Method for forming an extraction agent for the separation of actinides from lanthanides

DOEpatents

Klaehn, John R.; Harrup, Mason K.; Law, Jack D.; Peterman, Dean R.

2010-04-27

An extraction agent for the separation of trivalent actinides from lanthanides in an acidic media and a method for forming same are described, and wherein the methodology produces a stable regiospecific and/or stereospecific dithiophosphinic acid that can operate in an acidic media having a pH of less than about 7.

The lanthanide contraction beyond coordination chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

The lanthanide contraction beyond coordination chemistry

DOE PAGES

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.; ...

2016-04-06

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes 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 (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Aaron T.; Nash, Kenneth L.

The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less

Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME

DOE PAGES

Johnson, Aaron T.; Nash, Kenneth L.

2015-08-20

The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less

Combining CMPO and HEH[EHP] for Separating Trivalent Lanthanides from the Transuranic Elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braley, Jenifer C.; Lumetta, Gregg J.; Carter, Jennifer C.

2013-09-05

Combining octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) into a single process solvent for separating transuranic elements from liquid high-level waste is explored. The lanthanides and americium can be co-extracted from HNO3 into 0.2 mol/L CMPO + 1.0 mol/L HEH[EHP] in n-dodecane. The extraction is relatively insensitive to the HNO3 concentration within 0.1 to 5 mol/L HNO3. Americium can be selectively stripped from the CMPO/HEH[EHP] solvent into a citrate-buffered N-(2-hydroxyethyl)ethylenediaminetriacetic acid solution . Separation factors >14 can be achieved in the range pH 2.5 to 3.7, and the separation factors are relatively insensitive to pH, a major advantagemore » of this solvent formulation.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Li-Mei; Liu, Jing-Xin, E-mail: jxliu411@ahut.edu.cn

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 revealedmore » 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

Selective Separation of Trivalent Actinides from Lanthanides by Aqueous Processing with Introduction of Soft Donor Atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kenneth L. Nash

2009-09-22

Implementation of a closed loop nuclear fuel cycle requires the utilization of Pu-containing MOX fuels with the important side effect of increased production of the transplutonium actinides, most importantly isotopes of Am and Cm. Because the presence of these isotopes significantly impacts the long-term radiotoxicity of high level waste, it is important that effective methods for their isolation and/or transmutation be developed. Furthermore, since transmutation is most efficiently done in the absence of lanthanide fission products (high yield species with large thermal neutron absorption cross sections) it is important to have efficient procedures for the mutual separation of Am andmore » Cm from the lanthanides. The chemistries of these elements are nearly identical, differing only in the slightly stronger strength of interaction of trivalent actinides with ligand donor atoms softer than O (N, Cl-, S). Research being conducted around the world has led to the development of new reagents and processes with considerable potential for this task. However, pilot scale testing of these reagents and processes has demonstrated the susceptibility of the new classes of reagents to radiolytic and hydrolytic degradation. In this project, separations of trivalent actinides from fission product lanthanides have been investigated in studies of 1) the extraction and chemical stability properties of a class of soft-donor extractants that are adapted from water-soluble analogs, 2) the application of water soluble soft-donor complexing agents in tandem with conventional extractant molecules emphasizing fundamental studies of the TALSPEAK Process. This research was conducted principally in radiochemistry laboratories at Washington State University. Collaborators at the Radiological Processing Laboratory (RPL) at the Pacific Northwest National Laboratory (PNNL) have contributed their unique facilities and capabilities, and have supported student internships at PNNL to broaden their

Separation of thorium (IV) from lanthanide concentrate (LC) and water leach purification (WLP) residue

DOE Office of Scientific and Technical Information (OSTI.GOV)

AL-Areqi, Wadeeah M.; Majid, Amran Ab.; Sarmani, Sukiman

Thorium (IV) content in industrial residue produced from rare earth elements production industry is one of the challenges to Malaysian environment. Separation of thorium from the lanthanide concentrate (LC) and Water Leach Purification (WLP) residue from rare earth elements production plant is described. Both materials have been tested by sulphuric acid and alkaline digestions. Th concentrations in LC and WLP were determined to be 1289.7 ± 129 and 1952.9±17.6 ppm respectively. The results of separation show that the recovery of Th separation from rare earth in LC after concentrated sulphuric acid dissolution and reduction of acidity to precipitate Th wasmore » found 1.76-1.20% whereas Th recovery from WLP was less than 4% after concentrated acids and alkali digestion processes. Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) was used to determine Th concentrations in aqueous phase during separation stages. This study indicated that thorium maybe exists in refractory and insoluble form which is difficult to separate by these processes and stays in WLP residue as naturally occurring radioactive material (NORM)« less

Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clearfield, Abraham

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 3PC 6H 4PO 3) 1-x/2(APO 4)x·nH 2O: where M=Zr 4+, Sn 4+, A=H, Na,more » 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.« less

On the Suitability of Lanthanides as Actinide Analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szigethy, Geza; Raymond, Kenneth N.

2008-04-11

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 groupmore » 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.« less

On the suitability of lanthanides as actinide analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raymond, Kenneth; Szigethy, Geza

2008-07-01

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 groupmore » 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)« less

Selective Removal of Lanthanides from Natural Waters, Acidic Streams and Dialysate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yantasee, Wassana; Fryxell, Glen E.; Addleman, Raymond S.

2009-09-15

The increased demand for the lanthanides in commercial products result in increased production of lanthanide containing ores, increasing 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, Lu) binding properties of self-assembled monolayers on mesoporous silica supports (SAMMS®) that were functionalized with diphosphonic acid (DiPhos), acetamide phosphonic acid (AcPhos), propionamide phosphonic acid (ProPhos), 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 and compares their performance to a high surface area activated carbon.more » The properties include sorption affinity, capacity, and sorption kinetics. Stability and regenerability of SAMMS materials were also 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. While the activated carbon is as effective as 1,2-HOPO-SAMMS for capturing lanthanides in natural (alkaline) waters, it has no affinity in acid solutions (pH 2.4) and low affinity in carbonate-rich dialysate. Over 99% of 100 ug/L of Gd in dialysate was removed by the ProPhos-SAMMS after ten minutes. SAMMS can be regenerated with an acid wash (0.5 M HCl) without losing the binding properties, for a number of regeneration cycles. In acid solutions, PhoPhos- and 1,2-HOPO-SAMMS have differing affinity along the lanthanide series, suggesting their potential for chromatographic lanthanide separations. Thus, SAMMS materials have a great potential to be used as sorbents in large scale treatment of lanthanides, lanthanide separation prior to analytical instruments, and sorbent dialyzers for lanthanide clearances.« less

Improved method for extracting lanthanides and actinides from acid solutions

DOEpatents

Horwitz, E.P.; Kalina, D.G.; Kaplan, L.; Mason, G.W.

1983-07-26

A process for the recovery of actinide and lanthanide values from aqueous acidic solutions uses a new series of neutral bi-functional extractants, the alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high-level nuclear reprocessing waste solutions.

Rare earth separations by selective borate crystallization

PubMed Central

Yin, Xuemiao; Wang, Yaxing; Bai, Xiaojing; Wang, Yumin; Chen, Lanhua; Xiao, Chengliang; Diwu, Juan; Du, Shiyu; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific lanthanides that originates from Ln3+ coordination alterations, borate polymerization diversity and soft ligand coordination selectivity. Six distinct phases are obtained under identical reaction conditions across lanthanide series, further leading to an efficient and cost-effective separation strategy via selective crystallization. As proof of concept, Nd/Sm and Nd/Dy are used as binary models to demonstrate solid/aqueous and solid/solid separation processes. Controlling the reaction kinetics gives rise to enhanced separation efficiency of Nd/Sm system and a one-step quantitative separation of Nd/Dy with the aid of selective density-based flotation. PMID:28290448

Lateral diffusion contributes to FRET from lanthanide-tagged membrane proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lan, Tien-Hung; Wu, Guangyu; Lambert, Nevin A., E-mail: nelambert@gru.edu

2015-08-14

Diffusion can enhance Förster resonance energy transfer (FRET) when donors or acceptors diffuse distances that are similar to the distances separating them during the donor's excited state lifetime. Lanthanide donors remain in the excited state for milliseconds, which makes them useful for time-resolved FRET applications but also allows time for diffusion to enhance energy transfer. Here we show that diffusion dramatically enhances FRET between membrane proteins labeled with lanthanide donors. This phenomenon complicates interpretation of experiments that use long-lived donors to infer association or proximity of mobile membrane proteins, but also offers a method of monitoring diffusion in membrane domainsmore » in real time in living cells. - Highlights: • Diffusion enhances TR-FRET from membrane proteins labeled with lanthanide donors. • Diffusion-dependent FRET can overshadow FRET due to oligomerization or clustering. • FRET studies using lanthanide-tagged membrane proteins should consider diffusion. • FRET from lanthanide donors can be used to monitor membrane protein diffusion.« less

Method to synthesize lanthanide fluoride materials from lanthanide fluorinated alkoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyle, Timothy J.

Lanthanide fluorinated alkoxide derivatives can be synthesized from the alcoholysis reaction of the lanthanide bis-trimethylsilyl amide and an excess amount of hexafluoro iso-propanol. Nanoparticles can be formed from the lanthanide fluorinated alkoxide derivatives by a solvothermal or solution precipitation process.

Ligand-Sensitized Lanthanide Nanocrystals: Merging Solid-State Photophysics and Molecular Solution Chemistry

DOE PAGES

Agbo, Peter; Abergel, Rebecca J.

2016-06-30

To date, the breadth of scientific research that has been devoted to investigating the photochemical and photophysical behavior of the lanthanide elements has generally fallen into one of two camps: solution studies of luminescent lanthanide metal-ligand complexes or investigations of solid-state nanoparticles, composed primarily of, or doped with, lanthan ide lumiphores. In the latter case, most research of lanthanide nanocolloids has precluded any investigations regarding the use of organic ligands to overcome the difficulties associated with f-f excitation of lanthanides. Instead, most work on condensed-phase lanthanide luminescence has centered on strategies such as d-f charge separation in divalent lanthanides andmore » the sensitization of lanthanide excited states using quantum dots. Current work now aims at bridging the camps of condensed-phase lanthanide photophysics and the solution chemistry of ligand-lanthanide molecular complexes. Some recent efforts have partly focused on the fundamental characterization of NaGd 1-x Ln x F 4 nanoparticles featuring surface display of the sensitizer ligand 3,4,3-LI(1,2-HOPO), showing these structures to be capable of converting absorbed UV light into luminescence from Eu 3+ and Tb 3+ ions. Our results suggest such a use of the ligand sensitization as a tool of choice to overcome the constraints of UV solar spectrum/semiconductor band-gap mismatch and low absorption cross sections in solid-state lanthanide systems.« less

Secret lanthanides.

PubMed

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.

Secret Lanthanides

PubMed Central

Sturza, CM

2014-01-01

Abstract 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. PMID:25408760

Method for extracting lanthanides and actinides from acid solutions

DOEpatents

Horwitz, E. Philip; Kalina, Dale G.; Kaplan, Louis; Mason, George W.

1985-01-01

A process for the recovery of actinide and lanthanide values from aqueous acidic solutions with an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high level nuclear reprocessing waste solutions.

Characterization and thermogravimetric analysis of lanthanide hexafluoroacetylacetone chelates

DOE PAGES

Shahbazi, Shayan; Stratz, S. Adam; Auxier, John D.; ...

2016-08-30

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.

Shining light on the antenna chromophore in lanthanide based dyes.

PubMed

Junker, Anne Kathrine R; Hill, Leila R; Thompson, Amber L; Faulkner, Stephen; Sørensen, Thomas Just

2018-04-03

Lanthanide based dyes and assays exploit the antenna effect, where a sensitiser-chromophore is used as a light harvesting antenna and subsequent excited state energy transfer populates the emitting lanthanide centred excited state. A rudimentary understanding of the design criteria for designing efficient dyes and assays based on the antenna effect is in place. By preparing kinetically inert lanthanide complexes based on the DO3A scaffold, we are able to study the excited state energy transfer from a 7-methoxy-coumarin antenna chromophore to europium(iii) and terbium(iii) centred excited states. By contrasting the photophysical properties of complexes of metal centres with and without accessible excited states, we are able to separate the contributions from the heavy atom effect, photoinduced electron transfer quenching, excited state energy transfer and molecular conformations. Furthermore, by studying the photophysical properties of the antenna chromophore, we can directly monitor the solution structure and are able to conclude that excited state energy transfer from the chromophore singlet state to the lanthanide centre does occur.

Theoretical Prediction of Am(III)/Eu(III) Selectivity to Aid the Design of Actinide-Lanthanide Separation Agents

DOE PAGES

Bryantsev, Vyacheslav S.; Hay, Benjamin P.

2015-03-20

Selective extraction of minor actinides from lanthanides is a critical step in the reduction of radiotoxicity of spent nuclear fuels. However, the design of suitable ligands for separating chemically similar 4f- and 5f-block trivalent metal ions poses a significant challenge. Furthermore, first-principles calculations should play an important role in the design of new separation agents, but their ability to predict metal ion selectivity has not been systematically evaluated. We examine the ability of several density functional theory methods to predict selectivity of Am(III) and Eu(III) with oxygen, mixed oxygen–nitrogen, and sulfur donor ligands. The results establish a computational method capablemore » of predicting the correct order of selectivities obtained from liquid–liquid extraction and aqueous phase complexation studies. To allow reasonably accurate predictions, it was critical to employ sufficiently flexible basis sets and provide proper account of solvation effects. The approach is utilized to estimate the selectivity of novel amide-functionalized diazine and 1,2,3-triazole ligands.« less

Biological toxicity of lanthanide elements on algae.

PubMed

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.

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

PubMed

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.

Nonequivalent lanthanide defects: Energy level modeling

NASA Astrophysics Data System (ADS)

Joos, Jonas J.; Poelman, Dirk; Smet, Philippe F.

2016-11-01

Empirical charge-state transition level schemes are popular tools to model the properties of lanthanide-doped materials and their construction has become standard practice. Typically, it is implicitly assumed that all lanthanide ions form isostructural defects. However, in practice, multiple nonequivalent defects related to the same lanthanide can occur or different lanthanides can even incorporate in different ways. The consequences of these complications on the impurity energy levels are discussed in this article. It seems that small structural differences around the lanthanide dopant can give rise to important spectral differences in its emission. These are not always clearly reproduced by the charge-state transition level schemes. Improvements to the existing procedure are suggested and applied to the lanthanide ions in the well-studied host crystals SrAl2O4, Sr2Si5N8 and SrGa2S4.

Biological and Clinical Aspects of Lanthanide Coordination Compounds

PubMed Central

Misra, Sudhindra N.; M., Indira Devi; Shukla, Ram S.

2004-01-01

The coordinating chemistry of lanthanides, relevant to the biological, biochemical and medical aspects, makes a significant contribution to understanding the basis of application of lanthanides, particularly in biological and medical systems. The importance of the applications of lanthanides, as an excellent diagnostic and prognostic probe in clinical diagnostics, and an anticancer material, is remarkably increasing. Lanthanide complexes based X-ray contrast imaging and lanthanide chelates based contrast enhancing agents for magnetic resonance imaging (MRI) are being excessively used in radiological analysis in our body systems. The most important property of the chelating agents, in lanthanide chelate complex, is its ability to alter the behaviour of lanthanide ion with which it binds in biological systems, and the chelation markedly modifies the biodistribution and excretion profile of the lanthanide ions. The chelating agents, especially aminopoly carboxylic acids, being hydrophilic, increase the proportion of their complex excreted from complexed lanthanide ion form biological systems. Lanthanide polyamino carboxylate-chelate complexes are used as contrast enhancing agents for Magnetic Resonance Imaging. Conjugation of antibodies and other tissue specific molecules to lanthanide chelates has led to a new type of specific MRI contrast agents and their conjugated MRI contrast agents with improved relaxivity, functioning in the body similar to drugs. Many specific features of contrast agent assisted MRI make it particularly effective for musculoskeletal and cerebrospinal imaging. Lanthanide-chelate contrast agents are effectively used in clinical diagnostic investigations involving cerebrospinal diseases and in evaluation of central nervous system. Chelated lanthanide complexes shift reagent aided 23Na NMR spectroscopic analysis is used in cellular, tissue and whole organ systems. PMID:18365075

Ionization Energies of Lanthanides

ERIC Educational Resources Information Center

Lang, Peter F.; Smith, Barry C.

2010-01-01

This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

Aromatic triamide-lanthanide complexes

DOEpatents

Raymond, Kenneth N; Petoud, Stephane; Xu, Jide

2013-10-08

The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one phthalamidyl moiety. Also provided are probes incorporating the phthalamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

Method bacterial endospore quantification using lanthanide dipicolinate luminescence

NASA Technical Reports Server (NTRS)

Venkateswaran, Kasthuri J. (Inventor); Kirby, James Patrick (Inventor); Ponce, Adrian (Inventor)

2007-01-01

A lanthanide is combined with a medium to be tested for endospores. The dipicolinic acid released from the endospores binds the lanthanides, which have distinctive emission (i.e., luminescence) spectra, and are detected using photoluminescence. The concentration of spores is determined by preparing a calibration curve generated from photoluminescence spectra of lanthanide complex mixed with spores of a known concentration. A lanthanide complex is used as the analysis reagent, and is comprised of lanthanide ions bound to multidentate ligands that increase the dipicolinic acid binding constant through a cooperative binding effect with respect to lanthanide chloride. The resulting combined effect of increasing the binding constant and eliminating coordinated water and multiple equilibria increase the sensitivity of the endospore assay by an estimated three to four orders of magnitude over prior art of endospore detection based on lanthanide luminescence.

Lanthanides caged by the organic chelates; structural properties

NASA Astrophysics Data System (ADS)

Smentek, Lidia

2011-04-01

The structure, in particular symmetry, geometry and morphology of organic chelates coordinated with the lanthanide ions are analyzed in the present review. This is the first part of a complete presentation of a theoretical description of the properties of systems, which are widely used in technology, but most of all, in molecular biology and medicine. The discussion is focused on the symmetry and geometry of the cages, since these features play a dominant role in the spectroscopic activity of the lanthanides caged by organic chelates. At the same time, the spectroscopic properties require more formal presentation in the language of Racah algebra, and deserve a separate analysis. In addition to the parent systems of DOTA, DOTP, EDTMP and CDTMP presented here, their modifications by various antennas are analyzed. The conclusions that have a strong impact upon the theory of the energy transfer and the sensitized luminescence of these systems are based on the results of numerical density functional theory calculations.

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Jie-Cen; Wan, Fang; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln{sub 2}(phen){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub n} (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]{sub 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{sub 4}{sup 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 hybridmore » 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 {sup 5}D{sub 0}→{sup 7}F{sub J} (J=0–4) of the Eu(III)« less

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1984-05-21

A process has been developed for the extraction of multivalent lanthanide and actinide values from acidic waste solutions, and for the separation of these values from fission product and other values, which utilizes a new series of neutral bi-functional extractants, the alkyl(phenyl)-N, N-dialkylcarbamoylmethylphosphine oxides, in combination with a phase modifier to form an extraction solution. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

LANTHANIDE ENHANCE LUMINESCENCE (LEL) WITH ONE AND TWO PHOTON EXCITATION OF QUANTUM DYES LANTHANIDE (III) - MACROCYCLES

EPA Science Inventory

Title: Lanthanide Enhance Luminescence (LEL) with one and two photon excitation of Quantum Dyes? Lanthanide(III)-Macrocycles
Principal Author:
Robert C. Leif, Newport Instruments
Secondary Authors:
Margie C. Becker, Phoenix Flow Systems
Al Bromm, Virginia Commonw...

Selective biosorption of lanthanide (La, Eu, Yb) ions by Pseudomonas aeruginosa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Texier, A.C.; Andres, Y.; Cloirec, P. le

1999-02-01

The ability of Pseudomonas aeruginosa to adsorb selectively La{sup 3+}, Eu{sup 3+}, and Yb{sup 3+} from aqueous solution was investigated. The lanthanide biosorption equilibrium obeyed the Brunauer-Emmett-Teller isotherm model, indicating multilayer adsorption. Determined levels of maximum adsorption capacities were 397 {micro}mol/g for lanthanum, 290 {micro}mol/g for europium and 326 {micro}mol/g for ytterbium. The results indicated that there were about 100 preferential sites for lanthanum per g of dry biomass. Experiments with mixed-cation solutions showed that the sequence of preferential biosorption was Eu{sup 3+} = Yb{sup 3+} > La{sup 3+}. Biomass dried at 37 and 70 C showed the same selectivemore » behavior as wet biomass. Inert microbial biomass dried at 37 C appeared to be the most efficient form for experimental use. The uptake of lanthanide by P. aeruginosa cells was not affected by the presence of sodium, potassium, calcium, chloride, sulfate and nitrate ions. Aluminum was a strong inhibitor of lanthanide ions biosorption. 87% of the total Al{sup 3+} was removed from the 3 mM solution, whereas only 8%, 20% and 3% of the total La{sup 3+}, Eu{sup 3+}, and Yb{sup 3+}, respectively, were sorbed from 3 mM solutions. The results suggested that cells of Pseudomonas aeruginosa may find promising applications for removal and separation of lanthanide ions from aqueous effluents.« less

Gas chemical adsorption characterization of lanthanide hexafluoroacetylacetonates

DOE PAGES

Stratz, S. Adam; Jones, Steven J.; Mullen, Austin D.; ...

2017-03-21

Newly-established adsorption enthalpy and entropy values of 12 lanthanide hexafluoroacetylacetonates, denoted Ln[hfac] 4, along with the experimental and theoretical methodology used to obtain these values, are presented for the first time. The results of this work can be used in conjunction with theoretical modeling techniques to optimize a large-scale gas-phase separation experiment using isothermal chromatography. The results to date indicate average adsorption enthalpy and entropy values of the 12 Ln[hfac] 4 complexes ranging from -33 to -139 kJ/mol K and -299 to -557 J/mol, respectively.

Standard Materials for Microbeam Analysis of Lanthanides and Actinides

NASA Astrophysics Data System (ADS)

Ellis, I.; Gorton, M.; Rucklidge, J. C.

2010-12-01

Traces of Th and U in naturally-occuring minerals monazite, xenotime and zircon are used for dating host rocks. Natural variations of actinide concentrations in some rock formations are well documented. Microbeam techniques perform dating in-situ where grains of indicator minerals are left intact in thin sections. Separated individual grains of these minerals are also routinely dated by Pb-isotope mass spectrometry. Ideal calibration materials will be compatible with multiple techniques. Quantitative analysis of low levels of lanthanides (REE), U, Th and Pb found in natural minerals requires standards containing similar concentrations of these elements. The ideal low-level standard suite will have materials with each REE cation present below 5%, similar to natural rare-earth phosphate minerals. In contrast, REE orthophosphates LnPO4 have cation concentrations from 59 to 64%, and ultraphosphates LnP5O14 from 27% to 32%. The concentrations of U and Pb must also be in the 1% range in the host REE phosphate. There are two competing limits to the synthesis of crystals with multiple cations in the REE sites. The crystal structure limits potential cation mixtures to selections within groups (La,Ce, Pr, Nd, Sm, Eu), (Gd, Tb, Dy, Ho), and (Er, Tm,Yb, Lu, Y). Complex L X-ray spectra limit the use of contiguous REE in a single material. There are two general synthetic routes for the preparation of lanthanide/actinide standard materials for beam analysis and dating. Lanthanide orthophosphates (LnPO4) are crystallized from lead-free heterogeneous fluxes; oligomers (metaphosphates LnP3O9 and ultraphosphates LnP5O14) are formed by condensation of phosphoric acid in the presence of cations. All of these trivalent lanthanide phosphate crystal structures are hosts for Th+4 and U+4, and in synthetic materals, Ca+2 is used for charge compensation. Our work focuses on the preparation of mixed-cation lanthanide metaphosphates and ultraphosphates. The solvent (essentially P2O5) provides

Preparation of Lanthanide-Polymer Composite Material via Click Chemistry.

PubMed

Chen, Bin; Wen, Guian; Wu, Jiajie; Feng, Jiachun

2015-10-01

Covalently attaching lanthanide complexes to the polymer backbone can effectively reduce the clustering of lanthanides and thus become an important strategy to fully unleash their potential. In this Communication, a metal-free click reaction is used for the first time to link a lanthanide complex to the polymer matrix. A diene-bearing copolymer with anthracenylmethyl methacrylate as a monomer and a dienophile-bearing lanthanide complex with 5-maleimido-1,10-phenanthroline as the second ligand are synthesized and coupled together through a Diels-Alder cycloaddition (DA). A comparative investigation demonstrates that the composite material prepared by DA click reaction shows the highest quantum yields in the same lanthanide concentration as compared to materials prepared by widely used "directly doping" and "in situ coordinating lanthanide ions with macromolecular ligand" approaches. This work suggests that the "metal-free" DA click reaction can be a promising tool in the synthesis of high efficient lanthanide functionalized polymeric materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lanthanides in soils of the Cherepovets steel mill impact zone

NASA Astrophysics Data System (ADS)

Ladonin, D. V.

2017-06-01

Contents of different lanthanide forms in soddy-calcareous soils at different distances from the Cherepovets steel mill (Vologda oblast) have been studied. Increased contents of Pr and Tb are found in soils near the pollution source. Less manifested increases in the contents of other lanthanides (from La to Gd) are also observed. Along with the increase in total content, technogenic pollution increases the content of acid-soluble lanthanides and affects their degree of extraction. The residual fraction strongly bound to aluminosilicates contains 80 to 95% of lanthanides. Soil processes result in the partial binding of lanthanides with organic matter (5-18% of their total content) and Fe and Mn (hydr)oxides (0.1-5% of the total content). The individual properties of lanthanides are clearly manifested in their interaction with these soil components. The highest share of the fraction bound to organic matter contains medium lanthanides, and the highest share of the fraction bound to Fe and Mn (hydr)oxides contains heavy lanthanides.

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

NASA Astrophysics Data System (ADS)

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.

Lanthanide complexes of azidophenacyl-DO3A as new synthons for click chemistry and the synthesis of heterometallic lanthanide arrays.

PubMed

Tropiano, Manuel; Kenwright, Alan M; Faulkner, Stephen

2015-04-07

Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 1. Process Optimization and Flowsheet Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lumetta, Gregg J.; Levitskaia, Tatiana G.; Wilden, Andreas

A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration ofmore » the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.« less

Extraction of lanthanides using 1-hydroxy-6- N-octylcarboxamido-2(1 H)-pyridinone as an extractant via competitive ligand complexations between aqueous and organic phases

DOE PAGES

Williams, Neil J.; Do-Thanh, Chi -Linh; Stankovich, Joseph J.; ...

2015-12-10

Here, the ability to selectively extract lanthanides is crucial in hydrometallurgy and the nuclear fuel cycle. The capabilities of 1-hydroxy-6- N-octylcarboxamido-2(1 H)-pyridinone (octyl-HOPO) as an extractant for the separation of lanthanides and actinides were studied for the first time. Octyl-HOPO greatly outperformed the traditional ligand di-2-ethylhexyl phosphoric acid (DEHPA).

Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Xue-Qin, E-mail: songxq@mail.lzjtu.cn; Lei, Yao-Kun; Wang, Xiao-Run

2014-10-15

The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversitiesmore » indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.« less

Calibration beads containing luminescent lanthanide ion complexes

EPA Science Inventory

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...

A flowsheet concept for an Am/Ln separation based on Am{sup VI} solvent extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mincher, B.J.; Law, J.D.

2013-07-01

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 radiotoxicity of material interred in a future high-level waste repository. However, a separation amenable to process scale-up remains elusive. Higher oxidation states of americium have recently been used to demonstrate solvent extraction-based separations using conventional fuel cycle ligands. Here, the successful partitioning of Am{sup VI} from the bulk of lanthanides and curium using diamyl-amyl-phosphonate (DAAP) extraction is reported. Due to the instability of Am{sup VI} in the organic phasemore » it was readily selectively stripped to a new acidic aqueous phase to provide separation from co-extracted Ce{sup IV}. The use of NaBiO{sub 3} as an oxidant to separate Am from the lanthanides and Cm by solvent extraction has been successfully demonstrated on the bench scale. Based on these results, flowsheet concepts can be designed that result in 96 % Am recovery in the presence of a few percent of the remaining Cm and the lanthanides in two extraction contacts. Preliminary results also indicate that the DAAP extractant is robust toward γ- irradiation under realistic conditions of acidity and dissolved oxygen concentration.« less

Energetic lanthanide complexes: coordination chemistry and explosives applications

NASA Astrophysics Data System (ADS)

Manner, V. W.; Barker, B. J.; Sanders, V. E.; Laintz, K. E.; Scott, B. L.; Preston, D. N.; Sandstrom, M.; Reardon, B. L.

2014-05-01

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.

Energetic Lanthanide Complexes: Coordination Chemistry and Explosives Applications

NASA Astrophysics Data System (ADS)

Manner, Virginia; Barker, Beau; Sanders, Eric; Laintz, Kenneth; Scott, Brian; Preston, Daniel; Sandstrom, Mary; Reardon, Bettina

2013-06-01

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.

