination behaviour of the chelator with the said lanthanide ions have also been probed by potentiometric, UV - visible and fluorescence spectrophotometric method. TAME5OX forms protonated complex [Ln (H 4 L)] 4+ below pH ~4.0 which sequentially deprotonates through one proton process with increase of pH. The stability constants of neutral complexes have been determined to be in the range log β 110  = 32-34 and pLn in the range of 14-20, indicating TAME5OX is a good synthetic lanthanide chelator. Theoretical spectra were also calculated by ZINDO/s methodology at single excitations (CIS) level on PM7 as sparkle energy-minimized geometries.

  6. Novel open-framework architectures in lanthanide phosphonates

    Science.gov (United States)

    Groves, John A.; Stephens, Nicholas F.; Wright, Paul A.; Lightfoot, Philip

    2006-03-01

    Two novel three-dimensional lanthanide coordination polymers have been prepared hydrothermally with the phosphonic acid N,N-piperazine bis(methylenephosphonic acid), H 2O 3PCH 2N(C 2H 4) 2NCH 2PO 3H 2 ( LH 4). The structures of Gd 2( LH 2) 3ṡ3H 2O (I) and Nd 2( LH 2) 3ṡ9H 2O (II) have been characterised by single crystal X-ray techniques. One-dimensional 'lanthanide-phosphate' chains are a key feature in both structures, although there are major structural differences between the chains, with (I) displaying octahedral GdO 6 coordination and (II) showing eight-coordinate NdO 8 polyhedra. In each case, three-dimensional connectivity is completed by coordination of the phosphonate group resulting in open framework structures encapsulating loosely bound water molecules. Isostructural Y 3+ and Yb 3+ analogues of (I) have been prepared, suggesting that cation size is a key factor in controlling the differing reaction products. In the case of Y 2( LH 2) 3ṡ5H 2O, isostructural to (I), it is shown that the extra-framework water molecules may be removed reversibly without framework collapse. Structural relationships to other known lanthanide phosphonates are discussed.

  7. Thermodecomposition of lanthanides (III) and ytrium (III) glucoheptonates

    International Nuclear Information System (INIS)

    Giolito, J.

    1987-01-01

    The lanthanides (III) and yttrium (III) glucoheptonates as well the D-glucoheptono 1-4 lactone were studied using common analytical methods, elemental microanalysis of carbon and hydrogen, thermogravimetry and differential scanning calorimetry. These compounds were prepared from the reaction between the lanthanides (III) and yttrium (III) hydroxides and glucoheptonic acid aqueous solution obtained by means of the delta lactone hydrolysis of this acid. After stoichiometric reaction the compounds were precipitated by the addition of absolute ethanol, washed with the same solvent and dried in desiccator. Thermogravimetric the (TG) curves of the lanthanides glucoheptonates of the ceric group present thermal profiles with enough differences permitting an easy caracterization of each compound and the yttrium (III) glucoheptonate TG curve showed a great similarity with the erbium (III) compound TG curve. The differential scanning calometry (DSC) curves showed endothermic and exothermic peaks by their shape, height and position (temperature) permit an easy and rapid identification of each compound specially if DSC and TG curves were examined simultaneously. (author) [pt

  8. Citrate based ''TALSPEAK'' lanthanide-actinide separation process

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

    1994-09-01

    The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ''geological'' periods of time. The costs of building, maintaining, and operating a ''geological TRU repository'' can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ''TALSPEAK'' process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced

  9. Molecular dynamics simulations of ter-pyridine and bis-triazinyl-pyridine complexes with lanthanide cations; Etude de dynamique moleculaire de complexes de la bis-triazinyl-pyridine (BTP) et de la terpyridine avec des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Guilbaud, Ph. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France)

    2000-07-01

    The search for ligands which specifically separate actinides(III) from lanthanides(III) by liquid-liquid extraction has prompted considerable research in the Process Design and Modeling Department ('Service d'Etude et de Modelisation des Procedes'- SEMP). Ligands with soft donor atoms AS) that are able to perform this separation have already been investigated and research is currently under way to improve their performance for high acidic feeds. Theoretical chemistry research is conducted in the Theoretical and Structural Chemistry Laboratory ('Laboratoire de Chimie Theorique et Structurale') to improve our understanding of the complexation and extraction of these cations with such ligands. Theoretical studies were first carried out for the ter-pyridine (TPY) and bis-triazinyl-pyridine (BTP) ligands that display fairly good ability to separate and extract actinide(III) from lanthanide(III) ions. Molecular dynamics simulations were performed on ter-pyridine and bis-triazinyl-pyridine complexes with three lanthanide cations (La{sup 3+}, Eu{sup 3+} and Lu{sup 3+}) for vacuum and for water solutions. These calculations were carried out without counter-ions, with three nitrate (NO{sub 3}{sup -}) ions, and, in the case of ter-pyridine, with three {alpha}-bromo-caprate anions that are likely to be used experimentally as synergistic agents for the separation and extraction of An(III) from Ln(III). Molecular dynamics simulations were first performed for vacuum to evaluate the distances between nitrogen and lanthanide atoms (Ln{sup 3+},N) and intrinsic interaction energies to poly-nitrogenous ligands with or without NO{sub 3} ions, and for both ligands. The (Ln{sup 3+},N) distances decrease and the cation/ligand interaction energies increase along the La{sup 3+}, Eu{sup 3+}, Lu{sup 3+} series, with decreasing Ln(III) ion radii. The introduction of nitrate counter-ions makes the (Ln{sup 3+},N) distances slightly higher, and the TPY/Ln{sup 3+} and BTP

  10. Selective removal of lanthanides from natural waters, acidic streams and dialysate

    Energy Technology Data Exchange (ETDEWEB)

    Yantasee, Wassana, E-mail: wassana.yantasee@pnl.gov [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya [Pacific Northwest National Laboratory (PNNL), P.O. Box 999, Richland, WA 99352 (United States); Xu Jide; Raymond, Kenneth N. [Chemistry Department, University of California, Berkeley, CA 94720 (United States); LBNL, Berkeley, CA 94720 (United States)

    2009-09-15

    The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS{sup TM}), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 {mu}g/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

  11. Selective removal of lanthanides from natural waters, acidic streams and dialysate

    International Nuclear Information System (INIS)

    Yantasee, Wassana; Fryxell, Glen E.; Addleman, R. Shane; Wiacek, Robert J.; Koonsiripaiboon, View; Pattamakomsan, Kanda; Sukwarotwat, Vichaya; Xu Jide; Raymond, Kenneth N.

    2009-01-01

    The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, which increases public exposure to the lanthanides, both from various commercial products and from production wastes/effluents. This work investigates lanthanide (La, Ce, Pr, Nd, Eu, Gd and Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS TM ), that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (Prop-Phos), and 1-hydroxy-2-pyridinone (1,2-HOPO), from natural waters (river, ground and sea waters), acid solutions (to mimic certain industrial process streams), and dialysate. The affinity, capacity, and kinetics of the lanthanide sorption, as well as regenerability of SAMMS materials were investigated. Going from the acid side over to the alkaline side, the AcPhos- and DiPhos-SAMMS maintain their outstanding affinity for lanthanides, which enable the use of the materials in the systems where the pH may fluctuate. In acid solutions, Prop-Phos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their use in chromatographic lanthanide separation. Over 95% of 100 μg/L of Gd in dialysate was removed by the Prop-Phos-SAMMS after 1 min and 99% over 10 min. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties. Thus, they have a great potential to be used as in large-scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and in sorbent dialyzers for treatment of acute lanthanide poisoning.

  12. Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

    Science.gov (United States)

    Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

    2014-06-01

    A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates. © 2014 Wiley Periodicals, Inc.

  13. Ion-ion interaction and energy transfer of 4+ transuranium ions in cerium tetrafluoride

    International Nuclear Information System (INIS)

    Liu, G.K.; Beitz, J.V.

    1990-01-01

    Dynamics of excited 5f electron states of the transuranium ions Cm 4+ and Bk 4+ in CeF 4 are compared. Based on time- and wavelength-resolved laser-induced fluorescence, excitation energy transfer processes have been probed. Depending on concentration and electronic energy level structure of the studied 4+ transuranium ion, the dominant energy transfer mechanisms were identified as cross relaxation, exciton-exciton annihilation, and trapping. Energy transfer rates derived from the fitting of the observed fluorescence decays to theoretical models, based on electric multipolar ion-ion interactions, are contrasted with prior studies of 4f states of 3+ lanthanide and 3d states of transition metal ions. 16 refs., 1 tab

  14. Strong exchange and magnetic blocking in N₂³⁻-radical-bridged lanthanide complexes.

    Science.gov (United States)

    Rinehart, Jeffrey D; Fang, Ming; Evans, William J; Long, Jeffrey R

    2011-05-22

    Single-molecule magnets approach the ultimate size limit for spin-based devices. These complexes can retain spin information over long periods of time at low temperature, suggesting possible applications in high-density information storage, quantum computing and spintronics. Notably, the success of most such applications hinges upon raising the inherent molecular spin-inversion barrier. Although recent advances have shown the viability of lanthanide-containing complexes in generating large barriers, weak or non-existent magnetic exchange coupling allows fast relaxation pathways that mitigate the full potential of these species. Here, we show that the diffuse spin of an N(2)(3-) radical bridge can lead to exceptionally strong magnetic exchange in dinuclear Ln(III) (Ln = Gd, Dy) complexes. The Gd(III) congener exhibits the strongest magnetic coupling yet observed for that ion, while incorporation of the high-anisotropy Dy(III) ion gives rise to a molecule with a record magnetic blocking temperature of 8.3 K at a sweep rate of 0.08 T s(-1).

  15. Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

    International Nuclear Information System (INIS)

    Clearfield, Abraham

    2017-01-01

    As indicated in the previous annual report the goals of this project are to develop procedures for efficient separation of lanthanides from actinides and curium from americium. These processes are required for the nuclear fuel cycle to minimize the waste and recover the valuable actinides. The basis for our study is that we have prepared a group of compounds that are porous and favor the uptake of ions with charges 3+ and 4+ over ions of lesser charge. The general formula for these materials is M(O 3 PC 6 H 4 PO 3 ) 1-x/2 (APO 4 )x·nH 2 O: where M=Zr 4+ , Sn 4+ , A=H, Na, or K and X=O, 0.5, 0.8, 1.0, 1.33 and 1.61-3. One of our tasks is to determine which members of this group of compounds are effective in carrying out the required separations. A difficulty in obtaining this required information is that the compounds are amorphous. That is they are not crystalline, therefore we need to resort to synchrotron data to obtain structural data which will be presented in detail. This information will be provided as a separate section.

  16. Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Clearfield, Abraham [Texas A & M Univ., College Station, TX (United States)

    2017-10-24

    As indicated in the previous annual report the goals of this project are to develop procedures for efficient separation of lanthanides from actinides and curium from americium. These processes are required for the nuclear fuel cycle to minimize the waste and recover the valuable actinides. The basis for our study is that we have prepared a group of compounds that are porous and favor the uptake of ions with charges 3+ and 4+ over ions of lesser charge. The general formula for these materials is M(O3PC6H4PO3)1-x/2(APO4)x·nH2O: where M=Zr4+, Sn4+, A=H, Na, or K and X=O, 0.5, 0.8, 1.0, 1.33 and 1.61-3. One of our tasks is to determine which members of this group of compounds are effective in carrying out the required separations. A difficulty in obtaining this required information is that the compounds are amorphous. That is they are not crystalline, therefore we need to resort to synchrotron data to obtain structural data which will be presented in detail. This information will be provided as a separate section.

  17. Pulse EPR-enabled interpretation of scarce pseudocontact shifts induced by lanthanide binding tags

    Energy Technology Data Exchange (ETDEWEB)

    Abdelkader, Elwy H.; Yao, Xuejun [Australian National University, Research School of Chemistry (Australia); Feintuch, Akiva [Weizmann Institute of Science, Department of Chemical Physics (Israel); Adams, Luke A.; Aurelio, Luigi; Graham, Bim [Monash University, Monash Institute of Pharmaceutical Sciences (Australia); Goldfarb, Daniella [Weizmann Institute of Science, Department of Chemical Physics (Israel); Otting, Gottfried, E-mail: gottfried.otting@anu.edu.au [Australian National University, Research School of Chemistry (Australia)

    2016-01-15

    Pseudocontact shifts (PCS) induced by tags loaded with paramagnetic lanthanide ions provide powerful long-range structure information, provided the location of the metal ion relative to the target protein is known. Usually, the metal position is determined by fitting the magnetic susceptibility anisotropy (Δχ) tensor to the 3D structure of the protein in an 8-parameter fit, which requires a large set of PCSs to be reliable. In an alternative approach, we used multiple Gd{sup 3+}-Gd{sup 3+} distances measured by double electron–electron resonance (DEER) experiments to define the metal position, allowing Δχ-tensor determinations from more robust 5-parameter fits that can be performed with a relatively sparse set of PCSs. Using this approach with the 32 kDa E. coli aspartate/glutamate binding protein (DEBP), we demonstrate a structural transition between substrate-bound and substrate-free DEBP, supported by PCSs generated by C3-Tm{sup 3+} and C3-Tb{sup 3+} tags attached to a genetically encoded p-azidophenylalanine residue. The significance of small PCSs was magnified by considering the difference between the chemical shifts measured with Tb{sup 3+} and Tm{sup 3+} rather than involving a diamagnetic reference. The integrative sparse data approach developed in this work makes poorly soluble proteins of limited stability amenable to structural studies in solution, without having to rely on cysteine mutations for tag attachment.

  18. Impurity doping: a novel strategy for controllable synthesis of functional lanthanide nanomaterials.

    Science.gov (United States)

    Chen, Daqin; Wang, Yuansheng

    2013-06-07

    Many technological nanomaterials are intentionally 'doped' by introducing appropriate amounts of foreign elements into hosts to impart electronic, magnetic and optical properties. In fact, impurity doping was recently found to have significant influence on nucleation and growth of many functional nanocrystals (NCs), and provide a fundamental approach to modify the crystallographic phase, size, morphology, and electronic configuration of nanomaterials. In this feature article, we provide an overview of the most recent progresses in doping-induced control of phase structures, sizes, shapes, as well as performances of functional nanomaterials for the first time. Two kinds of impurity doping strategies, including the homo-valence ion doping and hetero-valence ion doping, are discussed in detail. We lay emphases on impurity doping induced modifications of microstructures and optical properties of upconversion (UC) lanthanide (Ln(3+)) NCs, but do not limit to them. In addition, we also illustrate the control of Ln(3+) activator distribution in the core@shell architecture, which has recently provided scientists with new opportunities for designing and tuning the multi-color emissions of Ln(3+)-doped UC NCs. Finally, the challenges and future perspectives of this novel impurity doping strategy are pointed out.

  19. Hybrid silica luminescent materials based on lanthanide-containing lyotropic liquid crystal with polarized emission

    Energy Technology Data Exchange (ETDEWEB)

    Selivanova, N.M., E-mail: natsel@mail.ru [Kazan National Research Technological University, 68 Karl Marx Str., Kazan 420015 (Russian Federation); Vandyukov, A.E.; Gubaidullin, A.T. [A.E. Arbuzov Institute of Organic and Physical Chemistry of the Kazan Scientific Center of the Russian Academy of Sciences, 8 Acad. Arbuzov Str., Kazan 420088 (Russian Federation); Galyametdinov, Y.G. [Kazan National Research Technological University, 68 Karl Marx Str., Kazan 420015 (Russian Federation)

    2014-11-14

    This paper represents the template method for synthesis of hybrid silica films based on Ln-containing lyotropic liquid crystal and characterized by efficient luminescence. Luminescence films were prepared in situ by the sol–gel processes. Lyotropic liquid crystal (LLC) mesophases C{sub 12}H{sub 25}O(CH{sub 2}CH{sub 2}O){sub 10}H/Ln(NO{sub 3}){sub 3}·6H{sub 2}O/H{sub 2}O containing Ln (III) ions (Dy, Tb, Eu) were used as template. Polarized optical microscopy, X-ray powder diffraction, and FT-IR-spectroscopy were used for characterization of liquid crystal mesophases and hybrid films. The morphology of composite films was studied by the atomic force microscopy method (AFM). The optical properties of the resulting materials were evaluated. It was found that hybrid silica films demonstrate significant increase of their lifetime in comparison with an LLC system. New effects of linearly polarized emission revealed for Ln-containing hybrid silica films. Polarization in lanthanide-containing hybrid composites indicates that silica precursor causes orientation of emitting ions. - Highlights: • We suggest a new simple approach for creating luminescence hybrid silica films. • Ln-containing hybrid silica films demonstrate yellow, green and red emissions. • Tb(III)-containing hybrid film have a high lifetime. • We report effects of linearly polarized emission in hybrid film.

  20. Dispersive liquid-liquid microextraction followed by flow injection-inductively coupled plasma mass spectrometry (FI-ICPMS) determination of 14 lanthanides from ground water

    International Nuclear Information System (INIS)

    Chandrasekaran, K.; Karunasagar, D.; Arunachalam, J.

    2011-01-01

    The aim of the present work was to develop a dispersive liquid-liquid microextraction (DLLME) method for the sensitive determination of REEs at a few parts per billion in groundwater by flow injection-inductively coupled plasma mass spectrometry (FI-ICPMS). In the developed method, methanol (500 μl) and chloroform (200μl) were used as the disperser and extractant respectively. The REEs were complexed with 4-(2-pyridylazo resorcinol) (PAR) at a pH of 7. Acetate ion was added as an auxiliary ligand for neutralization of the charge on the lanthanide-PAR complex. The disperser (MeOH) - extraction solvent (CHCl 3 ) mixture was rapidly injected using a disposable syringe, thereby forming a cloudy solution. The lanthanide-PAR complex was extracted into the fine droplets of the chloroform dispersed in the aqueous phase. The solution was centrifuged and the aqueous layer at the top was discarded. The REEs were back extracted from the chloroform layer with nitric acid for determination by ICPMS. Important parameters for complex formation and extraction, such as volume of extraction/disperser solvent, extraction time, pH and concentration of the chelating agent and the auxiliary ligand are being optimized using ICP-MS. The optimization is being carried out at 5 μg L -1 concentration level of REE in the initial water sample. Preliminary studies have shown an extraction recovery of 80-85% for all the 14 lanthanide elements and these will be presented

  1. Ce3+ 5d-centroid shift and vacuum referred 4f-electron binding energies of all lanthanide impurities in 150 different compounds

    International Nuclear Information System (INIS)

    Dorenbos, Pieter

    2013-01-01

    A review on the wavelengths of all five 4f–5d transitions for Ce 3+ in about 150 different inorganic compounds (fluorides, chlorides, bromides, iodides, oxides, sulfides, selenides, nitrides) is presented. It provides data on the centroid shift and the crystal field splitting of the 5d-configuration which are then used to estimate the Eu 2+ inter 4f-electron Coulomb repulsion energy U(6,A) in compound A. The four semi-empirical models (the redshift model, the centroid shift model, the charge transfer model, and the chemical shift model) on lanthanide levels that were developed past 12 years are briefly reviewed. It will be demonstrated how those models together with the collected data of this work and elsewhere can be united to construct schemes that contain the binding energy of electrons in the 4f and 5d states for each divalent and each trivalent lanthanide ion relative to the vacuum energy. As example the vacuum referred binding energy schemes for LaF 3 and La 2 O 3 will be constructed. - Highlights: ► An compilation on all five Ce 3+ 4f–5d energies in 150 inorganic compounds is presented. ► The relationship between the 5d centroid shift and host cation electronegativity id demonstrated. ► The electronic structure scheme of the lanthanides in La 2 O 3 and LaF 3 is presented.

  2. Complexation and extraction of series 4f, 5f and 4d ions by dialkyldithiophosphoric acids

    International Nuclear Information System (INIS)

    Fitoussi, Richard.

    1982-04-01

    A study was carried out on the complexing and extracting properties of various dialkyldithiophosphoric acids towards ions of the 4f, 5f and 4d series. Sulphurated donors complex and extract ions of the 4f and 5f series less strongly than their oxygenated homologues. However the affinity of trivalent actinide ions for dialkythiophosphate ions is shown to be greater than that of lanthanides. The conditions of ruthenium extraction from nitric acid are defined [fr

  3. Three-Dimensional Protein Fold Determination from Backbone Amide Pseudocontact Shifts Generated by Lanthanide Tags at Multiple Sites

    KAUST Repository

    Yagi, Hiromasa

    2013-06-01

    Site-specific attachment of paramagnetic lanthanide ions to a protein generates pseudocontact shifts (PCS) in the nuclear magnetic resonance (NMR) spectra of the protein that are easily measured as changes in chemical shifts. By labeling the protein with lanthanide tags at four different sites, PCSs are observed for most amide protons and accurate information is obtained about their coordinates in three-dimensional space. The approach is demonstrated with the chaperone ERp29, for which large differences have been reported between X-ray and NMR structures of the C-terminal domain, ERp29-C. The results unambiguously show that the structure of rat ERp29-C in solution is similar to the crystal structure of human ERp29-C. PCSs of backbone amides were the only structural restraints required. Because these can be measured for more dilute protein solutions than other NMR restraints, the approach greatly widens the range of proteins amenable to structural studies in solution. © 2013 Elsevier Ltd. All rights reserved.

  4. Controllable synthesis and upconversion emission of ultrasmall near-monodisperse lanthanide-doped Sr2LaF7 nanocrystals

    International Nuclear Information System (INIS)

    Mao, Yifu; Ma, Mo; Gong, Lunjun; Xu, Changfu; Ren, Guozhong; Yang, Qibin

    2014-01-01

    Highlights: • Apropos NaOH content facilitates the growth of pure phase Sr 2 LaF 7 NCs. • Yb 3+ doping is favorable to the formation of Sr 2 LaF 7 NCs with uniform size. • Ultrasmall near-monodispersed Sr 2 LaF 7 NCs(sub-10 nm) were synthesized for the first time. • Intense multicolor upconversion can be obtained by properly lanthanide doping. - Abstract: Fluorite phase Sr 2 LaF 7 nanocrystals (NCs) were synthesized via solvothermal method using oleic acid as capping ligands. The effects of preparing conditions on the phase structure, crystal size, morphology, and upconversion (UC) emission properties of the products were studied. The results reveal that just apropos NaOH content facilitates the growth of near-monodispersed pure phase Sr 2 LaF 7 NCs, and Yb 3+ doping is favorable to the formation of pure Sr 2 LaF 7 phase with more uniform size distribution. The average crystalline size of the products can be controlled less than 10 nm. Following appropriate lanthanide ions doping, the NCs show intense blue, yellow, and white-color UC emission under the excitation of a 980 nm laser. The energy transfer UC mechanisms for the fluorescent intensity were also investigated

  5. Photoluminescence properties of lanthanide-organic frameworks (LnOFs) with thiophene-2,5-dicarboxylate and acetate

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jing; Wei, Qing; Xie, Gang; Chen, Sanping [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); Zhang, Sheng [Key Lab. of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest Univ., Xi' an, Shaanxi (China); College of Chemistry and Chemical Engineering, Baoji Univ. of Arts and Science, Baoji, Shaanxi (China)

    2017-07-17

    S-heterocyclic dicarboxylic acid, thiophene-2,5-dicarboxylic acid (H{sub 2}TDC), was employed to construct a series of lanthanide-organic frameworks (LnOFs) with coligand acetate, formulated as [Ln(TDC)(OAc)(H{sub 2}O)]{sub n} [Ln = Eu (1), Tb (2), Gd (3), Dy (4), Sm (5)] under hydrothermal conditions. Structure analysis reveals that 1-5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC{sup 2-} and OAc{sup -} display (κ{sup 1}-κ{sup 1})-(κ{sup 1}-κ{sup 1})-μ{sub 4} and (κ{sup 2}-κ{sup 1})-μ{sub 2} coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 C. As for 1, 2, 4, and 5, the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with {sup 5}D{sub 4} lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H{sub 2}TDC ligand and the {sup 5}D{sub 4} state energy level of Tb{sup 3+}. The energy transfer mechanisms in compounds 1 and 2 were also discussed. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Adducts compounds of lanthanides (III) trifluoreacetates and yttrium and the N,N - dimenthylformamide

    International Nuclear Information System (INIS)

    Silva, M. das G. da.

    1983-01-01

    Some studies on lanthanides, f transition elements, and yttrium are presented. Adducts of lanthanides trifluoroacetates and N,N -dimethylformamide are described. The characterization of complexes from elementar analysis, conductance measurements, X-ray patterns, vibrational, electronics and fluorescence spectra are analysed. (M.J.C.) [pt

  7. Specification and comparative calculation of enthalpies and Gibbs formation energies of anhydrous lanthanide nitrates

    International Nuclear Information System (INIS)

    Del' Pino, Kh.; Chukurov, P.M.; Drakin, S.I.

    1980-01-01

    Analyzed are the results of experimental depermination of formation enthalpies of waterless nitrates of lanthane cerium, praseodymium, neodymium and samarium. Using method of comparative calculation computed are enthalpies of formation of waterless lanthanide and yttrium nitrates. Calculated values of enthalpies and Gibbs energies of waterless lanthanide nitrate formation are tabulated

  8. Tuning the sensitivity of lanthanide-activated NIR nanothermometers in the biological windows

    NARCIS (Netherlands)

    Cortelletti, P.; Skripka, A.; Facciotti, C.; Pedroni, M.; Caputo, G.; Pinna, N.; Quintanilla, M.; Benayas, A.; Vetrone, F.; Speghini, A.

    2018-01-01

    Lanthanide-activated SrF2 nanoparticles with a multishell architecture were investigated as optical thermometers in the biological windows. A ratiometric approach based on the relative changes in the intensities of different lanthanide (Nd3+ and Yb3+) NIR emissions was applied to investigate the

  9. Process for recovering yttrium and lanthanides from wet-process phosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Janssen, J.A.; Weterings, C.A.

    1983-06-28

    Process for recovering yttrium and lanthanides from wet-process phosphoric acid by adding a flocculant to the phosphoric acid, separating out the resultant precipitate and then recovering yttrium and lanthanides from the precipitate. Uranium is recovered from the remaining phosphoric acid.

  10. Recovery of uranium and lanthanides during the production of nitrophosphate fertilizers using tertiary amyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Habashi, F; Awadalla, F T

    1986-01-01

    When phosphate rock is dissolved in nitric acid, phosphoric acid and uranium can be selectively extracted by tertiary amyl alcohol; other impurities including the lanthanides remain in the aqueous phase. Uranium can be recovered from the alcohol phase by selective stripping and the lanthanides from the raffinate by extraction with tributyl phosphate.

  11. Preparation, characterization and thermal behaviour study of double selenates of lanthanides, yttrium and beryllium

    International Nuclear Information System (INIS)

    Ribeiro, C.A.

    1988-01-01

    The lanthanides (III) and yttrium (III) double selenates were studied using common analytical methods, atomic absorption, X-ray diffraction infra-red absorption, thermogravimetry and differential thermal analysis. These compounds were prepared from the mixture of lanthanides (III) and yttrium (III) selenates aqueous solution and basic beryllium selenates aqueous solution, obeying equimolar relation (1:1) to the cation

  12. Electrodeposition of Actinide and Lanthanide Elements

    International Nuclear Information System (INIS)

    Baerring, N.E.