Luminescent macrocyclic lanthanide complexes

DOEpatents

Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide

2014-05-20

The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

Luminescent lanthanide chelates and methods of use

DOEpatents

Selvin, Paul R.; Hearst, John

1997-01-01

The invention provides lanthanide chelates capable of intense luminescence. The celates comprise a lanthanide chelator covalently joined to a coumarin-like or quinolone-like sensitizer. Exemplary sensitzers include 2- or 4-quinolones, 2- or 4-coumarins, or derivatives thereof e.g. carbostyril 124 (7-amino-4-methyl-2-quinolone), coumarin 120 (7-amino-4-methyl-2-coumarin), coumarin 124 (7-amino-4-(trifluoromethyl)-2-coumarin), aminomethyltrimethylpsoralen, etc. The chelates form high affinity complexes with lanthanides, such as terbium or europium, through chelator groups, such as DTPA. The chelates may be coupled to a wide variety of compounds to create specific labels, probes, diagnostic and/or therapeutic reagents, etc. The chelates find particular use in resonance energy transfer between chelate-lanthanide complexes and another luminescent agent, often a fluorescent non-metal based resonance energy acceptor. The methods provide useful information about the structure, conformation, relative location and/or interactions of macromolecules.

La preparacion en ciencia de los candidatos a maestros del nivel elemental primario segun la reforma de la educacion cientifica en Puerto Rico: Una propuesta de secuencia curricular

NASA Astrophysics Data System (ADS)

Rodriguez Plaza, Evelyn

El proposito de esta investigacion fue identificar los componentes de la preparacion en ciencia que deben recibir los estudiantes del Bachillerato en Artes en Educacion Elemental, Nivel Primario, de acuerdo a los documentos que dirigen la reforma de la educacion cientifica en Puerto Rico. Tambien, se identificaron los componentes de los cursos que forman parte de la preparacion en ciencia de estos estudiantes. Se compararon los componentes de la preparacion en ciencia y los componentes de los cursos para determinar congruencias y discrepancias. Con los datos recopilados se identificaron los componentes de los cursos de una secuencia curricular para la preparacion en ciencia de los candidatos a maestros del nivel elemental primario. La secuencia curricular que se propone en esta investigacion incluye cursos de contenido cientifico y de metodologia en la ensenanza de la ciencia disenados para satisfacer las necesidades de los candidatos. Se recomienda que en los procesos para el diseno, la implantacion y la evaluacion de estos cursos participen profesores de ciencia, profesores de educacion y maestros del nivel elemental primario. Todos los cursos de la secuencia curricular deben tener un enfoque constructivista. Las experiencias educativas que se incluyan en los cursos deben aspirar a desarrollar en los candidatos los atributos de la cultura cientifica y actitudes positivas hacia la ciencia y hacia la ensenanza de esta disciplina. El modelaje por parte de los profesores que ensenen los cursos de la secuencia curricular es fundamental en el desarrollo profesional de los candidatos. Se recomienda que en los cursos de contenido cientifico se estudien los conceptos y los conocimientos cientificos que forman parte del curriculo de Kindergarten a tercer grado de forma integrada y con una profundidad universitaria. Estos cursos deben tener un enfoque interdisciplinario e incluir el estudio de la naturaleza de la ciencia y un componente de laboratorio para desarrollar los

Nonaqueous method for dissolving lanthanide and actinide metals

DOEpatents

Crisler, L.R.

1975-11-11

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.

Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as a novel eluent.

PubMed

Kifle, Dejene; Wibetoe, Grethe

2013-09-13

One of the major difficulties in the rare earth elements separation is purification of yttrium from heavy rare earth elements. Thus, an HPLC method using acetic acid as novel eluent was explored for selective separation of yttrium form the heavy rare earth elements. When acetic acid is used as a mobile phase yttrium eluted with the lighter lanthanides. This is contrary to its relative position amongst heavier lanthanides when eluents commonly used for separation of rare earth elements were employed. The shift in elution position of yttrium with acetic acid as eluent may reflect a relatively lower stability constant of the yttrium-AcOH complex (in the same order as for the lighter lanthanides) compared to the corresponding AcOH complexes with heavy lanthanides, enabling selective separation of yttrium from the latter. The method was successfully used for selective separation of yttrium in mixed rare earth sample containing about 80% of yttrium and about 20% of heavy rare earth oxides. Thus, the use of AcOH as eluent is an effective approach for separating and determining the trace amounts of heavy rare earth elements in large amounts of yttrium matrix. Separation was performed on C18 column by running appropriate elution programs. The effluent from the column was monitored with diode array detector at absorbance wavelength of 658nm after post column derivatization with Arsenazo III. Copyright © 2013 Elsevier B.V. All rights reserved.

Acidic 1,3-propanediaminetetraacetato lanthanides with luminescent and catalytic ester hydrolysis properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Mao-Long; Shi, Yan-Ru; Yang, Yu-Chen

2014-11-15

In acidic solution, a serials of water-soluble coordination polymers (CPs) were isolated as zonal 1D-CPs 1,3-propanediaminetetraacetato lanthanides [Ln(1,3-H{sub 3}pdta)(H{sub 2}O){sub 5}]{sub n}·2Cl{sub n}·3nH{sub 2}O [Ln=La, 1; Ce, 2; Pr, 3; Nd, 4; Sm, 5] (1,3-H{sub 4}pdta=1,3-propanediaminetetraacetic acid, C{sub 11}H{sub 18}N{sub 2}O{sub 8}) in high yields. When 1 eq. mol potassium hydroxide was added to the solutions of 1D-CPs, respectively, two 1D-CPs [Ln(1,3-H{sub 2}pdta)(H{sub 2}O){sub 3}]{sub n}·Cl{sub n}·2nH{sub 2}O [Ln=Sm, 6; Gd, 7] were isolated at room temperature and seven 2D-CPs [Ln(1,3-H{sub 2}pdta)(H{sub 2}O){sub 2}]{sub n}·Cl{sub n}·2nH{sub 2}O [Ln=La, 8; Ce, 9; Pr, 10; Nd, 11; Sm, 12; Eu, 13; Gd,more » 14] were isolated at 70 °C. When the crystals of 1–4 were hydrothermally heated at 180 °C with 1–2 eq. mol potassium hydroxide, four 3D-CPs [Ln(1,3-Hpdta)]{sub n}·nH{sub 2}O [Ln=La, 15; Ce, 16; Pr, 17; Nd, 18] were obtained. The two 2D-CPs [Ln(1,3-Hpdta)(H{sub 2}O)]{sub n}·4nH{sub 2}O (Sm, 19; Eu, 20) were isolated in similar reaction conditions. With the increments of pH value in the solution and reaction temperature, the structure becomes more complicated. 1–5 are soluble in water and 1 was traced by solution {sup 13}C({sup 1}H) NMR technique, the water-soluble lanthanides 1 and 5 show catalytic activity to ester hydrolysis reaction respectively, which indicate their important roles in the hydrolytic reaction. The europium complexes 13 and 20 show visible fluorescence at an excitation of 394 nm. The structure diversity is mainly caused by the variation of coordinated ligand in different pH values and lanthanide contraction effect. Acidic conditions are favorable for the isolations of lanthanide complexes in different structures and this may helpful to separate different lanthanides. The thermal stability investigations reveal that acidic condition is favorable to obtain the oxides at a lower temperature. - Graphical abstract: A

Electronic structure of lanthanide scandates

NASA Astrophysics Data System (ADS)

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.

Effect of lanthanides on the aromatic system of benzoic acid

NASA Astrophysics Data System (ADS)

Lewandowski, Włlodzimierz

1983-08-01

The stucture of lanthanide complexes with benzoic acid was investigated by IR and UV absorption spectra. To determine the effect of metal coordination on the aromatic system of benzoic acid, IR spectra of Ln(OBz) 3 (Ln is a lanthanide except promethium; BzO is benzoic acid radical) were compared with ligand and sodium benzoate spectra. Also, changes in frequency and relative intensity of the ? bands in the 1600-1400 cm -1 region, were analyzed in terms of the atomic number of lanthanides. It is shown that lanthanides disturb the aromatic system of the benzoate ligand less than sodium. This effect is discussed in terms of the bonds formed.

A review on solid phase extraction of actinides and lanthanides with amide based extractants.

PubMed

Ansari, Seraj A; Mohapatra, Prasanta K

2017-05-26

Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation. Copyright © 2017 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao Jing; Liang Jingjing; Pan Yingli

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){sub 2}(dien)({eta}{sup 2}-SbSe{sub 4})] (Ln=Ce(1a), Nd(1b)), [Ln(en){sub 2}(dien)(SbSe{sub 4})] (Ln=Sm(2a), Gd(2b), Dy(2c)), [Ln(en)(trien)({mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4})]{sub {infinity}} (Ln=Ce(3a), Nd(3b)) and [Sm(en)(trien)({eta}{sup 2}-SbSe{sub 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{sub 4}]{sup 3-} acts as a monodentate ligand mono-SbSe{sub 4}, a bidentate chelating ligand {eta}{sup 2}-SbSe{sub 4} or a tridentate bridging ligand {mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4} to the lanthanide(III) center depending on themore » Ln{sup 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{sub 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{sub 4}]{sup 3-} anion acts as a mono-SbSe{sub 4}, a {eta}{sup 2}-SbSe{sub 4} or a {mu}-{eta}{sup 1},{eta}{sup 2}-SbSe{sub 4} ligand to the Ln{sup 3+} ions. > The soft base ligand [SbSe{sub 4}]{sup 3-} can be controlled to coordinate to the Ln{sup 3+} ions with en+dien and en+trien as co-ligands.« less

Lanthanide co-ordination frameworks: Opportunities and diversity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Robert J.; Long, De-Liang; Hubberstey, Peter

2005-08-15

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 moremore » 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.« less

Lanthanide-doped upconverting phosphors for bioassay and therapy

NASA Astrophysics Data System (ADS)

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.

Physiological Effect of XoxG(4) on Lanthanide-Dependent Methanotrophy

DOE PAGES

Zheng, Yue; Huang, Jing; Zhao, Feng; ...

2018-03-27

ABSTRACT A recent surprising discovery of the activity of rare earth metals (lanthanides) as enzyme cofactors as well as transcriptional regulators has overturned the traditional assumption of biological inertia of these metals. However, so far, examples of such activities have been limited to alcohol dehydrogenases. Here we describe the physiological effects of a mutation in xoxG , a gene encoding a novel cytochrome, XoxG(4), and compare these to the effects of mutation in XoxF, a lanthanide-dependent methanol dehydrogenase, at the enzyme activity level and also at the community function level, using Methylomonas sp. strain LW13 as a model organism. Throughmore » comparative phenotypic characterization, we establish XoxG as the second protein directly involved in lanthanide-dependent metabolism, likely as a dedicated electron acceptor from XoxF. However, mutation in XoxG caused a phenotype that was dramatically different from the phenotype of the mutant in XoxF, suggesting a secondary function for this cytochrome, in metabolism of methane. We also purify XoxG(4) and demonstrate that this protein is a true cytochrome c , based on the typical absorption spectra, and we demonstrate that XoxG can be directly reduced by a purified XoxF, supporting one of its proposed physiological functions. Overall, our data continue to suggest the complex nature of the interplay between the calcium-dependent and lanthanide-dependent alcohol oxidation systems, while they also suggest that addressing the roles of these alternative systems is essential at the enzyme and community function level, in addition to the gene transcription level. IMPORTANCE The lanthanide-dependent biochemistry of living organisms remains a barely tapped area of knowledge. So far, only a handful of lanthanide-dependent alcohol dehydrogenases have been described, and their regulation by lanthanides has been demonstrated at the transcription level. Little information is available regarding the concentrations

Physiological Effect of XoxG(4) on Lanthanide-Dependent Methanotrophy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Yue; Huang, Jing; Zhao, Feng

ABSTRACT A recent surprising discovery of the activity of rare earth metals (lanthanides) as enzyme cofactors as well as transcriptional regulators has overturned the traditional assumption of biological inertia of these metals. However, so far, examples of such activities have been limited to alcohol dehydrogenases. Here we describe the physiological effects of a mutation in xoxG , a gene encoding a novel cytochrome, XoxG(4), and compare these to the effects of mutation in XoxF, a lanthanide-dependent methanol dehydrogenase, at the enzyme activity level and also at the community function level, using Methylomonas sp. strain LW13 as a model organism. Throughmore » comparative phenotypic characterization, we establish XoxG as the second protein directly involved in lanthanide-dependent metabolism, likely as a dedicated electron acceptor from XoxF. However, mutation in XoxG caused a phenotype that was dramatically different from the phenotype of the mutant in XoxF, suggesting a secondary function for this cytochrome, in metabolism of methane. We also purify XoxG(4) and demonstrate that this protein is a true cytochrome c , based on the typical absorption spectra, and we demonstrate that XoxG can be directly reduced by a purified XoxF, supporting one of its proposed physiological functions. Overall, our data continue to suggest the complex nature of the interplay between the calcium-dependent and lanthanide-dependent alcohol oxidation systems, while they also suggest that addressing the roles of these alternative systems is essential at the enzyme and community function level, in addition to the gene transcription level. IMPORTANCE The lanthanide-dependent biochemistry of living organisms remains a barely tapped area of knowledge. So far, only a handful of lanthanide-dependent alcohol dehydrogenases have been described, and their regulation by lanthanides has been demonstrated at the transcription level. Little information is available regarding the concentrations

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

NASA Astrophysics Data System (ADS)

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

Salicylamide-lanthanide complexes for use as luminescent markers

DOEpatents

Raymond, Kenneth N.; Petoud, Stephane; Cohen, Seth; Xu, Jide

2002-01-01

The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

Salicylamide-lanthanide complexes for use as luminescent markers

DOEpatents

Raymond, Kenneth N [Berkeley, CA; Petoud, Stephane [Berkeley, CA; Cohen, Seth [Boston, MA; Xu, Jide [Berkeley, CA

2008-07-29

The present invention provides luminescent lanthanide metal chelates comprising a metal ion of the lanthanide series and a complexing agent comprising at least one salicylamidyl moiety. Also provided are probes incorporating the salicylamidyl ligands of the invention and methods utilizing the ligands of the invention and probes comprising the ligands of the invention.

Lanthanide-Dependent Regulation of Methylotrophy in Methylobacteriumaquaticum Strain 22A.

PubMed

Masuda, Sachiko; Suzuki, Yutaka; Fujitani, Yoshiko; Mitsui, Ryoji; Nakagawa, Tomoyuki; Shintani, Masaki; Tani, Akio

2018-01-01

Methylobacterium species are representative of methylotrophic bacteria. Their genomes usually encode two types of methanol dehydrogenases (MDHs): MxaF and XoxF. The former is a Ca 2+ -dependent enzyme, and the latter was recently determined to be a lanthanide-dependent enzyme that is necessary for the expression of mxaF . This finding revealed the unexpected and important roles of lanthanides in bacterial methylotrophy. In this study, we performed transcriptome sequencing (RNA-seq) analysis using M. aquaticum strain 22A grown in the presence of different lanthanides. Expression of mxaF and xoxF1 genes showed a clear inverse correlation in response to La 3+ . We observed downregulation of formaldehyde oxidation pathways, high formaldehyde dehydrogenase activity, and low accumulation of formaldehyde in the reaction with cells grown in the presence of La 3+ ; this might be due to the direct oxidation of methanol to formate by XoxF1. Lanthanides induced the transcription of AT-rich genes, the function of most of which was unknown, and genes possibly related to cellular survival, as well as other MDH homologues. These results revealed not only the metabolic response toward altered primary methanol oxidation, but also the possible targets to be investigated further in order to better understand methylotrophy in the presence of lanthanides. IMPORTANCE Lanthanides have been considered unimportant for biological processes. In methylotrophic bacteria, however, a methanol dehydrogenase (MDH) encoded by xoxF was recently found to be lanthanide dependent, while the classic-type mxaFI is calcium dependent. XoxF-type MDHs are more widespread in diverse bacterial genera, suggesting their importance for methylotrophy. Methylobacterium species, representative methylotrophic and predominating alphaproteobacteria in the phyllosphere, contain both types and regulate their expression depending on the availability of lanthanides. RNA-seq analysis showed that the regulation takes place

Fracture-resistant lanthanide scintillators

DOEpatents

Doty, F Patrick [Livermore, CA

2011-01-04

Lanthanide halide alloys have recently enabled scintillating gamma ray spectrometers comparable to room temperature semiconductors (<3% FWHM energy resolutions at 662 keV). However brittle fracture of these materials upon cooling hinders the growth of large volume crystals. Efforts to improve the strength through non-lanthanide alloy substitution, while preserving scintillation, have been demonstrated. Isovalent alloys having nominal compositions of comprising Al, Ga, Sc, Y, and In dopants as well as aliovalent alloys comprising Ca, Sr, Zr, Hf, Zn, and Pb dopants were prepared. All of these alloys exhibit bright fluorescence under UV excitation, with varying shifts in the spectral peaks and intensities relative to pure CeBr.sub.3. Further, these alloys scintillate when coupled to a photomultiplier tube (PMT) and exposed to .sup.137Cs gamma rays.

The solution structure of Ln (DOTP) 5- complexxes. A comparison of lanthanide-induced paramagnetic shifts with the MMX energy-minimized structure

NASA Astrophysics Data System (ADS)

Geraldes, Carlos F. G. C.; Sherry, A. Dean; Kiefer, Garry E.

Complexes between the trivalent lanthanide ions and the macrocyclic chelate 1,4,7,10-tetraazacyclododecane- N,N',N″,N‴-tetra(methylene phosphonate) (DOTP) have been examined by high-resolution NMR spectroscopy. The proton spectra of the diamagnetic La(DOTP) 5- and Lu(DOTP) 5- complexes provide evidence for very rigid chelate structures with the ethylenediamine-containing chelate rings essentially locked into a single conformation at room temperature. The activation energy for ethylenediamine chelate ring interconversions in these complexes is approximately 100 kJ mol -1, considerably higher than that reported previously for the corresponding Ln(DOTA) - complexes (DOTA is the tetraacetate analog of DOTP). Lanthanide-induced shifts are reported for all 1H, 13C, and 31P nuclei in 11 Ln(DOTP) 5- complexes. The proton spectra of these complexes display unusually large lanthanide-induced shifts, one showing a spectrum in which the 1H resonances span 900 ppm. The contact and pseudocontact contributions to these shifts were separated using Reilley's temperature-independent method and the resulting pseudocontact lanthanide-induced NMR shifts were in excellent agreement with those calculated for a structure derived using MMX molecular modeling methods. The pseudocontact shifts provide evidence for Ln (DOTP) 5- chelates which have virtually identical structures along the lanthanide series, with the possible exception of Tm(DOTP) 5-.

Shear viscosity coefficient of liquid lanthanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, H. P., E-mail: patel.harshal2@gmail.com; Thakor, P. B., E-mail: pbthakore@rediffmail.com; Prajapati, A. V., E-mail: anand0prajapati@gmail.com

2015-05-15

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

Shear viscosity coefficient of liquid lanthanides

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.; Prajapati, A. V.

2015-05-01

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

PubMed

Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui; Su, Jing; Wang, Guanjun; Lu, Jun-Bo; Chen, Mohua; Zhou, Mingfei; Li, Jun

2016-06-06

The chemistry of lanthanides (Ln=La-Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2 (+) complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward lanthanide containing coordination polymers and nanomaterials

NASA Astrophysics Data System (ADS)

Greig, Natalie E.

The focus of this thesis is to develop lanthanide (Ln) luminescent materials through the exploration of coordination polymers and nanomaterials. Herein, dimethyl-3,4-furanedicarboxylate acid undergoes hydrolysis under hydrothermal conditions to form coordination polymers with lanthanide ions. The resulting coordination polymers exhibited luminescent properties, with quantum yields and lifetimes for the Eu- and Tb-CP of 1.14±0.31% and 0.387±0.0001 ms, and 3.33±0.82% and 0.769±0.006 ms, respectively. While the incorporation of lanthanides was not achieved in this work, progress toward the production of pure phase InP in the nanoregime has been made, using a low-cost, hydrothermal method. Though SEM and PXRD conflict, it is believed that pure InP particles with a size range of 58-81 nm were successfully synthesized.

Studies of Lanthanide Transport in Metallic Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinsuo; Taylor, Christopher

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.

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

DOE PAGES

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

2017-05-17

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, spinmore » 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

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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, spinmore » 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

Electronic Structure of Small Lanthanide Containing Molecules

NASA Astrophysics Data System (ADS)

Kafader, Jared O.; Ray, Manisha; Topolski, Josey E.; Chick Jarrold, Caroline

2016-06-01

Lanthanide-based materials have unusual electronic properties because of the high number of electronic degrees of freedom arising from partial occupation of 4f orbitals, which make these materials optimal for their utilization in many applications including electronics and catalysis. Electronic spectroscopy of small lanthanide molecules helps us understand the role of these 4f electrons, which are generally considered core-like because of orbital contraction, but are energetically similar to valence electrons. The spectroscopy of small lanthanide-containing molecules is relatively unexplored and to broaden this understanding we have completed the characterization of small cerium, praseodymium, and europium molecules using photoelectron spectroscopy coupled with DFT calculations. The characterization of PrO, EuH, EuO/EuOH, and CexOy molecules have allowed for the determination of their electron affinity, the assignment of numerous anion to neutral state transitions, modeling of anion/neutral structures and electron orbital occupation.

Fourier transform infrared characterization of the acidic phosphoric extractant system containing lanthanide

NASA Astrophysics Data System (ADS)

Shen, Y.-H.; Yao, S.-K.; Wang, D.-J.; Zhou, Weijin; Li, Ying Xue; Peng, Q.; Wu, JinGuang; Xu, Guang-Xian

1994-01-01

The aggregation states and FTIR spectra of the extractive organic phases of saponified HDEHP [di(2-ethylhexyl) phosphoric acid] (1). DMHPA [di(1-methylheptyl) phosphoric acid] (2) and (HDEHP + DMHPA) (3) containing lanthanides were studied, respectively. Transparent solution formed in system (1) while transparent gel formed in system (2) when the loading of lanthanides was more than 50%. The aggregation state of system (3) depends on the molar ratio of HDEHP:DMHPA and the loading percentage of lanthanide. From their FTIR spectra, it can be seen that the P equals O band of gel split into 1164, 1199, and 1232 cm-1, and the P-O-C band split into 1015, 1076, and 1083 cm-1 as well. The results suggested that the aggregation state of lanthanide complex changes considerably in the three systems, and multiple coordination states of p equals o with lanthanide result in the band split. Multiple interactions between P equals O, P-O-C and lanthanide ions form 3-D network in the gel.

Lanthanide-Dependent Regulation of Methylotrophy in Methylobacterium aquaticum Strain 22A

PubMed Central

Masuda, Sachiko; Suzuki, Yutaka; Fujitani, Yoshiko; Mitsui, Ryoji; Nakagawa, Tomoyuki

2018-01-01

ABSTRACT Methylobacterium species are representative of methylotrophic bacteria. Their genomes usually encode two types of methanol dehydrogenases (MDHs): MxaF and XoxF. The former is a Ca2+-dependent enzyme, and the latter was recently determined to be a lanthanide-dependent enzyme that is necessary for the expression of mxaF. This finding revealed the unexpected and important roles of lanthanides in bacterial methylotrophy. In this study, we performed transcriptome sequencing (RNA-seq) analysis using M. aquaticum strain 22A grown in the presence of different lanthanides. Expression of mxaF and xoxF1 genes showed a clear inverse correlation in response to La3+. We observed downregulation of formaldehyde oxidation pathways, high formaldehyde dehydrogenase activity, and low accumulation of formaldehyde in the reaction with cells grown in the presence of La3+; this might be due to the direct oxidation of methanol to formate by XoxF1. Lanthanides induced the transcription of AT-rich genes, the function of most of which was unknown, and genes possibly related to cellular survival, as well as other MDH homologues. These results revealed not only the metabolic response toward altered primary methanol oxidation, but also the possible targets to be investigated further in order to better understand methylotrophy in the presence of lanthanides. IMPORTANCE Lanthanides have been considered unimportant for biological processes. In methylotrophic bacteria, however, a methanol dehydrogenase (MDH) encoded by xoxF was recently found to be lanthanide dependent, while the classic-type mxaFI is calcium dependent. XoxF-type MDHs are more widespread in diverse bacterial genera, suggesting their importance for methylotrophy. Methylobacterium species, representative methylotrophic and predominating alphaproteobacteria in the phyllosphere, contain both types and regulate their expression depending on the availability of lanthanides. RNA-seq analysis showed that the regulation takes place

Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants

PubMed Central

Basualto, Carlos; Gaete, José; Molina, Lorena; Valenzuela, Fernando; Yañez, Claudia; Marco, Jose F

2015-01-01

In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe3O4) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core–shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g−1 and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12–14 mgLa/gMNP. The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet. PMID:27877811

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

DOE PAGES

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias; ...

2017-11-26

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zehnder, Ralph A.; Jenkins, James; Zeller, Matthias

Here, using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln 2(Glut) 2Cl 2(H 2O) 8]·2H 2O·THF, with Ln = La , Ce, Pr, Nd. They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO 10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln 2(Glut) 3(H 2O) 3]·5H 2O, withmore » Ln = La, Ce, Pr, and [Nd 2(Glut) 3(H 2O) 2]·3.5H 2O.« less

Effect of indium addition in U-Zr metallic fuel on lanthanide migration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Yeon Soo; Wiencek, T.; O'Hare, E.

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 wasmore » 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.« less

Semiempirical Quantum Chemistry Model for the Lanthanides: RM1 (Recife Model 1) Parameters for Dysprosium, Holmium and Erbium

PubMed Central

Filho, Manoel A. M.; Dutra, José Diogo L.; Rocha, Gerd B.; Simas, Alfredo M.; Freire, Ricardo O.

2014-01-01

Complexes of dysprosium, holmium, and erbium find many applications as single-molecule magnets, as contrast agents for magnetic resonance imaging, as anti-cancer agents, in optical telecommunications, etc. Therefore, the development of tools that can be proven helpful to complex design is presently an active area of research. In this article, we advance a major improvement to the semiempirical description of lanthanide complexes: the Recife Model 1, RM1, model for the lanthanides, parameterized for the trications of Dy, Ho, and Er. By representing such lanthanide in the RM1 calculation as a three-electron atom with a set of 5 d, 6 s, and 6 p semiempirical orbitals, the accuracy of the previous sparkle models, mainly concentrated on lanthanide-oxygen and lanthanide-nitrogen distances, is extended to other types of bonds in the trication complexes’ coordination polyhedra, such as lanthanide-carbon, lanthanide-chlorine, etc. This is even more important as, for example, lanthanide-carbon atom distances in the coordination polyhedra of the complexes comprise about 30% of all distances for all complexes of Dy, Ho, and Er considered. Our results indicate that the average unsigned mean error for the lanthanide-carbon distances dropped from an average of 0.30 Å, for the sparkle models, to 0.04 Å for the RM1 model for the lanthanides; for a total of 509 such distances for the set of all Dy, Ho, and Er complexes considered. A similar behavior took place for the other distances as well, such as lanthanide-chlorine, lanthanide-bromine, lanthanide, phosphorus and lanthanide-sulfur. Thus, the RM1 model for the lanthanides, being advanced in this article, broadens the range of application of semiempirical models to lanthanide complexes by including comprehensively many other types of bonds not adequately described by the previous models. PMID:24497945

Lanthanide-halide based humidity indicators

DOEpatents

Beitz, James V [Hinsdale, IL; Williams, Clayton W [Chicago, IL

2008-01-01

The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

The Lanthanides: The Forgotten Elements but an Excellent Teaching Resource

ERIC Educational Resources Information Center

Talbot, Christopher

2017-01-01

This article aims to introduce the lanthanides (also known as the lanthanoids) to teachers and their students. The lanthanides are not mere "footnotes" at the bottom of the periodic table but make up a group of interesting and unique metallic elements. They and their compounds have widespread technological applications that have become…

The effect of lanthanides on photosynthesis, growth, and chlorophyll profile of the green alga Desmodesmus quadricauda.

PubMed

Řezanka, Tomáš; Kaineder, Katrin; Mezricky, Dana; Řezanka, Michal; Bišová, Kateřina; Zachleder, Vilém; Vítová, Milada

2016-12-01

Lanthanides (La, Gd, Nd, Ce) accumulated in the green alga Desmodesmus quadricauda but their intracellular localizations were distinctly different: lanthanum and gadolinium were localized in cytoplasm, while neodymium and cerium were in the chloroplast. The effect of lanthanum and neodymium, as representatives of these two groups, on growth, chlorophyll content and photosynthetic rate at different light intensities was studied. At the lowest light intensity used (50 µmol photons m -2  s -1 ), in the presence of lanthanides (Nd), growth was enhanced by as much as 36 % over lanthanide free control, and the photosynthetic rate increased by up to 300 %. At high light intensities (238, 460, and 750 µmol photons m -2 s -1 ), photosynthetic rate increased markedly, but there was no significant difference between rates in the presence or absence of lanthanides. However, growth, measured as a percentage of dry weight, if compared with lanthanide free control, increased at all light intensities (31, 39, and 20 %, respectively). The total amount of chlorophyll after lanthanide treatment increased by up to 21 % relative to the control culture, mainly due to an increase in the level of chlorophyll b. Addition of lanthanides caused a change in the chlorophyll a/b ratio from 4.583 in control cultivation, to 1.05. Possible mechanisms of lanthanide-induced photosynthetic change, alterations in photosynthetic structures, and increases in growth are discussed and compared with findings in higher plants. The hypothesis that the lanthanide effect could be due to formation of lanthanide-pheophytins was not confirmed as lanthanide pheophytins were not found in D. quadricauda. Furthermore, we have shown that the preferential incorporation of heavy isotopes of magnesium, namely 25 Mg and 26 Mg, into chlorophyll during photosynthesis that occurred in controls was diminished in the presence of lanthanides.

Robust lanthanide emitters in polyelectrolyte thin films for photonic applications

NASA Astrophysics Data System (ADS)

Greenspon, Andrew S.; Marceaux, Brandt L.; Hu, Evelyn L.