    1966-02-01

    Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given

  13. Electrodeposition of Actinide and Lanthanide Elements

    Energy Technology Data Exchange (ETDEWEB)

    Baerring, N E

    1966-02-15

    Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given.

  14. Structural trends in a series of isostructural lanthanide-copper metallacrown sulfates (Ln(III) = Pr, Nd, Sm, Eu, Gd, Dy and Ho): hexaaquapentakis[μ3-glycinehydroxamato(2-)]sulfatopentacopper(II)lanthanide(III) heptaaquapentakis[μ3-glycinehydroxamato(2-)]sulfatopentacopper(II)lanthanide(III) sulfate hexahydrate.

    Science.gov (United States)

    Pavlishchuk, Anna V; Kolotilov, Sergey V; Fritsky, Igor O; Zeller, Matthias; Addison, Anthony W; Hunter, Allen D

    2011-07-01

    The seven isostructural complexes, [Cu(5)Ln(C(2)H(4)N(2)O(2))(5)(SO(4))(H(2)O)(6.5)](2)(SO(4))·6H(2)O, where Ln(III) = Pr, Nd, Sm, Eu, Gd, Dy and Ho, are representatives of the 15-metallacrown-5 family. Each dianion of glycinehydroxamic acid (GlyHA) links two Cu(II) cations forming a cyclic [CuGlyHA](5) frame. The Ln(III) cations are located at the centre of the [CuGlyHA](5) rings and are bound by the five hydroxamate O atoms in the equatorial plane. Five water molecules are coordinated to Cu(II) cations, and one further water molecule, located close to an inversion centre between two adjacent [Cu(5)Ln(GlyHA)(5)](2+) cations, is disordered around this inversion centre and coordinated to a Cu(II) cation of either the first or second metallacrown ether. Another water molecule and one of the two crystallographically independent sulfate anions are coordinated, the latter in a bidentate fashion, to the Ln(III) cation in the axial positions. The second sulfate anion is not coordinated to the cation, but is located in an interstitial position on a crystallographic inversion centre, thus leading to disorder of the O atoms around the centre of inversion. The Ln-O bond distances follow the trend of the lanthanide contraction. The apical Ln-O bond distances are very close to the sums of the ionic radii. However, the Ln-O distances within the metallacrown units are slightly compressed and the Ln(III) cations protrude significantly from the plane of the otherwise flat metallacrown ligand, thus indicating that the cavity is somewhat too small to accommodate the Ln(III) ions comfortably. This effect decreases with the size of the lanthanide cation from complex (I) (Ln(III) = Pr; 0.459) to complex (VII) (Ln(III) = Ho; 0.422), which indicates that the smaller lanthanide cations fit the cavity of the pentacopper metallacrown ring better than the larger ones. The diminished contraction of Ln-O distances within the metallacrown planes leads to an aniostropic contraction of the unit

  15. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yeon Soo, E-mail: yskim@anl.gov [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Wiencek, T.; O' Hare, E.; Fortner, J.; Wright, A. [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Cheon, J.S.; Lee, B.O. [Korea Atomic Energy Research Institute, 989-111 Daedeok-daero, Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

    2017-02-15

    Advanced fast reactor concepts to achieve ultra-high burnup (∼50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  16. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yeon Soo; Wiencek, T.; O' Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

    2017-02-01

    Advanced fast reactor concepts to achieve ultra-high burnup (~50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  17. Separation of Am from lanthanides by a synergistic mixture of purified Cyanex 301 and TBP

    International Nuclear Information System (INIS)

    Xinghai Wang; Yongjun Zhu; Rongzhou Jiao

    2002-01-01

    The dependence of the distribution ratios of 241 Am and lanthanides between purified Cyanex 301 (HBTMPDTP)-TBP-kerosene/nitrate solution on pH, lanthanide concentration in aqueous phase and degree of saponification of HBTMPDTP was investigated. The distribution ratios of 241 Am and lanthanides increase with pH and degree of saponification of HBTMPDTP and decrease with lanthanides concentration. Countercurrent multistage extraction consisting of 7 extraction, 3 washing and 2 stripping stages showed that more than 99,99% of 241 Am and less than 0.04% of lanthanides were extracted. The pH 1/2 value of Am was 2.45 compared to 3.16 in case of HBTMPDTP-kerosene extraction. (author)

  18. Series of isostructural planar lanthanide complexes [Ln(III)4(mu3-OH)2(mdeaH)2(piv)8] with single molecule magnet behavior for the Dy4 analogue.

    Science.gov (United States)

    Abbas, Ghulam; Lan, Yanhua; Kostakis, George E; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

    2010-09-06

    A series of five isostructural tetranuclear lanthanide complexes of formula [Ln(4)(mu(3)-OH)(2)(mdeaH)(2)(piv)(8)], (mdeaH(2) = N-methyldiethanolamine; piv = pivalate; Ln = Tb (1), Dy (2), Ho (3), Er (4), and Tm (5)) have been synthesized and characterized. These clusters have a planar "butterfly" Ln(4) core. Magnetically, the Ln(III) ions are weakly coupled in all cases; the Dy(4) compound 2 shows Single Molecule Magnet (SMM) behavior.

  19. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

    Science.gov (United States)

    Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

    2015-01-01

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln2(phen)2(SO4)3(H2O)2]n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO4 2 - anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic-inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.

  20. Recent progress in actinide and lanthanide solvent extraction

    International Nuclear Information System (INIS)

    Musikas, C.; Hubert, H.; Benjelloun, N.; Vitorge, P.; Bonnin, M.; Forchioni, A.; Chachaty, C.

    1983-04-01

    Work in progress on actinide solvent extraction is briefly reviewed in this paper. 1 H and 31 P NMR are used to elucidate several fundamental unsolved problems concerning organophosphorous extractants often used in actinides extraction: determination of site of dialkylthiophosphate protonation and addition of basic phosphine oxide to dibutylthiophosphoric acid dimer. Extraction of Am III and Eu from high radioactivity level wastes by tetrasubsituted methylene diamides is investigated. Trivalent actinide-lanthanide group are separated by solvent extraction using soft donor ligand complexes which are more stable. The synergism of dinonylnaphtalene sulfonic acid (HDNNS) associated with several neutral donors like TBP, TOPO, amides are examined in the trivalent and tetravalent actinide extraction

  1. Reaction between phenyl derivatives of lanthanides and carbonyl compounds

    International Nuclear Information System (INIS)

    Sigalov, A.B.; Petrov, Eh.S.; Rybakova, L.F.; Beletskaya, I.P.

    1983-01-01

    Reactions of PhLnI (Ln=Yb, Eu, Sm, Ce) with α, β-unsaturated ketons (trans-chalcone and benzalacetone) are considered as well as with 9-fluorene and benzophenone. The regioselectivity of the reaction of PhLnI addition to enones is compared with similar reactions of PhMgX and PhLi. The reaction between PhLnI and trans-chalcone proceeds regiospecifically as 1, 2-addition in contrast with reactions of PhMgI and PhLi. A new reaction of lanthanide carbinolate deoxygenation under the effect of reducers was found. The reaction product yields are presented

  2. Method of cerium separation from other lanthanides and yttrium

    International Nuclear Information System (INIS)

    Tran, Duc Hiep; Mostecky, J.

    1988-01-01

    Cerium is separated from a suspension produced during the aerial oxidation process. The suspension is subject to a cyclic process of two-stage fractional dissolution. Following the first dissolution, almost all cerium remains undissolved while 95% of the other lanthanides pass into the solution. The filtrate of the second stage of dissolution containing about 5% of ceriumm is returned for oxidation with the next batch of hydroxide mixed concentrate. Following oxidation, the two-stage fractional dissolution is repeated. This cycling provides quantitative cerium separation from other rare earth elements. (E.S.)

  3. Synthesis, characterization and reactivity of some lanthanide organometallics

    International Nuclear Information System (INIS)

    Marchal, N.

    1991-12-01

    Organo lanthanides with reactive metal-carbon bonds are obtained by direct synthesis of the metal (powder) and a hydrocarbon in ether medium, like with alkali metals. Two types of synthesis are envisaged: formation of covalent bonds by opening cycles, only biphenylene is reactive enough in regard to ytterbium and samarium, these organometallic compounds can also be prepared by the classical way, i.e. reaction of 2.2'-dilithio biphenyl on rare earth halogenides and coupling of 6.6-dimethylfulvene leading to dicyclopentadienyl compounds with Sm and Yb. The reactivity of these complexes is studied by catalysis of ethylene polymerization

  4. Lanthanides and actinides extraction by calixarenes containing CMPO groups

    International Nuclear Information System (INIS)

    Garcia Carrera, A.

    2001-01-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  5. X-ray powder diffraction data on miscellaneous lanthanide compounds

    International Nuclear Information System (INIS)

    Ferguson, I.F.; Hughes, T.E.

    1978-08-01

    Recent work on neutron absorbing materials has produced various new X-ray diffraction powder patterns of compounds of the lanthanides. Various inconsistencies in previously published data have been noted, and accurate measurements have been made of the lattice parameters of the rare earth oxides Sm 2 0 3 , Eu 2 0 3 , Gd 2 0 3 which have the monoclinic rare earth type B- structure, as well as Eu0. These data are recorded for reference. The optimum conditions for obtaining X-ray powder diffraction data from europium compounds are also noted. (author)

  6. Magnetic Circular Dichroism of Porphyrin Lanthanide M3+ Complexes

    Czech Academy of Sciences Publication Activity Database

    Andrushchenko, Valery; Padula, Daniele; Zhivotova, E.; Yamamoto, S.; Bouř, Petr

    2014-01-01

    Roč. 26, č. 10 (2014), s. 655-662 ISSN 0899-0042 R&D Projects: GA ČR GA13-03978S; GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:GA AV ČR(CZ) M200550902 Institutional support: RVO:61388963 Keywords : magnetic circular dichroism * lanthanides * porphyrin complexes * density functional theory * sum over state computations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.886, year: 2014

  7. Status of the lanthanides and actinides in the periodic table

    International Nuclear Information System (INIS)

    Holden, N.E.

    1985-01-01

    In extended discussions and correspondence with Ekkehard Fluck, the author was made aware of a problem with the Periodic Table, i.e., which element should be shown in the main table as the representative of the lanthanide series and the actinide series. In earlier discussion, he came to the conclusion that lanthanum and actinium are not the elements which should appear, but rather lutetium and lawrencium are more appropriate for inclusion in their place. This paper will attempt to justify the reasons for the above conclusions. 4 refs

  8. Strong blue and white photoluminescence emission of BaZrO{sub 3} undoped and lanthanide doped phosphor for light emitting diodes application

    Energy Technology Data Exchange (ETDEWEB)

    Romero, V.H. [Centro de Investigaciones en Optica, A. P. 1-948, Leon Gto., 37160 (Mexico); De la Rosa, E., E-mail: elder@cio.mx [Centro de Investigaciones en Optica, A. P. 1-948, Leon Gto., 37160 (Mexico); Salas, P. [Centro de Fisica Aplicada y Tecnologia Avanzada, Universidad Nacional Autonoma de Mexico, A.P. 1-1010, Queretaro, Qro. 76000 (Mexico); Velazquez-Salazar, J.J. [Department of Physics and Astronomy, The University of Texas at San Antonio One UTSA Circle, San Antonio TX 78249 (United States)

    2012-12-15

    In this paper, we report the obtained strong broadband blue photoluminescence (PL) emission centered at 427 nm for undoped BaZrO{sub 3} observed after 266 nm excitation of submicron crystals prepared by hydrothermal/calcinations method. This emission is enhanced with the introduction of Tm{sup 3+} ions and is stronger than the characteristic PL blue emission of such lanthanide. The proposed mechanism of relaxation for host lattice emission is based on the presence of oxygen vacancies produced during the synthesis process and the charge compensation due to the difference in the electron valence between dopant and substituted ion in the host. Brilliant white light emission with a color coordinate of (x=0.29, y=0.32) was observed by combining the blue PL emission from the host with the green and red PL emission from Tb{sup 3+} and Eu{sup 3+} ions, respectively. The color coordinate can be tuned by changing the ratio between blue, green and red band by changing the concentration of lanthanides. - Graphical abstract: Strong blue emission from undoped BaZrO{sub 3} phosphor and white light emission by doping with Tb{sup 3+} (green) and Eu{sup 3+} (red) after 266 nm excitation. Highlights: Black-Right-Pointing-Pointer Blue emission from BaZrO{sub 3} phosphor. Black-Right-Pointing-Pointer Blue emission enhanced with Tm{sup 3+}. Black-Right-Pointing-Pointer White light from BaZrO{sup 3+} phosphor.

  9. Structural, luminescence and biological studies of trivalent lanthanide complexes with N,N Prime -bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine Schiff base ligand

    Energy Technology Data Exchange (ETDEWEB)

    Taha, Ziyad A., E-mail: tahaz33@just.edu.jo [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110 (Jordan); Ajlouni, Abdulaziz M. [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110 (Jordan); Al Momani, Waleed [Department of Allied Medical Sciences, Al Balqa Applied University (Jordan)

    2012-11-15

    New eight lanthanide metal complexes were prepared. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis ({sup 1}H NMR, FT-IR, UV-vis), luminescence and thermal gravimetric analysis. All Ln(III) complexes were 1:1 electrolytes as established by their molar conductivities. The microanalysis and spectroscopic analysis revealed eight-coordinated environments around lanthanide ions with two nitrate ligands behaving in a bidentate manner. The other four positions were found to be occupied with tetradentate L{sub III} ligand. Tb-L{sub III} and Sm-L{sub III} complexes exhibited characteristic luminescence emissions of the central metal ions and this was attributed to efficient energy transfer from the ligand to the metal center. The L{sub III} and Ln-L{sub III} complexes showed antibacterial activity against a number of pathogenic bacteria. - Highlights: Black-Right-Pointing-Pointer Ln(III) ion adopts an eight-coordinate geometry. Black-Right-Pointing-Pointer Luminescence spectra of Sm-L{sub III} and Tb-L{sub III} complexes display the metal centered line emission. Black-Right-Pointing-Pointer Energy transfer process from L{sub III} to Sm in Sm-L{sub III} complex is more efficient than to Tb in Tb-L{sub III} complex. Black-Right-Pointing-Pointer Ln(III) complexes may serve as models for biologically important species.