2018-02-01

Trivalent lanthanides provide stable emission sources at wavelengths spanning the ultraviolet through the near infrared with uses in telecommunications, lighting, and biological sensing and imaging. We describe a method for incorporating an organometallic lanthanide complex within polyelectrolyte multilayers, producing uniform, optically active thin films on a variety of substrates. These films demonstrate excellent emission with narrow linewidths, stable over a period of months, even when bound to metal substrates. Utilizing different lanthanides such as europium and terbium, we are able to easily tune the resulting wavelength of emission of the thin film. These results demonstrate the suitability of this platform as a thin film emitter source for a variety of photonic applications such as waveguides, optical cavities, and sensors.

Thermodynamical properties of liquid lanthanides-A variational approach

NASA Astrophysics Data System (ADS)

Patel, H. P.; Thakor, P. B.; Sonvane, Y. A.

2015-06-01

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.

Thermodynamical properties of liquid lanthanides-A variational approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, H. P.; Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat; Thakor, P. B., E-mail: pbthakor@rediffmail.com

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.

Hot-pressed silicon nitride with various lanthanide oxides as sintering additives

NASA Technical Reports Server (NTRS)

Ueno, K.; Toibana, Y.

1984-01-01

The effects of addition of various lanthanide oxides and their mixture with Y2O3 on the sintering of Si3N4 were investigated. The addition of simple and mixed lanthanide oxides promoted the densification of Si3N4 in hot-pressing at 1800 C under 300-400kg/ centimeters squared for 60 min. The crystallization of yttrium and lanthanide-silicon oxynitrides which was observed inn the sintered body containing yttrium-lanthanide mixed oxides as additives led to the formation of a highly refractory Si3N4 ceramic having a bending strength of 82 and 84 kg/millimeters squared at room temperature and 1300 C respectively. In a Y2O3+La2O3 system, a higher molar ratio of La2O3 to Y2O3 gave a higher hardness and strength at high temperatures. It was found that 90 min was an optimum sintering time for the highest strength.

Nanometrization of Lanthanide-Based Coordination Polymers.

PubMed

Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

2015-11-23

Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Determination of Energy Transfer Processes and Influence of Symmetry in Lanthanide(III) Complexes: Methodological Considerations.

PubMed

Beltrán-Leiva, María J; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2018-05-07

This work presents a theoretical protocol to analyze the symmetry effect on the allowed character of the transitions and to estimate the probability of energy transfer in lanthanide(III) complexes. For this purpose, a complete study was performed based on the multireference CASSCF/PT2 technique along with TDDFT, to build the energy level diagrams and determine the spectral overlap integrals, respectively. This approach was applied on a series of LnIII complexes, viz. [LnCl 3 (DMF) 2 (Dpq)]/[Ln(NO 3 ) 3 (DMF) 2 (Dpq)], where Ln = Sm III , Tb III , Er III /Eu III , Nd III and dpq = dipyridoquinoxaline, synthesized and characterized by Patra et al. ( Dalton Trans. 2015 , 44 ( 46 ), 19844 - 19855 ; CrystEngComm 2016 , 18 ( 23 ), 4313 - 4322 ; Inorg. Chim. Acta 2016 , 451 , 73 - 81 ). A fragmentation scheme was applied where both the ligand and the lanthanide fragments were treated separately but at the same level of theory. The symmetry analysis only partially reproduced the expected results, and a more detailed analysis of the crystal field became necessary. On the other hand, the most probable energy transfer pathways that take place in the complexes were elucidated from the energy gaps between the ligand-localized triplet state and the emitting levels of the lanthanide fragments. These gaps, which are related to the energy transfer rate, properly reproduced the trend reported experimentally for the best and worst yields. Finally, the spectral overlap integral was calculated from the emission spectra of the dpq ligand and the absorption spectra of the lanthanide fragment. The obtained values are in good agreement with the quantum yields calculated for the systems. The most remarkable aspect of this protocol was its ability to explain the emission and nonemission of the studied compounds.

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.

PubMed

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.

Lanthanide doped strontium-barium cesium halide scintillators

DOEpatents

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.

MxaY regulates the lanthanide-mediated methanol dehydrogenase switch in Methylomicrobium buryatense

DOE PAGES

Chu, Frances; Beck, David A. C.; Lidstrom, Mary E.

2016-09-07

Many methylotrophs, microorganisms that consume carbon compounds lacking carbon–carbon bonds, use two different systems to oxidize methanol for energy production and biomass accumulation. The MxaFI methanol dehydrogenase (MDH) contains calcium in its active site, while the XoxF enzyme contains a lanthanide in its active site. The genes encoding the MDH enzymes are differentially regulated by the presence of lanthanides. In this study, we found that the histidine kinase MxaY controls the lanthanide-mediated switch in Methylomicrobium buryatense 5GB1C. MxaY controls the transcription of genes encoding MxaFI and XoxF at least partially by controlling the transcript levels of the orphan response regulatormore » MxaB. We identify a constitutively active version of MxaY, and identify the mutated residue that may be involved in lanthanide sensing. Finally, we find evidence to suggest that tight control of active MDH production is required for wild-type growth rates.« less

Use of lanthanides to alleviate the effects of metal ion-deficiency in Desmodesmus quadricauda (Sphaeropleales, Chlorophyta)

PubMed Central

Goecke, Franz; Jerez, Celia G.; Zachleder, Vilém; Figueroa, Félix L.; Bišová, Kateřina; Řezanka, Tomáš; Vítová, Milada

2015-01-01

Lanthanides are biologically non-essential elements with wide applications in technology and industry. Their concentration as environmental contaminants is, therefore, increasing. Although non-essential, lanthanides have been proposed (and even used) to produce beneficial effects in plants, even though their mechanisms of action are unclear. Recently, it was suggested that they may replace essential elements. We tested the effect of low concentrations of lanthanides on the common freshwater microalga Desmodesmus quadricauda, grown under conditions of metal ion-deficiency (lower calcium or manganese concentrations). Our goal was to test if lanthanides can replace essential metals in their functions. Physiological stress was recorded by studying growth and photosynthetic activity using a pulse amplitude modulation (PAM) fluorimeter. We found that nutrient stress reduced parameters of growth and photosynthesis, such as maximal quantum yield, relative electron transport rate, photon capturing efficiency and light saturation irradiance. After adding low concentrations of five lanthanides, we confirmed that they can produce a stimulatory effect on microalgae, depending on the nutrient (metal) deprivation. In the case of a calcium deficit, the addition of lanthanides partly alleviated the adverse effects, probably by a partial substitution of the element. In contrast, with manganese deprivation (and at even lower concentrations), lanthanides enhanced the deleterious effect on cellular growth and photosynthetic competence. These results show that lanthanides can replace essential elements, but their effects on microalgae depend on stress and the nutritional state of the microalgae, raising the possibility of environmental impacts at even low concentrations. PMID:25674079

Sol-Gel Electrolytes Incorporated by Lanthanide Luminescent Materials and Their Photophysical Properties

NASA Astrophysics Data System (ADS)

Yu, Chufang; Zhang, Zhengyang; Fu, Meizhen; Gao, Jinwei; Zheng, Yuhui

2017-10-01

A group of silica gel electrolytes with lanthanide luminescent hybrid materials were assembled and investigated. Photophysical studies showed that terbium and europium hybrids displayed characteristic green and red emissions within the electrolytes. The influence of different concentration of the lanthanide hybrids on the electrochemical behavior of a gelled electrolyte valve-regulated lead-acid battery were studied through cyclic voltammograms, electrochemical impedance spectroscopy, water holding experiments and mobility tests. The morphology and particle size were analyzed by scanning electron microscopy. The results proved that lanthanide (Tb3+/Eu3+) luminescent materials are effective additives which will significantly improve the electrochemical properties of lead-acid batteries.

Giant exchange interaction in mixed lanthanides

PubMed Central

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

Lanthanide heterometallic terephthalates: Concentration quenching and the principles of the "multiphotonic emission"

NASA Astrophysics Data System (ADS)

Utochnikova, V. V.; Grishko, A. Yu.; Koshelev, D. S.; Averin, A. A.; Lepnev, L. S.; Kuzmina, N. P.

2017-12-01

The principles of the "multiphotonic emission", i.e. multiple emission from one lanthanide ion, in heterometallic lanthanide terephthalates were determined. Thanks to it, another system with the same effect, namely EuxY1-x(dbm)3(Phen) (Hdbm - dibenzoylmethanate, Phen - o-phenanthroline (mistape)) was found. The criteria for concentration quenching appearance were formulated and demonstrated.

Ion-Size-Dependent Formation of Mixed Titanium/Lanthanide Oxo Clusters.

PubMed

Artner, Christine; Kronister, Stefan; Czakler, Matthias; Schubert, Ulrich

2014-11-01

The mixed-metal oxo clusters LnTi 4 O 3 (O i Pr) 2 (OMc) 11 (Ln = La, Ce; OMc = methacrylate), Ln 2 Ti 6 O 6 (OMc) 18 (HO i Pr) (Ln = La, Ce, Nd, Sm) and Ln 2 Ti 4 O 4 (OMc) 14 (HOMc) 2 (Ln = Sm, Eu, Gd, Ho) have been synthesized from titanium isopropoxide, the corresponding lanthanide acetate and methacrylic acid. The type of cluster obtained strongly depends on the size of the lanthanide ion.

Analysis of Performance of Selected AFC, ATF Fuels, and Lanthanide Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Unal, Cetin; Galloway, Jack D.

2015-09-29

We started to look at the performance of ATF concept in LWRs late in FY14 and finish our studies in FY15. The work has been presented in AFC review meetings, ICAPP and TOPFUEL conferences. The final version of the work is accepted for publication in Nuclear Engineering and Science Journal (NES). The copy of ICAPP and NES papers are attached separately to this document as our milestone deliverables. We made an important progress in the modeling of lanthanide transport in FY15. This work produced an ANS Winter Meeting paper and GLOBAL 2015 paper. GLOBAL 2015 paper is also attached asmore » deliverable of FY15. The work on the lanthanide transport is preliminary. We are exploring other potential mechanisms, in addition to “liquid-like” diffusion mechanisms, proposed by Robert Mariani [1] before we analyze data that will be taken by Ohio State University. This year, we concentrate on developing diffusion kernels and principles of modeling. Next year, this work will continue and analyze the Ohio State data and develop approaches to solve multicomponent diffusion. In addition to three papers we attached to this report, we have done some research on coupling and the development of gas release model for metallic fuels in FY15. They are also preliminary in nature; therefore, we give the summary of what we found rather than an extended report that will be done in FY16.« less

Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pindwal, Aradhana

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.

Method for providing oxygen ion vacancies in lanthanide oxides

DOEpatents

Kay, D. Alan R.; Wilson, William G.

1989-12-05

A method for desulfurization of fuel gases resulting from the incomplete combustion of sulfur containing hydrocarbons whereby the gases are treated with lanthanide oxides containing large numbers of oxygen-ion vacancies providing ionic porosity which enhances the ability of the lanthanide oxides to react more rapidly and completely with the sulfur in the fuel gases whereby the sulfur in such gases is reduced to low levels suitable for fuels for firing into boilers of power plants generating electricity with steam turbine driven generators, gas turbines, fuel cells and precursors for liquid fuels such as methanol and the like.

Lattice dynamics of the lanthanides: Samarium at high pressure

NASA Astrophysics Data System (ADS)

Olijnyk, H.; Jephcoat, A. P.

2005-02-01

Sm was studied by Raman spectroscopy at pressures up to 20 GPa. The Raman-active phonon modes, both of the Sm-type phase and the dhcp phase, show a frequency decrease as pressure increases. There is evidence that the entire structural sequence hcp → Sm-type → dhcp → fcc under pressure for the individual regular lanthanides is associated with softening of certain acoustic and optical-phonon modes as well as elastic anomalies. Comparison is made to corresponding transitions between close-packed lattices in other metals and possible relations to the lanthanide's electronic structure are addressed.

Parameter study of r-process lanthanide production and heating rates in kilonovae

NASA Astrophysics Data System (ADS)

Lippuner, Jonas; Roberts, Luke F.

2015-04-01

Explosive r-process nucleosynthesis in material ejected during compact object mergers may lead to radioactively powered transients called kilonovae. The timescale and peak luminosity of these transients are sensitive to the composition of the material after nuclear burning ceases, as the composition determines the local heating rate from nuclear decays and the opacity. The presence of lanthanides in the ejecta can drastically increase the opacity. We use the new general-purpose nuclear reaction network SkyNet to run a parameter study of r-process nucleosynthesis for a range of initial electron fractions Ye, initial entropies s, and density decay timescales τ. We find that the ejecta is lanthanide-free for Ye >~ 0 . 22 - 0 . 3 , depending on s and τ. The heating rate is insensitive to s and τ, but certain, larger values of Ye lead to reduced heating rates, because single nuclides dominate the heating. With a simple model we estimate the luminosity, time, and effective temperature at the peak of the light curve. Since the opacity is much lower in the lanthanide-free case, we find the luminosity peaks much earlier at ~ 1 day vs. ~ 15 days in the lanthanide-rich cases. Although there is significant variation in the heating rate with Ye, changes in the heating rate do not mitigate the effect of the lanthanides. This research is partially supported by NSF under Award Numbers AST-1333520 and AST-1205732.

A Bridge to Coordination Isomer Selection in Lanthanide(III) DOTA-tetraamide Complexes

PubMed Central

Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircso, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A.Dean

2008-01-01

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other, in consequence inclusion of the bridging unit in the complexes means only a twisted square antiprismatic coordination geometry is observed for complexes of 8O2-bridged-DOTAM. PMID:17295475

Separation of Trivalent Actinides from Lanthanides Using a Capillary Electrophoresis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mori, Tomotaka; Ishii, Yasuo; Hayashi, Kazunori

2007-07-01

A separation of {sup 241}Am(III) from {sup 152,154}Eu(III) was carried out using a capillary electrophoresis technique in a mixed solvent (CH{sub 3}OH/H{sub 2}O) system containing thiocyanate ion. First, the formation constants ({beta}{sub n}) between thiocyanate ion and Eu(III) or Am(III) were investigated in the mixed solvent solutions by a back-extraction technique using bis (2-ethylhexyl) hydrogen phosphate-toluene. The mean charges calculated on the basis of the data of {beta}{sub n} for Eu(III) were comparatively higher than those for Am(III). Based on the differences between the mean charges of Eu(III) and Am(III), separations for Am(III)/Eu(III) by means of capillary electrophoresis technique weremore » tried in the (H{sup +}, Na{sup +})(SCN{sup -}, ClO{sub 4}{sup -}) mixed solvent solutions. It was proved that Am(III) was completely separated from Eu(III). (authors)« less

Lanthanide Oleates: Chelation, Self-assembly, and Exemplification of Ordered Nanostructured Colloidal Contrast Agents for Medical Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Guozhen; Conn, Charlotte E.; Drummond, Calum J.

2010-01-12

Eight lanthanide(III) oleates have been prepared and characterized. The chelation and self-assembly structures of these rare-earth oleates have been studied by elemental analysis, Fourier transfer infrared spectroscopy (FTIR), and X-ray powder diffraction (XRD) analysis. Elemental analysis and FTIR results indicate that three oleate anions are complexed with one lanthanide cation and, with the exception of anhydrous cerium(III) oleate, form either a mono- or a hemihydrate. The X-ray analysis showed that the neat lanthanide soaps have a lamellar bilayer structure at room temperature. The thermal behavior has been investigated by cross-polarized optical microscopy (POM), differential scanning calorimetry (DSC), and thermogravimetric analysismore » (TGA). POM scans showed that all the lanthanide oleates form a lamellar phase in the presence of excess water. Small-angle X-ray scattering (SAXS) and XRD were used to investigate the internal structure of the bulk lanthanide oleates in excess water, and these X-ray results confirmed that the lanthanide oleates do not swell in water. Select lanthanide oleates were dispersed in water to form nonswelling lamellar submicrometer particles, confirmed by dynamic light scattering (DLS) and synchrotron SAXS measurements. NMR results indicated that colloidal dispersions of lanthanide oleates containing paramagnetic ions, such as gadolinium(III), terbium(III), and dysprosium(III), have a significant effect on the longitudinal (T{sub 1}) and transverse (T{sub 2}) relaxation times of protons in water. Time-resolved fluorescence measurements have demonstrated that colloidal dispersions of europium(III) oleate exhibit strong luminescence. The rare earth metal soaps exemplify the potential of self-assembled chelating amphiphiles as contrast agents in medical imaging modalities such as magnetic resonance imaging (MRI) and fluorescence imaging.« less

Near-infrared emissive lanthanide hybridized nanofibrillated cellulose nanopaper as ultraviolet filter.

PubMed

Xue, Bailiang; Zhang, Zhao; Sun, Yongchang; Wang, Junjie; Jiang, Huie; Du, Min; Chi, Congcong; Li, Xinping

2018-04-15

The lanthanide complexes [Yb(fac) 3 (H 2 O) 2 , Yb(tta) 3 (H 2 O) 2 , Nd(tta) 3 (H 2 O) 2 ] functionalized nanofibrillated cellulose (Ln-NFC) nanopapers with near-infrared (NIR) luminescence and high transparency are rapidly fabricated after solvent exchange using a simple suction filtration film-making method. The effects of NFC and lanthanide complexes content on their photophysical properties of Ln-NFC nanopapers and their mechanism of UV filters are fully investigated. With increasing lanthanide complexes content in the Ln-NFC nanopaper, their transmittances are gradually decreased while their NIR luminescences are obviously increased. Yb-fac NFC nanopaper has high UVB block rate at 298 nm, whereas the high UVA block ratio of Ln-tta NFC nanopaper is observed at 345 nm. Ln-NFC nanopapers show a much higher photostability without decomposition under UV irradiation at 365 nm over 5 h. The emission spectra of the Ln-NFC nanopaper process the NIR luminescence of the corresponding lanthanide ions through the efficient triplet-triplet energy transfer process. Ln-NFC nanopapers can bring a brilliant future for UV filters, labeling fields and marking soft materials application. Copyright © 2018 Elsevier Ltd. All rights reserved.

Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turov, A.V.; Khilya, V.P.

1994-10-01

The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn; Chen Wulin; Zheng Jun

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-Signmore » 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.« less

Chemical purification of lanthanides for low-background experiments

NASA Astrophysics Data System (ADS)

Boiko, R. S.

2017-10-01

There are many potentially active isotopes among the lanthanide elements which are possible to use for low-background experiments to search for double β decay, dark matter, to investigate rare α and β decays. These kind of experiments require very low level of radioactive contamination, but commercially available compounds of lanthanides are always contamined by uranium, thorium, radium, potassium, etc. A simple chemical method based on liquid-liquid extraction has been applied for the purification of CeO2, Nd2O3 and Gd˙2O˙3 from radioactive traces. Detailed schemes of purification procedure are described. Measurements by using HPGe spectrometry demonstrate high efficiency in K, Ra, Th, U contaminations reduction on at least one order of magnitude.

EXAFS characterisation of metal bonding in highly luminescent, UV stable, water-soluble and biocompatible lanthanide complexes

NASA Astrophysics Data System (ADS)

Kalyakina, A.; Utochnikova, V.; Trigub, A.; Zubavichus, Y.; Kuzmina, N.; Bräse, S.

2016-05-01

The combination of X-ray diffraction with EXAFS was employed to assess the coordination environment of lanthanide complexes in solutions. This method is based on the assumption that the local structure of lanthanide complexes in solution combines elements of the crystal structure of the complex in the solid state (single- or polycrystalline) and the elements of the local structure of a lanthanide salt, completely dissociated in the solvent (usually chlorides). The success of this approach is demonstrated with the lanthanide (III) 2,3,4,5,6-pentafluorobenzoate complexes, where the local structure in aqueous and methanol solutions were estimated. Moreover, the dissociation degree of the complexes in aqueous and methanol solutions was evaluated.

Separation of the rare earths by anion-exchange in the presence of lactic acid

NASA Technical Reports Server (NTRS)

Faris, J. P.

1969-01-01

Investigation of adsorption of rare earths and a few other elements to an anion-exchange resin from mixed solvents containing lactic acid shows that the lanthanides are absorbed more strongly than from the alpha-hydroxyisobutryric acid system, but with less separation between adjacent members of the series.

Materials and methods for the separation of oxygen from air

DOEpatents

MacKay, Richard; Schwartz, Michael; Sammells, Anthony F.

2003-07-15

Metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes having the formula: O.sub.5+z where: x and x' are greater than 0; y and y' are greater than 0; x+x' is equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides, Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof and B" is Co or Mg, with the exception that when B" is Mg, A' and A" are not Mg. The metal oxides are useful for preparation of dense membranes which may be formed from dense thin films of the mixed metal oxide on a porous metal oxide element. The invention also provides methods and catalytic reactors for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula.

Radiation-induced disorder in compressed lanthanide zirconates.

PubMed

Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

2018-02-28

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange.

PubMed

Shen, Xiang; Yan, Bing

2016-04-15

A multicolored photoluminescent hybrid system based on lanthanide ions-doped metal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application. Copyright © 2016 Elsevier Inc. All rights reserved.

DFTB+ and lanthanides

NASA Astrophysics Data System (ADS)

Hourahine, B.; Aradi, B.; Frauenheim, T.

2010-07-01

DFTB+ 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.

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

PubMed

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.

Complexation of lanthanides and actinides by acetohydroxamic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, R.J.; Sinkov, S.I.; Choppin, G.R.

2008-07-01

Acetohydroxamic acid (AHA) has been proposed as a suitable reagent for the complexant-based, as opposed to reductive, stripping of plutonium and neptunium ions from the tributylphosphate solvent phase in advanced PUREX or UREX processes designed for future nuclear-fuel reprocessing. Stripping is achieved by the formation of strong hydrophilic complexes with the tetravalent actinides in nitric acid solutions. To underpin such applications, knowledge of the complexation constants of AHA with all relevant actinide (5f) and lanthanide (4f) ions is therefore important. This paper reports the determination of stability constants of AHA with the heavier lanthanide ions (Dy-Yb) and also U(IV) andmore » Th(IV) ions. Comparisons with our previously published AHA stability-constant data for 4f and 5f ions are made. (authors)« less

The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

NASA Astrophysics Data System (ADS)

Platt, Andrew W. G.; Singh, Kuldip

2016-05-01

The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

Extraction chromatographic separation of Am(III) and Eu(III) by TPEN-immobilized gel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeshita, K.; Ogata, T.; Oaki, H.

2013-07-01

A TPEN derivative with 4 vinyl groups, N,N,N',N' -tetrakis-(4-propenyloxy-2-pyridylmethyl)ethylenediamine (TPPEN) was synthesized for the separation of trivalent minor actinides (Am(III)) and lanthanides (Eu(III)). A co-polymer gel with TPPEN and N-isopropylacrylamide (NIPA) showed a high separation factor of Am(III) over Eu(III) (SF[Am/Eu]), which was evaluated to be 26 at pH=5. Thin film of NIPA-TPPEN gel (average thickness: 2-40 nm) was immobilized on the pore surface in porous silica particles (particle diameter : 50 μm, average pore diameter : 50 and 300 nm) and a chromatographic column (diameter: 6 mm, height: 11 mm) packed with the gel-coated particles was prepared. A smallmore » amount of weakly acidic solution (pH=4) containing Am(III) and Eu(III) was supplied in the column and the elution tests of Am(III) and Eu(III) were carried out. Eu(III) was recovered separately by a weakly acidic eluent (pH=4) at 313 K and Am(III) by a highly acidic eluent (pH=2) at 298 K. These results suggest that the contentious separation of minor actinides and lanthanides is attainable by a new extraction chromatographic process with two columns adjusted to 298 K and 313 K. (authors)« less

Picosecond dynamics from lanthanide chloride melts

NASA Astrophysics Data System (ADS)

Kalampounias, Angelos G.

2012-12-01

The picosecond dynamics of molten lanthanide chlorides is studied by means of vibrational spectroscopy. Polarized Raman spectra of molten LaCl3, NdCl3, GdCl3, DyCl3, HoCl3 and YCl3 are fitted to a model enabling to obtain the times of vibrational dephasing, tν and vibrational frequency modulation tω. Our aim is to find possible sensitive indicators of short-time dynamics. It has been found that all lanthanide chlorides exhibit qualitative similarities in the vibrational relaxation and frequency modulation times in the molten state. It appears that the vibrational correlation functions of all melts comply with the Rothschild approach assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α indicates the deviation of the melts from the model simple liquid and the similar local environment in which the oscillator is placed and with which it is coupled. The "packing" of the anions around central La3+ cation seems to be the key factor for the structure and the dynamics of the melts. The results are discussed in the framework of the current phenomenological status of the field.

Nanoparticles of adaptive supramolecular networks self-assembled from nucleotides and lanthanide ions.

PubMed

Nishiyabu, Ryuhei; Hashimoto, Nozomi; Cho, Ten; Watanabe, Kazuto; Yasunaga, Takefumi; Endo, Ayataka; Kaneko, Kenji; Niidome, Takuro; Murata, Masaharu; Adachi, Chihaya; Katayama, Yoshiki; Hashizume, Makoto; Kimizuka, Nobuo

2009-02-18

Amorphous nanoparticles of supramolecular coordination polymer networks are spontaneously self-assembled from nucleotides and lanthanide ions in water. They show intrinsic functions such as energy transfer from nucleobase to lanthanide ions and excellent performance as contrast enhancing agents for magnetic resonance imaging (MRI). Furthermore, adaptive inclusion properties are observed in the self-assembly process: functional materials such as fluorescent dyes, metal nanoparticles, and proteins are facilely encapsulated. Dyes in these nanoparticles fluoresce in high quantum yields with a single exponential decay, indicating that guest molecules are monomerically wrapped in the network. Gold nanoparticles and ferritin were also wrapped by the supramolecular shells. In addition, these nucleotide/lanthanide nanoparticles also serve as scaffolds for immobilizing enzymes. The adaptive nature of present supramolecular nanoparticles provides a versatile platform that can be utilized in a variety of applications ranging from material to biomedical sciences. As examples, biocompatibility and liver-directing characteristics in in vivo tissue localization experiments are demonstrated.

Magnetic relaxation pathways in lanthanide single-molecule magnets.

PubMed

Blagg, Robin J; Ungur, Liviu; Tuna, Floriana; Speak, James; Comar, Priyanka; Collison, David; Wernsdorfer, Wolfgang; McInnes, Eric J L; Chibotaru, Liviu F; Winpenny, Richard E P

2013-08-01

Single-molecule magnets are compounds that exhibit magnetic bistability caused by an energy barrier for the reversal of magnetization (relaxation). Lanthanide compounds are proving promising as single-molecule magnets: recent studies show that terbium phthalocyanine complexes possess large energy barriers, and dysprosium and terbium complexes bridged by an N2(3-) radical ligand exhibit magnetic hysteresis up to 13 K. Magnetic relaxation is typically controlled by single-ion factors rather than magnetic exchange (whether one or more 4f ions are present) and proceeds through thermal relaxation of the lowest excited states. Here we report polylanthanide alkoxide cage complexes, and their doped diamagnetic yttrium analogues, in which competing relaxation pathways are observed and relaxation through the first excited state can be quenched. This leads to energy barriers for relaxation of magnetization that exceed 800 K. We investigated the factors at the lanthanide sites that govern this behaviour.

Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth.

PubMed

Vu, Huong N; Subuyuj, Gabriel A; Vijayakumar, Srividhya; Good, Nathan M; Martinez-Gomez, N Cecilia; Skovran, Elizabeth

2016-04-01

Methylobacterium extorquens AM1 has two distinct types of methanol dehydrogenase (MeDH) enzymes that catalyze the oxidation of methanol to formaldehyde. MxaFI-MeDH requires pyrroloquinoline quinone (PQQ) and Ca in its active site, while XoxF-MeDH requires PQQ and lanthanides, such as Ce and La. Using MeDH mutant strains to conduct growth analysis and MeDH activity assays, we demonstrate that M. extorquens AM1 has at least one additional lanthanide-dependent methanol oxidation system contributing to methanol growth. Additionally, the abilities of different lanthanides to support growth were tested and strongly suggest that both XoxF and the unknown methanol oxidation system are able to use La, Ce, Pr, Nd, and, to some extent, Sm. Further, growth analysis using increasing La concentrations showed that maximum growth rate and yield were achieved at and above 1 μM La, while concentrations as low as 2.5 nM allowed growth at a reduced rate. Contrary to published data, we show that addition of exogenous lanthanides results in differential expression from the xox1 and mxa promoters, upregulating genes in the xox1 operon and repressing genes in the mxa operon. Using transcriptional reporter fusions, intermediate expression from both the mxa and xox1 promoters was detected when 50 to 100 nM La was added to the growth medium, suggesting that a condition may exist under which M. extorquens AM1 is able to utilize both enzymes simultaneously. Together, these results suggest that M. extorquens AM1 actively senses and responds to lanthanide availability, preferentially utilizing the lanthanide-dependent MeDHs when possible. The biological role of lanthanides is a nascent field of study with tremendous potential to impact many areas in biology. Our studies demonstrate that there is at least one additional lanthanide-dependent methanol oxidation system, distinct from the MxaFI and XoxF MeDHs, that may aid in classifying additional environmental organisms as methylotrophs. Further

Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth

PubMed Central

Vu, Huong N.; Subuyuj, Gabriel A.; Vijayakumar, Srividhya; Good, Nathan M.; Martinez-Gomez, N. Cecilia

2016-01-01

ABSTRACT Methylobacterium extorquens AM1 has two distinct types of methanol dehydrogenase (MeDH) enzymes that catalyze the oxidation of methanol to formaldehyde. MxaFI-MeDH requires pyrroloquinoline quinone (PQQ) and Ca in its active site, while XoxF-MeDH requires PQQ and lanthanides, such as Ce and La. Using MeDH mutant strains to conduct growth analysis and MeDH activity assays, we demonstrate that M. extorquens AM1 has at least one additional lanthanide-dependent methanol oxidation system contributing to methanol growth. Additionally, the abilities of different lanthanides to support growth were tested and strongly suggest that both XoxF and the unknown methanol oxidation system are able to use La, Ce, Pr, Nd, and, to some extent, Sm. Further, growth analysis using increasing La concentrations showed that maximum growth rate and yield were achieved at and above 1 μM La, while concentrations as low as 2.5 nM allowed growth at a reduced rate. Contrary to published data, we show that addition of exogenous lanthanides results in differential expression from the xox1 and mxa promoters, upregulating genes in the xox1 operon and repressing genes in the mxa operon. Using transcriptional reporter fusions, intermediate expression from both the mxa and xox1 promoters was detected when 50 to 100 nM La was added to the growth medium, suggesting that a condition may exist under which M. extorquens AM1 is able to utilize both enzymes simultaneously. Together, these results suggest that M. extorquens AM1 actively senses and responds to lanthanide availability, preferentially utilizing the lanthanide-dependent MeDHs when possible. IMPORTANCE The biological role of lanthanides is a nascent field of study with tremendous potential to impact many areas in biology. Our studies demonstrate that there is at least one additional lanthanide-dependent methanol oxidation system, distinct from the MxaFI and XoxF MeDHs, that may aid in classifying additional environmental organisms as

Gold coated lanthanide phosphate nanoparticles for targeted alpha generator radiotherapy.

PubMed

McLaughlin, Mark F; Woodward, Jonathan; Boll, Rose A; Wall, Jonathan S; Rondinone, Adam J; Kennel, Stephen J; Mirzadeh, Saed; Robertson, J David

2013-01-01

Targeted radiotherapies maximize cytotoxicty to cancer cells. In vivo α-generator targeted radiotherapies can deliver multiple α particles to a receptor site dramatically amplifying the radiation dose delivered to the target. The major challenge with α-generator radiotherapies is that traditional chelating moieties are unable to sequester the radioactive daughters in the bioconjugate which is critical to minimize toxicity to healthy, non-target tissue. The recoil energy of the (225)Ac daughters following α decay will sever any metal-ligand bond used to form the bioconjugate. This work demonstrates that an engineered multilayered nanoparticle-antibody conjugate can deliver multiple α radiations and contain the decay daughters of (225)Ac while targeting biologically relevant receptors in a female BALB/c mouse model. These multi-shell nanoparticles combine the radiation resistance of lanthanide phosphate to contain (225)Ac and its radioactive decay daughters, the magnetic properties of gadolinium phosphate for easy separation, and established gold chemistry for attachment of targeting moieties.

First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

NASA Astrophysics Data System (ADS)

Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang

2008-05-01

Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.

The Role of Chromohalobacter on Transport of Lanthanides and Cesium in the Dolomite Mineral System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zengotita, Frances; Emerson, Hilary Palmer; Dittrich, Timothy M.

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 (Nd 3+, Eu 3+) 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 bothmore » minerals and bacteria depending on which the Ln contacts first.« less

Solvothermal syntheses, and characterization of [Ln(en){sub 4}(SbSe{sub 4})] (Ln=Ce, Pr) and [Ln(en){sub 4}]SbSe{sub 4}.0.5en (Ln=Eu, Gd, Er, Tm, Yb): The effect of lanthanide contraction on the crystal structures of lanthanide selenidoantimonates(V)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia Dingxian; Zhu Aimei; Jin Qinyan

Two types of lanthanide selenidoantimonates [Ln(en){sub 4}(SbSe{sub 4})] (Ln=Ce(1a), Pr(1b)) and [Ln(en){sub 4}]SbSe{sub 4}.0.5en (Ln=Eu(2a), Gd(2b), Er(2c), Tm(2d), Yb(2e); en=ethylenediamine) were solvothermally synthesized by reactions of LnCl{sub 3}, Sb and Se with the stoichiometric ratio in en solvent at 140 deg. C. The four-en coordinated lanthanide complex cation [Ln(en){sub 4}]{sup 3+} formed in situ balances the charge of SbSe{sub 4}{sup 3-} anion. In compounds 1a and 1b, the SbSe{sub 4}{sup 3-} anion act as a monodentate ligand to coordinate complex [Ln(en){sub 4}]{sup 3+} and the neutral compound [Ln(en){sub 4}(SbSe{sub 4})] is formed. The Ln{sup 3+} ion has a nine-coordinated environmentmore » involving eight N atoms and one Se atom forming a distorted monocapped square antiprism. In 2a-2e the lanthanide(III) ion exists as isolated complex [Ln(en){sub 4}]{sup 3+}, in which the Ln{sup 3+} ion is in a bicapped trigonal prism geometry. A systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series. TG curves show that compounds 1a-1b and 2a-2e remove their organic components in one and two steps, respectively. - Graphical abstract: Two types of lanthanide selenidoantimonates [Ln(en){sub 4}(SbSe{sub 4})] (Ln=Ce, Pr) and [Ln(en){sub 4}]SbSe{sub 4}.0.5en (Ln=Eu, Gd, Er, Tm, Yb; en=ethylenediamine) have been synthesized under the mild solvothermal conditions, and a systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series.« less

Intrinsic and Carrier Colloid-facilitated transport of lanthanides through discrete fractures in chalk

NASA Astrophysics Data System (ADS)

Weisbrod, N.; Tran, E. L.; Klein-BenDavid, O.; Teutsch, N.

2015-12-01

Geological disposal of high-level radioactive waste is the long term solution for the disposal of long lived radionuclides and spent fuel. However, some radionuclides might be released from these repositories into the subsurface as a result of leakage, which ultimately make their way into groundwater. Engineered bentonite barriers around nuclear waste repositories are generally considered sufficient to impede the transport of radionuclides from their source to the groundwater. However, colloidal-sized mobile bentonite particles ("carrier" colloids) originating from these barriers have come under investigation as a potential transport vector for radionuclides sorbed to them. As lanthanides are generally accepted to have the same chemical behaviors as their more toxic actinide counterparts, lanthanides are considered an acceptable substitute for research on radionuclide transportation. This study aims to evaluate the transport behaviors of lanthanides in colloid-facilitated transport through a fractured chalk matrix and under geochemical conditions representative the Negev desert, Israel. The migration of Ce both with and without colloidal particles was explored and compared to the migration of a conservative tracer (bromide) using a flow system constructed around a naturally fractured chalk core. Results suggest that mobility of Ce as a solute is negligible. In experiments conducted without bentonite colloids, the 1% of the Ce that was recovered migrated as "intrinsic" colloids in the form of carbonate precipitates. However, the total recovery of the Ce increased to 9% when it was injected into the core in the presence of bentonite colloids and 13% when both bentonite and precipitate colloids were injected. This indicates that lanthanides are essentially immobile in chalk as a solute but may be mobile as carbonate precipitates. Bentonite colloids, however, markedly increase the mobility of lanthanides through fractured chalk matrices.

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications.

PubMed

Ai, Xiangzhao; Lyu, Linna; Mu, Jing; Hu, Ming; Wang, Zhimin; Xing, Bengang

2017-11-10

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical properties, which allow for the absorption of near-infrared (NIR) light and can subsequently convert it into multiplexed emissions that span over a broad range of regions from the UV to the visible to the NIR. This article presents detailed experimental procedures for high-temperature co-precipitation synthesis of core-shell UCNs that incorporate different lanthanide ions into nanocrystals for efficiently converting deep-tissue penetrable NIR excitation (808 nm) into a strong blue emission at 480 nm. By controlling the surface modification with biocompatible polymer (polyacrylic acid, PAA), the as-prepared UCNs acquires great solubility in buffer solutions. The hydrophilic nanocrystals are further functionalized with specific ligands (dibenzyl cyclooctyne, DBCO) for localization on the cell membrane. Upon NIR light (808 nm) irradiation, the upconverted blue emission can effectively activate the light-gated channel protein on the cell membrane and specifically regulate the cation (e.g., Ca 2+ ) influx in the cytoplasm. This protocol provides a feasible methodology for the synthesis of core-shell lanthanide-doped UCNs and subsequent biocompatible surface modification for further cellular applications.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf])

NASA Astrophysics Data System (ADS)

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J.; Cisneros, G. Andrés

2018-01-01

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]).

PubMed

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés

2018-01-14

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17 O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO 4 ]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf] - anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

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

NASA Astrophysics Data System (ADS)

Zhuang, Gui-lin; Chen, Wu-lin; Zheng, Jun; Yu, Hui-you; Wang, Jian-guo

2012-08-01

A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H3SIDA) and Ln(NO3)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 Gd3+ ions for anti-anti and syn-anti carboxylate bridges are -1.0×10-3 and -5.0×10-3 cm-1, respectively, which reveals weak antiferromagnetic interaction in 4.

Lanthanide-doped upconversion nanocrystals: Synthesis and optical properties study

NASA Astrophysics Data System (ADS)

Sun, Qiang

Upconversion phosphor materials have attracted considerable attention in recent years for their potential applications in a wide range of fields, including three-dimensional displays technologies, bio-imaging and photovoltaics. This dissertation aims to develop novel lanthanide-doped upconversion luminescent nanomaterials by using wet chemistry methods. Considerable efforts have been devoted to manipulating the optical properties of the synthesized lanthanide-doped nanoparticles under excitation of different wavelengths, for example, 808, 980 and 1532 nm. In the first research work, a novel core-shell-shell design has been developed for finely tuning of energy migration upconversion of activators without long-lived mediated states, such as Eu3+ and Tb3+ upon excitation at 808 nm by using Nd3+ as sensitizer. Exquisite control the composition of each layer gives rise to maximized upconversion emissions of the activators. For example, with the use of core layer for energy harvesting (NaGdF4:Yb/Nd, active core), the optimal doping concentrations of Eu3+ and Tb3+ is fixed to 15 and 15 mol%, respectively. In contrast, active shell can also provide access to strong upconversion of Eu3+ and Tb3+ by doping Nd (40 mol%) into the outmost layer. Note that the effect of active shell is much stronger than active core in generating upconversion emissions of Eu3+ and Tb3+. Next, upconversion emission tuning of Er/Tm/Yb-doped NaYF4 upconversion nanoparticles has been conducted under excitation at 1532 nm. The output color of the nanoparticles is tunable by changing the doping levels of the lanthanides. With the use of core-shell design, the optical properties of the doped nanoparticles can be further optimized, for example, strongest upconversion emission was observed for NaYF4:Er(10 mol%) NaYF4:Er(0.5 mol%) with a relative emission of green-to-red of 1.2. This work provides a new dimension to control the color output of upconversion nanoparticles. It should be noted that the

Heterobimetallic lanthanide/sodium phenoxides: efficient catalysts for amidation of aldehydes with amines.

PubMed

Li, Junmei; Xu, Fan; Zhang, Yong; Shen, Qi

2009-03-20

Heterobimetallic lanthanide/sodium phenoxides were found to be efficient catalysts for amidation of aldehydes with amines under mild conditions. The reactivity follows the order Nd < Y < Sm for metals and 2,6-(Me)2C6H3O < 2,6-(iPr)2C6H3O < 2,6-(tBu)2C6H3O for phenoxide groups. In comparison with the corresponding monometallic complexes, heterobimetallic complexes show higher activity and a wider range of scope of amines. A cooperation of lanthanide and sodium in this process is proposed to contribute to the high activity of the present catalyst.

Lanthanides determination in red wine using ultrasound assisted extraction, flow injection, aerosol desolvation and ICP-MS.

PubMed

Bentlin, Fabrina R S; dos Santos, Clarissa M M; Flores, Erico M M; Pozebon, Dirce

2012-01-13

This paper deals with the determination of the fourteen naturally occurring elements of the lanthanide series in red wine. Ultrasound (US) was used for sample preparation prior lanthanides determination using ICP-MS. Flow injection (FI) and pneumatic nebulization/aerosol desolvation were used for nebulization of aliquots of 50 μL of sample and its subsequent transportation to plasma. Sample preparation procedures, matrix interference and time of sonication were evaluated. Better results for lanthanides in red wine were obtained by sonication with US probe for 90 s and sample 10-fold diluted. The limits of detection of La, Ce, Nd, Sm, Gd, Pr, Eu, Tb, Dy, Ho, Er, Tm, Lu and Yb were 6.57, 10.8, 9.97, 9.38, 2.71, 1.29, 1.22, 0.52, 2.35, 0.96, 2.30, 0.45, 0.24 and 1.35 ng L(-1), respectively. Red wines of different varieties from three countries of South America were discriminated according to the country of origin by means of multivariate analysis of lanthanides concentration. Copyright © 2011 Elsevier B.V. All rights reserved.

Superabsorbing gel for actinide, lanthanide, and fission product decontamination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaminski, Michael D.; Mertz, Carol J.

The present invention provides an aqueous gel composition for removing actinide ions, lanthanide ions, fission product ions, or a combination thereof from a porous surface contaminated therewith. The composition comprises a polymer mixture comprising a gel forming cross-linked polymer and a linear polymer. The linear polymer is present at a concentration that is less than the concentration of the cross-linked polymer. The polymer mixture is at least about 95% hydrated with an aqueous solution comprising about 0.1 to about 3 percent by weight (wt %) of a multi-dentate organic acid chelating agent, and about 0.02 to about 0.6 molar (M)more » carbonate salt, to form a gel. When applied to a porous surface contaminated with actinide ions, lanthanide ions, and/or other fission product ions, the aqueous gel absorbs contaminating ions from the surface.« less

Magnetic hysteresis in a lanthanide molecular magnet dimer system

NASA Astrophysics Data System (ADS)

Atkinson, James; Cebulka, Rebecca; Del Barco, Enrique; Roubeau, Olivier; Velasco, Veronica; Barrios, Leo; Aromi, Guillem

Molecular magnets present a wonderful means for studying the dynamics of spin. Often synthesized as a crystal lattice of identical systems, ensemble measurements enable thorough detailing of the internal degrees of freedom. Here we present the results of characterization performed on a dimer system, CeTm(HL)2(H2L)NO3pyH2O (L = ligand, C45H31O15N3), consisting of two lanthanide spins (Cerium and Thulium) with expected local axial anisotropies tilted with respect to each other. Microwave EPR spectroscopy at low temperature reveals hysteresis in observed absorption features, with angle dependence studies indicating the presence of several ``easy axis'' orientations. We attempt to understand this system through modelling via a spin Hamiltonian, and to determine the strength and nature of the coupling between the lanthanide centers. This research was funded through NSF Grant # 24086159.

A self-assembling lanthanide molecular nanoparticle for optical imaging†

PubMed Central

Brown, Katherine A.; Yang, Xiaoping; Schipper, Desmond; Hall, Justin W.; DePue, Lauren J.; Gnanam, Annie J.; Arambula, Jonathan F.; Jones, Jessica N.; Swaminathan, Jagannath; Dieye, Yakhya; Vadivelu, Jamuna; Chandler, Don J.; Marcotte, Edward M.; Sessler, Jonathan L.; Ehrlich, Lauren I. R.; Jones, Richard A.

2015-01-01

Chromophores that incorporate f-block elements have considerable potential for use in bioimaging applications because of their advantageous photophysical properties compared to organic dye, which are currently widely used. We are developing new classes of lanthanide-based self-assembling molecular nanoparticles as reporters for imaging and as multi-functional nanoprobes or nanosensors for use with biological samples. One class of these materials, which we call lanthanide “nano-drums”, are homogeneous 4d–4f clusters approximately 25 to 30 Å in diameter. These are capable of emitting from the visible to near-infrared wavelengths. Here, we present the synthesis, crystal structure, photophysical properties and comparative cytotoxicity data for a 32 metal Eu-Cd nano-drum [Eu8Cd24L12(OAc)48] (1). We also explored the imaging capabilities of this nano-drum using epifluorescence, TIRF, and two-photon microscopy platforms. PMID:25512085

Realizing up-conversion fluorescence tuning in lanthanide-doped nanocrystals by femtosecond pulse shaping method

PubMed Central

Zhang, Shian; Yao, Yunhua; Shuwu, Xu; Liu, Pei; Ding, Jingxin; Jia, Tianqing; Qiu, Jianrong; Sun, Zhenrong

2015-01-01

The ability to tune color output of nanomaterials is very important for their applications in laser, optoelectronic device, color display and multiplexed biolabeling. Here we first propose a femtosecond pulse shaping technique to realize the up-conversion fluorescence tuning in lanthanide-doped nanocrystals dispersed in the glass. The multiple subpulse formation by a square phase modulation can create different excitation pathways for various up-conversion fluorescence generations. By properly controlling these excitation pathways, the multicolor up-conversion fluorescence can be finely tuned. This color tuning by the femtosecond pulse shaping technique is realized in single material by single-color laser field, which is highly desirable for further applications of the lanthanide-doped nanocrystals. This femtosecond pulse shaping technique opens an opportunity to tune the color output in the lanthanide-doped nanocrystals, which may bring a new revolution in the control of luminescence properties of nanomaterials. PMID:26290391

The inhibition of mitochondrial calcium transport by lanthanides and Ruthenium Red

PubMed Central

Reed, Ken C.; Bygrave, Fyfe L.

1974-01-01

An EGTA (ethanedioxybis(ethylamine)tetra-acetic acid)-quench technique was developed for measuring initial rates of 45Ca2+ transport by rat liver mitochondria. This method was used in conjunction with studies of Ca2+-stimulated respiration to examine the mechanisms of inhibition of Ca2+ transport by the lanthanides and Ruthenium Red. Ruthenium Red inhibits Ca2+ transport non-competitively with Ki 3×10−8m; there are 0.08nmol of carrier-specific binding sites/mg of protein. The inhibition by La3+ is competitive (Ki=2×10−8m); the concentration of lanthanide-sensitive sites is less than 0.001nmol/mg of protein. A further difference between their modes of action is that lanthanide inhibition diminishes with time whereas that by Ruthenium Red does not. Binding studies showed that both classes of inhibitor bind to a relatively large number of external sites (probably identical with the `low-affinity' Ca2+-binding sites). La3+ competes with Ruthenium Red for most of these sites, but a small fraction of the bound Ruthenium Red (less than 2nmol/mg of protein) is not displaced by La3+. The results are discussed briefly in relation to possible models for a Ca2+ carrier. PMID:4375957

Thermal NF3 fluorination/oxidation of cobalt, yttrium, zirconium, and selected lanthanide oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.

2013-02-01

This paper presents results of our continuing investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. This article focuses on fission products that do not have volatile fluorides or oxyfluorides at expected operations temperatures. Our thermodynamic calculations show that nitrogen trifluoride has the potential to completely fluorinate fission product oxides to their fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of cobalt, zirconium, and the lanthanides are fluorinated but do not formmore » volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550°C. Our studies of gadolinium-doped commercial nuclear fuel indicate that nitrogen trifluoride can extract uranium from the non-volatile gadolinium.« less

Ab Initio Crystal Field for Lanthanides.

PubMed

Ungur, Liviu; Chibotaru, Liviu F

2017-03-13

An ab initio methodology for the first-principle derivation of crystal-field (CF) parameters for lanthanides is described. The methodology is applied to the analysis of CF parameters in [Tb(Pc) 2 ] - (Pc=phthalocyanine) and Dy 4 K 2 ([Dy 4 K 2 O(OtBu) 12 ]) complexes, and compared with often used approximate and model descriptions. It is found that the application of geometry symmetrization, and the use of electrostatic point-charge and phenomenological CF models, lead to unacceptably large deviations from predictions based on ab initio calculations for experimental geometry. It is shown how the predictions of standard CASSCF (Complete Active Space Self-Consistent Field) calculations (with 4f orbitals in the active space) can be systematically improved by including effects of dynamical electronic correlation (CASPT2 step) and by admixing electronic configurations of the 5d shell. This is exemplified for the well-studied Er-trensal complex (H 3 trensal=2,2',2"-tris(salicylideneimido)trimethylamine). The electrostatic contributions to CF parameters in this complex, calculated with true charge distributions in the ligands, yield less than half of the total CF splitting, thus pointing to the dominant role of covalent effects. This analysis allows the conclusion that ab initio crystal field is an essential tool for the decent description of lanthanides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relaxation-based distance measurements between a nitroxide and a lanthanide spin label

NASA Astrophysics Data System (ADS)

Jäger, H.; Koch, A.; Maus, V.; Spiess, H. W.; Jeschke, G.

2008-10-01

Distance measurements by electron paramagnetic resonance techniques between labels attached to biomacromolecules provide structural information on systems that cannot be crystallized or are too large to be characterized by NMR methods. However, existing techniques are limited in their distance range and sensitivity. It is anticipated by theoretical considerations that these limits could be extended by measuring the enhancement of longitudinal relaxation of a nitroxide label due to a lanthanide complex label at cryogenic temperatures. The relaxivity of the dysprosium complex with the macrocyclic ligand DOTA can be determined without direct measurements of longitudinal relaxation rates of the lanthanide and without recourse to model compounds with well defined distance by analyzing the dependence of relaxation enhancement on either temperature or concentration in homogeneous glassy frozen solutions. Relaxivities determined by the two calibration techniques are in satisfying agreement with each other. Error sources for both techniques are examined. A distance of about 2.7 nm is measured in a model compound of the type nitroxide-spacer-lanthanide complex and is found in good agreement with the distance in a modeled structure. Theoretical considerations suggest that an increase of the upper distance limit requires measurements at lower fields and temperatures.

Probing the Influence of Disorder on Lanthanide Luminescence Using Eu-Doped LaPO4 Nanoparticles

PubMed Central

2017-01-01

Lanthanide-doped nanocrystals (NCs) differ from their bulk counterparts due to their large surface to volume ratio. It is generally assumed that the optical properties are not affected by size effects as electronic transitions occur within the well-shielded 4f shell of the lanthanide dopant ions. However, defects and disorder in the surface layer can affect the luminescence properties. Trivalent europium is a suitable ion to investigate the subtle influence of the surface, because of its characteristic luminescence and high sensitivity to the local environment. Here, we investigate the influence of disorder in NCs on the optical properties of lanthanide dopants by studying the inhomogeneous linewidth, emission intensity ratios, and luminescence decay curves for LaPO4:Eu3+ samples of different sizes (4 nm to bulk) and core–shell configurations (core, core–isocrystalline shell, and core–silica shell). We show that the emission linewidths increase strongly for NCs. The ratio of the intensities of the forced electric dipole (ED) and magnetic dipole (MD) transitions, a measure for the local symmetry distortion around Eu3+ ions, is higher for samples with a large fraction of Eu3+ ions close to the surface. Finally, we present luminescence decay curves revealing an increased nonradiative decay rate for Eu3+ in NCs. The effects are strongest in core and core–silica shell NCs and can be reduced by growth of an isocrystalline LaPO4 shell. The present systematic study provides quantitative insight into the role of surface disorder on the optical properties of lanthanide-doped NCs. These insights are important in emerging applications of lanthanide-doped nanocrystals. PMID:28919934

Facile synthesis of upconversion nanoparticles with high purity using lanthanide oleate compounds

NASA Astrophysics Data System (ADS)

Kang, Ning; Ai, Chao-Chao; Zhou, Ya-Ming; Wang, Zuo; Ren, Lei

2018-02-01

A novel strategy for preparing highly pure NaYF4-based upconversion nanoparticles (UCNPs) was developed using lanthanide oleate compounds [Ln(OA)3] as the precursor, denoted as the Ln-OA preparation method. Compared to the conventional solvothermal method for synthesizing UCNPs using lanthanide chloride compounds (LnCl3) as the precursor (denoted as the Ln-Cl method), the Ln-OA strategy exhibited the merits of high purity, reduced purification process and a uniform size in preparing core and core-shell UCNPs excited by a 980 or 808 nm near infrared (NIR) laser. This work sheds new insight on the preparation of UCNPs and promotes their application in biomedical fields.

Heterobimetallic dinuclear lanthanide alkoxide complexes as acid-base difunctional catalysts for transesterification.

PubMed

Zeng, Ruijie; Sheng, Hongting; Zhang, Yongcang; Feng, Yan; Chen, Zhi; Wang, Junfeng; Chen, Man; Zhu, Manzhou; Guo, Qingxiang

2014-10-03

A practical lanthanide(III)-catalyzed transesterification of carboxylic esters, weakly reactive carbonates, and much less-reactive ethyl silicate with primary and secondary alcohols was developed. Heterobimetallic dinuclear lanthanide alkoxide complexes [Ln2Na8{(OCH2CH2NMe2)}12(OH)2] (Ln = Nd (I), Sm (II), and Yb (III)) were used as highly active catalysts for this reaction. The mild reaction conditions enabled the transesterification of various substrates to proceed in good to high yield. Efficient activation of transesterification may be endowed by the above complexes as cooperative acid-base difunctional catalysts, which is proposed to be responsible for the higher reactivity in comparison with simple acid/base catalysts.

Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

DOEpatents

Raymond, Kenneth N.; Xu, Jide; Moore, Evan G.; Werner, Eric J.

2013-10-15

The present invention provides luminescent complexes between a lanthanide ion and an organic ligand which contains 1,2-hydroxypyridinone units. The complexes of the invention are stable in aqueous solutions and are useful as molecular probes, for example in medical diagnostics and bioanalytical assay systems. The invention also provides methods of using the complexes of the invention.

Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

DOEpatents

Raymond, Kenneth N.; Xu, Jide; Moore, Evan G.; Werner, Eric J.

2017-01-31

The present invention provides luminescent complexes between a lanthanide ion and an organic ligand which contains 1,2-hydroxypyridinone units. The complexes of the invention are stable in aqueous solutions and are useful as molecular probes, for example in medical diagnostics and bioanalytical assay systems. The invention also provides methods of using the complexes of the invention.

Lanthanide Contraction as a Design Factor for High-Performance Half-Heusler Thermoelectric Materials.

PubMed

Liu, Yintu; Fu, Chenguang; Xia, Kaiyang; Yu, Junjie; Zhao, Xinbing; Pan, Hongge; Felser, Claudia; Zhu, Tiejun

2018-06-25

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half-Heusler alloys, n-type (Zr,Hf)NiSn and p-type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n-type (Zr,Hf)CoSb-based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb-based half-Heusler compounds due to the matched n-type and p-type thermoelectric performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coherent manipulation of mononuclear lanthanide-based single-molecule magnets

NASA Astrophysics Data System (ADS)

Datta, Saiti; Ghosh, Sanhita; Krzystek, Jurek; Hill, Stephen; Del Barco, Enrique; Cardona-Serra, Salvador; Coronado, Eugenio

2010-03-01

Using electron spin echo (ESE) spectroscopy, we report measurements of the longitudinal (T1) and transverse (T2) relaxation times of diluted single-crystals containing recently discovered mononuclear lanthanide-based single-molecule magnets (SMMs) encapsulated in polyoxometallate cages [AlDamen et al. J. Am. Chem. Soc. 130, 8874 -- 8875 (2008)]. This encapsulation offers the potential for preserving bulk SMM properties outside of a crystal, e.g. in molecular spintronic devices. The magnetic anisotropy in these complexes arises from the spin-orbit splitting of the ground state J multiplet of the lanthanide ion in the presence of a ligand field. At low frequencies only hyperfine-split transitions within the lowest ground state ±mJ doublet are observed. Spin relaxation times were measured for a holmium complex, and the results were compared for different hyperfine transitions and crystal dilutions. Clear Rabi oscillations were also observed, indicating that one can manipulate the spin coherently in these complexes.

Deep-UV biological imaging by lanthanide ion molecular protection

PubMed Central

Kumamoto, Yasuaki; Fujita, Katsumasa; Smith, Nicholas Isaac; Kawata, Satoshi

2015-01-01

Deep-UV (DUV) light is a sensitive probe for biological molecules such as nucleobases and aromatic amino acids due to specific absorption. However, the use of DUV light for imaging is limited because DUV can destroy or denature target molecules in a sample. Here we show that trivalent ions in the lanthanide group can suppress molecular photodegradation under DUV exposure, enabling a high signal-to-noise ratio and repetitive DUV imaging of nucleobases in cells. Underlying mechanisms of the photodegradation suppression can be excitation relaxation of the DUV-absorptive molecules due to energy transfer to the lanthanide ions, and/or avoiding ionization and reactions with surrounding molecules, including generation of reactive oxygen species, which can modify molecules that are otherwise transparent to DUV light. This approach, directly removing excited energy at the fundamental origin of cellular photodegradation, indicates an important first step towards the practical use of DUV imaging in a variety of biological applications. PMID:26819825

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

PubMed

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.

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

PubMed

Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

2017-05-15

Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

Lanthanide-Substituted Magnetite Nanoparticles Using a New Mixed Precursor Method by Thermoanaerobacter ethanolicus

NASA Astrophysics Data System (ADS)

Moon, J.; Roh, Y.; Yeary, L. W.; Lauf, R. J.; Phelps, T. J.

2006-12-01

A metal reducing bacterium, Thermoanaerobacter ethanolicus successfully converted the precursor of L (lanthanide)-mixed akaganeite (LxFe1-xOOH) phase to L-substituted magnetite (LyFe3-yO4) while avoiding the potentially toxic effects of soluble L-ions. Antibiotic elements, lanthanide (Nd, Gd, Tb, Ho, and Er)-substituted magnetites were produced by microbial fermentation using LxFe1-xOOH, where x was up to 0.02 which is equivalent to 0.72 mM. Combining lanthanides into the akaganeite precursor phase mitigated some of the toxicity when compared to the traditional method by using pure akaganeite and the dissolved L-salt form. This new technique showed that an upper limit of L-concentrations between 0.02 and 0.1 mM might suppress bacterial activity. At the equivalent L-cation mole fraction, the traditional method increased the concentration of soluble toxic L ions in the final media. The precursor method enabled production of microbially synthesized L- substituted magnetite with an L-concentration 36-fold greater than could be obtained when the lanthanides were added as soluble salts. These results were confirmed by protein assay. The increase of L-concentration in the magnetite evidently manipulates its physical properties such as decreasing Curie temperature and decreasing saturation magnetism of L-substituted magnetite. This mixed precursor method can therefore be used to extend the application for nanofermentation and other bacterial synthesis fields where there is a need for economically low-energy consumable microbial production of nanoscale materials that should involve toxic or inhibitory elements to bacterial growth.