  10. Studies for the yttrium determination by activation analysis, in the presence of lanthanides. Application of the substoichiometric technique

    International Nuclear Information System (INIS)

    Silva, D.I.T. da.

    1978-01-01

    Some methods using extraction chromatography for the separation of yttrium from the lanthanide elements were applied. The separation of yttrium was studied, using di-(2 ethylhexyl) orthophosphoric acid as stationary phase, Kieselguhr as support and HNO 3 of concentration between 4,5 and 5,0 N as the mobile phase. In these conditions, about 50% of pure yttrium was obtained. The substoichiometric technique was applied to the determination of yttrium. The elements was partially complexed and the Y 3 + ions were separated from the complex (EDTA-Y) - by means of a cationic resin. The sensitivity, precision and accuracy which can be expected in the analytical results were studied. The possibility of the analysis of a sample containing 1 part per million of yttrium with an error just above 8% was demonstrated. It was also shown that, admitting an error of 10%, it is possible to determine 60 parts per billion of yttrium [pt

  11. Synthesis, Tunable Multicolor Output, and High Pure Red Upconversion Emission of Lanthanide-Doped Lu2O3 Nanosheets

    Directory of Open Access Journals (Sweden)

    Lingzhen Yin

    2013-01-01

    Full Text Available Yb3+ and Ln3+ (Ln = Er, Ho codoped Lu2O3 square nanocubic sheets were successfully synthesized via a facile hydrothermal method followed by a subsequent dehydration process. The crystal phase, morphology, and composition of hydroxide precursors and target oxides were characterized by X-ray diffraction (XRD, field emission scanning electron microscope (FE-SEM, and energy-dispersive X-ray spectroscope (EDS. Results present the as-prepared Lu2O3 crystallized in cubic phase, and the monodispersed square nanosheets were maintained both in hydroxide and oxides. Moreover, under 980 nm laser diode (LD excitation, multicolor output from red to yellow was realized by codoped different lanthanide ions in Lu2O3. It is noteworthy that high pure strong red upconversion emission with red to green ratio of 443.3 of Er-containing nanocrystals was obtained, which is beneficial for in vivo optical bioimaging.

  12. Ionic Liquid and Supercritical Fluid Hyphenated Techniques for Dissolution and Separation of Lanthanides, Actinides, and Fission Products

    International Nuclear Information System (INIS)

    Wai, Chien M.; Mincher, Bruce

    2012-01-01

    This project is investigating techniques involving ionic liquids (IL) and supercritical (SC) fluids for dissolution and separation of lanthanides, actinides, and fission products. The research project consists of the following tasks: Study direct dissolution of lanthanide oxides, uranium dioxide and other actinide oxides in [bmin][Tf 2 N] with TBP(HNO 3 ) 1.8 (H 2 O) 0.6 and similar types of Lewis acid-Lewis base complexing agents; Measure distributions of dissolved metal species between the IL and the sc-CO 2 phases under various temperature and pressure conditions; Investigate the chemistry of the dissolved metal species in both IL and sc-CO 2 phases using spectroscopic and chemical methods; Evaluate potential applications of the new extraction techniques for nuclear waste management and for other projects. Supercritical carbon dioxide (sc-CO 2 ) and ionic liquids are considered green solvents for chemical reactions and separations. Above the critical point, CO 2 has both gas- and liquid-like properties, making it capable of penetrating small pores of solids and dissolving organic compounds in the solid matrix. One application of sc-CO 2 extraction technology is nuclear waste management. Ionic liquids are low-melting salts composed of an organic cation and an anion of various forms, with unique properties making them attractive replacements for the volatile organic solvents traditionally used in liquid-liquid extraction processes. One type of room temperature ionic liquid (RTIL) based on the 1-alkyl-3-methylimidazolium cation [bmin] with bis(trifluoromethylsulfonyl)imide anion [Tf 2 N] is of particular interest for extraction of metal ions due to its water stability, relative low viscosity, high conductivity, and good electrochemical and thermal stability. Recent studies indicate that a coupled IL sc-CO 2 extraction system can effectively transfer trivalent lanthanide and uranyl ions from nitric acid solutions. Advantages of this technique include operation at

  13. Two- and three-dimensional lanthanide-organic frameworks constructed using 1-hydro-6-oxopyridine-3-carboxylate and oxalate ligands.

    Science.gov (United States)

    Liu, Cai-Ming; Xiong, Ming; Zhang, De-Qing; Du, Miao; Zhu, Dao-Ben

    2009-08-07

    6-Hydroxypyridine-3-carboxylic acid (6-HOPy-3-CO(2)H) reacts with Ln(2)O(3) (Ln = Nd, Sm, Eu, Gd) and oxalic acid (H(2)OX) under hydrothermal conditions to generate four novel lanthanide-organic coordination polymeric networks [Ln(2)(1H-6-Opy-3-CO(2))(2)(OX)(2)(H(2)O)(3)] x 2.5 H(2)O (Ln = Nd, 1; Sm, 2; 1H-6-Opy-3-CO(2)(-) = 1-hydro-6-oxopyridine-3-carboxylate) and [Ln(1H-6-Opy-3-CO(2))(OX)(H(2)O)(2)] x H(2)O (Ln = Eu, 3; Gd, 4). The new co-ligand 1H-6-Opy-3-CO(2)(-) anion was generated by the autoisomerization of the single deprotonated 6-HOPy-3-CO(2)(-) anion (from the enol form into the ketone one). 1 and 2 are isomorphous, they possess a three-dimensional architecture constructed from Ln(3+) ions bridged by oxalate anions and two types of 1H-6-Opy-3-CO(2)(-) bridges, showing a three-nodal (4,5)-connected topology (3.4(2).5(2).6(3).7.8)(2)(3.5(3).6(2))(2)(3(2).6.7(2).8) or a simplified uninodal 6-connected topology (3(3).4(6).5(5).6), both topologies are completely new; while only one type of 1H-6-Opy-3-CO(2)(-) bridge is used to construct the two-dimensional layer networks of 3 and 4 besides oxalate bridges, both complexes 3 and 4 are isostructural, exhibiting the honeycomb topology 6(3). The lanthanide contraction effect is believed to play a key role in directing the formation of a particular structure. A magnetic study of 1-3 indicated that the coupling interaction between Ln(3+) ions is weak.

  14. Application of on-line HPLC-ICP-MS for the determination of the nuclide abundances of lanthanides produced via spallation reactions in an irradiated tantalum target of a spallation neutron source

    International Nuclear Information System (INIS)

    Kerl, W.; Becker, J.S.; Dietze, H.J.

    1998-01-01

    An analytical procedure has been developed for the determination of spallation nuclides in an irradiated tantalum target using HPLC coupled on-line to ICP-MS after dissolution and separation of the tantalum matrix. Pieces of tantalum were taken from different locations of the irradiated tantalum target which had been used as the target material in a spallation neutron source. Tantalum was dissolved in a HNO 3 /HF mixture and the tantalum matrix was separated by liquid-liquid extraction so that only the spallation nuclides were left in the sample solutions. The major fraction of the spallation nuclides in the tantalum target are lanthanide metals in the μg g -1 concentration range determined in the present study. Additional reaction products are formed by the irradiation of trace impurities in the original tantalum target. The nuclide abundances of the lanthanide metals measured in the tantalum target differ significantly from the natural isotopic composition so that a lot of isobaric interferences of long-lived radionuclides and stable isotopes in the mass spectrum are to be expected. Therefore, all the lanthanide metals had to be separated chemically prior to their mass spectrometric determination. The separation of all rare earth elements was performed by ion chromatography on-line to ICP-MS. The nuclide abundances of each lanthanide were determined using a sensitive double-focusing sector field inductively coupled plasma mass spectrometer. The nuclide abundances of the lanthanides in the irradiated tantalum target calculated theoretically and the experimental results obtained by on-line HPLC-ICP-MS proved to be in good agreement. (orig.)

  15. Electromotive force measurement of lanthanides in Bi solution

    International Nuclear Information System (INIS)

    Sheng, Jiawei; Yamana, Hajimu; Moriyama, Hirotake

    2000-01-01

    The thermodynamic properties of Tb, Dy and Ho dissolved in liquid Bi were determined by the electromotive force (EMF) measurement method. The EMF of the following galvanic cell was measured in the range of 500-800degC over a wide range of solute concentration. Ln(solid)|KCl-LiCl|Ln-Bi (solution) There was observed a linear relationship between the EMFs and the lanthanide (Ln) concentrations in liquid Bi phase at a constant temperature, which agreed with the Nernst's equation. The obtained activity coefficients of lanthanides in liquid Bi solution were almost constant at a fixed temperature condition. Temperature effects on the activity coefficients could be expressed by the following equation: log γ=a+b/T, where a and b are experimental constants which correspond to the entropy and enthalpy of the formation of Ln-Bi compound in the melt, respectively. The thermodynamic quantities obtained were discussed in terms of their systematics along the 4f series. (author)

  16. Lanthanide-based fluorescent tracers in complex media

    International Nuclear Information System (INIS)

    Brichart, Thomas

    2014-01-01

    Tracers are objects allowing the determination of the position or the distribution of a product; tracers are currently used in a great variety of domains. Despite the fact that each field has it's own specifications, it is possible to find tracers in medicine (contrast agents), anti-counterfeiting or geological exploration. We have developed lanthanide complex tracers for oil field injection waters. Those tracers, derived from the DOTA, have been detected at concentration lower than 1 ppb, thanks to a simple and compact apparatus. This detection has been made possible by the use of time-resolved fluorescence spectroscopy, this technique allows us to get rid of the background noise created by the intrinsic fluorescence of oil residues that are present in production waters. We also demonstrated how we can, through a reverse microemulsion synthesis, encapsulate several different dyes inside a single nanoparticle composed of a gold core and a silica shell. We showed as well, how those particles can be used as smart tracers to gather data, such as temperature, pH, solvents, etc. inside the well. Finally the use of lanthanides and scale inhibitors properties allowed us to create a simple and fast dosing protocol of such scale inhibitors in injection waters. This dosage will then allow the quick adjustment of their concentration inside each well. (author) [fr

  17. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  18. Thermochemistry of selected lanthanide and actinide hydroxycarbonates and carbonates

    International Nuclear Information System (INIS)

    Merli, L.; Fuger, J.

    1996-01-01

    Lanthanide and actinide carbonates and hydroxycarbonates are, together with the hydroxides, important compounds in the problematics of high level waste disposal, since such and related compounds may appear as solid phases as a result of the interaction of the waste with natural waters. Experimental results on the stability and relationships between these compounds, particularly the hydroxycarbonates, are relatively fragmentary and arise mainly from solubility measurements, and, to a lesser extent, from enthalpy of formation determinations. We report here the enthalpies of formation of a number of well characterized hydroxycarbonates of trivalent lanthanides, namely those of neodymium, samarium, dysprosium, ytterbium, and of americium, as well as that of neodymium sesquicarbonate, using solution calorimetry in acidic media. The obtained values are discussed in the light of literature data on existing solubility and enthalpy of formation of related compounds. Our results have been obtained with a newly conceived sealed calorimeter, briefly described in the paper, in which the CO 2 produced during the dissolution reaction is maintained in solution, thus eliminating the problem of the kinetically slow evolution of the CO 2 (g) from the medium and the irregularities in the associated thermal effect. (orig.)

  19. Energetic lanthanide complexes: coordination chemistry and explosives applications

    International Nuclear Information System (INIS)

    Manner, V W; Barker, B J; Sanders, V E; Laintz, K E; Scott, B L; Preston, D N; Sandstrom, M; Reardon, B L

    2014-01-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  20. Determination of lanthanides in rare earths concentrates by emission optical spectrography

    International Nuclear Information System (INIS)

    Friedmann, R.; Lordello, A.R.; Abrao, A.

    1978-01-01

    A spectrochemical method has been developed for the determination of Y, Pr, Sm, Eu, Gd and Dy in purified lanthanum oxide; Y, La, Nd, Sm, Gd and Dy in purified cerium oxide and Y, La, Sm, Eu, Gd and Dy in purified neodymium oxide. The technique consists of an almost total consumption of the sample in a 17 ampere direct current arc. The rare earth oxides are mixed with an equal amount by weight of spectrographic graphite and the electrodes are arced in an argon (80%)-oxygen (20%) atmosphere, inside a specially desingned chamber, to suppress cyanogen bands. The concentration ranges are approximatelly 0.002 - 2%, depending on the matrix and the elements to be analysed. The presicion, accuracy and acceptability of the method are calculated for all elements. The total error values are approximately in the range of 18-48%. The method was developed for quality control of the individual fractions held by pulsed and ion exchange columns in the lanthanide separations, in the Chemical Engineering Centre, Atomic Energy Institute, Sao Paulo [pt

  1. Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Deyun; Guo, Haifu; Qin, Liang [Zhaoqing Univ., Zhaoqing (China); Xu, Jun [Jinan Univ., Guangzhou (China)

    2013-09-15

    Two new isostructural dinuclear complexes, Ln{sub 2}(4-cpa){sub 6}(bpy){sub 2} (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenyl-acetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with Ln···Ln separations of 3.967(2) and 3.956(3) A, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

  2. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

    Science.gov (United States)

    Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

    2017-02-01

    Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

  3. Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection.