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

NASA Astrophysics Data System (ADS)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

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 themore » 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.« less

Lanthanide-IMAC enrichment of carbohydrates and polyols.

PubMed

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.

Development and Application of Multifunctional Lanthanide-Doped Nanoparticles in Medical Imaging

NASA Astrophysics Data System (ADS)

Pedraza, Francisco J., III

Medical imaging has become one of the most important tools of modern medicine soon after it was developed. Presently, several imaging modalities are available to clinicians for the detection of skeletal fractures and functional abnormalities of organs and tissues; and also an excellent tool during surgical procedures. Unfortunately, each imaging technique possesses its own strengths and inherent limitations which can be mitigated via the use of multiple imaging modalities and imaging probes. Through the use of multiple imaging modalities, it is possible to gather complementary information for a more reliable diagnosis. Each imaging technique requires its own imaging probes, providing selectivity and improved contrast. However, conventional contrast agents are incapable of providing what the new generation of multifunctional nanomaterials offer. In addition to improved selectivity and contrast, multifunctional materials possess therapeutic capabilities such as photo-thermal therapy and controlled drug delivery. Lanthanide-based nanomaterials are viable candidates for multimodal imaging agents due to possessing multifunctional capabilities, optical and chemical stability, and an intense tunable emission. This doctoral dissertation will delve into the development of lanthanide-based nanoparticles by proposing a novel multifunctional contrast agent for Near Infrared Fluorescence Imaging and Magnetic Resonance Imaging. Furthermore, the study of surface modification effects on upconversion emission and nanoparticle-cell interactions was performed. Results presented will confirm the potential application of multifunctional lanthanide-based nanomaterials as multimodal imaging probes.

Lanthanide/Actinide Opacities

NASA Astrophysics Data System (ADS)

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.

Lanthanide complex coordination polyhedron geometry prediction accuracies of ab initio effective core potential calculations.

PubMed

Freire, Ricardo O; Rocha, Gerd B; Simas, Alfredo M

2006-03-01

lanthanide coordination compounds efficiently and accurately is central for the design of new ligands capable of forming stable and highly luminescent complexes. Accordingly, we present in this paper a report on the capability of various ab initio effective core potential calculations in reproducing the coordination polyhedron geometries of lanthanide complexes. Starting with all combinations of HF, B3LYP and MP2(Full) with STO-3G, 3-21G, 6-31G, 6-31G* and 6-31+G basis sets for [Eu(H2O)9]3+ and closing with more manageable calculations for the larger complexes, we computed the fully predicted ab initio geometries for a total of 80 calculations on 52 complexes of Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III) and Tm(III), the largest containing 164 atoms. Our results indicate that RHF/STO-3G/ECP appears to be the most efficient model chemistry in terms of coordination polyhedron crystallographic geometry predictions from isolated lanthanide complex ion calculations. Moreover, both augmenting the basis set and/or including electron correlation generally enlarged the deviations and aggravated the quality of the predicted coordination polyhedron crystallographic geometry. Our results further indicate that Cosentino et al.'s suggestion of using RHF/3-21G/ECP geometries appears to be indeed a more robust, but not necessarily, more accurate recommendation to be adopted for the general lanthanide complex case. [Figure: see text].

Complications in complexation kinetics for lanthanides with DTPA using dye probe molecules in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsson, K.; Cullen, T. D.; Mezyk, S. P.

The complexation kinetics for the polyaminopolycarboxylic ligand DTPA to lanthanides in acidic aqueous solution were investigated using the dye ligand displacement technique and stopped-flow spectroscopy. Significant rate differences were obtained for different dye probes used, indicating that the kinetics of the dissociation of the dye molecule significantly impacts the overall measured kinetics when using this common methodology. The conditions of the solution also influenced the dye-lanthanide-DTPA interactions, which reconciled previously disparate data in the literature.

Complications in complexation kinetics for lanthanides with DTPA using dye probe molecules in aqueous solution

DOE PAGES

Larsson, K.; Cullen, T. D.; Mezyk, S. P.; ...

2017-05-17

The complexation kinetics for the polyaminopolycarboxylic ligand DTPA to lanthanides in acidic aqueous solution were investigated using the dye ligand displacement technique and stopped-flow spectroscopy. Significant rate differences were obtained for different dye probes used, indicating that the kinetics of the dissociation of the dye molecule significantly impacts the overall measured kinetics when using this common methodology. The conditions of the solution also influenced the dye-lanthanide-DTPA interactions, which reconciled previously disparate data in the literature.

Precipitation synthesis of lanthanide hydroxynitrate anion exchange materials, Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O (Ln=Y, Eu-Er)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hindocha, Sheena A.; McIntyre, Laura J.; Fogg, Andrew M., E-mail: afogg@liverpool.ac.u

2009-05-15

Layered lanthanide hydroxynitrate anion exchange host lattices have been prepared via a room temperature precipitation synthesis. These materials have the composition Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O and are formed for Y and the lanthanides from Eu to Er and as such include the first Eu containing nitrate anion exchange host lattice. The interlayer separation of these materials, approximately 8.5 A, is lower than in the related phases Ln{sub 2}(OH){sub 5}NO{sub 3}.1.5H{sub 2}O which have a corresponding value of 9.1 A and is consistent with the reduction in the co-intercalated water content of these materials. These new intercalation hosts have beenmore » shown to undergo facile anion exchange reactions with a wide range of organic carboxylate and sulfonate anions. These reactions produce phases with up to three times the interlayer separation of the host lattice demonstrating the flexibility of these materials. - Graphical abstract: New anion exchangeable layered hydroxynitrates, Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O (Ln=Y, Eu - Er) have been synthesized via a precipitation route. These materials have been shown to be very flexible intercalation hosts undergoing facile exchange reactions with organic carboxylate and sulfonate anions.« less

Accumulation of several heavy metals and lanthanides in mushrooms (Agaricales) from the Chicago region.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aruguete, D. M.; Aldstadt, J. H., III; Mueller, G. M.

1998-01-01

This study explored the differences in metal uptake in sporocarps of ectomycorrhizae-forming fungi relative to (1) fungal species; (2) collection location; (3) differential metal uptake and variation within single-species, single-area populations; and (4) mobile metal content of soil substrate for the fungi. In addition, this study examined levels of some of the lanthanides in these mushrooms, as lanthanide uptake in higher fungi has not been quantified to date. In 1995 and 1996, sporocarps from three species of ectomycorrhizal fungi (Amanita flavorubescens, Amanita rubescens, and Russula pectinatoides) were collected from Cowles Bog, Indiana Dunes National Lakeshore (near an industrial area) andmore » the Palos forest preserves (near a residential area). Soil was also collected from the Cowles Bog plots; metals were extracted from the soil, either with local Lake Michigan water or with nitric acid. These two extractions were meant to simulate the natural soil equilibrium concentrations of soluble metals and the maximum possible effects of any fungal chelating chemicals, respectively. An inductively coupled plasma mass spectrometer was used to analyze soil extracts and nitric acid digests of whole sporocarps for the target analytes. The metals found at elevated levels in the mushrooms included four of environmental interest (Ag, Cd, Ba, and Pb) and three lanthanides (La, Ce, and Nd). Significant differences in uptake of metals were observed between A. rubescens and R. pectinatoides, while A. rubescens and A. flavorubescens were not significantly different. With regard to location, more cadmium was found in Cowles Bog collections of A. rubescens, while Palos forest A. rubescens had more of the lanthanides and barium. Significant specimen-to-specimen variation occurred in all populations examined. Correlation analysis between pairs of trace elements within each sporocarp population revealed strong positive correlations between the lanthanides. Sporocarps

Ferromagnetic interactions and slow magnetic relaxation behaviors of two lanthanide coordination polymers bridged by 2,6-naphthalenedicarboxylate ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Ming; Li, Xiuhua; Cui, Ping

2015-03-15

Two lanthanide-based frameworks: (Ln(phen)(NDA){sub 1.5}(H{sub 2}O)){sub n} (Ln=Gd(1), NDA=2,6-naphthalenedicarboxylate anion, phen=1,10-phenanthroline), and ([Dy(phen)(NDA){sub 1.5}]·0.5H{sub 2}NDA){sub n} (2) were structurally and magnetically characterized. Compound 1 exhibits 2D layer structure, belonging to the triclinic system with space group P−1, while compound 2 features a 3D framework with space group P−1. The magnetic studies revealed that ferromagnetic coupling existed between adjacent lanthanide ions in 1 and 2, and frequency-dependence out-of-phase signals in the measurement of alternate-current susceptibilities were observed for 2, albeit without reaching the characteristic maxima above 2 K, implying slow magnetic relaxation behavior in 2. After the application of a dcmore » field, good peak shapes of ac signal were obtained and got the energy barrier ΔE/k{sub B}=29 K and the pre-exponential factor τ{sub 0}=4.47×10{sup −7} s at 2000 Oe field; and when the dc field was in 5000 Oe, giving ΔE/k{sub B}=40 K and τ{sub 0}=2.82×10{sup −6}. - Graphical abstract: Two novel lanthanide-based frameworks 1 and 2 were structurally and magnetically characterized. The results revealed that ferromagnetic coupling exists between adjacent lanthanide ions in 1 and 2, and 2 displayed slow magnetic relaxation behavior with the energy barrier of 29 K. - Highlights: • Two lanthanide frameworks were synthesized and magnetically characterized. • The magnetism studies indicate slow magnetic relaxation behavior in 2. • Weak ferromagnetic coupling existing between adjacent lanthanide centers.« less

Mean-field potential approach for thermodynamic properties of lanthanide: Europium as a prototype

NASA Astrophysics Data System (ADS)

Kumar, Priyank; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

2018-03-01

In the present paper, a simple conjunction scheme [mean-field potential (MFP) + local pseudopotential] is used to study the thermodynamic properties of divalent lanthanide europium (Eu) at extreme environment. Present study has been carried out due to the fact that divalent nature of Eu arises because of stable half-filled 4f-shell at ambient condition, which has great influence on the thermodynamic properties at extreme environment. Due to such electronic structure, it is different from remaining lanthanides having incomplete 4f-shell. The presently computed results of thermodynamic properties of Eu are in good agreement with the experimental results. Looking to such success, it seems that the concept of MFP approach is successful to account contribution due to nuclear motion to the total Helmholtz free energy at finite temperatures and pressure-induced inter-band transfer of electrons for condensed state of matter. The local pseudopotential is used to evaluate cold energy and hence MFP accounts the s-p-d-f hybridization properly. Looking to the reliability and transferability along with its computational and conceptual simplicity, we would like to extend the present scheme for the study of thermodynamic properties of remaining lanthanides and actinides at extreme environment.

An initial demonstration of hierarchically porous niobium alkylphosphonates coordination polymers as potent radioanalytical separation materials.

PubMed

Lv, Kai; Yang, Chu-Ting; Han, Jun; Hu, Sheng; Wang, Xiao-Lin

2017-06-30

Combining the merits of soft-templating and perchlorate oxidation methods, the first-case investigation of niobium alkylphosphonates has uncovered their unique morphology, backbone composition, thermal behavior and huge potentiality as radioanalytical separation materials. These hierarchically porous solids are random aggregates of densely stacked nanolayers perforated with worm-like holes or vesicular voids, manifesting the massif-, tower-like "polymer brush" elevated up to ∼150nm driven by the minimal surface free energy principle. These coordination polymers consist of distorted niobium (V) ions strongly linked with tetrahedral alkylphosphonate building units, exposing uncoordinated phosphonate moieties and defective metal sites. Despite the amorphous features, they demonstrate multimodal porosity covering continuous micropores, segregated mesopores and fractional macropores, beneficial for the sequestration by active Lewis acid-base center. Evidenced by the maximum distribution coefficients of thorium, lanthanides reaching 9.0×10 4 , 9.5×10 4 mLg -1 and large separation factor at pH≤1 20-element cocktail, this category of niobium alkylphosphonates are capable of harvesting thorium, lanthanides directly from the radionuclide surrogate, comparable to or even surpass the performance of the metal (IV) arylphosphonates counterparts. They also display appreciable SF Eu/Sm ∼20 in 1molL -1 HNO 3 , shedding light on dual approaches to achieve the isolation of americium from curium. A combinatorial radioanalytical separation protocol has been proposed to enrich thorium and europium, revealing facile utilization of these highly stable, phosphonated hybrids in sustainable development of radioanalytical separation. Copyright © 2017 Elsevier B.V. All rights reserved.

A series of binuclear lanthanide(III) complexes: Crystallography, antimicrobial activity and thermochemistry properties studies

NASA Astrophysics Data System (ADS)

Zhang, Ying-Ying; Ren, Ning; Xu, Su-Ling; Zhang, Jian-Jun; Zhang, Da-Hai

2015-02-01

A series of novel lanthanide complexes with the general formula [Ln(3,4-DClBA)3phen]2 (Ln = Ho(1), Nd(2), Sm(3), Dy(4), Eu(5), Tb(6), Yb(7) and Er(8), 3,4-DClBA = 3,4-dichlorobenzoate, phen = 1,10-phenanthroline) were prepared at room temperature and characterized. The crystal structures of complexes 1-8 have been determined by single crystal X-ray diffraction. These complexes are isomorphous and lanthanide ions are all eight-coordinated to oxygen atoms and nitrogen atoms with distorted square-antiprism geometry. The thermal decomposition mechanism and TG-FTIR spectra of gaseous products of thermal decomposition processes for complexes 1-8 were acquired through TG/DSC-FTIR system. The heat capacities of complexes 1-8 were measured using DSC technology and fitted to a polynomial equation by the least-squares method. Complexes 3-6 display characteristic lanthanide emission bands in the visible region. Meanwhile, these complexes exhibit in good antimicrobial activity against Candida albicans, Escherichia coli, and Staphylococcus aureu.

Increasing lanthanide luminescence by use of the RETEL effect.

PubMed

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

Methods for separating oxygen from oxygen-containing gases

DOEpatents

Mackay, Richard; Schwartz, Michael; Sammells, Anthony F.

2000-01-01

This invention provides mixed conducting metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes. The materials of this invention have the general formula: A.sub.x A'.sub.x A".sub.2-(x+x') B.sub.y B'.sub.y B".sub.2-(y+y') O.sub.5+z ; where x and x' are greater than 0; y and y' are greater than 0; x+x' is less than or equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the f block lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides or Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof; and B' and B" are different elements and are independently selected from the group of elements Mg or the d-block transition elements. The invention also provides methods for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula. Examples of the materials used for the preparation of the membrane include A.sub.x Sr.sub.x' B.sub.y Fe.sub.y' Co.sub.2-(y+y') O.sub.5+z, where x is about 0.3 to about 0.5, x' is about 1.5 to about 1.7, y is 0.6, y' is between about 1.0 and 1.4 and B is Ga or Al.

Does the 4f-shell contribute to bonding in tetravalent lanthanide halides?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ji, Wen-Xin; School of Chemistry and Chemical Engineering, Ningxia University, 750015 Yinchuan; Xu, Wei

2014-12-28

Lanthanide tetrahalide molecules LnX{sub 4} (Ln = Ce, Pr, Tb; X = F, Cl, Br, I) have been investigated by density functional theory at the levels of the relativistic Zero Order Regular Approximation and the relativistic energy-consistent pseudopotentials, using frozen small- and medium-cores. The calculated bond lengths and vibrational frequencies are close to the experimental data. Our calculations indicate 4f shell contributions to bonding in LnX{sub 4}, in particular for the early lanthanides, which show significant overlap between the Ln 4f-shell and the halogen np-shells. The 4f shells contribute to Ln-X bonding in LnX{sub 4} about one third more thanmore » in LnX{sub 3}.« less

X-ray spectroscopy studies of nonradiative energy transfer processes in luminescent lanthanide materials

NASA Astrophysics Data System (ADS)

Pacold, Joseph I.

Luminescent materials play important roles in energy sciences, through solid state lighting and possible applications in solar energy utilization, and in biomedical research and applications, such as in immunoassays and fluorescence microscopy. The initial excitation of a luminescent material leads to a sequence of transitions between excited states, ideally ending with the emission of one or more optical-wavelength photons. It is essential to understand the microscopic physics of this excited state cascade in order to rationally design materials with high quantum efficiencies or with other fine-tuning of materials response. While optical-wavelength spectroscopies have unraveled many details of the energy transfer pathways in luminescent materials, significant questions remain open for many lanthanide-based luminescent materials. For organometallic dyes in particular, quantum yields remain limited in comparison with inorganic phosphors. This dissertation reports on a research program of synchrotron x-ray studies of the excited state electronic structure and energy-relaxation cascade in trivalent lanthanide phosphors and dyes. To this end, one of the primary results presented here is the first time-resolved x-ray absorption near edge spectroscopy studies of the transient 4f excited states in lanthanide-activated luminescent dyes and phosphors. This is a new application of time-resolved x-ray absorption spectroscopy that makes it possible to directly observe and, to some extent, quantify intramolecular nonradiative energy transfer processes. We find a transient increase in 4f spectral weight associated with an excited state confined to the 4f shell of trivalent Eu. This result implies that it is necessary to revise the current theoretical understanding of 4f excitation in trivalent lanthanide activators: either transient 4f-5d mixing effects are much stronger than previously considered, or else the lanthanide 4f excited state has an unexpectedly large contribution

An Efficient Lanthanide-Dependent DNAzyme Cleaving 2'-5'-Linked RNA.

PubMed

Zhou, Wenhu; Ding, Jinsong; Liu, Juewen

2016-05-17

RNA can form two types of linkage. In addition to the predominant 3'-5' linkage, 2'-5'-linked RNA is also important in biology, medicine, and prebiotic studies. Here, in vitro selection was used to isolate a DNAzyme that specifically cleaves 2'-5' RNA by using Ce(3+) as the metal cofactor, but leaves the 3'-5' counterpart intact. This Ce5 DNAzyme requires trivalent light lanthanide ions and shows a rate of 0.16 min(-1) in the presence of 10 μm Ce(3+) ; the activity decreases with heavier lanthanide ions. This is the fastest DNAzyme reported for this reaction, and it might enable applications in chemical biology. As a proof-of-concept, using this DNAzyme, the reactions between phosphorothioate-modified RNA and strongly thiophilic metals (Hg(2+) and Tl(3+) ) were studied as a function of pH. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water molecule-enhanced CO{sub 2} insertion in lanthanide coordination polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo Liushan; Huang Xiaoyuan; Wang Ning

2009-08-15

Two new lanthanide coordination polymers H{sub 2}N(CH{sub 3}){sub 2}.[Eu{sup III}{sub 2}(L{sub 1}){sub 3}(L{sub 2})] (1, L{sub 1}=isophthalic acid dianion, L{sub 2}=formic acid anion) and [La{sup III}(2,5-PDC)(L{sub 2})](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L{sub 2}) is not contained in the stating materials, but arises from the water molecule-enhanced CO{sub 2} insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO{sub 2} insertion resulting in the formation of formic anion and dimethylammonium cation weremore » synthesized under solvothermal conditions.« less

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

NASA Astrophysics Data System (ADS)

Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

2016-10-01

Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all 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 classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

NASA Astrophysics Data System (ADS)

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.

Photo-reactive charge trapping memory based on lanthanide complex.

PubMed

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

2015-10-09

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 10(4) 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.

Photo-reactive charge trapping memory based on lanthanide complex

NASA Astrophysics Data System (ADS)

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.

Purification of lanthanides for double beta decay experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polischuk, O. G.; Barabash, A. S.; Belli, P.

2013-08-08

There are several potentially double beta active isotopes among the lanthanide elements. However, even high purity grade lanthanide compounds contain {sup 238}U, {sup 226}Ra and {sup 232,228}Th typically on the level of ∼ (0.1 - 1) Bq/kg. The liquid-liquid extraction technique was used to remove traces of U, Ra and Th from CeO{sub 2}, Nd{sub 2}O{sub 3} and Gd{sub 2}O{sub 3}. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe γ spectrometry at the underground Gran Sasso National Laboratories of the INFN (Italy). After the purification the radioactive contamination of gadolinium oxidemore » by Ra and Th was decreased at least one order of magnitude. The efficiency of the approach to purify cerium oxide from Ra was on same level, while the radioactive contamination of neodymium sample before and after the purification is below the sensitivity of analytical methods. The purification method is much less efficient for chemically very similar radioactive elements like lanthanum, lutetium and actinium. R and D of the methods to remove the pollutions with improved efficiency is in progress.« less

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

PubMed

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.

A Long Journey in Lanthanide Chemistry: From Fundamental Crystallogenesis Studies to Commercial Anticounterfeiting Taggants.

PubMed

Guillou, Olivier; Daiguebonne, Carole; Calvez, Guillaume; Bernot, Kevin

2016-05-17

Lanthanide ions have unique physical properties and are essential for numerous technological devices. Indeed, much research has been undertaken in order to understand and optimize their luminescent behavior. From a chemical and more specific point of view, lanthanides can be used to build coordination polymers (CPs). CPs are materials in which metal ions are associated with organic molecules (ligands) to form extended networks. They present great structural diversity and a wide range of unique properties such as great porosity, strong catalytic activities, and original magnetic and luminescent behaviors. In this Account, we highlight recent research advances obtained by our team in the field of lanthanide-based CPs. However, rather than present a simple chronological description of successive investigations, we have chosen present our own experience in order to show how standard academic studies can be successfully turned into applied research and finally into a viable startup that commercializes these products as anticounterfieting taggants. A taggant is a compound that can be dispersed in a host matrix at parts per million rates for it to be labeled. Its economic advantages over traditional anticounterfeiting techniques (labels, chips, etc.) are its very low cost and its ability to label a raw material at every stage of its processing, unlike traditional techniques that label only the final product. It thus permits traceability of a given material over a wide range of suppliers/subcontractors/sellers or customers at every step of its life. After 15 years of fundamental crystallogenesis research, we identified a very stable phase of lanthanide-based CPs in which strong lanthanide luminescence can be observed. We investigated this phase further and showed that a heteronuclear approach can give access to billions of different compositions and makes it possible to turn these powders into taggants. After the creation of a startup, we refocused on fundamental studies

The Effects of Trivalent Lanthanide Cationization on the Electron Transfer Dissociation of Acidic Fibrinopeptide B and its Analogs

NASA Astrophysics Data System (ADS)

Commodore, Juliette J.; Cassady, Carolyn J.

2016-09-01

Electrospray ionization (ESI) on mixtures of acidic fibrinopeptide B and two peptide analogs with trivalent lanthanide salts generates [M + Met + H]4+, [M + Met]3+, and [M + Met -H]2+, where M = peptide and Met = metal (except radioactive promethium). These ions undergo extensive and highly efficient electron transfer dissociation (ETD) to form metallated and non-metallated c- and z-ions. All metal adducted product ions contain at least two acidic sites, which suggest attachment of the lanthanide cation at the side chains of one or more acidic residues. The three peptides undergo similar fragmentation. ETD on [M + Met + H]4+ leads to cleavage at every residue; the presence of both a metal ion and an extra proton is very effective in promoting sequence-informative fragmentation. Backbone dissociation of [M + Met]3+ is also extensive, although cleavage does not always occur between adjacent glutamic acid residues. For [M + Met - H ]2+, a more limited range of product ions form. All lanthanide metal peptide complexes display similar fragmentation except for europium (Eu). ETD on [M + Eu - H]2+ and [M + Eu]3+ yields a limited amount of peptide backbone cleavage; however, [M + Eu + H]4+ dissociates extensively with cleavage at every residue. With the exception of the results for Eu(III), metallated peptide ion formation by ESI, ETD fragmentation efficiencies, and product ion formation are unaffected by the identity of the lanthanide cation. Adduction with trivalent lanthanide metal ions is a promising tool for sequence analysis of acidic peptides by ETD.

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

PubMed

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.

Simulating the synthesis and thermodynamic characteristics of the desolvation of lanthanide borohydride tris-Tetrahydrofuranates

NASA Astrophysics Data System (ADS)

Gafurov, B. A.; Mirsaidov, I. U.; Nasrulloeva, D. Kh.; Badalov, A.

2013-10-01

Lanthanide borohydride tris-tetrahydrofuranates (Ln(BH4) · 3THF, where THF is tetrahydrofuran and Ln is La, Nd, Sm, Gd, Er, Yb, and Lu) is synthesized via the exchange reaction of lanthanide(III) chloride and sodium borohydride in THF. It is found that synthesis proceeds according to a stepwise mechanism and the product of the reaction (lanthanide borohydride) initiates the process. The two-step character of the desolvation of Ln(BH4)3 · 3THF under steady-state conditions in the temperature range of 300 to 400 K is determined through X-ray phase and chemical analyses, tensiometry, and gas volumetry. It is established that one mole and then two moles of THF are removed from the initial sample at the first and second steps, respectively. Equations for barograms are obtained and the thermodynamic characteristics of desolvation of Ln(BH4)3 · 3THF under study are calculated. Gibbs energy values of the stages of process are determined semi-empirically. The law of its change for the entire series of Ln(BH4)3 · 3THF is determined with the emergence of the tetrad effect.

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

PubMed

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.

Method for extracting lanthanides and actinides from acid solutions by modification of purex solvent

DOEpatents

Horwitz, E. Philip; Kalina, Dale G.

1986-01-01

A process for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

Development and Testing of Diglycolamide Functionalized Mesoporous Silica for Sorption of Trivalent Actinides and Lanthanides

DOE PAGES

Shusterman, Jennifer A.; Mason, Harris E.; Bowers, Jon; ...

2015-09-03

Sequestration of trivalent actinides and lanthanides present in used nuclear fuel and legacy wastes is necessary for appropriate long-term stewardship of these metals, particularly to prevent their release into the environment. Organically modified mesoporous silica is an efficient material for recovery and potential subsequent separation of actinides and lanthanides because of its high surface area, tunable ligand selection, and chemically robust substrate. Here, we have synthesized the first novel hybrid material composed of SBA-15 type mesoporous silica functionalized with diglycolamide ligands (DGA-SBA). Because of the high surface area substrate, the DGA-SBA was found to have the highest Eu capacity reportedmore » so far in the literature of all DGA solid-phase extractants. The sorption behavior of europium and americium on DGA-SBA in nitric and hydrochloric acid media was tested in batch contact experiments. DGA-SBA was found to have high sorption of Am and Eu in pH 1, 1 M, and 3 M nitric and hydrochloric acid concentrations, which makes it promising for sequestration of these metals from used nuclear fuel or legacy waste. The kinetics of Eu sorption were found to be two times slower than that for Am in 1 M HNO 3. Additionally, the short-term susceptibility of DGA-SBA to degradation in the presence of acid was probed using 29Si and 13C solid-state NMR spectroscopy. Finally, the material was found to be relatively stable under these conditions, with the ligand remaining intact after 24 h of contact with 1 M HNO 3, an important consideration in use of the DGA-SBA as an extractant from acidic media.« less

Development and Testing of Diglycolamide Functionalized Mesoporous Silica for Sorption of Trivalent Actinides and Lanthanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shusterman, Jennifer A.; Mason, Harris E.; Bowers, Jon

Sequestration of trivalent actinides and lanthanides present in used nuclear fuel and legacy wastes is necessary for appropriate long-term stewardship of these metals, particularly to prevent their release into the environment. Organically modified mesoporous silica is an efficient material for recovery and potential subsequent separation of actinides and lanthanides because of its high surface area, tunable ligand selection, and chemically robust substrate. Here, we have synthesized the first novel hybrid material composed of SBA-15 type mesoporous silica functionalized with diglycolamide ligands (DGA-SBA). Because of the high surface area substrate, the DGA-SBA was found to have the highest Eu capacity reportedmore » so far in the literature of all DGA solid-phase extractants. The sorption behavior of europium and americium on DGA-SBA in nitric and hydrochloric acid media was tested in batch contact experiments. DGA-SBA was found to have high sorption of Am and Eu in pH 1, 1 M, and 3 M nitric and hydrochloric acid concentrations, which makes it promising for sequestration of these metals from used nuclear fuel or legacy waste. The kinetics of Eu sorption were found to be two times slower than that for Am in 1 M HNO 3. Additionally, the short-term susceptibility of DGA-SBA to degradation in the presence of acid was probed using 29Si and 13C solid-state NMR spectroscopy. Finally, the material was found to be relatively stable under these conditions, with the ligand remaining intact after 24 h of contact with 1 M HNO 3, an important consideration in use of the DGA-SBA as an extractant from acidic media.« less

Lanthanide-Functionalized Metal-Organic Framework Hybrid Systems To Create Multiple Luminescent Centers for Chemical Sensing.