    Science.gov (United States)

    Ai, Yu; Tu, Datao; Zheng, Wei; Liu, Yongsheng; Kong, Jintao; Hu, Ping; Chen, Zhuo; Huang, Mingdong; Chen, Xueyuan

    2013-07-21

    Trivalent lanthanide ions (Ln(3+))-doped inorganic nanoparticles (NPs) as potential luminescent bioprobes have been attracting tremendous interest because of their unique upconversion (UC) and downconversion (DC) luminescence properties. NaScF4, as an important host material, has been rarely reported and its crystal structure remains unclear. Herein, based on the single crystal X-ray diffraction, the space group of NaScF4 crystals was determined to be P31 containing multiple sites of Sc(3+) with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu(3+) at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln(3+) NPs were synthesized via a facile thermal decomposition method. The biotinylated NaScF4:Er(3+)/Yb(3+) NPs were demonstrated for their applications as a heterogeneous UC luminescence bioprobe to detect avidin with a detection limit of 180 pM. After bioconjugation with amino-terminal fragment (ATF) of urokinase plasminogen activator (uPA), NaScF4:Ln(3+) NPs also exhibited specific recognition of cancer cells overexpressed with uPA receptor (uPAR, an important marker of tumor biology and metastasis), showing great potentials in tumor-targeted bioimaging.

  4. Refractive Index Tuning of Hybrid Materials for Highly Transmissive Luminescent Lanthanide Particle-Polymer Composites.

    Science.gov (United States)

    Kim, Paul; Li, Cheng; Riman, Richard E; Watkins, James

    2018-03-14

    High-refractive-index ZrO 2 nanoparticles were used to tailor the refractive index of a polymer matrix to match that of luminescent lanthanide-ion-doped (La 0.92 Yb 0.075 Er 0.005 F 3 ) light-emitting particles, thereby reducing scattering losses to yield highly transparent emissive composites. Photopolymerization of blends of an amine-modified poly(ether acrylate) oligomer and tailored quantities of ZrO 2 nanoparticles yielded optically transparent composites with tailored refractive indices between 1.49 and 1.69. By matching the refractive index of the matrix to that of La 0.92 Yb 0.075 Er 0.005 F 3 , composites with high transmittance (>85%) and low haze from the visible to infrared regions, bright 1530 nm optical emissions were achieved at solids loadings of La 0.92 Yb 0.075 Er 0.005 F 3 , ranging from 5 to 30 vol %. These optical results suggest that a hybrid matrix approach is a versatile strategy for the fabrication of functional luminescent optical composites of high transparency.

  5. Separation of actinides and lanthanides from acidic nuclear wastes by supported liquid membranes

    International Nuclear Information System (INIS)

    Danesi, P.R.; Chiarizia, R.; Rickert, P.; Horwitz, E.P.

    1985-01-01

    Supported liquid membranes, SLM, consisting of a solution of 0.25 M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 0.75 M tributylphosphate (TBP) in decalin absorbed on thin microporous polypropylene supports, have been studied for their ability to perform selective separations and concentrations of actinide and lanthanide ions from synthetic acidic nuclear wastes. The permeability coefficients of selected actinides (Am, Pu, U, Np) and of some of the other major components of the wastes have been measured using SLMs in flat-sheet and hollow-fiber configurations. The results have shown that with the thin (25 μm) flat-sheet SLMs, using Celgard 2500 as support, the membrane permeation process is mainly controlled by the rate of diffusion through the aqueous boundary layers. With the thicker (430 μm) hollow-fiber SLMs, using Accurel hollow-fibers as support, the membrane permeation process is controlled by the rate of diffusion through both the SLM and the aqueous boundary layers. Hollow-fibers SLMs exhibited lower permeability coefficients and longer life-times. The experiments have shown that the actinides can be very efficiently removed from the synthetic waste solutions to the point that the resulting solution could be considered a non-transuranic waste (less than 100 mCi/g of disposed form). The work has demonstrated that actinide removal from synthetic waste solutions is a feasible chemical process at the laboratory scale level

  6. Chromatographic behavior of carbonate complexes of lanthanides and of thorium in alumina

    International Nuclear Information System (INIS)

    Tomida, E.K.

    1977-01-01

    The chromatographic behavior of some rare earth elements and thorium on alumina is studied in order to evaluate the possibility of separation from concentration of trace rare earths from high-purity thorium compounds. The effect of some factors on complex thorium carbonate formation and the extent of thorium solubility in sodium and potassium carbonate solutions investigated. The sorption of rare earth elements and thoriuum on alumina from alkali carbonate solution is observed, despite the reports that alumina acts as a cation exchanger in alkali media and that thorium and rare earths form stable anionic carbonate complexes. The formation of these elements between alumina and potassium carbonate solutions is studied as a function of pH, carbonate concentration and metal ion concentration. Also the elution of rare earths from alumina is studied and the best results are obtained with mineral acids and EDTA plus alkali carbonate solutions. The effect of some parameters as column aging, mixed solvents, column treatment with organic solvents, temperature, aluant concentration is investigated. Attempting to understand this sorption mechanism, some experiments with strongly basic anion exchanger and cation exchangers of strongly acid and weakly acid type are accomplished. It is observed that there are significant differences, in some conditions, between the behavior of rare earths and of thorium, pointing our the possibility of separation of one lanthanide from others and of these from thorium [pt

  7. 2,2',-bipyridine and 1,10-phenanthroline complexes of lanthanide(III) trifluoroacetates

    International Nuclear Information System (INIS)

    Misra, S.N.; Singh, M.

    1983-01-01

    The syntheses and characterization of lanthanide(III) triflloroacetate complexes with 2,2'-bipyridine and 1,10-phenanthroline are reported. Lanthanide(III) trifluoroacetates yield compounds of the type Ln(CF 3 COO) 3 .bipy or phen with 2,2'-bipyridine and 1,10-phenanthroline. Their properties and structures have been studied using chemical analyses. electronic and infrared spectra. Thermal analysis of a few complexes have also been done. The infrared data show that the trifluoroacetate group acts as a bidentate ligand making the coordination number of lanthanide eight. (author)

  8. Compaction of lanthanide oxide porous microspheres: experimental approach and numerical simulation

    International Nuclear Information System (INIS)

    Parant, Paul

    2016-01-01

    One option envisioned for the future management of high level nuclear waste is the transmutation of minor actinides into short-lived fission products in sodium fast reactor. This route requires the development of pellet fabrication processes to prepare Minor Actinide Bearing Blanket (MABB) for the transmutation of americium. Currently, those ceramic pellets are produced by powder metallurgy processes involving numerous grinding and milling steps that generate very fine and highly contaminating and irradiating particles. a viable option for reducing the amount of those fine particles would be to develop a dustless process by working on much coarser particles. In this context, this study is concerned with the pelletizing of porous and spherical lanthanides oxide precursors (surrogates of actinides). The present work uses both experimental data and numerical simulations to optimize the pelletizing step. The final aim is to obtain, after sintering, homogeneous, dense and undistorted ceramic pellets. Firstly, this study concerns the synthesis and characterization of these oxide microspheres precursors by the Weak acid Resin process, which consists in loading beads of ion exchange resin with lanthanides cations and mineralizing the metal loaded resin leads into sub-millimetric-sized oxide microspheres. Comprehensive characterizations of the microstructure were carried out in function of the synthesis parameters such as calcination temperature, metal nature and diameter size /distribution of the resin beads starting materials to better understand their behaviour into the matrix when producing pellets. Secondly, the mechanical properties of a single microsphere were investigated in order to better understand its behaviour during compaction steps. They were also analysed using multi-scale simulations based on the Discrete Element Method (DEM), which is well suited for such particulate materials. In a second approach, compaction studies were carried out in a three parts die

  9. Application of ion chromatography to the control of materials of nuclear interest

    International Nuclear Information System (INIS)

    Pires, M.A.F.

    1989-01-01

    The present work concerns ion chromatrography (IC) with conductometric detection as analytical technique for controling several materials of nuclear interest by determining the chemical elements present in them. Priority has been given to the individual determination of the lanthanide elements and yttrium. Complexing agents were used as eluents for the elements studied. Several experiments were performed in which the eluent composition as well as its pH were varied, so obtaining the eluent's iso-pH and iso-concentration values for each of the lanthanide and yttrium. The importance of the presence of the ethylenediamine ion on the separation and elution of the rare-earths was investigated. The determination of the alkaline metals and ammonium ion, alkaline-earth elements, fluoride, chloride, nitrate and phosphate anions in several solutions and in different materials that are involved in the chemical processes belonging to the fuel cycle was carried out. Single column ion chromatography technique was applied for determining all the lanthanide elements as well as yttrium, magnesium, calcium, strontium and barium and the sensibility of the measurements determined. A rapid chromatographic method for determining gadolinium in urania-gadolinia matrix is also proposed. Quantitative data on the separation of the lanthanide elements and yttrium from large amounts or other ions, rare earths for example, are presented. (author) [pt

  10. Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Troy A [Univ. of Nevada, Las Vegas, NV (United States)

    2011-08-01

    This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd3+, Na+, lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd3+ loading of the HDEHP led to Nd3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP)2]x; (with x > 1). By substituting lanthanum (La3+) for Nd3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous

  11. Partitioning-separation of metal ions using heterocyclic ligands

    International Nuclear Information System (INIS)

    Hudson, M.J.; Drew, M.G.B.; Iveson, P.B.; Russell, M.L.

    2001-01-01

    Some guidelines are proposed for the effective design of heterocyclic ligands for partitioning because there is no doubt that the correct design of a molecular extractant is required for the effective separation of metal ions such as actinides(III) from lanthanides(III). Heterocyclic ligands with aromatic ring systems have a rich chemistry, which is only now becoming sufficiently well understood in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-carboxy-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with lanthanide ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazole-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. (author)

  12. Conception, synthesis and application of tripodands in actinide/lanthanide separation

    International Nuclear Information System (INIS)

    Bobet, Josselin

    1997-01-01

    The purpose of this work is the synthesis of C, H, O and N containing compounds able to separate '4f' and '5f' elements by liquid/liquid extraction. In a first part, the literature's study allow us to point out actinide and lanthanide ions actual nature and the different ways offered by organic chemistry to share two metallic ions between two liquid phases. On one hand, these trivalent cations' high coordination numbers drive us to synthesize tripodands with hard sites which were fitted for complexation. On the other hand, it appeared that carboxylate or even less-hard site like pyridine chelate selectively actinides, allowing separation. In a second part, 60 ligands were synthesized. In each of the ligands families, a structural parameter changes (site nature, distance between two neighbouring sites, sites respective orientation, lipophilicity and rigidity). 2,2-dihydroxymethyl-dodecanol and 1,3,5- tri(chlorocarbonyl) benzene were chosen as core. O-alkylation and amidation reactions were also peculiarly studied. Rekker's proceeding for lipophilicity calculation was used in order to establish a structure-activity relationship. In a third part, extraction assays with radioactive effluents ( 152 Eu and 241 Am) point out extraction and separation abilities of our compounds. Different operating ways were used according as ligand is soluble in aqueous or organic phase. Organic phase-soluble compounds were compared to DcH18C6, pyridine ones to 2,4,6-tri(2-pyridyl)-l,3,5-triazine (TPTZ) and carboxylate ones to diethylenetriamine-tetracetic acid (DTPA, Talspeak proceeding). The third phase phenomenon was encountered and studied. Influence of salt, pH and organic phase were also studied. (author) [fr

  13. Flexible Photonics: Polymer LEDs Made from Monochromatic Red Emitting Lanthanide/Polymer Blends. Phase 1

    National Research Council Canada - National Science Library

    O'Regan, Marie

    1999-01-01

    .... Spectrally pure, red emitting flexible LEDs have been fabricated. Close to a four-fold increase in device efficiency is obtained when a suitable lanthanide complex is blended with the semi-conducting host polymer...

  14. Separation of interfering elements in the neutron activation analysis of lanthanides in geological materials

    International Nuclear Information System (INIS)

    Saiki, M.

    1988-01-01

    A chemical procedure has been developed for the separation of U, Th, Fe, Sc, Na,Ta, and Mo which interfere in the neutron activation analysis of the lanthanide elements in geological materials. This procedure is based on the solvent extraction of interferents using a solution of tetracycline in benzyl alcohol. The lanthanide elements remaining in the aqueous phase are coprecipitated on calcium oxalate or ferric hydroxide for irradiation and subsequent determination by gamma ray spectrometry. The chemical separation procedure was applied in the analysis of lanthanides in two international geological reference materials GSP-1 (USGS), GS-N (CRPG) and in the analysis of a volcanic rock from Pocos de Caldas, MG, Brazil. The sensitivities for all the lanthanides were determined. (author) [pt

  15. Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

    KAUST Repository

    Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

    2016-01-01

    lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large

  16. FY17 Progress in Modeling of Lanthanide Transport in Metallic Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Unal, Cetin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Matthews, Christopher [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-09-19

    A critical review of fuel-clad-chemical interactions along with modelling requirements is published. The mechanism of lanthanide transport is studied experimentally (NEUP collaboration) and using simulations and initial results are published in Refs.

  17. Adducts of between lanthanide (III) trifluoromethanesulfonate and yttrium (III) and tetramethylene sulphoxide ligand

    International Nuclear Information System (INIS)

    Assis Araujo, F. de.