PubMed

Yan, Bing

2017-11-21

Metal-organic frameworks (MOFs) possess an important advantage over other candidate classes for chemosensory materials because of their exceptional structural tunability and properties. Luminescent sensing using MOFs is a simple, intuitive, and convenient method to recognize species, but the method has limitations, such as insufficient chemical selectivity and signal loss. MOFs contain versatile building blocks (linkers or ligands) with special chemical reactivity, and postsynthetic modification (PSM) provides an opportunity to exploit and expand their unique properties. The linkers in most MOFs contain aromatic subunits that can readily display luminescence after ultraviolet or visible (typically blue) excitation, and this is the main luminescent nature of most MOFs. The introduction of photoactive lanthanide ions (Ln 3+ ) into the MOF hosts may produce new luminescent signals at different positions from that of the MOF linker, but this depends on the intramolecular energy transfer (antenna effect) from the MOF (linkers) to the Ln 3+ ions. Controlling the Ln 3+ content in MOF hybrids may create multiple luminescent centers. The nature of the unique luminescent centers may cause different responses to sensing species (i.e., ratiometric sensing), which may provide a new opportunity for luminescence research with applications to chemical sensing. In this Account, recent research progress on using lanthanide-functionalized MOF hybrid materials to create multiple luminescent centers for chemical sensing is described. Here we propose a general strategy to functionalize MOF hosts with lanthanide ions, compounds, or other luminescent species (organic dyes or carbon dots) and to assemble types of photofunctional hybrid systems based on lanthanide-functionalized MOFs. Five main methods were used to functionalize the MOFs and assemble the hybrid materials: in situ composition, ionic doping, ionic exchange, covalent PSM, and coordinated PSM. Through the lanthanide

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN

2014-04-01

Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 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{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groupsmore » 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{sub 3}pdc was decomposed into (ox){sup 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.« less

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

PubMed

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.

Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants

DOE PAGES

McCann, Billy W.; Silva, Nuwan De; Windus, Theresa L.; ...

2016-02-17

Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R 2(O)P-link-P(O)R 2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theorymore » and the performance of known bis-phosphine oxide extractants. For the case where link is -CH 2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the ‘anomalous aryl strengthening’ effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.« less

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

PubMed

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.

Bright Photon Upconversion on Composite Organic Lanthanide Molecules through Localized Thermal Radiation.

PubMed

Ye, Huanqing; Bogdanov, Viktor; Liu, Sheng; Vajandar, Saumitra; Osipowicz, Thomas; Hernández, Ignacio; Xiong, Qihua

2017-12-07

Converting low-energy photons via thermal radiation can be a potential approach for utilizing infrared (IR) photons to improve photovoltaic efficiency. Lanthanide-containing materials have achieved great progress in IR-to-visible photon upconversion (UC). Herein, we first report bright photon, tunable wavelength UC through localized thermal radiation at the molecular scale with low excitation power density (<10 W/cm 2 ) realized on lanthanide complexes of perfluorinated organic ligands. This is enabled by engineering the pathways of nonradiative de-excitation and energy transfer in a composite of ytterbium and terbium perfluoroimidodiphosphinates. The IR-excited thermal UC and wavelength control is realized through the terbium activators sensitized by the ytterbium sensitizers having high luminescence efficiency. The metallic molecular composite thus can be a potential energy material in the use of the IR solar spectrum for thermal photovoltaic applications.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1996-10-16

The gas-phase reactivity of the fluorinated hydrocarbons CF{sub 4}, CHF{sub 3}, CH{sub 3}F, C{sub 2}F{sub 6}, 1,1-C{sub 2}H{sub 4}F{sub 2}, and C{sub 6}F{sub 6} with the lanthanide cations Ce{sup +}, Pr{sup +}, Sm{sup +}, Ho{sup +}, Tm{sup +}, and Yb{sup +} and the reactivity of C{sub 6}H{sub 5}F with all lanthanide cations Ln{sup +} (Ln = La-Lu, with the exception of Pm{sup +}) 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,more » 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{sup +}RF. The most reactive lanthanides La{sup +}, Ce{sup +}, Gd{sup +}, and Tb{sup +} and also the formal closed-shell species Lu{sup +} 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{sup +} and Yb{sup +} the formation of neutral LnF{sub 3} is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs.« less

Role of Lanthanides in the Traceability of the Milk Production Chain.

PubMed

Aceto, Maurizio; Musso, Davide; Calà, Elisa; Arieri, Fabio; Oddone, Matteo

2017-05-24

The traceability and authentication of milk were studied using trace and ultratrace elements as chemical markers. Among these variables, the group of lanthanides resulted in being particularly useful for this purpose as a result of their homogeneous distribution inside milk, which showed on the contrary to be intrinsically inhomogeneous from the elemental point of view. Using in this pilot study milk samples from a factory in Piedmont (Italy), we demonstrated that the distribution of lanthanides can be used as a fingerprint to put into relation the soil of the pasture land on which cows graze and the bottled milk produced in the factory. In fact, the distribution is maintained nearly unaltered along the production chain of milk, apart from the passage into the stomachs of the cows. Using the same variables, it was possible to discriminate between milk produced in the factory and milk samples taken from the large-scale retail trade.

Lanthanide anilido complexes: synthesis, characterization, and use as highly efficient catalysts for hydrophosphonylation of aldehydes and unactivated ketones.

PubMed

Liu, Chengwei; Qian, Qinqin; Nie, Kun; Wang, Yaorong; Shen, Qi; Yuan, Dan; Yao, Yingming

2014-06-14

Lanthanide anilido complexes stabilized by the 2,6-diisopropylanilido ligand have been synthesized and characterized, and their catalytic activity for hydrophosphonylation reaction was explored. A reaction of anhydrous LnCl3 with 5 equivalents of LiNHPh-(I)Pr2-2,6 in THF generated the heterobimetallic lanthanide-lithium anilido complexes (2,6-(I)Pr2PhNH)5LnLi2(THF)2 [Ln = Sm(1), Nd(2), Y(3)] in good isolated yields. These complexes are well characterized by elemental analysis, IR, NMR (for complex ) and single-crystal structure determination. Complexes 1 - 3 are isostructural. In these complexes, the lanthanide metal ion is five-coordinated by five nitrogen atoms from five 2,6-diisopropylanilido ligands to form a distorted trigonal bipyramidal geometry. The lithium ion is coordinated by two nitrogen atoms from two 2,6-diisopropylanilido ligands, and one oxygen atom from a THF molecule. It was found that these simple lanthanide anilido complexes are highly efficient for catalyzing hydrophosphonylation reactions of various aldehydes and unactivated ketones to generate α-hydroxyphosphonates in good to excellent yields (up to 99%) within a short time (5 min for aldehydes, 20 min for ketones). Furthermore, the mechanism of hydrophosphonylation reactions has also been elucidated via(1)H NMR monitoring of reaction.

Controlled synthesis of bright and compatible lanthanide-doped upconverting nanocrystals

DOEpatents

Cohen, Bruce E.; Ostrowski, Alexis D.; Chan, Emory M.; Gargas, Daniel J.; Katz, Elan M.; Schuck, P. James; Milliron, Delia J.

2017-01-31

Certain nanocrystals possess exceptional optical properties that may make them valuable probes for biological imaging, but rendering these nanoparticles biocompatible requires that they be small enough not to perturb cellular systems. This invention describes a phosphorescent upconverting sub-10 nm nanoparticle comprising a lanthanide-doped hexagonal .beta.-phase NaYF.sub.4 nanocrystal and methods for making the same.

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1986-03-04

A process is described for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula as shown in a diagram where [phi] is phenyl, R[sup 1] is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R[sup 2] is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions. 6 figs.

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

PubMed

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

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

NASA Astrophysics Data System (ADS)

Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

2008-03-01

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

Investigation of aggregation in solvent extraction of lanthanides by acidic extractants (organophosphorus and naphthenic acid)

USGS Publications Warehouse

Zhou, N.; Wu, J.; Yu, Z.; Neuman, R.D.; Wang, D.; Xu, G.

1997-01-01

Three acidic extractants (I) di(2-ethylhexyl) phosphoric acid (HDEHP), (II) 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEHPEHE) and (III) naphthenic acid were employed in preparing the samples for the characterization of the coordination structure of lanthanide-extractant complexes and the physicochemical nature of aggregates formed in the organic diluent of the solvent extraction systems. Photo correlation spectroscopy (PCS) results on the aggregates formed by the partially saponified HDEHP in n-heptane showed that the hydrodynamic radius of the aggregates was comparable to the molecular dimensions of HDEHP. The addition of 2-octanol into the diluent, by which the mixed solvent was formed, increased the dimensions of the corresponding aggregates. Aggregates formed from the lanthanide ions and HDEHP in the organic phase of the extraction systems were found very unstable. In the case of naphthenic acid, PCS data showed the formation of w/o microemulsion from the saponified naphthenic acid in the mixed solvent. The extraction of lanthanides by the saponified naphthenic acid in the mixed solvent under the given experimental conditions was a process of destruction of the w/o microemulsion. A possible mechanism of the breakdown of the w/o microemulsion droplets is discussed.

Characteristics of water and ion exchange of Elodea nuttallii cells at high concentrations of lanthanides.

PubMed

Vorob'ev, Vladimir N; Mirziev, Samat I; Alexandrov, Evgeniy A; Sibgatullin, Timur A

2016-12-01

Changes of diffusive permeability of membranes of Elodea nuttallii cells following a short-term (60 min) treatment with high concentrations of lanthanides were recorded by the 1 H NMR-diffusometry and conductometry methods. The 1-h infiltration of segments of Elodea nuttallii internodes in 10 mM solutions of nitrates of La, Nd and Lu resulted in the increased leakage of electrolytes from cells, but has no effect on a water diffusive permeability of membranes. In samples subjected to a 30 min pretreatment with a water channel inhibitor HgCl 2 the water diffusive permeability of membranes (P d ) drops down under the influence of lanthanides, as well as an outcome of electrolytes. To explain the observed effects the change of spontaneous curvature of membrane lipid layer has been taken into consideration. The interaction of lanthanides with lipids of plasmalemma leads to the negative spontaneous curvature of lipid layer at which membrane channels are unclosed. Blocking of the ionic and water channels by mercury ions compensate the effect of change of spontaneous curvature of lipid layer. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen, E-mail: guwen68@nankai.edu.cn

2016-12-15

A 3D lanthanide MOF with formula [Sm{sub 2}(abtc){sub 1.5}(H{sub 2}O){sub 3}(DMA)]·H{sub 2}O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol. - Highlights: • A three-dimensional lanthanide metal-organic framework has been synthesized. • Complex 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. • Complex 1 displays amore » turn-on luminescence sensing with respect to ethanol among different alcohol molecules.« less

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Troy A

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 (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ 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 Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ 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 (La 3+) for Nd 3+ 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 phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of

Effect of polyoxyethylene n-alkyl ethers on carrier-mediated transport of lanthanide ions through cellulose triacetate membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sugiura, Masaaki

1992-02-01

Fluxes of 14 kinds of lanthanides across cellulose triacetate membranes were determined by using mixtures of o-nitrophenyl n-octyl ether and a series of polyoxythylene n-alkyl ethers (POE ethers) as plasticizers, and hinokitiol as carrier. Effects of alkyl and polyoxyethylene (POE) chains of POE ether on the flux were demonstrated. The transport of the lanthanides was coupled to a flow of hydrogen ions. The POE ethers used (C{sub n}H{sub 2n+1}(OCH{sub 2}CH{sub 2}){sub x}OH, referred to as C{sub n}E{sub x}) were C{sub 10}E{sub 3}, C{sub 12}E{sub 3}, C{sub 14}E{sub 3}, C{sub 16}E{sub 3}, C{sub 12}E{sub 2}, C{sub 12}E{sub 4}, C{sub 12}E{sub 6}more » and C{sub 12}E{sub 8}, In all cases, high fluxes were observed for the lanthanides from samarium to lutetium. On the contrary, the fluxes for lanthanum to neodymium were extremely low. In experiments testing the effect of the alkyl chain, the order of the POE ethers in the lanthanide flux for samarium to lutetium was C{sub 12}E{sub 3} > C{sub 10}E{sub 3} > C{sub 14}E{sub 3} >C{sub 16}E{sub 3}. In experiments testing the effect of the POE chain, the flux decreased with an increase in the chain length.« less

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

PubMed

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.

Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Jie; Li, Yuan; Chen, Yingnan

Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology andmore » structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.« less

Lanthanide Triangles Supported by Radical Bridging Ligands.

PubMed

Dolinar, Brian S; Alexandropoulos, Dimitris I; Vignesh, Kuduva R; James, Tia'Asia; Dunbar, Kim R

2018-01-24

The first examples of metallacycles containing rare earth ions bridged by radicals are reported. The molecular triangles [Ln 3 (hfac) 6 (bptz •- ) 3 ] (Ln = Dy III , Y III ; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) consist of lanthanide ions bridged by bptz radical anion (bptz •- ) ligands. Magnetic susceptibility measurements and CASSCF calculations performed on [Dy 3 (hfac) 6 (bptz •- ) 3 ] reveal the presence of antiferromagnetic coupling between the Dy III centers and the bptz •- ligands, with J = -6.62 cm -1 .

Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wall, Nathalie; Nash, Ken; Martin, Leigh

In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste.more » As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO 3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the

Thermodynamics of La and U and the separation factor of U/La in fused Me(Ga-40 wt.% In)/3LiCl-2KCl system

NASA Astrophysics Data System (ADS)

Smolenski, Valeri; Novoselova, Alena; Volkovich, Vladimir A.

2017-11-01

Separation of lanthanides and actinides can be achieved in a unique "molten chloride - liquid metal" system. Electrode potentials were recorded vs. Cl-/Cl2 reference electrode and the temperature dependencies of the apparent standard potentials of La-(Ga-In) and U-(Ga-In) alloys were determined. Thermodynamic properties and separation factor of lanthanum and uranium were calculated. The obtained data show the perspective for using this system in future innovation method for recovery of nuclear waste.

Bioadsorption of Rare Earth Elements through Cell Surface Display of Lanthanide Binding Tags.

PubMed

Park, Dan M; Reed, David W; Yung, Mimi C; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Fujita, Yoshiko; Riman, Richard E; Navrotsky, Alexandra; Jiao, Yongqin

2016-03-01

With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

Preliminary survey of separations technology applicable to the pretreatment of Hanford tank waste (1992--1993)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawrence, W.E.; Kurath, D.E.

1994-04-01

The US Department of Energy has established the Tank Waste Remediation System (TWRS) to manage and dispose of radioactive wastes stored at the Hanford Site. Within this program are evaluations of pretreatment system alternatives through literature reviews. The information in this report was collected as part of this project at Pacific Northwest Laboratory. A preliminary survey of literature on separations recently entered into the Hanford electronic databases (1992--1993) that have the potential for pretreatment of Hanford tank waste was conducted. Separation processes that can assist in the removal of actinides (uranium, plutonium, americium), lanthanides, barium, {sup 137}Cs, {sup 90}Sr,{sup 129more » }I, {sup 63}Ni, and {sup 99}Tc were evaluated. Separation processes of interest were identified through literature searches, journal reviews, and participation in separation technology conferences. This report contains brief descriptions of the potential separation processes, the extent and/or selectivity of the separation, the experimental conditions, and observations. Information was collected on both national and international separation studies to provide a global perspective on recent research efforts.« less

Lanthanide-binding peptides with two pendant aminodiacetate arms: impact of the sequence on chelation.

PubMed

Niedźwiecka, Agnieszka; Cisnetti, Federico; Lebrun, Colette; Gateau, Christelle; Delangle, Pascale

2012-03-21

Lanthanide complexes with a series of hexapeptides-incorporating two unnatural chelating amino acids with aminodiacetate groups, Ada(1) and Ada(2)-have been examined in terms of their speciation, structure, stability and luminescence properties. Whereas Ada(2) acts as a tridentate donor in all cases, Ada(1) may act as a tetradentate donor thanks to the coordination of the amide carbonyl function assisted by the formation of a six-membered chelate ring. The position of the Ada(1) residue in the sequence is demonstrated to be critical for the lanthanide complex speciation and structure. Ada(1) promotes the coordination of the backbone amide function to afford a highly dehydrated Ln complex and an S-shape structure of the peptide backbone, only when found in position 2.

A new heterometallic hybrid based on polymeric iodoplumbate and lanthanide metal-carboxylic coordination polycation

NASA Astrophysics Data System (ADS)

Gong, An-Weng; Wu, Hong-Yan; Lian, Zhao-Xun; Dong, Hai-Jun; Li, Hao-Hong; Chen, Zhi-Rong

2013-03-01

A 3-D supramolecular hybrid {[La(EPC)3(H2O)3]2(Pb6I18)}n (EPC+ = N-ethyl-pyridium-4-carboxylate) (1) has been structurally determined, which assume significance for its incorporating lanthanide metal-carboxylic coordination polycation into polymeric iodoplumbate to get heterometallics. 1 consists of 1-D (PbI)n6n- zigzag-like anion chains with lanthanide metalcarboxylic [La(EPC)3(HO)3]n3n+ polycations, which arrange in a criss-cross configuration. C-H⋯I and C-H⋯O hydrogen bonds among inorganic anions and polycations contribute to the formation of a 3-D supramolecular framework. Moreover, the framework displays an absorption edge at 2.46 eV which is comparable to PbI2's absorption edge.

Prediction of trivalent actinide amino(poly)carboxylate complex stability constants using linear free energy relationships with the lanthanide series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uhnak, Nic E.

Prediction of Trivalent Actinide Amino(poly)carboxylate Complex Stability Constants Using Linear Free Energy Relationships with the Lanthanide Series Alternative title: LFER Based Prediction of An(III) APC Stability Constants There is a gap in the literature regarding the complexation of amino(poly)carboxylate (APC) ligands with trivalent actinides (An(III))). The chemistry of the An(III) is nearly identical to that of the trivalent lanthanides Lns, but the An(III) express a slight enhancement when binding APC ligands. Presented in this report is a simple method of predicting the stability constants of the An(III), Pu, Am, Cm, Bk and Cf by using linear free energy relationships (LFER)more » of the An and the lanthanide (Ln) series for 91 APCs. This method produced An stability constants within uncertainty to available literature values for most ligands.« less

Understanding the complexation of Eu3+ with potential ligands used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle: A luminescence investigation.

PubMed

Sengupta, Arijit; Kadam, R M

2017-02-15

A systematic photoluminescence based investigation was carried out to understand the complexation of Eu 3+ with different ligands (TBP: tri-n-butyl phosphate, DHOA: di-n-hexyl octanamide, Cyanex 923: tri-n-alkyl phosphine oxide and Cyanex 272: Bis (2,4,4 trimethyl) pentyl phosphinic acid) used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle. In case of TBP and DHOA complexes, 3 ligand molecules coordinated in monodentate fashion and 3 nitrate ion in bidentate fashion to Eu 3+ to satisfy the 9 coordination of Eu. In case of Cyanex 923 and Cyanex 272 complexes, 3 ligand molecules, 3 nitrate ion and 3 water molecules coordinated to Eu 3+ in monodentate fashion. The Eu complexes of TBP and DHOA were found to have D 3h local symmetry while that for Cyanex 923 and Cyanex 272 were C 3h . Judd-Ofelt analysis of these systems revealed that the covalency of EuO bond followed the trend DHOA>TBP>Cyanex 272>Cyanex 923. Different photophysical properties like radiative and non-radiative life time, branching ratio for different transitions, magnetic and electric dipole moment transition probabilities and quantum efficiency were also evaluated and compared for these systems. The magnetic dipole transition probability was found to be almost independent of ligand field perturbation while electric dipole transition probability for 5 D 0 - 7 F 2 transition was found to be hypersensitive with ligand field with a trend DHOA>TBP>Cyanex 272>Cyanex 923. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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.

Physical characteristics of lanthanide complexes that act as magnetization transfer (MT) contrast agents

NASA Astrophysics Data System (ADS)

Zhang, Shanrong; Sherry, A. Dean

2003-02-01

Rapid water exchange is normally considered a prerequisite for efficient Gd3+-based MRI contrast agents. Yet recent measures of exchange rates in some Gd3+ complexes have shown that water exchange can become limiting when such complexes are attached to larger macromolecular structures. A new class of lanthanide complexes that display unusually slow water exchange (bound water lifetimes (τM298) > 10 μs) has recently been reported. This apparent disadvantage may be taken advantage of by switching the metal ion from gadolinium(III) to a lanthanide that shifts the bound water resonance substantially away from bulk water. Given appropriate water exchange kinetics, one can then alter the intensity of the bulk water signal by selective presaturation of this highly shifted, Ln3+-bound water resonance. This provides the basis of a new method to alter MR image contrast in tissue. We have synthesized a variety of DOTA-tetra(amide) ligands to evaluate as potential magnetization transfer (MT) contrast agents and found that the bound water lifetimes in these complexes are sensitive to both ligand structure (a series of Eu3+ complexes have τM298 values that range from 1 to 1300 μs) and the identity of the paramagnetic Ln3+ cation (from 3 to 800 μs for a single ligand). This demonstrates that it may be possible either to fine-tune the ligand structure or to select proper lanthanide cation to create an optimal MT agent for any clinical imaging field.

Preparation and Quality Control of the [153Sm]-Samarium Maltolate Complex as a Lanthanide Mobilization Product in Rats

PubMed Central

Naseri, Zohreh; Hakimi, Amir; Jalilian, Amir R.; Nemati Kharat, Ali; Bahrami-Samani, Ali; Ghannadi-Maragheh, Mohammad

2011-01-01

Development of lanthanide detoxification agents and protocols is of great importance in management of overdoses. Due to safety of maltol as a detoxifying agent in metal overloads, it can be used as a lanthanide detoxifying agent. In order to demonstrate the biodistribution of final complex, [153Sm]-samarium maltolate was prepared using Sm-153 chloride (radiochemical purity >99.9%; ITLC and specific activity). The stability of the labeled compound was determined in the final solution up to 24h as well as the partition coefficient. Biodistribution studies of Sm-153 chloride, [153Sm]-samarium maltolate were carried out in wild-type rats comparing the critical organ uptakes. Comparative study for Sm3+ cation and the labeled compound was conducted up to 48 h, demonstrating a more rapid wash out for the labeled compound. The effective and biological half lives of 2.3 h and 2.46h were calculated for the complex. The data suggest the detoxification property of maltol formulation for lanthanide overdoses. PMID:21773065

Self-Assembled Peptide-Lanthanide Nanoclusters for Safe Tumor Therapy: Overcoming and Utilizing Biological Barriers to Peptide Drug Delivery.

PubMed

Yan, Jin; He, Wangxiao; Yan, Siqi; Niu, Fan; Liu, Tianya; Ma, Bohan; Shao, Yongping; Yan, Yuwei; Yang, Guang; Lu, Wuyuan; Du, Yaping; Lei, Bo; Ma, Peter X

2018-02-27

Developing a sophisticated nanomedicine platform to deliver therapeutics effectively and safely into tumor/cancer cells remains challenging in the field of nanomedicine. In particular, reliable peptide drug delivery systems capable of overcoming biological barriers are still lacking. Here, we developed a simple, rapid, and robust strategy to manufacture nanoclusters of ∼90 nm in diameter that are self-assembled from lanthanide-doped nanoparticles (5 nm), two anticancer peptides with different targets (BIM and PMI), and one cyclic peptide iNGR targeted to cancer cells. The peptide-lanthanide nanoclusters (LDC-PMI-BIM-iNGR) enhanced the resistance of peptide drugs to proteolysis, disassembled in response to reductive conditions that are present in the tumor microenvironment and inhibited cancer cell growth in vitro and in vivo. Notably, LDC-PMI-BIM-iNGR exhibited extremely low systemic toxicity and side effects in vivo. Thus, the peptide-lanthanide nanocluster may serve as an ideal multifunctional platform for safe, targeted, and efficient peptide drug delivery in cancer therapy.

Separation of protactinum, actinium, and other radionuclides from proton irradiated thorium target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fassbender, Michael E.; Radchenko, Valery

Protactinium, actinium, radium, radiolanthanides and other radionuclide fission products were separated and recovered from a proton-irradiated thorium target. The target was dissolved in concentrated HCl, which formed anionic complexes of protactinium but not with thorium, actinium, radium, or radiolanthanides. Protactinium was separated from soluble thorium by loading a concentrated HCl solution of the target onto a column of strongly basic anion exchanger resin and eluting with concentrated HCl. Actinium, radium and radiolanthanides elute with thorium. The protactinium that is retained on the column, along with other radionuclides, is eluted may subsequently treated to remove radionuclide impurities to afford a fractionmore » of substantially pure protactinium. The eluate with the soluble thorium, actinium, radium and radiolanthanides may be subjected to treatment with citric acid to form anionic thorium, loaded onto a cationic exchanger resin, and eluted. Actinium, radium and radiolanthanides that are retained can be subjected to extraction chromatography to separate the actinium from the radium and from the radio lanthanides.« less

Optimizing the Readout of Lanthanide-DOTA Complexes for the Detection of Ligand-Bound Copper(I).

PubMed

Hanna, Jill R; Allan, Christopher; Lawrence, Charlotte; Meyer, Odile; Wilson, Neil D; Hulme, Alison N

2017-05-14

The CuAAC 'click' reaction was used to couple alkyne-functionalized lanthanide-DOTA complexes to a range of fluorescent antennae. Screening of the antenna components was aided by comparison of the luminescent output of the resultant sensors using data normalized to account for reaction conversion as assessed by IR. A maximum 82-fold enhanced signal:background luminescence output was achieved using a Eu(III)-DOTA complex coupled to a coumarin-azide, in a reaction which is specific to the presence of copper(I). This optimized complex provides a new lead design for lanthanide-DOTA complexes which can act as irreversible 'turn-on' catalytic sensors for the detection of ligand-bound copper(I).

Cooperative loading of multisite receptors with lanthanide containers: an approach for organized luminescent metallopolymers.

PubMed

Babel, Lucille; Guénée, Laure; Besnard, Céline; Eliseeva, Svetlana V; Petoud, Stéphane; Piguet, Claude

2018-01-14

Metal-containing (bio)organic polymers are materials of continuously increasing importance for applications in energy storage and conversion, drug delivery, shape-memory items, supported catalysts, organic conductors and smart photonic devices. The embodiment of luminescent components provides a revolution in lighting and signaling with the ever-increasing development of polymeric light-emitting devices. Despite the unique properties expected from the introduction of optically and magnetically active lanthanides into organic polymers, the deficient control of the metal loading currently limits their design to empirical and poorly reproducible materials. We show here that the synthetic efforts required for producing soluble multi-site host systems L k are largely overcome by the virtue of reversible thermodynamics for mastering the metal loading with the help of only two parameters: (1) the affinity of the luminescent lanthanide container for a single binding site and (2) the cooperative effect which modulates the successive fixation of metallic units to adjacent sites. When unsymmetrical perfluorobenzene-trifluoroacetylacetonate co-ligands (pbta - ) are selected for balancing the charge of the trivalent lanthanide cations, Ln 3+ , in six-coordinate [Ln(pbta) 3 ] containers, the explored anti-cooperative complexation processes induce nearest-neighbor intermetallic interactions twice as large as thermal energy at room temperature ( RT = 2.5 kJ mol -1 ). These values have no precedent when using standard symmetrical containers and they pave the way for programming metal alternation in luminescent lanthanidopolymers.

Inkjet Printing of Lanthanide-Organic Frameworks for Anti-Counterfeiting Applications.

PubMed

da Luz, Leonis L; Milani, Raquel; Felix, Jorlandio F; Ribeiro, Igor R B; Talhavini, Márcio; Neto, Brenno A D; Chojnacki, Jaroslaw; Rodrigues, Marcelo O; Júnior, Severino A

2015-12-16

Photoluminescent lanthanide-organic frameworks (Ln-MOFs) were printed onto plastic and paper foils with a conventional inkjet printer. Ln-MOF inks were used to reproduce color images that can only be observed under UV light irradiation. This approach opens a new window for exploring Ln-MOF materials in technological applications, such as optical devices (e.g., lab-on-a-chip), as proof of authenticity for official documents.

Multi-component lanthanide hybrids based on zeolite A/L and zeolite A/L-polymers for tunable luminescence.

PubMed

Chen, Lei; Yan, Bing

2015-02-01

Some multi-component hybrids based on zeolite L/A are prepared. Firstly, zeolite A/L is loaded with lanthanide complexes (Eu-DBM or Tb-AA (acetylacetone = AA, dibenzoylmethane = DBM)) into its channels. Secondly, 3-methacryloyloxypropyltrimethoxysilane (γ-MPS) is used to covalently graft onto the surface of functionalized zeolite A/L (Si-[ZA/L⊃Eu-DBM(Tb-AA)]). Thirdly, lanthanide ions (Eu(3+)/Tb(3+)) are coordinated to the functionalized zeolite A/L and ligands (phen(1,10-phenanthroline) or bipy (2,2'-bipyridyl)) are introduced by a ship-in-bottle method. The inside-outside double modifications of ZA/L with lanthanide complexes afford the final hybrids and these are characterized by means of XRD, FT-IR, UV-vis DRS, SEM and luminescence spectroscopy, some of which display white or near-white light emission. Furthermore, selected above-mentioned hybrids are incorporated into PEMA/PMMA (poly ethyl methylacryate/poly methyl methacrylate) hosts to prepare luminescent polymer films. These results provide abundant data that these hybrid materials can be expected to have potential application in various practical fields.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita

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 themore » 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.« less

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

PubMed

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.

Rational composition control of mixed-lanthanide metal-organic frameworks by an interfacial reaction with metal ion-doped polymer substrates

NASA Astrophysics Data System (ADS)

Tsuruoka, Takaaki; Miyanaga, Ayumi; Ohhashi, Takashi; Hata, Manami; Takashima, Yohei; Akamatsu, Kensuke

2017-09-01

A simple composition control route to mixed-lanthanide metal-organic frameworks (MOFs) was developed based on an interfacial reaction with mixed-lanthanide metal ion-doped polymer substrates. By controlling the composition of lanthanide ion (Eu3+ and Tb3+) dopants in polymer substrates to be used as metal ion precursors and scaffolding for the formation of MOFs, [EuxTb2-x(bdc)3(H2O)4]n crystals with a tunable metal composition could be routinely prepared on polymer substrates. Inductively coupled plasma (ICP) measurements revealed that the composition of the obtained frameworks was almost the same as that of the initial polymer substrates. In addition, the resulting [EuxTb2-x(bdc)3(H2O)4]n crystals showed strong phosphorescence because of Eu3+ transitions, indicating that the energy transfer from Tb3+ to Eu3+ ions in the frameworks could be achieved with high efficiency.