    1983-01-01

    The synthesis, characterization and spectroscopic properties of lanthanides trifluoromethanesulfonate complexes with tetramethylenesulfoxide (TMSO), are described. The interpretation of X-ray powder patterns show one isomorphous series. (M.J.C.) [pt

  18. Handbook on the physics and chemistry of rare earths: Volume 19: Lanthanides/Actinides: Physics, 2

    International Nuclear Information System (INIS)

    Gschneidner, Karl A.; Eyring, LeRoy; Choppin, G.R.; Lander, G.H.

    1994-01-01

    This handbook comprises five chapters on the lanthanide and actinide materials. In the first chapter the inelastic neutron scattering behaviors of the lanthanides and actinides are compared. In the next chapter the focus is on neutron scattering by heavy fermion single crystal materials, including metallic materials with a paramagnetic ground state, superconductors, metallic and semiconducting antiferromagnets and nearly insulating paramagnets. In chapter three a comprehensive review of intermediate valence and heavy fermions in a wide variety of lanthanide and actinide compounds is given, ranging from metallic to insulating materials. In chapter four two issues on the high pressure behaviours of anomalous cerium, ytterbium and uranium compounds are dealt with. In the final chapter an extensive review is given the thermodynamic properties of lanthanide and actinide metallic systems

  19. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, K. M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a ''hard'' anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized

  20. Lanthanide-activated Na5Gd9F32 nanocrystals precipitated from a borosilicate glass: Phase-separation-controlled crystallization and optical property

    International Nuclear Information System (INIS)

    Chen, Daqin; Wan, Zhongyi; Zhou, Yang; Chen, Yan; Yu, Hua; Lu, Hongwei; Ji, Zhenguo; Huang, Ping

    2015-01-01

    Highlights: • Na 5 Gd 9 F 32 nanocrystals embedded glass ceramics were fabricated for the first time. • Such glass ceramics were achieved by phase-separation-controlled crystallization. • Elemental mapping evidenced the segregation of activators into the Na 5 Gd 9 F 32 lattice. • Luminescent color could be tuned by controlling glass crystallization temperature. - Abstract: Lanthanide-activated cubic Na 5 Gd 9 F 32 nanocrystals were precipitated from a borosilicate glass with a specifically designed composition. The precursor glass is already phase-separated after melt-quenching, which is beneficial to the realization of the controllable glass crystallization for affording desirable size, morphology and activator partition. Elemental mapping in the scanning transmission electron microscopy evidenced that the segregation of lanthanide ions into the Na 5 Gd 9 F 32 lattice was in situ formed without the requirement of long-range ionic diffusion. Impressively, such fabricated glass ceramic co-doped with Yb 3+ /Er 3+ ions exhibited intense upconversion luminescence, which was about 500 times higher than that of the precursor glass, and its luminescent color could be easily tuned from red to green by controlling glass crystallization temperature. It is anticipated that such phase-separation synthesis strategy with precise control over nanostructure of glass ceramics offer a great opportunity to design other highly transparent nanocomposites with a wide range of tunable optical properties

  1. Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

    Science.gov (United States)

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

    2014-04-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln2(Hpdc)2(C2O4)(H2O)4]n·2nH2O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H3pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H3pdc was decomposed into (ox)2- with Cu(II)-Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P21/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1-4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities.

  2. Co-ordination properties of diglycol-amide (DGA) to trivalent curium and lanthanides studied by XAS, XRD and XPS methods

    International Nuclear Information System (INIS)

    Yaita, T.; Hirata, M.; Narita, H.; Tachimori, S.; Yamamoto, H.; Edelstein, N.M.; Bucher, J.J.; Shuh, D.K.; Rao, L.

    2001-01-01

    Co-ordination properties of diglycol-amide (DGA) to trivalent curium and to the trivalent lanthanides were studied by the EXAFS, the XRD and the XPS methods. The structural determinations by both the crystal XRD and the solution EXAFS methods showed that the DGA co-ordinated to the trivalent lanthanide ion in a tridentate fashion: co-ordination of three oxygen atoms of each ligand to the metal ion. The bond distances of Er-O (carbonyl) and Er-O (ether) in the Er-DGA complex were 2.35 Angstrom, and 2.46 Angstrom, respectively, while the atom distances of Cm-O (carbonyl) and Cm-O (ether) in the Cm-DGA complex were 2.42 Angstrom and 3.94 Angstrom, respectively from the EXAFS data for the Cm-DGA complex. Accordingly, the DGA would behave only as a semi-tridentate in the co-ordination to trivalent curium in solution. We determined the valence band structures of the Er-DGA complex by the XPS in order to clarify the bond properties of the complex, and assigned the XPS spectrum by using the DV-DS molecular orbital calculation method. (authors)

  3. Synthesis, crystal structure and luminescent properties of lanthanide extended structure with asymmetrical dinuclear units based on 2-(methylthio)benzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Cristiane K.; Souza, Viviane P. de; Luz, Leonis L. da [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil); Menezes Vicenti, Juliano R. de [Escola de Química e Alimento, FURG, 96203-900 Rio Grande, RS (Brazil); Burrow, Robert A. [Departamento de Química, UFSM, 97105-900 Santa Maria, RS (Brazil); Severino Alves; Longo, Ricardo L. [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil); Malvestiti, Ivani, E-mail: ivani@ufpe.br [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil)

    2016-02-15

    , quantitative relationships between the transition rates between the lanthanide centers and their decaying rates. In the case of compound 2, the same strong interactions are present and, additionally, a ligand-to-metal charge transfer (LMCT) state was invoked to account for the dependence of the quantum yields with the excitation wavelength. Hydrothermal syntheses were also performed; however, X-ray powder diffraction and luminescence spectra showed more asymmetric structures around the lanthanide ion when compared to the crystalline compounds. - Highlights: • A symmetric dinuclear lanthanide units. • Spectral lanthanide–lanthanide interactions. • Energy transfer between lanthanide centers.

  4. SEPARATION OF EUROPIUM FROM OTHER LANTHANIDE RAE EARTHS BY SOLVENT EXTRACTION

    Science.gov (United States)

    Peppard, D.F.; Horwitz, E.P.; Mason, G.W.

    1963-02-12

    This patent deals with a process of separating europium from other lanthanides present in aqueous hydrochloric or sulfuric acid solutions. The europium is selectively reduced to the divalent state with a divalent chromium salt formed in situ from chromium(III) salt plus zinc amalgam. The other trivalent lanthanides are then extracted away from the divalent europium with a nitrogen-flushed phosphoric acid ester or a phosphonic acid ester. (AEC)

  5. Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

    Energy Technology Data Exchange (ETDEWEB)

    Pindwal, Aradhana [Iowa State Univ., Ames, IA (United States)

    2016-01-01

    The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

  6. NMR studies of structures of lanthanide dicarboxylate complexes in solution

    International Nuclear Information System (INIS)

    Choppin, G.R.; Kullberg, L.

    PMR pand 13 C shift data were measured for complexes of Pr(III), Eu(III) and Yb(III) with ethylene 1,2-dioxydiacetate (EDODA), ethylene 1,2-dithiodiacetate (EDSDA), and ethylene, 1,2-diaminodiacetate (EDDA). Solubility problems limited analysis of the EDSDA and EDDA data to qualitative evaluation. In the EDSDA complexes, the data indicate that the sulfur atoms do not participate in bonding to the lanthanide cations. Moreover, both carboxylate groups seem to bind Pr and Eu while Yb interacts with only a single carboxylate group. The EDDA complexes are tetradentate with long lived (NMR scale) Ln-N bonds. Shift theory allowed more quantitative analysis of the EDODA complexes. They are tetradentate with a puckered chelate ring and Ln-O(ether) distances of 2.3 A

  7. Organic derivatives of lanthanides containing metal in cycle

    International Nuclear Information System (INIS)

    Syutkina, O.P.; Rybakova, L.F.; Egorova, E.N.; Sigalov, A.B.; Beletskaya, I.P.

    1983-01-01

    The reaction of 2.2'-dilithium biphenyl with LnBr 3 (Ln=Pr, Sm, Gd, Ho, Yb here bromium atoms are comparatively easily replaced. Previously unknown organic derivatives of lanthanides containing metal in the cycle are obtained. It is established that a successful extraction of the compound requires reaction conditions, such as the use of ether as a solvent with the followinq addition of TGP, the order of addition of reagents. Compounds are extracted in the form of solvates containing TGP melecules. The complexes prepared are coloured, depending on the metal, beige (Pr, Sm) brown (Gd, Yb) and red-brown (Ho). They dissolve readily in TGP moderately in benzen toluene, CCl 4 . When stored their solubility in benzene and CCl 4 decreases considerably, and after 3-2 days, they are practically insoluhle. The compounds prepared are characterized by the elementary analysis, IR and PMR spectra

  8. Chelation studies involving decontamination of light lanthanides by polyaminopolycarboxylic

    International Nuclear Information System (INIS)

    Hassan, N.E.H.

    1985-01-01

    The present thesis constitutes chelation studies involving decontamination of light lanthanides, cobalt , and uranium with 2,2-bis-acryloyliminomethylene- acid (BAETA) using the spectrophotometric method. the work carried out aimed to clear up the effectiveness of BAETA as a decontaminating agent for radioactive nuclides from human body . the thesis includes a general introduction , outlines the aim of work and contains three main chapters . the results of the work are discussed at the end of the thesis. the first chapter deals with a comprehensive survey of the relevant literature. this includes the metabolism and toxicity of cerium, uranium, cobalt and Ln +3 elements, general methodologies of internal decontamination, choice and effectiveness of chelating agents

  9. Migration study of actinides and lanthanides in compacted bentonite

    International Nuclear Information System (INIS)

    Sastrowardoyo, P.B.; Susilowati, D.; Suganda, D.

    1998-01-01

    Migration study of actinide and lanthanide elements in compacted bentonite has been conducted. Data of these elements mobilities have been shown, and it is showed that the diffusion coefficient was varied as the function of solution phase condition as well as the origin/composition of bentonite. It is showed that the diffusion coefficient decreased by the increasing of density, as well as the increasing of montmorillonite content in bentonite. The ratio of bentonite/silica-sand used was related to the increasing of elements mobility. In many case the difference of diffusion coefficient was related to the variation of pH and redox condition, as well as the presence of complexant in solution phase. The Lower diffusion coefficient could give the higher retardation factor, which is a favourable factor to retard the radionuclides release from a disposal facility to geosphere. (author)

  10. Lanthanide-based laser-induced phosphorescence for spray diagnostics

    Energy Technology Data Exchange (ETDEWEB)

    Voort, D. D. van der, E-mail: d.d.v.d.voort@tue.nl; Water, W. van de; Kunnen, R. P. J.; Clercx, H. J. H.; Heijst, G. J. F. van [Applied Physics Department, Eindhoven University of Technology, 5612 AZ Eindhoven (Netherlands); Maes, N. C. J.; Sweep, A. M.; Dam, N. J. [Mechanical Engineering Department, Eindhoven University of Technology, 5612 AZ Eindhoven (Netherlands); Lamberts, T. [Institute of Theoretical Chemistry, University of Stuttgart, D-70569 Stuttgart (Germany)

    2016-03-15

    Laser-induced phosphorescence (LIP) is a relatively recent and versatile development for studying flow dynamics. This work investigates certain lanthanide-based molecular complexes for their use in LIP for high-speed sprays. Lanthanide complexes in solutions have been shown to possess long phosphorescence lifetimes (∼1-2 ms) and to emit light in the visible wavelength range. In particular, europium and terbium complexes are investigated using fluorescence/phosphorescence spectrometry, showing that europium-thenoyltrifluoracetone-trioctylphosphineoxide (Eu-TTA-TOPO) can be easily and efficiently excited using a standard frequency-tripled Nd:YAG laser. The emitted spectrum, with maximum intensity at a wavelength of 614 nm, is shown not to vary strongly with temperature (293-383 K). The decay constant of the phosphorescence, while independent of ambient pressure, decreases by approximately 12 μs/K between 323 and 373 K, with the base level of the decay constant dependent on the used solvent. The complex does not luminesce in the gas or solid state, meaning only the liquid phase is visualized, even in an evaporating spray. By using an internally excited spray containing the phosphorescent complex, the effect of vaporization is shown through the decrease in measured intensity over the length of the spray, together with droplet size measurements using interferometric particle imaging. This study shows that LIP, using the Eu-TTA-TOPO complex, can be used with different solvents, including diesel surrogates. Furthermore, it can be easily handled and used in sprays to investigate spray breakup and evaporation.

  11. High temperature vaporization/decomposition studies of lanthanide and actinide fluorides

    International Nuclear Information System (INIS)

    Gibson, J.K.; Haire, R.G.

    1987-01-01

    Binary fluorides of the lanthanide and actinide elements comprise a fundamental class of compounds. The authors' investigations of their basic high temperature vaporization and/or decomposition behavior are aimed at elucidating more fully the thermal properties of selected tri- and tetrafluorides and extending such investigations to fluorides which have not been studied previously. Depending on the particular system and the specific experimental conditions, the authors' measurements can provide such information as the enthalpy associated with a congruent vaporization process and/or the relative stabilities of fluorides containing a lanthanide/actinide element in different oxidation states. The authors are also studying the congruent vaporization of selected lanthanide trifluorides with particular emphasis on two areas. The first concerns the variation in the enthalpies of sublimation of the trifluorides across the lanthanide series. Although this variation is rather small (δ5 kcal where ΔH/sub subl/ is approximately 100 kcal), it is larger than observed for other lanthanide trihalides and is unusually irregular. To examine this reported variation more closely, they are attempting to measure relative vapor pressures/enthalpies of vaporization by studying mixtures of two or more lanthanide trifluorides by the technique discussed above

  12. Ternary complex formation of lanthanides and radiolanthanides with phosphate and serum proteins

    International Nuclear Information System (INIS)

    Neumaier, B.; Roesch, F.

    1999-01-01

    Radioyttrium was recently reported to form ternary complexes with phosphate and serum proteins in blood. In the present work it was investigated whether the trivalent radiolanthanides react in a chemically similar way. In systematic binding studies using gel filtration a ternary complex formation between different lanthanides, phosphate and serum proteins could be identified. The tendency to build a ternary compound of the type Ln III - phosphate - serum protein, however, is dependent on the ionic radii of the lanthanides. Whereas the light and transition lanthanides have a strong inclination to build a ternary complex, this tendency is weaker for the heavier ones. Taking into account the high content of phosphate in human blood, the corresponding ternary complexes of radiolanthanides represent an important transport form of these elements in blood. This finding may contribute to an understanding of the nuclear medical observation on the biodistribution of radiolanthanides. The heavy radiolanthanides can be classified as bone seeking metals, whereas the light and transition lanthanide elements accumulate mainly in the liver and the spleen. For the lighter radiolanthanides the corresponding ternary complexes thus represent an important transport form in blood. This physicochemical form of lanthanides mainly results in reticulo endothelial accumulation; on the other hand, the lower tendency of heavier lanthanides leads to preferential skeletal deposition. (orig.)

  13. Lanthanide fission product separation from the transuranics in the integral fast reactor fuel cycle demonstration

    International Nuclear Information System (INIS)

    Goff, K.M.; Mariani, R.D.; Benedict, R.W.; Ackerman, J.P.

    1993-01-01

    The Integral Fast Reactor (IFR) is an innovative reactor concept being developed by Argonne National Laboratory. This reactor uses liquid-metal cooling and metallic fuel. Its spent fuel will be reprocessed using a pyrochemical method employing molten salts and liquid metals in an electrofining operation. The lanthanide fission products are a concern during reprocessing because of heating and fuel performance issues, so they must be removed periodically from the system to lessen their impact. The actinides must first be removed form the system before the lanthanides are removed as a waste stream. This operation requires a relatively good lanthanide-actinide separation to minimize both the amount of transuranic material lost in the waste stream and the amount of lanthanides collected when the actinides are first removed. A computer code, PYRO, that models these operations using thermodynamic and empirical data was developed at Argonne and has been used to model the removal of the lanthanides from the electrorefiner after a normal operating campaign. Data from this model are presented. The results demonstrate that greater that 75% of the lanthanides can be separated from the actinides at the end of the first fuel reprocessing campaign using only the electrorefiner vessel

  14. Hydrocarbons conversions over mineral ion-exchangers used in uranium ore waste treatment

    International Nuclear Information System (INIS)

    Azzouz, A.

    1988-05-01

    Preliminary experiments were carried out in order to investigate catalytic activities in hydrocarbons reactions of natural and synthetic zeolites previously loaded with heavy elements as lanthanides and actinides in yellow cake treatment. This way could be considered as an interesting low coast alternative in revalorifying these mineral ion-exchangers. (author)

  15. Benzene-centered tripodal diglycolamides : Synthesis, metal ion extraction, luminescence spectroscopy, and DFT studies

    NARCIS (Netherlands)

    Leoncini, Andrea; Ansari, Seraj Ahmad; Mohapatra, Prasanta Kumar; Boda, Anil; Musharaf Ali, Sheikh; Sengupta, Arijit; Huskens, Jurriaan; Verboom, Willem

    2017-01-01

    Three benzene-centered tripodal diglycolamides (Bz-T-DGAs) were synthesized and evaluated for actinide, lanthanide, and fission product ion extraction. 1,3,5-Triethylbenzene-based tripodal DGA (LI) showed high distribution ratio (D) values for Am3+ and Eu3+ in a mixture of 95% n-dodecane and 5%

  16. 3,4,3-LI(1,2-HOPO): In Vitro Formation of Highly Stable Lanthanide Complexes Translates into Efficacious In Vivo Europium Decorporation

    Energy Technology Data Exchange (ETDEWEB)

    Sturzbecher-Hoehne, Manuel; Ng Pak Leung, Clara; Daleo, Anthony; Kullgren, Birgitta; Prigent, Anne-Laure; Shuh, David K.; Raymond, Kenneth N.; Abergel, Rebecca J.

    2011-07-13

    The spermine-based hydroxypyridonate octadentate chelator 3,4,3-LI(1,2-HOPO) was investigated for its ability to act as an antennae that sensitizes the emission of Sm{sup III}, Eu{sup III}, and Tb{sup III} in the Visible range (Φ{sub tot} = 0.2 - 7%) and the emission of Pr{sup III}, Nd{sup III}, Sm{sup III}, and Yb{sup III} in the Near Infra-Red range, with decay times varying from 1.78 μs to 805 μs at room temperature. The particular luminescence spectroscopic properties of these lanthanide complexes formed with 3,4,3-LI(1,2-HOPO) were used to characterize their respective solution thermodynamic stabilities as well as those of the corresponding La{sup III}, Gd{sup III}, Dy{sup III}, Ho{sup III}, Er{sup III}, Tm{sup III}, and Lu{sup III} complexes. The remarkably high affinity of 3,4,3-LI(1,2-HOPO) for lanthanide metal ions and the resulting high complex stabilities (pM values ranging from 17.2 for La{sup III} to 23.1 for Yb{sup III}) constitute a necessary but not sufficient criteria to consider this octadentate ligand an optimal candidate for in vivo metal decorporation. The in vivo lanthanide complex stability and decorporation capacity of the ligand were assessed, using the radioactive isotope {sup 152}Eu as a tracer in a rodent model, which provided a direct comparison with the in vitro thermodynamic results and demonstrated the great potential of 3,4,3-LI(1,2-HOPO) as a therapeutic metal chelating agent.

  17. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides

    International Nuclear Information System (INIS)

    Belair, S.

    2003-01-01

    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO 3 ) 3 -HNO 3 -H 2 O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  18. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Adam, Christian

    2016-01-15

    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T

  19. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Belair, S

    2003-07-01

    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  20. Extensive studies of host lattices and activators in lanthanide phosphors based on efficient synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Yuhui; Huo, Jiansheng; Yang, Jinglian; Hu, Jing [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Gao, Jinwei [Institute for Advanced Materials, Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006 (China); Wang, Qianming, E-mail: qmwang@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou 510006 (China)

    2016-08-15

    Uniform and dispersive NaLa(MoO{sub 4}){sub 2-x}(WO{sub 4}){sub x} (abbreviated as NLMW): Eu{sup 3+}/Tb{sup 3+}(5 mol%) microspheres were successfully synthesized at low temperature (393 K). The incorporation of Bi{sup 3+} or Mn{sup 2+} into CaMoO{sub 4}: Eu{sup 3+} with tetragonal crystalline phase has also been studied. The structure, morphology, and luminescent properties of these powder samples were examined by means of X-ray diffraction (abbreviated as XRD), scanning electron microscopy (abbreviated as SEM), and fluorescent spectrophotometry, respectively. SEM images substantiated that these phosphors have uniform sphere-shaped morphologies. The samples exhibited the characteristic emission of Eu{sup 3+}({sup 5}D{sub 0} → {sup 7}F{sub J})/Tb{sup 3+}({sup 5}D{sub 4} → {sup 7}F{sub J}) under ultraviolet excitation. Effects of the ratio of MoO{sub 4}/WO{sub 4} on the luminescence behavior were investigated in detail. The MoO{sub 4}/WO{sub 4} ratio was optimized as 1/1. The international commission on illumination (abbreviated CIE for its French name) chromaticity coordinates of NLMW: Eu{sup 3+} and NLMW: Tb{sup 3+} indicate the emissions were located in the red and green region, which will be beneficial for the potential device fabrication. Encapsulation of Bi{sup 3+} and Mn{sup 2+} both can effectively sensitize europium (III) ions, generating stronger red emissions ({sup 5}D{sub 0} → {sup 7}F{sub J}). - Highlights: • Lanthanide molybdate–tungstates have been synthesized by SMC method. • Regular microspheres have been observed. • Effects of different hosts on the luminescence were investigated.

  1. Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

    Science.gov (United States)

    Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

    2015-11-01

    In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

  2. Coupling of the 4f Electrons in Lanthanide Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kazhdan, Daniel [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    (C5Me5)2LnOTf where Ln = La, Ce, Sm, Gd, and Yb have been synthesized and these derivatives are good starting materials for the synthesis of (C5Me5)2LnX derivatives. (C5Me5)2Ln(2,2'-bipyridine), where Ln = La, Ce, Sm, and Gd, along with several methylated bipyridine analogues have been synthesized and their magnetic moments have been measured as a function of temperature. In lanthanum, cerium, and gadolinium complexes the bipyridine ligand ligand is unequivocally the radical anion, and the observed magnetic moment is the result of intramolecular coupling of the unpaired electron on the lanthanide fragment with the unpaired electron on the bipyridine along with the intermolecular coupling between radicals. Comparison with the magnetic moments of the known compounds (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine) leads to an understanding of the role of the SmII/SmIII and YbII/YbIII couple in the magnetic properties of (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine). In addition, crystal structures of (C5Me5)2Ln(2,2'-bipyridine) and [(C5Me5)2Ln(2,2'-bipyridine)][BPh4](Ln= Ce and Gd), where the lanthanide is unequivocally in the +3 oxidation state, give the crystallographic characteristics of bipyridine as an anion and as a neutral ligand in the same coordination environment, respectively. Substituted bipyridine ligands coordinated to (C5Me5)2Yb are studied to further understand how the magnetic coupling in (C5Me5)2Yb(2,2'-bipyridine) changes with substitutions. In the cases of (C5Me5)2Yb(5,5&apos

  3. Features of the Thermodynamics of Trivalent Lanthanide/Actinide Distribution Reactions by Tri-n-Octylphosphine Oxide and Bis(2-EthylHexyl) Phosphoric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Travis S. Grimes; Peter R. Zalupski

    2014-11-01

    A new methodology has been developed to study the thermochemical features of the biphasic transfer reactions of trisnitrato complexes of lanthanides and americium by a mono-functional solvating ligand (tri-n-octyl phosphine oxide - TOPO). Stability constants for successive nitrato complexes (M(NO3)x3-x (aq) where M is Eu3+, Am3+ or Cm3+) were determined to assist in the calculation of the extraction constant, Kex, for the metal ions under study. Enthalpies of extraction (?Hextr) for the lanthanide series (excluding Pm3+) and Am3+ by TOPO have been measured using isothermal titration calorimetry. The observed ?Hextr were found to be constant at ~29 kJ mol-1across the series from La3+-Er3+, with a slight decrease observed from Tm3+-Lu3+. These heats were found to be consistent with enthalpies determined using van ’t Hoff analysis of temperature dependent extraction studies. A complete set of thermodynamic parameters (?G, ?H, ?S) was calculated for Eu(NO3)3, Am(NO3)3 and Cm(NO3)3 extraction by TOPO and Am3+ and Cm3+ extraction by bis(2-ethylhexyl) phosphoric acid (HDEHP). A discussion comparing the energetics of these systems is offered. The measured biphasic extraction heats for the transplutonium elements, ?Hextr, presented in these studies are the first ever direct measurements offered using two-phase calorimetric techniques.

  4. Synthesis, crystal structure, optical and thermal properties of lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho).

    Science.gov (United States)

    Förg, Katharina; Höppe, Henning A

    2015-11-28

    Lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho) were synthesised as colourless (Ln = Tb, Dy) and light pink (Ln = Ho) crystalline powders by reaction of Tb4O7/Dy2O3/Ho2O3 with H3PO3 at 380 °C. All compounds crystallise isotypically (P2(1)/c (no. 14), Z = 4, a(Tb) = 1368.24(4) pm, b(Tb) = 710.42(2) pm, c(Tb) = 965.79(3) pm, β(Tb) = 101.200(1)°, 3112 data, 160 parameters, wR2 = 0.062, a(Ho) = 1363.34(5) pm, b(Ho) = 709.24(3) pm, c(Ho) = 959.07(4) pm, β(Ho) = 101.055(1)°, 1607 data, 158 parameters, wR2 = 0.058). The crystal structure comprises two different infinite helical chains of corner-sharing phosphate tetrahedra. In-between these chains the lanthanide ions are located, coordinated by seven oxygen atoms belonging to four different polyphosphate chains. Vibrational, UV/Vis and fluorescence spectra of Ln[H(PO3)4] (Ln = Tb, Dy, Ho) as well as Dy[H(PO3)4]:Ln (Ln = Ce, Eu) and the magnetic and thermal behaviour of Tb[H(PO3)4] are reported.

  5. Coordination chemistry of several radius-sensitive complexones and applications to lanthanide-actinide separations

    Energy Technology Data Exchange (ETDEWEB)

    Potter, M.W.

    1981-10-01

    The relationships between the lanthanide complex formation equilibria and the lanthanide-actinide separation application of three radius sensitive ligands have been studied. The consecutive stepwise formation constants of the 1:1, 2:1, and 3:1 chelate species formed by the interaction of DHDMB and the tripositive lanthanides and yttrium were determined potentiometrically at 0.1 M ionic strength and 25/sup 0/C. Results indicate that three different coordination modes, one tridentate and two bidentate are in evidence. Tracer level /sup 241/Am - /sup 155/Eu cation-exchange experiments utilizing DHDMB eluents indicate that this dihydroxycarboxylate does not form a sufficiently strong americium complex to elute that actinide ahead of europium. The overall stability of the americium 3:1 complex appears intermediate between samarium and europium. Cation-exchange elutions of /sup 241/Am, /sup 155/Eu, and /sup 160/Tb mixtures with EEDTA solutions prove that the EEDTA ligand is capable of eluting americium ahead of all of the tripositive lanthanide cations. The minimum separation occurs with terbium, where the Am-Tb separation factor is 1.71. 1,5-diaminopentane-N,N,N',N'-tetraacetic acid (PMDTA) was synthesized using cation exchange. A mathematical method was developed for the formation constants of the protonated and unprotonated lanthanide-PMDTA complexes from potentiometry. Cation-exchange elutions of tracer quantities of Am, Eu, and Tb revealed that terbium is eluted ahead of both americium and europium.