Detection of phosphorylation states by intermolecular sensitization of lanthanide-peptide conjugates.

PubMed

Pazos, Elena; Goličnik, Marko; Mascareñas, José L; Vázquez, M Eugenio

2012-10-04

The luminescence of a designed peptide equipped with a coordinatively-unsaturated lanthanide complex is modulated by the phosphorylation state of a serine residue in the sequence. While the phosphorylated state is weakly emissive, even in the presence of an external antenna, removal of the phosphate allows coordination of the sensitizer to the metal, yielding a highly emissive supramolecular complex.

Study of 3-Ethylamino-but-2-enoic acid phenylamide as a new ligand for preconcentration of lanthanides from aqueous media by liquid-liquid extraction prior to ICP-MS analysis.

PubMed

Varbanova, Evelina K; Angelov, Plamen A; Stefanova, Violeta M

2016-11-01

In the present work the potential of a new ligand 3-Ethylamino-but-2-enoic acid phenylamide (representing the class of enaminones) for selective preconcentration of lanthanides (La, Ce, Eu, Gd and Er) from aqueous medium is examined. Liquid-liquid extraction parameters, such as pH of the water phase, type and volume of organic solvent, quantity of ligand and reaction time are optimized on model solutions. Recovery of lanthanides by re-extraction with nitric acid makes the LLE procedure compatible with Inductively Coupled Plasma Mass Spectrometry. Spectral and non-spectral interferences are studied. Two isotopes per element are measured (with exception of La) for dynamic evaluation of the potential risk of spectral interference in variable real samples. The selectivity of complex formation reaction towards concomitant alkali and alkali-earth elements eliminates the interferences from sample matrix. Subjecting the standards to the optimized extraction procedure in combination with Re as internal standard is recommended as calibration strategy. The accuracy of developed method is approved by analysis of CRM Bush branches and leaves (NCS DC 73348) and recovery of spiked water and plant samples. The method's limits of detection for both studied objects are in the ranges from 0.2 ((158)Gd) to 3.7 ((139)La) ngl(-1) and 0.02 ((158)Gd) to 0.37((139)La) ngg(-1) for waters and plants respectively. The studied compound is an effective new ligand for preconcentration/separation of lanthanides from aqueous medium by LLE and subsequent determination by ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective separation of trivalent f-ions using 1,10-phenanthroline-2,9-dicarboxamide ligands in ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dehaudt, Jeremy; Williams, Neil J.; Shkrob, Ilya A.

1,10-Phenanthroline-2,9-dicarboxamide complexants decorated with alkyl chains and imidazolium cations have been studied for extraction of trivalent f-ions into imidazolium ionic liquids. The dicationic complexants are shown to extract Am over Eu with separation factors > 50 and high extraction efficiencies. Lastly, the different size selectivities for lanthanide ions were observed for these two types of the complexants, highlighting the importance of the positive charge in controlling both extraction efficiencies and extraction selectivities.

Selective separation of trivalent f-ions using 1,10-phenanthroline-2,9-dicarboxamide ligands in ionic liquids

DOE PAGES

Dehaudt, Jeremy; Williams, Neil J.; Shkrob, Ilya A.; ...

2016-06-13

1,10-Phenanthroline-2,9-dicarboxamide complexants decorated with alkyl chains and imidazolium cations have been studied for extraction of trivalent f-ions into imidazolium ionic liquids. The dicationic complexants are shown to extract Am over Eu with separation factors > 50 and high extraction efficiencies. Lastly, the different size selectivities for lanthanide ions were observed for these two types of the complexants, highlighting the importance of the positive charge in controlling both extraction efficiencies and extraction selectivities.

Chemistry of Selected Core Samples, Concentrate, Tailings, and Tailings Pond Waters: Pea Ridge Iron (-Lanthanide-Gold) Deposit, Washington County, Missouri

USGS Publications Warehouse

Grauch, Richard I.; Verplanck, Philip L.; Seeger, Cheryl M.; Budahn, James R.; Van Gosen, Bradley S.

2010-01-01

The Minerals at Risk and for Emerging Technologies Project of the U.S. Geological Survey (USGS) Mineral Resources Program is examining potential sources of lanthanide elements (rare earth elements) as part of its objective to provide up-to-date geologic information regarding mineral commodities likely to have increased demand in the near term. As part of the examination effort, a short visit was made to the Pea Ridge iron (-lanthanide-gold) deposit, Washington County, Missouri in October 2008. The deposit, currently owned by Wings Enterprises, Inc. of St. Louis, Missouri (Wings), contains concentrations of lanthanides that may be economic as a primary product or as a byproduct of iron ore production. This report tabulates the results of chemical analyses of the Pea Ridge samples and compares rare earth elements contents for world class lanthanide deposits with those of the Pea Ridge deposit. The data presented for the Pea Ridge deposit are preliminary and include some company data that have not been verified by the USGS or by the Missouri Department of Natural Resources, Division of Geology and Land Survey (DGLS), Geological Survey Program (MGS). The inclusion of company data is for comparative purposes only and does not imply an endorsement by either the USGS or MGS.

Ab initio approaches for the determination of heavy element energetics: Ionization energies of trivalent lanthanides (Ln = La-Eu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterson, Charles; Penchoff, Deborah A.; Wilson, Angela K., E-mail: wilson@chemistry.msu.edu

2015-11-21

An effective approach for the determination of lanthanide energetics, as demonstrated by application to the third ionization energy (in the gas phase) for the first half of the lanthanide series, has been developed. This approach uses a combination of highly correlated and fully relativistic ab initio methods to accurately describe the electronic structure of heavy elements. Both scalar and fully relativistic methods are used to achieve an approach that is both computationally feasible and accurate. The impact of basis set choice and the number of electrons included in the correlation space has also been examined.

Highly Luminescent, Water-Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates.

PubMed

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.

Understanding the complexation of Eu3 + with potential ligands used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle: A luminescence investigation

NASA Astrophysics Data System (ADS)

Sengupta, Arijit; Kadam, R. M.

2017-02-01

A systematic photoluminescence based investigation was carried out to understand the complexation of Eu3 + with different ligands (TBP: tri-n-butyl phosphate, DHOA: di-n-hexyl octanamide, Cyanex 923: tri-n-alkyl phosphine oxide and Cyanex 272: Bis (2,4,4 trimethyl) pentyl phosphinic acid) used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle. In case of TBP and DHOA complexes, 3 ligand molecules coordinated in monodentate fashion and 3 nitrate ion in bidentate fashion to Eu3 + to satisfy the 9 coordination of Eu. In case of Cyanex 923 and Cyanex 272 complexes, 3 ligand molecules, 3 nitrate ion and 3 water molecules coordinated to Eu3 + in monodentate fashion. The Eu complexes of TBP and DHOA were found to have D3h local symmetry while that for Cyanex 923 and Cyanex 272 were C3h. Judd-Ofelt analysis of these systems revealed that the covalency of Eusbnd O bond followed the trend DHOA > TBP > Cyanex 272 > Cyanex 923. Different photophysical properties like radiative and non-radiative life time, branching ratio for different transitions, magnetic and electric dipole moment transition probabilities and quantum efficiency were also evaluated and compared for these systems. The magnetic dipole transition probability was found to be almost independent of ligand field perturbation while electric dipole transition probability for 5D0-7F2 transition was found to be hypersensitive with ligand field with a trend DHOA > TBP > Cyanex 272 > Cyanex 923. Supplementary Table 2: Determination of inner sphere water molecules from the different empirical formulae reported in the literature.

Lanthanide-based laser-induced phosphorescence for spray diagnostics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voort, D. D. van der, E-mail: d.d.v.d.voort@tue.nl; Water, W. van de; Kunnen, R. P. J.

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 (293-383more » 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.« less

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.

PubMed

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.

Probing the Crystal Structure and Formation Mechanism of Lanthanide-Doped Upconverting Nanocrystals

DOE PAGES

Hudry, Damien; Abeykoon, A. M. M.; Dooryhee, E.; ...

2016-11-23

Lanthanide (Ln)-doped upconverting nanocrystals (UCNCs), such as NaLnF 4 (with Ln = lanthanide), constitute an important class of nanoscale materials due to their capacity to convert near-infrared photons into near-ultraviolet or visible light. Although under intense investigation for more than a decade, UCNCs have been relatively underexplored especially regarding their crystal structure and mechanisms of formation in organic media. The former is needed to explain the relationship between atomic scale structure and upconversion (UC) properties of UCNCs (i.e., local symmetry for 4f–4f transition probability, Ln 3+ distances for energy migration), while the latter is essential to finely tune the size, morphology, chemical composition, and architecture of well-defined upconverting nanostructures, which constitute the experimental levers to modify the optical properties. In this contribution, we use synchrotron-based diffraction experiments coupled to Rietveld and pair distribution function (PDF) analyses to understand the formation of NaGdF 4:Yb:Er UCNCs in organic media and to investigate their crystal structure. Our results reveal a complex mechanism of the formation of NaGdF 4:Yb:Er UCNCs based on chemical reactions involving molecular clusters and in situ-generated, crystalline sodium fluoride at high temperature. Additionally, a detailed crystallographic investigation of NaGdF 4:Yb:Er UCNCs is presented. Our Rietveld and PDF analyses show that the space group Pmore » $$\\bar{6}$$ is the one that best describes the crystal structure of NaGdF 4:Yb:Er UCNCs contrary to what has been recently proposed. Further, our Rietveld and PDF data reveal the formation of bulk-like crystal structure down to 10 nm with limited distortions. Finally, the results presented in this paper constitute an important step toward the comprehensive understanding of the underlying picture that governs UC properties of lanthanide-doped nanostructures.« less

Bioadsorption of rare earth elements through cell surface display of lanthanide binding tags

DOE PAGES

Park, Dan M.; Reed, David W.; Yung, Mimi C.; ...

2016-02-02

In this study, with the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb 3+ could be effectively recovered usingmore » citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb 3+ by citrate. No reduction in Tb 3+ adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.« less

TPE/REE separation with the use of zirconium salt of HDBP

NASA Astrophysics Data System (ADS)

Glekov, R. G.; Shmidt, O. V.; Palenik, Yu. V.; Goletsky, N. D.; Sukhareva, S. Yu.; Fedorov, Yu. S.; Zilberman, B. Ya.

2003-01-01

Partitioning of long-lived radionuclides (minor actinides, fission products) is considered as TBP-compatible ZEALEX-process for extraction separation of transplutonium elements (TPE) and rare-earth elements (REE), as well as Y, Mo, Fe and residual amounts of Np, Pu, U. Zirconium salt of dibutyl phosphoric acid (ZS-HDBP) dissolved in 30 % TBP is used as a solvent. The process was tested in multistage centrifugal contactors. Lanthanides, Y and TPE, as well as Mo, Fe were extracted from high-level Purex raffinate, Am and ceric subgroup of REE being separated from the polyvalent elements by stripping with HNO3. TPE/REE partitioning was achieved in the second cycle of the ZEALEX-process using DTPA in formic acid media. The integral decontamination factor of Am from La and Ce after both cycles is >200, from Pr and Nd 20-30 and from Sm and Eu 3.6; REE strips in both cycles contained <0,1% of the initial amount of TPE.

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

NASA Astrophysics Data System (ADS)

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.

Mechanistic insights into the luminescent sensing of organophosphorus chemical warfare agents and simulants using trivalent lanthanide complexes.

PubMed

Dennison, Genevieve H; Johnston, Martin R

2015-04-20

Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular-based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular-based approaches using non-covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second-generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide-based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimized auxiliary basis sets for density fitted post-Hartree-Fock calculations of lanthanide containing molecules

NASA Astrophysics Data System (ADS)

Chmela, Jiří; Harding, Michael E.

2018-06-01

Optimised auxiliary basis sets for lanthanide atoms (Ce to Lu) for four basis sets of the Karlsruhe error-balanced segmented contracted def2 - series (SVP, TZVP, TZVPP and QZVPP) are reported. These auxiliary basis sets enable the use of the resolution-of-the-identity (RI) approximation in post Hartree-Fock methods - as for example, second-order perturbation theory (MP2) and coupled cluster (CC) theory. The auxiliary basis sets are tested on an enlarged set of about a hundred molecules where the test criterion is the size of the RI error in MP2 calculations. Our tests also show that the same auxiliary basis sets can be used together with different effective core potentials. With these auxiliary basis set calculations of MP2 and CC quality can now be performed efficiently on medium-sized molecules containing lanthanides.

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

PubMed

Lian, J; Helean, K B; Kennedy, B J; Wang, L M; Navrotsky, A; Ewing, R C

2006-02-09

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure

Snynthesis and magnetization of BaLn2O4 (Ln = lanthanide)

NASA Astrophysics Data System (ADS)

Lundberg, Matthew

The BaLn2O4 family has been synthesized successfully as single crystals by the flux-growth method. The phases crystallize in the CaV2O4 structure prototype in space group Pnma (# 62). The structure has been studied using single-crystal x-ray diffraction, and stoichiometry confirmed with EDS, and the unit cell parameters and atomic positions have been determined for the whole lanthanide series (with the exception of the Lu compound). The effects of the lanthanide ionic radius on the atomic positions in the unit cell has been studied in terms of fractional atomic coordinates, bond lengths and angles, and bond valence sums. Magnetic measurements have been performed on the series with the exception of the La, Eu, and Lu members in the form of susceptibility versus temperature. The crystals all show signs of geometric antiferromagnetic frustration with the Neel temperatures significantly below the temperature predicted by the Weiss constant. Additionally some members of the family, namely BaCe2O4, BaNd2O4, BaPr 2O4, BaSm2O4, BaTb2O 4, and BaYb2O4 show significant crystal field splitting, that causes deviation from Currie-Weiss behavior.

Recent Advances in Inorganic Nanoparticle-Based NIR Luminescence Imaging: Semiconductor Nanoparticles and Lanthanide Nanoparticles.

PubMed

Kim, Dokyoon; Lee, Nohyun; Park, Yong Il; Hyeon, Taeghwan

2017-01-18

Several types of nanoparticle-based imaging probes have been developed to replace conventional luminescent probes. For luminescence imaging, near-infrared (NIR) probes are useful in that they allow deep tissue penetration and high spatial resolution as a result of reduced light absorption/scattering and negligible autofluorescence in biological media. They rely on either an anti-Stokes or a Stokes shift process to generate luminescence. For example, transition metal-doped semiconductor nanoparticles and lanthanide-doped inorganic nanoparticles have been demonstrated as anti-Stokes shift-based agents that absorb NIR light through two- or three-photon absorption process and upconversion process, respectively. On the other hand, quantum dots (QDs) and lanthanide-doped nanoparticles that emit in NIR-II range (∼1000 to ∼1350 nm) were suggested as promising Stokes shift-based imaging agents. In this topical review, we summarize and discuss the recent progress in the development of inorganic nanoparticle-based luminescence imaging probes working in NIR range.

Superprotonic conduction through one-dimensional ordered alkali metal ion chains in a lanthanide-organic framework

DOE PAGES

Wang, Xia; Wang, Yanlong; Silver, Mark A.; ...

2018-01-01

An ultrahigh proton conductivity of 2.91 × 10 −2 S cm −1 and an ultralow activation energy of 0.10 eV were observed in an anionic lanthanide-organic framework. Both values approach the records for proton-conducting MOF materials.

Method of loading organic materials with group III plus lanthanide and actinide elements

DOEpatents

Bell, Zane W [Oak Ridge, TN; Huei-Ho, Chuen [Oak Ridge, TN; Brown, Gilbert M [Knoxville, TN; Hurlbut, Charles [Sweetwater, TX

2003-04-08

Disclosed is a composition of matter comprising a tributyl phosphate complex of a group 3, lanthanide, actinide, or group 13 salt in an organic carrier and a method of making the complex. These materials are suitable for use in solid or liquid organic scintillators, as in x-ray absorption standards, x-ray fluorescence standards, and neutron detector calibration standards.

Lanthanide coordination polymers based on multi-donor ligand containing pyridine and phthalate moieties: Structures, luminescence and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Xun; Liu, Lang; College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022

2013-10-15

A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this casemore » results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.« less

Tough photoluminescent hydrogels doped with lanthanide.

PubMed

Wang, Mei Xiang; Yang, Can Hui; Liu, Zhen Qi; Zhou, Jinxiong; Xu, Feng; Suo, Zhigang; Yang, Jian Hai; Chen, Yong Mei

2015-03-01

Photoluminescent hydrogels have emerged as novel soft materials with potential applications in many fields. Although many photoluminescent hydrogels have been fabricated, their scope of usage has been severely limited by their poor mechanical performance. Here, a facile strategy is reported for preparing lanthanide (Ln)-alginate/polyacrylamide (PAAm) hydrogels with both high toughness and photoluminescence, which has been achieved by doping Ln(3+) ions (Ln = Eu, Tb, Eu/Tb) into alginate/PAAm hydrogel networks, where Ln(3+) ions serve as both photoluminescent emitters and physical cross-linkers. The resulting hydrogels exhibit versatile advantages including excellent mechanical properties (∼ MPa strength, ≈ 20 tensile strains, ≈ 10(4) kJ m(-3) energy dissipation), good photoluminescent performance, tunable emission color, excellent processability, and cytocompatibility. The developed tough photoluminescent hydrogels hold great promises for expanding the usage scope of hydrogels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orientational Order in Liquid Crystal Complexes Based on Lanthanides

NASA Astrophysics Data System (ADS)

Dobrun, L. A.; Kovshik, A. P.; Ryumtsev, E. I.; Kalinkin, A. A.

2018-04-01

In this study, we have for the first time determined the degree of an orientational order S for a series of liquid-crystal complexes based on lanthanides (Eu+3, Gd+3, Tb+3, Dy+3) with the same ligand composition in the temperature range of existence of the nematic phase by using experimental refractometry results. We have also found an even-odd alternative S as number of protons in the ions complexing agent has consecutively increased. The obtained values of S have been compared with the corresponding degrees of order of the calamite organic liquid crystals.

Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang Qun; Liu Shuxia, E-mail: liusx@nenu.edu.cn; Liang Dadong

2012-06-15

A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}][W{sub 6}O{sub 19}] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W{sub 6}O{sub 19}]{sup 2-} and dimeric [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}]{sup 2+} cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can movemore » away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln{sub 2}(DNBA){sub 4}]{sup 2+} remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations. - Graphical abstract: 3D POMs-based lanthanide-organic complexes performed the solvent effect on the luminescence property. The origin of such solvent effect can be understood and explained on the basis of the existence of coordinated active sites by the studies of ESI-MS. Highlights: Black-Right-Pointing-Pointer The solvent effect on the luminescence property of POMs-based lanthanide-organic complexes. Black-Right-Pointing-Pointer ESI-MS analyses illuminate the correlation between the structure and luminescence property. Black-Right-Pointing-Pointer The dimeric cations have eight active sites of solvent coordination. Black-Right-Pointing-Pointer The aggregated state structure of dimer cation remains unchanged in solution. Black-Right-Pointing-Pointer Luminescence associating with ESI-MS is a new method for investigating the interaction of complex and solvent.« less

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

NASA Technical Reports Server (NTRS)

Thompson, David W.

1993-01-01

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on

Lanthanide-labeled clay: A new method for tracing sediment transport in Karst

USGS Publications Warehouse

Mahler, B.J.; Bennett, P.C.; Zimmerman, M.

1998-01-01

Mobile sediment is a fundamental yet poorly characterized aspect of mass transport through karst aquifers. Here the development and field testing of an extremely sensitive particle tracer that may be used to characterize sediment transport in karst aquifers is described. The tracer consists of micron-size montmorillonite particles homoionized to the lanthanide form; after injection and retrieval from a ground water system, the lanthanide ions are chemically stripped from the clay and quantified by high performance liquid chromatography. The tracer meets the following desired criteria: low detection limit; a number of differentiable signatures; inexpensive production and quantification using standard methods; no environmental risks; and hydrodynamic properties similar to the in situ sediment it is designed to trace. The tracer was tested in laboratory batch experiments and field tested in both surface water and ground water systems. In surface water, arrival times of the tracer were similar to those of a conservative water tracer, although a significant amount of material was lost due to settling. Two tracer tests were undertaken in a karst aquifer under different flow conditions. Under normal flow conditions, the time of arrival and peak concentration of the tracer were similar to or preceded that of a conservative water tracer. Under low flow conditions, the particle tracer was not detected, suggesting that in low flow the sediment settles out of suspension and goes into storage.Mobile sediment is a fundamental yet poorly characterized aspect of mass transport through karst aquifers. Here the development and field testing of an extremely sensitive particle tracer that may be used to characterize sediment transport in karst aquifers is described. The tracer consists of micron-size montmorillonite particles homoionized to the lanthanide form; after injection and retrieval from a ground water system, the lanthanide ions are chemically stripped from the clay and

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process.

PubMed

Zhang, Wenzhong; Hietala, Sami; Khriachtchev, Leonid; Hatanpää, Timo; Doshi, Bhairavi; Koivula, Risto

2018-06-21

The lanthanides (Ln) are an essential part of many advanced technologies. Our societal transformation toward renewable energy drives their ever-growing demand. The similar chemical properties of the Ln pose fundamental difficulties in separating them from each other, yet high purity elements are crucial for specific applications. Here, we propose an intralanthanide separation method utilizing a group of titanium(IV) butyl phosphate coordination polymers as solid-phase extractants. These materials are characterized, and they contain layered structures directed by the hydrophobic interaction of the alkyl chains. The selective Ln uptake results from the transmetalation reaction (framework metal cation exchange), where the titanium(IV) serves as sacrificial coordination centers. The "tetrad effect" is observed from a dilute Ln 3+ mixture. However, smaller Ln 3+ ions are preferentially extracted in competitive binary separation models between adjacent Ln pairs. The intralanthanide ion-exchange selectivity arises synergistically from the coordination and steric strain preferences, both of which follow the reversed Ln contraction order. A one-step aqueous separation of neodymium (Nd) and dysprosium (Dy) is quantitatively achievable by simply controlling the solution pH in a batch mode, translating into a separation factor of greater than 2000 and 99.1% molar purity of Dy in the solid phase. Coordination polymers provide a versatile platform for further exploring selective Ln separation processes via the transmetalation process.

Structural Studies on Dy to 119 GPa and Applications to Lanthanide Systematics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, J; Akella, J

2005-05-31

The Rare Earth elements (REE) are known to undergo crystallographic as well as electronic structure changes with applied pressure. On increasing pressure, the trivalent lanthanides follow the sequence hcp {yields} Sm-type {yields} dhcp {yields} fcc {yields} dfcc. In this report we present room-temperature high-pressure x-ray diffraction data for Dy as well as our observations on the post-dfcc phases and concomitant volume changes in the heavy REE.

Enhanced electric dipole transition in lanthanide complex with organometallic ruthenocene units.

PubMed

Hasegawa, Yasuchika; Sato, Nao; Hirai, Yuichi; Nakanishi, Takayuki; Kitagawa, Yuichi; Kobayashi, Atsushi; Kato, Masako; Seki, Tomohiro; Ito, Hajime; Fushimi, Koji

2015-05-21

Enhanced luminescence of a lanthanide complex with dynamic polarization of the excited state and molecular motion is introduced. The luminescent lanthanide complex is composed of one Eu(hfa)3 (hfa, hexafluoroacetylacetonate) and two phosphine oxide ligands with ruthenocenyl units Rc, [Eu(hfa)3(RcPO)2] (RcPO = diphenylphosphorylruthenocene). The ruthenocenyl units in the phosphine oxide ligands play an important role of switching for dynamic molecular polarization and motion in liquid media. The oxidation states of the ruthenocenyl unit (Rc(1+)/Rc(1+)) are controlled by potentiostatic polarization. Eu(III) complexes attached with bidentate phosphine oxide ligands containing ruthenocenyl units, [Eu(hfa)3(RcBPO)] (RcBPO = 1,1'-bis(diphenylphosphoryl)ruthenocene), and with bidentate phosphine oxide ligands, [Eu(hfa)3(BIPHEPO)] (BIPHEPO =1,1'-biphenyl-2,2'-diylbis(diphenylphosphine oxide), were also prepared as references. The coordination structures and electrochemical properties were analyzed using single crystal X-ray analysis, cyclic voltammetry, and absorption spectroscopy measurements. The luminescence properties were estimated using an optoelectrochemical cell. Under potentiostatic polarization, a significant enhancement of luminescence was successfully observed for [Eu(hfa)3(RcPO)2], while no spectral change was observed for [Eu(hfa)3(RcBPO)]. In this study, the remarkable enhanced luminescence phenomena of Eu(III) complex based on the dynamic molecular motion under potentiostatic polarization have been performed.

Lanthanide behavior in hypersaline evaporation ponds at Guerrero Negro, Baja California, Mexico - an environment with halophiles

NASA Astrophysics Data System (ADS)

Choumiline, K.; López-Cortés, A.; Grajeda-Muñoz, M.; Shumilin, E.; Sapozhnikov, D.

2013-12-01

Lanthanides are known, in some cases, to be sensitive to changes in water column or sediment chemistry, a fact that allows them to be used as environmental fingerprints. Nevertheless, the behavior of these elements in hypersaline environments is insufficiently understood, especially in those colonized by bacteria, archaea and eukarya halophiles. Extreme environments like the mentioned exist in the artificially-controlled ponds of the 'Exportadora de Sal' salt-producing enterprise located in Guerrero Negro (Baja California, Mexico). Sediment cores from various ponds were collected, subsampled and measured by ICP-MS and INAA. This allowed differencing the behavior of lanthanides and trace elements under a water column salinity gradient along the evaporation sequence of ponds. Sediment profiles (30 mm long), obtained in Pond 5, dominated by Ca and Mg precipitation and at the same time rich in organic matter due to bacterial mat presence, showed highs and lows of the shale-normalized patterns along different in-core depths. Two groups of elements could be distinguished with similar trends: set A (La, Ce, Pr and Nd) and set B (Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The first 'group A' had two prominent peaks at 15 mm and around 22 mm, whereas the 'group B' showed only slight increase at 15 mm and none at 22 mm. Microscopic analyses of prokaryotic cells of a stratified mat in Pond 5 (collected in 2004) showed filamentous bacteria and cyanobacteria with a cell abundance and morphotype richness maxima of prokaryotic cells in a chemocline from 3 mm to 7 mm depth which co-exists nine morphotypes of aerobic and anaerobic prokaryotes Microcoleus chthonoplastes, Leptolyngbya, Cyanothece, Geitlerinema, Spirulina, Chloroflexus, Beggiatoa, Chromatium and Thioploca. Below the 7 mm depth, oxygenic photosynthesis depletes and sulfur reducing compounds increase. The highs of the shale-normalized lanthanide contents of the 'group A' (at 15 mm depth) seem to correlate with the

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Neil J.; Dehaudt, Jeremy; Bryantsev, Vyacheslav S.

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination ofmore » X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.« less

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

DOE PAGES

Williams, Neil J.; Dehaudt, Jeremy; Bryantsev, Vyacheslav S.; ...

2017-02-10

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination ofmore » X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.« less

Photon parameters for gamma-rays sensing properties of some oxide of lanthanides

NASA Astrophysics Data System (ADS)

Issa, Shams A. M.; Sayyed, M. I.; Zaid, M. H. M.; Matori, K. A.

2018-06-01

In the present research work, the mass attenuation coefficients (μm) representing the interaction of gamma photons with some oxide of lanthanides (Lu2O3Yb2O3, Er2O3, Sm2O3, Dy2O3, Eu2O3, Nd2O3, Pr6O11, La2O3 and Ce2O3) were investigated using WinXCom software in the wide energy range of 1 keV-100 GeV. The calculated values of μm afterwards were used to evaluate some gamma rays sensing properties as effective atomic effective atomic numbers (Zeff), effective electron densities (Nel), half value layer (HVL) and mean free path (MFP). The computed data observes that, the Lu2O3 shown excellent γ-rays sensing response in the broad energy range. At the absorption edges of the high elements present in the lanthanide compounds, more than a single value of Zeff were found due to the non-uniform variation of μm. Comparisons with experiments wherever possible have been achieved for the calculated μm and Zeff values. The calculated properties are beneficial expanded use of designing in radiation shielding, gas sensors, glass coloring agent and in electronic sensing devices.

High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

PubMed Central

Naccache, Rafik; Rodríguez, Emma Martín; Bogdan, Nicoleta; Sanz-Rodríguez, Francisco; de la Cruz, Maria del Carmen Iglesias; de la Fuente, Ángeles Juarranz; Vetrone, Fiorenzo; Jaque, Daniel; Solé, José García; Capobianco, John A.

2012-01-01

During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR) excitation (in the biological window) have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs) and metal nanoparticles, mostly gold nanorods (GNRs), are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide) ions: The excited donor ions (usually Yb3+ ion) that absorb the NIR excitation and the acceptor ions (usually Er3+, Ho3+ or Tm3+), that are responsible for the emitted visible (or also near infrared) radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to “in vitro” and “in vivo” cancer imaging, selective targeting and treatment are examined in this review. PMID:24213500

Photofunctional hybrids of lanthanide functionalized bio-MOF-1 for fluorescence tuning and sensing.