  6. Ultrafast magnetization dynamics of lanthanide metals and alloys

    Energy Technology Data Exchange (ETDEWEB)

    Sultan, Muhammad

    2012-05-14

    In this study, the laser-induced magnetization dynamics of the lanthanide ferromagnets Gadolinium (Gd), Terbium (Tb) and their alloys is investigated using femtosecond (fs) time-resolved x-ray magnetic circular dichroism (XMCD), the magneto-optical Kerr effect (MOKE) and magnetic second harmonic generation (MSHG). The magnetization dynamics is analyzed from the time scale of a few fs up to several hundred picoseconds (ps). The contributions of electrons, phonons, spin fluctuations, as well as the temporal regimes corresponding to the spin-orbit and exchange interactions are disentangled. In addition to possible applications in magnetic storage devices, understanding magnetization dynamics in lanthanides is also important because of their different magnetic structure compared to well-studied itinerant ferromagnets. Lanthanides are model Heisenberg-ferromagnets with localized 4f magnetic moments and long range magnetic ordering through indirect exchange interaction. By optical excitation of the conduction electrons, which mediate the exchange interaction, and studying the induced dynamics of the localized 4f and delocalized 5d6s magnetic moments, one can obtain insight into the angular momentum transfer at ultrafast time scales. Moreover, lanthanides offer the possibility to tune spin-lattice coupling via the 4f shell occupation and the concomitant changes in the 4f spin and orbital moments due to Hund's rules. Utilizing this fact, the importance of spin-lattice coupling in laser-induced demagnetization is also analyzed by comparing the magnetization dynamics in Gd and Tb. By investigating the magnetization dynamics of localized 4f moments of Gd and Tb using time-resolved XMCD, it is found that the demagnetization proceeds in both metals in two time scales, following fs laser excitation, which are classified as: (i) non-equilibrium (t > 1 ps), with respect to equilibration of electron and phonon temperatures. The

  7. Lanthanide shift reagents, binding, shift mechanisms and exchange

    International Nuclear Information System (INIS)

    Boer, J.W.M. de

    1977-01-01

    Paramagnetic lanthanide shift reagents, when added to a solution of a substrate, induce shifts in the nuclear magnetic resonance (NMR) spectrum of the substrate molecules. The induced shifts contain information about the structure of the shift reagent substrate complex. The structural information, however, may be difficult to extract because of the following effects: (1) different complexes between shift reagent and substrate may be present in solution, e.g. 1:1 and 1:2 complexes, and the shift observed is a weighed average of the shifts of the substrate nuclei in the different complexes; (2) the Fermi contact interaction, arising from the spin density at the nucleus, contributes to the induced shift; (3) chemical exchange effects may complicate the NMR spectrum. In this thesis, the results of an investigation into the influence of these effects on the NMR spectra of solutions containing a substrate and LSR are presented. The equations describing the pseudo contact and the Fermi contact shift are derived. In addition, it is shown how the modified Bloch equations describing the effect of the chemical exchange processes occurring in the systems studied can be reduced to the familiar equations for a two-site exchange case. The binding of mono- and bifunctional ethers to the shift reagent are reported. An analysis of the induced shifts is given. Finally, the results of the experiments performed to study the exchange behavior of dimethoxyethane and heptafluorodimethyloctanedionato ligands are presented

  8. Lattice disorder in strongly correlated lanthanide and actinide intermetallics

    International Nuclear Information System (INIS)

    Booth, C.H.; Bauer, E.D.; Maple, M.B.; Lawrence, J.M.; Kwei, G.H.; Sarrao, J.L.

    2001-01-01

    Lanthanide and actinide intermetallic compounds display a wide range of correlated-electron behavior, including ferromagnetism, antiferromagnetism, nonmagnetic (Kondo) ground states, and so-called 'non-Fermi liquid' (NFL) behavior. The interaction between f electrons and the conduction band is a dominant factor in determining the ground state of a given system. However, lattice disorder can create a distribution of interactions, generating unusual physical properties. These properties may include NFL behavior in many materials. In addition, lattice disorder can cause deviations from standard Kondo behavior that is less severe than NFL behavior. A review of the lattice disorder mechanism within a tight-binding model is presented, along with measurements of the YbBCu 4 and UPd x Cu 5-x systems, demonstrating the applicability of the model. These measurements indicate that while the YbBCu 4 system appears to be well ordered, both site interchange and continuous bond-length disorder occur in the UPd x Cu 5-x series. Nevertheless, the measured bond-length disorder in UPdCu 4 does not appear to be enough to explain the NFL properties simply with the Kondo disorder model. (au)

  9. Photo-reactive charge trapping memory based on lanthanide complex

    Science.gov (United States)

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V. A. L.

    2015-10-01

    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 104 s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

  10. Dissolution of lanthanide alumino-silicate oxynitride glasses

    Science.gov (United States)

    Bois, L.; Barré, N.; Guillopé, S.; Guittet, M. J.; Gautier-Soyer, M.; Duraud, J. P.; Trocellier, P.; Verdier, P.; Laurent, Y.

    2000-01-01

    The aqueous corrosion behavior of lanthanide aluminosilicate glasses has been studied under static conditions ( T=96°C, duration=1 and 3 months, glass surface area/leachate volume, S/ V=0.3 cm -1) by means of solution and solid analyses. It was found that these glasses exhibit a high chemical durability. The influence of yttrium, magnesium and nitrogen, which are supposed to improve the mechanical properties, on the chemical durability, has been investigated. After a one-month experiment, lanthanum and yttrium releases were found to be about 10 -7 mol l -1, while silicon and aluminum releases were about 10 -5 mol l -1. Yttrium seems to improve the chemical durability. The presence of nitrogen does not seem to modify the glass constituents releases, but seems to improve the surface state of the altered glass. XPS experiments reveal that lanthanum and yttrium are more concentrated near the surface (20-30 Å) of the glass after the leaching test.

  11. Structural and thermodynamic study of rare earth(III) complexation by poly-hydroxylated carboxylic acids: synthesis of new extractants and outlook for the extraction of these cations; Etude structurale et thermodynamique de la complexation de lanthanides (III) par des acides carboxyliques polyhydroxyles: synthese de nouveaux extractants et perspectives pour l'extraction de ces cations

    Energy Technology Data Exchange (ETDEWEB)

    Aury, S

    2002-12-15

    The aim of this work is: to improve the knowledge on the binding sites of the poly-hydroxylated carboxylic acids with the trivalent lanthanide(III) ions by comparing them to gluconic acid (previously studied) and to molecules with different configuration and with a variable number of OH functions (threonic acid, glyceric acid, 2-hydroxy-butanoic acid, 3-hydroxy-butanoic acid). To find the best complexing agent among different acids (aldonic acids, aldaric acids, di-hydroxybenzoic acids) (determination of the set of complexes and their stability constants by potentiometry, NMR and UV-Visible spectroscopy). To synthesize hydrophobic monoamides from one lactone form of saccharic acid, to study their complexing power and their capacity to extract the trivalent lanthanide(III) ions. (author)

  12. New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

    Science.gov (United States)

    Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

    2013-02-18

    We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

  13. Extended lanthanide-transition metal arrays with cyanide bridges: syntheses, structures, and catalytic applications

    International Nuclear Information System (INIS)

    Liu Shengming; Poplaukhin, Pavel; Ding Errun; Plecnik, Christine E.; Chen Xuenian; Keane, Mark A.; Shore, Sheldon G.

    2006-01-01

    Systematic synthetic procedures produced several different structural types of extended lanthanide-transition metal (group 10) complexes with cyanide bridges. Of these, one-dimensional ladder arrays containing a Yb-Pd combination have been converted to bimetallic heterogeneous catalysts on an oxide (SiO 2 ) surface that is more effective than supported Pd alone. Two lanthanide-Cu(I) complexes have been prepared. One type, an inclusion complex consists of lanthanide(III) cations encapsulated in the pockets of a three-dimensional anionic array that contains Cu(I)-CN-Cu(I) bridges. The second type, an extended layer complex, consists of joined five-membered rings in a 'tile-like' pattern with Ln-CN-Cu and Cu-CN-Cu bridges

  14. Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers

    International Nuclear Information System (INIS)

    Du, H.S.; Wood, D.J.; Elshani, Sadik; Wai, C.M.

    1993-01-01

    Thorium and the lanthanides are extracted by α-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed. (author)

  15. Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers.

    Science.gov (United States)

    Du, H S; Wood, D J; Elshani, S; Wai, C M

    1993-02-01

    Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.

  16. Effect of the Lithium Oxide Concentration on a Reduction of Lanthanide Oxides

    International Nuclear Information System (INIS)

    Choi, In-Kyu; Jeong, Myeong-Soo; Do, Jae-Bum; Seo, Chung-Seok

    2007-01-01

    The pyrochemical reduction process of spent oxide fuel is one of the options to handle spent PWR fuels in Korea. After spent oxide fuel is converted to a metallic form, fission products will be removed from the resultant uranium and higher actinide metals by an electrorefining process. The chemical behaviors of lanthanide oxides during the pyrochemical process has been extensively studied. It was also reported that about 30 to 50% of several lanthanide oxides were reduced to corresponding metals by an electrolytic reduction process having 1 wt% of a lithium oxide concentration. Korea Atomic Energy Research Institute (KAERI), however, has been used 3 wt% of lithium oxide to increase the applied current of the electrolytic reduction process. Though it was reported that U 3 O 8 was reduced to uranium metal having a high reduction yield at 3 wt% of the Li 2 O concentration, the effect of the lithium oxide concentration on the reduction of lanthanide oxides has not been clarified

  17. The Role of Chromohalobacter on Transport of Lanthanides and Cesium in the Dolomite Mineral System

    Energy Technology Data Exchange (ETDEWEB)

    Zengotita, Frances [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Emerson, Hilary Palmer [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Dittrich, Timothy M. [Wayne State Univ., Detroit, MI (United States); Swanson, Juliet S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Reed, Donald T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-12-01

    The chemical behavior of actinide series elements and fission products is a concern for the Waste Isolation Pilot Plant repository due to their uncertain mobility in the subsurface salt formation. In this work, we are observing the behavior of the halophilic bacterium, Chromohalobacter, and its effect on the mobility of lanthanides and cesium in the presence of dolomite. Batch and minicolumn experiments were conducted with Cs+ and lanthanides (Nd3+, Eu3+) to quantify potential transport with bacteria. Preliminary results show that Cs does not interact strongly with dolomite or Chromohalobacter, while the lanthanides can interact strongly with both minerals and bacteria depending on which the Ln contacts first.

  18. Molecular design of highly efficient extractants for separation of lanthanides and actinides by computational chemistry

    International Nuclear Information System (INIS)

    Uezu, Kazuya; Yamagawa, Jun-ichiro; Goto, Masahiro

    2006-01-01

    Novel organophosphorus extractants, which have two functional moieties in the molecular structure, were developed for the recycle system of transuranium elements using liquid-liquid extraction. The synthesized extractants showed extremely high extractability to lanthanides elements compared to those of commercially available extractants. The results of extraction equilibrium suggested that the structural effect of extractants is one of the key factors to enhance the selectivity and extractability in lanthanides extractions. Furthermore, molecular modeling was carried out to evaluate the extraction properties for extraction of lanthanides by the synthesized extractants. Molecular modeling was shown to be very useful for designing new extractants. The new concept to connect some functional moieties with a spacer is very useful and is a promising method to develop novel extractants for treatment of nuclear fuel. (author)

  19. Extraction of lanthanide(III) nitrates from water-salt solutions with n.-octanol

    International Nuclear Information System (INIS)

    Keskinov, V.A.; Kudrova, A.V.; Valueva, O.V.; Pyartman, A.K.

    2004-01-01

    Extraction of lanthanide(III) nitrates (Ln=La-Nd, Sm-Gd) from aqueous-salt solutions at 298.15 K was studied using solution of n.-octanol, its concentration 6.31 mol/l. It was ascertained that at Ln(NO 3 ) 3 concentration in aqueous phase below 0.6 mol/l, there is actually no extraction. At higher concentrations of nitrates in aqueous phase the content of lanthanides(III) in organic phase increases in the series La-Gd. Isotherms of extraction were ascertained, its phase equilibria being described mathematically. It is shown that extraction of lanthanide(III) nitrates with n.-octanol should be realized from concentrated aqueous solutions [ru

  20. A generic biokinetic model for predicting the behaviour of the lanthanide elements in the human body

    International Nuclear Information System (INIS)

    Taylor, D.M.; Leggett, R.W.

    2003-01-01

    Information on the biokinetics of the 15 elements of the lanthanide series, 57 La to 71 Lu, is too sparse to permit individual development of meaningful biokinetic models to describe the behaviour of each of the elements in humans. The lanthanides show a regular gradation in chemical properties across the series, and animal studies indicate that this is reflected in regular differences in their deposition in tissues such as the liver and skeleton. These regular differences in chemical and biological behaviour have been utilised to construct a generic lanthanide biokinetic model and to define element-specific parameters for each element in the series. This report describes the use of the available biokinetic data for humans and animals to derive the parameters for each of the elements. (author)