PubMed

Shen, Xiang; Yan, Bing

2015-08-01

A series of luminescent Ln(3+)@bio-MOF-1 (Ln=Eu, Tb, bio-MOF-1=Zn8(ad)4(BPDC)6O⋅2Me2NH2 (ad=adeninate, BPDC=biphenyldicarboxylate)) are synthesized via postsynthetic cation exchange by encapsulating lanthanide ions into an anionic metal-organic framework (MOF), and their photophysical properties are studied. After loading 2-thenoyltrifluroacetone (TTA) as sensitized ligand by a gas diffusion ("ship-in-bottle") method, it is found that the luminescent intensity of Eu(3+) is enhanced. Especially, when loading two different lanthanide cations into bio-MOF-1, the luminescent color can be tuned to close white (light pink) light output. Additionally, bio-MOF-1 and Eu(3+)@bio-MOF-1 are selected as representative samples for sensing metal ions. When bio-MOF-1 is immersed in the aqueous solutions of different metal ions, it shows highly sensitive sensing for Fe(3+) as well as Eu(3+)@bio-MOF-1 immersed in the DMF solutions of different metal ion. The results are benefit for the further application of functionalized bio-MOFs in practical fields. Copyright © 2015 Elsevier Inc. All rights reserved.

Luminescent Lanthanide MOFs: A Unique Platform for Chemical Sensing

PubMed Central

Zhao, Shu-Na; Wang, Guangbo

2018-01-01

In recent years, lanthanide metal–organic frameworks (LnMOFs) have developed to be an interesting subclass of MOFs. The combination of the characteristic luminescent properties of Ln ions with the intriguing topological structures of MOFs opens up promising possibilities for the design of LnMOF-based chemical sensors. In this review, we present the most recent developments of LnMOFs as chemical sensors by briefly introducing the general luminescence features of LnMOFs, followed by a comprehensive investigation of the applications of LnMOF sensors for cations, anions, small molecules, nitroaromatic explosives, gases, vapors, pH, and temperature, as well as biomolecules. PMID:29642458

CERES: An ab initio code dedicated to the calculation of the electronic structure and magnetic properties of lanthanide complexes.

PubMed

Calvello, Simone; Piccardo, Matteo; Rao, Shashank Vittal; Soncini, Alessandro

2018-03-05

We have developed and implemented a new ab initio code, Ceres (Computational Emulator of Rare Earth Systems), completely written in C++11, which is dedicated to the efficient calculation of the electronic structure and magnetic properties of the crystal field states arising from the splitting of the ground state spin-orbit multiplet in lanthanide complexes. The new code gains efficiency via an optimized implementation of a direct configurational averaged Hartree-Fock (CAHF) algorithm for the determination of 4f quasi-atomic active orbitals common to all multi-electron spin manifolds contributing to the ground spin-orbit multiplet of the lanthanide ion. The new CAHF implementation is based on quasi-Newton convergence acceleration techniques coupled to an efficient library for the direct evaluation of molecular integrals, and problem-specific density matrix guess strategies. After describing the main features of the new code, we compare its efficiency with the current state-of-the-art ab initio strategy to determine crystal field levels and properties, and show that our methodology, as implemented in Ceres, represents a more time-efficient computational strategy for the evaluation of the magnetic properties of lanthanide complexes, also allowing a full representation of non-perturbative spin-orbit coupling effects. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Barium titanate microparticles as potential carrier platform for lanthanide radionuclides for their use in the treatment of arthritis.

PubMed

Chakraborty, Sudipta; Vimalnath, K V; Sharma, Jyothi; Shetty, Priyalata; Sarma, H D; Chakravarty, Rubel; Prakash, Deep; Sinha, P K; Dash, Ashutosh

2018-06-15

Since the inception of radiation synovectomy, a host of radioactive colloids and microparticles incorporating suitable therapeutic radionuclides have been proposed for the treatment of arthritis. The present article reports the synthesis and evaluation of barium titanate microparticles as an innovative and effective carrier platform for lanthanide radionuclides in the preparation of therapeutic agents for treatment of arthritis. The material was synthesized by mechanochemical route and characterized by X-ray diffraction, scanning electron microscopy, surface area, and particle size distribution analyses. Loading of lanthanide radionuclides ( 166 Ho, 153 Sm, 177 Lu, and 169 Er) on the microparticles was achieved in high yield (> 95%) resulting in the formulation of loaded particulates with excellent radiochemical purities (> 99%). Radiolanthanide-loaded microparticles exhibited excellent in vitro stability in human serum. In vitro diethylene triamine pentaacetic acid challenge study indicated fairly strong chemical association of lanthanides with barium titanate microparticles. Long-term biodistribution studies carried out after administration of 177 Lu-loaded microparticles into one of the knee joints of normal Wistar rats revealed near-complete retention of the formulation (> 96% of the administered radioactivity) within the joint cavity even 14 days post-administration. The excellent localization of the loaded microparticles was further confirmed by sequential whole-body radio-luminescence imaging studies carried out using 166 Ho-loaded microparticles. Copyright © 2018 John Wiley & Sons, Ltd.

Syntheses, structures and luminescent properties of a series of 3D lanthanide coordination polymers with tripodal semirigid ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin Junsheng; Department of Applied Chemistry, Jilin Institute of Chemical Technology, Jilin 132022; Du Dongying

2011-02-15

Reactions of the tripodal bridging ligand 5-(4-carboxy-phenoxy)-isophthalic acid (abbreviated as H{sub 3}cpia) with lanthanide salts lead to the formation of a family of different coordination polymers, that is, [Ln(cpia)(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (Ln=Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Dy (7), Er (8), Tm (9) and Y (10)) in the presence of formic acid or diethylamine, which are characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TGA), XRPD spectrum and single-crystal X-ray diffraction. Compounds 1-10 are isostructural and exhibit three-dimensional microporous frameworks. Furthermore, the photoluminescent properties of 4, 5 and 7 have been studiedmore » in detail. -- Graphical abstract: Reactions of the tripodal bridging ligand (H{sub 3}cpia) with lanthanide ions lead to the formation of a series of coordination polymers in the presence of formic acid or diethylamine. Display Omitted Research Highlights: {yields} Ten new lanthanides-based coordination polymers (1-10) have been synthesized. {yields} 1-10 exhibit 3D (4,8)-connected fluorite topology networks with 1D channel parallel to the b-axis. {yields} Compounds 4, 5 and 7 exhibit characteristic luminescence of Sm{sup 3+}, Eu{sup 3+} and Dy{sup 3+} ions, respectively.« less

Porphyrin framework solids. Synthesis and structure of hybrid coordination polymers of tetra(carboxyphenyl)porphyrins and lanthanide-bridging ions.

PubMed

Muniappan, Sankar; Lipstman, Sophia; George, Sumod; Goldberg, Israel

2007-07-09

New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures. Several modes of coordination polymerization were revealed by single-crystal X-ray diffraction. They differ by the spatial functionality of the porphyrin building blocks, the coordination patterns of the lanthanide-carboxylate assemblies, and the topology of the resulting frameworks. The seven new reported structures exhibit periodically spaced 0.4-0.6 nm wide channel voids that perforate the respective crystalline polymeric architectures and are accessible to solvent components. Materials based on the m-carboxyphenyl derivative reveal smaller channels than those based on the p-carboxyphenyl analogues. An additional complex of the former with a smaller third-row transition metal (Co) is characterized by coordination connectivity in two dimensions only. Thermal and powder-diffraction analyses confirm the stability of the lanthanide-TmCPP (TmCPP=tetra(m-carboxyphenyl)porphyrin) frameworks.

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

PubMed

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.

Single crystal synthesis and magnetism of the Ba Ln 2O 4 family ( Ln = lanthanide)

DOE PAGES

Besara, Tiglet; Lundberg, Matthew S.; Sun, Jifeng; ...

2014-05-27

The series of compounds in the Ba Ln 2O 4 family (Ln = La–Lu, Y) has been synthesized for the first time in single crystalline form, using a molten metal flux. The series crystallizes in the CaV 2O 4 structure type with primitive orthorhombic symmetry (space group Pnma, #62), and a complete structural study of atomic positions, bonds, angles, and distortions across the lanthanide series is presented. With the exception of the Y, La, Eu, and Lu members, magnetic susceptibility measurements were performed between 2 K and 300 K. BaCe 2O 4 and BaYb 2O 4 display large crystal fieldsmore » effects and suppression of magnetic ordering. As a result, all compounds show signs of magnetic frustration due to the trigonal arrangements of the trivalent lanthanide cations in the structure.« less

Syntheses, crystal structures, and properties of six new lanthanide(III) transition metal tellurium(IV) oxyhalides with three types of structures.

PubMed

Shen, Yue-Ling; Mao, Jiang-Gao

2005-07-25

Solid-state reactions of lanthanide(III) oxide (and lanthanide(III) oxyhalide), transition metal halide (and transition metal oxide), and TeO(2) at high temperature lead to six new lanthanide transition metal tellurium(IV) oxyhalides with three different types of structures, namely, DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, ErCuTe(2)O(6)Br, Sm(2)Mn(Te(5)O(13))Cl(2), Dy(2)Cu(Te(5)O(13))Br(2), and Nd(4)Cu(TeO(3))(5)Cl(3). Compounds DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, and ErCuTe(2)O(6)Br are isostructural. The lanthanide(III) ion is eight-coordinated by eight oxygen atoms, and the copper(II) ion is five-coordinated by four oxygens and a halide anion in a distorted square pyramidal geometry. The interconnection of Ln(III) and Cu(II) ions by bridging tellurite anions results in a three-dimensional (3D) network with tunnels along the a-axis; the halide anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels. Compounds Sm(2)Mn(Te(5)O(13))Cl(2) and Dy(2)Cu(Te(5)O(13))Br(2) are isostructural. The lanthanide(III) ions are eight-coordinated by eight oxygens, and the divalent transition metal ion is octahedrally coordinated by six oxygens. Two types of polymeric tellurium(IV) oxide anions are formed: Te(3)O(8)(4)(-) and Te(4)O(10)(4)(-). The interconnection of the lanthanide(III) and divalent transition metal ions by the above two types of polymeric tellurium(IV) oxide anions leads to a 3D network with long, narrow-shaped tunnels along the b-axis. The halide anions remain isolated and are located at the above tunnels. Nd(4)Cu(TeO(3))(5)Cl(3) features a different structure. All five of the Nd(III) ions are eight-coordinated (NdO(8) for Nd(1), Nd(2), Nd(4), and Nd(5) and NdO(7)Cl for Nd(3)), and the copper(I) ion is tetrahedrally coordinated by four chloride anions. The interconnection of Nd(III) ions by bridging tellurite anions resulted in a 3D network with large tunnels along the b-axis. The CuCl(4) tetrahedra are interconnected into

Electrical resistivity of liquid lanthanides using charge hard sphere system

NASA Astrophysics Data System (ADS)

Sonvane, Y. A.; Thakor, P. B.; Jani, A. R.

2013-06-01

In the present paper, we have studied electrical resistivity (ρ) of liquid lanthanides. To describe the structural information, the structure factor S(q) due to the charged hard sphere (CHS) reference systems is used along with our newly constructed model potential. To see the influence of exchange and correlation effect on the electrical resistivity (ρ) have used different local field correction functions like Hartree (H), Sarkar et al (S) and Taylor (T). Lastly we conclude that the proper choice of the model potential along with local field correction function plays a vital role to the study of the electrical resistivity (ρ).

Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding.

PubMed

Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

2011-06-01

Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilden, Andreas; Lumetta, Gregg J.; Sadowski, Fabian

A solvent extraction system has been developed for separating trivalent actinides from lanthanides. This “Advanced TALSPEAK” system uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanides into a n-dodecane-based solvent phase, while the actinides are retained in a citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid. Batch distribution measurements indicate that the separation of americium from the light lanthanides decreases as the pH decreases. For example, the separation factor between La and Am increases from 2.5 at pH 2.0 to 19.3 at pH 3.0. However, previous investigations indicated that the extraction rates for the heavier lanthanides decrease with increasing pH.more » So, a balance between these two competing effects is required. An aqueous phase in which the pH was set at 2.6 was chosen for further process development because this offered optimal separation, with a minimum separation factor of ~8.4, based on the separation between La and Am. Centrifugal contactor single-stage efficiencies were measured to characterize the performance of the system under flow conditions.« less

The Crystal-Chemical Effect of REE Separation in Minerals: Causes and Practical Values

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.

2018-03-01

Contrast variations in the type of REE distribution from a distinctly negative mode to a positive mode is revealed in zonal fluorites of Eastern Transbaikal, with a pronounced decrease in the Ce/Y ratios in successive zones of increasing Y accompanied by a gradual decrease in the temperature and salinity of fluid inclusions in the fluorites. It is assumed that these facts are caused by the appearance of nm-size phases of REE minerals characterized by various crystalline structures and demonstrating selective concentrations of lanthanides, i.e., exhibiting a crystal-chemical differentiation of REEs that is widespread in the processes of mineral formation. Based on this natural mechanism, the development of a procedure of selective REE extraction from the concentrates is proposed. The primary laboratory experiments resulted in the discovery of the difference in REE concentrations in the sediment and filtrate with the separation coefficient varying by a factor of 76. The results obtained allow one to expect a true separation possibility for Nd along with the medium and heavy REEs. In view of the data obtained, the crystalline-chemical separation of REEs has some advantages compared to the processes currently used, especially extraction.

The first quaternary lanthanide(III) nitride iodides: NaM{sub 4}N{sub 2}I{sub 7} (M=La-Nd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schurz, Christian M.; Schleid, Thomas, E-mail: schleid@iac.uni-stuttgart.d

In attempts to synthesize lanthanide(III) nitride iodides with the formula M{sub 2}NI{sub 3} (M=La-Nd), moisture-sensitive single crystals of the first quaternary sodium lanthanide(III) nitride iodides NaM{sub 4}N{sub 2}I{sub 7} (orthorhombic, Pna2{sub 1}; Z=4; a=1391-1401, b=1086-1094, c=1186-1211 pm) could be obtained. The dominating structural features are {sup 1}{sub {infinity}}{l_brace}[NM{sub 4/2}{sup e}]{sup 3+}{r_brace} chains of trans-edge linked [NM{sub 4}]{sup 9+} tetrahedra, which run parallel to the polar 2{sub 1}-axis [001]. Between the chains, direct bonding via special iodide anions generates cages, in which isolated [NaI{sub 6}]{sup 5-} octahedra are embedded. The IR spectrum of NaLa{sub 4}N{sub 2}I{sub 7} recorded from 100 tomore » 1000 cm{sup -1} shows main bands at {upsilon}=337, 373 and 489 cm{sup -1}. With decreasing radii of the lanthanide trications these bands, which can be assigned as an influence of the vibrations of the condensed [NM{sub 4}]{sup 9+} tetrahedra, are shifted toward higher frequencies for the NaM{sub 4}N{sub 2}I{sub 7} series (M=La-Nd), following the lanthanide contraction. - Abstract: View at the main structural features of the NaM{sub 4}N{sub 2}I{sub 7} series (M=La-Nd): The {sup 1}{sub {infinity}}{l_brace}[NM{sub 4/2}{sup e}]{sup 3+}{r_brace} chains, consisting of trans-edge connected [NM{sub 4}]{sup 9+} tetrahedra, and the special kind of iodide anions, namely (I7){sup -}, form cages, in which isolated [NaI{sub 6}]{sup 5-} octahedra are embedded.« less

A novel strategy for phosphopeptide enrichment using lanthanide phosphate co-precipitation.

PubMed

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.

A luminescent Lanthanide-free MOF nanohybrid for highly sensitive ratiometric temperature sensing in physiological range.

PubMed

Zhou, You; Zhang, Denan; Zeng, Jin; Gan, Ning; Cuan, Jing

2018-05-01

Luminescent MOF materials with tunable emissions and energy/charge transfer processes have been extensively explored as ratiometric temperature sensors. However, most of the ratiometric MOF thermometers reported thus far are based on the MOFs containing photoactive lanthanides, which are potentially facing cost issue and serious supply shortage. Here, we present a ratiometric luminescent thermometer based on a dual-emitting lanthanide-free MOF hybrid, which is developed by encapsulation of a fluorescent dye into a robust nanocrystalline zirconium-based MOF through a one-pot synthesis approach. The structure and morphology of the hybrid product was characterized by Powder X-ray diffraction (PXRD), N 2 adsorption-desorption measurement and Scanning electron microscopy (SEM). The pore confinement effect well isolates the guest dye molecules and therefore suppresses the nonradiative energy transfer process between dye molecules. The incorporated dye emission is mainly sensitized by the organic linkers within MOF through fluorescence resonance energy transfer. The ratiometric luminescence of the MOF hybrid shows a significant response to temperature due to the thermal-related back energy transfer process from dye molecules and organic linkers, thus can be exploited for self-calibrated temperature sensing. The maximum thermometric sensitivity is 1.19% °C -1 in the physiological temperature range, which is among the highest for the ratiomtric MOF thermometers that operating in 25-45°C. The temperature resolution is better than 0.1°C over the entire operative range (20-60°C). By integrating the advantages of excellent stability, nanoscale nature, and high sensitivity and precision in the physiological temperature range, this dye@MOF hybrid might have potential application in biomedical diagnosis. What' more, this work has expanded the possibility of non-lanthanide luminescent MOF materials for the development of ratiometric temperature sensors. Copyright © 2018

Two sodium and lanthanide(III) MOFs based on oxalate and V-shaped 4,4‧-oxybis(benzoate) ligands: Hydrothermal synthesis, crystal structure, and luminescence properties

NASA Astrophysics Data System (ADS)

Wang, Chongchen; Guo, Guangliang; Wang, Peng

2013-01-01

Two lanthanide based metal-organic frameworks, [NaLn(oba)(ox)(H2O)] (Lndbnd6 Eu(1) and Sm(2)) were obtained from 4,4'-oxybisbenzoic acid, sodium oxalate and corresponding lanthanide salts by hydrothermal synthesis. They were characterized by single-crystal X-ray diffraction, IR spectra, and photoluminescent spectra. The crystallographic data reveals that complexes 1 and 2 are isomorphous and isostructural, composed of three-dimensional framework built up of distorted tricapped trigonal EuO9 units, distorted octahedron NaO6 units, 4,4'-oxybis(benzoate) and oxalate. The carboxylate oxygen atoms of the 4,4'-oxybis(benzoate) and oxalate ligand are coordinated to lanthanide ions and sodium ions, resulting into two-dimensional inorganic sheets, which are further linked into three-dimensional network by organic ligands. Thermogravimetric analyses of 1-2 display a considerable thermal stability. Photoluminescent measurements indicated that europium complex 1 displayed strong red emission.

Deep desulfurization by amphiphilic lanthanide-containing polyoxometalates in ionic-liquid emulsion systems under mild conditions.

PubMed

Xu, Junhua; Zhao, Shen; Ji, Yuanchun; Song, Yu-Fei

2013-01-07

Amphiphilic lanthanide-containing polyoxometalates (POMs) were prepared by surfactant encapsulation. Investigation of these lanthanide-containing POMs in oxidative desulfurization (ODS) showed that highly efficient deep desulfurization could be achieved in only 14 min with 100% conversion of dibenzothiophene under mild conditions by using (DDA)(9)LaW(10)/[omim]PF(6) (DDA=dimethyldioctadecylammonium, omim=1-octyl-3-methyl-imidazolium) in the presence of H(2) O(2) . Furthermore, deep desulfurization proceeds smoothly in model oil with an S content as low as 50 ppm. A scaled-up experiment in which the volume of model oil was increased from 5 to 1000 mL with S content of 1000 ppm indicated that about 99% sulfur removal can be achieved in 40 mins in an ionic-liquid emulsion system. To the best of our knowledge, the (DDA)(9)LaW(10)/[omim]PF(6) catalyst system with H(2)O(2) as oxidant is one of the most efficient desulfurization systems reported so far. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anionic Lanthanide MOFs as a Platform for Iron-Selective Sensing, Systematic Color Tuning, and Efficient Nanoparticle Catalysis.

PubMed

Wu, Ya-Pan; Xu, Guo-Wang; Dong, Wen-Wen; Zhao, Jun; Li, Dong-Sheng; Zhang, Jian; Bu, Xianhui

2017-02-06

New porous anionic Ln-MOFs, namely, [Me 2 NH 2 ][Ln(CPA) 2 (H 2 O) 2 ] (Ln = Eu, Gd), have been prepared through the self-assembly of 5-(4-carboxy phenyl)picolinic acid (H 2 CPA) and lanthanide ions. They feature open anionic frameworks with 1-D hydrophilic channels and exchangeable dimethylamine ions. The Eu phase could detect Fe 3+ ions with high selectivity and sensitivity in either aqueous solution or biological condition. The ratios of lanthanide ions on this structure platform could be rationally tuned to not only achieve dichromatic emission colors with linear correlation but also attain three primary colors (RGB) and even white light with favorable correlated color temperature. Furthermore, the Ag(I)-exchanged phases can be readily reduced to afford Ag nanoparticles. The as-prepared Ag@Ln-MOFs composite shows highly efficient catalytic performance for the reduction of 4-nitrophenol.

Measurement of Magnetic Exchange in Asymmetric Lanthanide Dimetallics: Toward a Transferable Theoretical Framework.

PubMed

Giansiracusa, Marcus J; Moreno-Pineda, Eufemio; Hussain, Riaz; Marx, Raphael; Martínez Prada, María; Neugebauer, Petr; Al-Badran, Susan; Collison, David; Tuna, Floriana; van Slageren, Joris; Carretta, Stefano; Guidi, Tatiana; McInnes, Eric J L; Winpenny, Richard E P; Chilton, Nicholas F

2018-02-21

Magnetic exchange interactions within the asymmetric dimetallic compounds [hqH 2 ][Ln 2 (hq) 4 (NO 3 ) 3 ]·MeOH, (Ln = Er(III) and Yb(III), hqH = 8-hydroxyquinoline) have been directly probed with EPR spectroscopy and accurately modeled by spin Hamiltonian techniques. Exploitation of site selectivity via doping experiments in Y(III) and Lu(III) matrices yields simple EPR spectra corresponding to isolated Kramers doublets, allowing determination of the local magnetic properties of the individual sites within the dimetallic compounds. CASSCF-SO calculations and INS and far-IR measurements are all employed to further support the identification and modeling of the local electronic structure for each site. EPR spectra of the pure dimetallic compounds are highly featured and correspond to transitions within the lowest-lying exchange-coupled manifold, permitting determination of the highly anisotropic magnetic exchange between the lanthanide ions. We find a unique orientation for the exchange interaction, corresponding to a common elongated oxygen bridge for both isostructural analogs. This suggests a microscopic physical connection to the magnetic superexchange. These results are of fundamental importance for building and validating model microscopic Hamiltonians to understand the origins of magnetic interactions between lanthanides and how they may be controlled with chemistry.

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

PubMed

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.

Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts.

PubMed

Sugimoto, Masumi; Liu, Xin-Ling; Tsunega, Seiji; Nakajima, Erika; Abe, Shunsuke; Nakashima, Takuya; Kawai, Tsuyoshi; Jin, Ren-Hua

2018-05-02

Recently, circularly polarized luminescence (CPL)-active systems have become a very hot and interesting subject in chirality- and optics-related areas. The CPL-active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL-active system by "luminescent guest-chiral host" strategy is proposed. Luminescent sub-10 nm lanthanide oxides (Eu 2 O 3 or Tb 2 O 3 ) nanoparticles (guests) were encapsulated into chiral non-helical SiO 2 nanofibres (host) through calcination of chiral SiO 2 hybrid nanofibres, trapping Eu 3+ (or Tb 3+ ). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu 3+ and 545 nm for Tb 3+ . This work has implications for inorganic-based CPL-active systems by incorporation of various luminescent guests within chiral inorganic hosts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural properties of lanthanide and actinide compounds within the plane wave pseudopotential approach

PubMed

Pickard; Winkler; Chen; Payne; Lee; Lin; White; Milman; Vanderbilt

2000-12-11

We show that plane wave ultrasoft pseudopotential methods readily extend to the calculation of the structural properties of lanthanide and actinide containing compounds. This is demonstrated through a series of calculations performed on UO, UO2, UO3, U3O8, UC2, alpha-CeC2, CeB6, CeSe, CeO2, NdB6, TmOI, LaBi, LaTiO3, YbO, and elemental Lu.

Lanthanide complexes with aromatic o-phosphorylated ligands: synthesis, structure elucidation and photophysical properties.

PubMed

Shuvaev, Sergey; Utochnikova, Valentina; Marciniak, Łukasz; Freidzon, Alexandra; Sinev, Ilya; Van Deun, Rik; Freire, Ricardo O; Zubavichus, Yan; Grünert, Wolfgang; Kuzmina, Natalia

2014-02-28

Lanthanide complexes LnL3 (Ln = Sm, Eu, Tb, Dy, Tm, Yb, Lu) with aromatic o-phosphorylated ligands (HL(1) and HL(2)) have been synthesized and identified. Their molecular structure was proposed on the basis of a new complex approach, including DFT calculations, Sparkle/PM3 modelling, EXAFS spectroscopy and luminescent probing. The photophysical properties of all of the complexes were investigated in detail to obtain a deeper insight into the energy transfer processes.

Sparkle model for the calculation of lanthanide complexes: AM1 parameters for Eu(III), Gd(III), and Tb(III).

PubMed

Freire, Ricardo O; Rocha, Gerd B; Simas, Alfredo M

2005-05-02

Our previously defined Sparkle model (Inorg. Chem. 2004, 43, 2346) has been reparameterized for Eu(III) as well as newly parameterized for Gd(III) and Tb(III). The parameterizations have been carried out in a much more extensive manner, aimed at producing a new, more accurate model called Sparkle/AM1, mainly for the vast majority of all Eu(III), Gd(III), and Tb(III) complexes, which possess oxygen or nitrogen as coordinating atoms. All such complexes, which comprise 80% of all geometries present in the Cambridge Structural Database for each of the three ions, were classified into seven groups. These were regarded as a "basis" of chemical ambiance around a lanthanide, which could span the various types of ligand environments the lanthanide ion could be subjected to in any arbitrary complex where the lanthanide ion is coordinated to nitrogen or oxygen atoms. From these seven groups, 15 complexes were selected, which were defined as the parameterization set and then were used with a numerical multidimensional nonlinear optimization to find the best parameter set for reproducing chemical properties. The new parameterizations yielded an unsigned mean error for all interatomic distances between the Eu(III) ion and the ligand atoms of the first sphere of coordination (for the 96 complexes considered in the present paper) of 0.09 A, an improvement over the value of 0.28 A for the previous model and the value of 0.68 A for the first model (Chem. Phys. Lett. 1994, 227, 349). Similar accuracies have been achieved for Gd(III) (0.07 A, 70 complexes) and Tb(III) (0.07 A, 42 complexes). Qualitative improvements have been obtained as well; nitrates now coordinate correctly as bidentate ligands. The results, therefore, indicate that Eu(III), Gd(III), and Tb(III) Sparkle/AM1 calculations possess geometry prediction accuracies for lanthanide complexes with oxygen or nitrogen atoms in the coordination polyhedron that are competitive with present day ab initio/effective core potential

A Physicochemical Method for Separating Rare Earths: Addressing an Impending Shortfall

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schelter, Eric

2017-03-14

There are currently zero operating suppliers of critical rare earth elements La–Lu, Sc, Y (REs), in the western hemisphere. REs are critical materials due to their importance in clean energy and defense applications, including permanent magnets in wind turbines and phosphors in energy efficient lighting. It is not economically viable to produce pure REs in the U.S. given current separations technology. REs production is dominated by suppliers in the People’s Republic of China (PRC) because of their capacity in liquid­liquid solvent extraction (SX) used to purify mixtures. Weak environmental regulations in the PRC also contribute to a competitive advantage. SXmore » is a cost, time, solvent and waste intensive process but is highly optimized and scalable. The low efficiency of SX derives from the small thermodynamic differences in solvation enthalpy between the RE3+ cations. To foster stable domestic RE production there is a critical need for fundamentally new REs chemistry that contributes to disruptive technologies in RE separations. The overall goal of this project was to develop new thermodynamic bases, and apply them, for the solution separation of rare earth metals. We have developed the chemistry of rare earth metals: La–Lu, Sc and Y, with redox active ligands. Our hypothesis for the project was that electron­hole coupling in complexes of certain lanthanide metals with redox active ligands can be used to manifest chemical distinctiveness and affect separations. We also developed separations based on unique solution equilibria from tailored ligands.« less

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

PubMed

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Dissolution of lanthanide alumino-silicate oxynitride glasses

NASA Astrophysics Data System (ADS)

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.

Computational discovery of lanthanide doped and Co-doped Y{sub 3}Al{sub 5}O{sub 12} for optoelectronic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, Kamal; Chernatynskiy, Aleksandr; Phillpot, Simon R.

2015-09-14

We systematically elucidate the optoelectronic properties of rare-earth doped and Ce co-doped yttrium aluminum garnet (YAG) using hybrid exchange-correlation functional based density functional theory. The predicted optical transitions agree with the experimental observations for single doped Ce:YAG, Pr:YAG, and co-doped Er,Ce:YAG. We find that co-doping of Ce-doped YAG with any lanthanide except Eu and Lu lowers the transition energies; we attribute this behavior to the lanthanide-induced change in bonding environment of the dopant atoms. Furthermore, we find infrared transitions only in case of the Er, Tb, and Tm co-doped Ce:YAG and suggest Tm,Ce:YAG and Tb,Ce:YAG as possible functional materials formore » efficient spectral up-conversion devices.« less

Thermodynamics properties of lanthanide series near melting point-A pseudopotential approach

NASA Astrophysics Data System (ADS)

Suthar, P. H.; Gajjar, P. N.

2018-04-01

The present paper deals with computational study of thermodynamics properties for fifteen elements of lanthanide series. The Helmholtz free energy (F), Internal energy (E) and Entropy (S)have been computed using variational method based on the Gibbs-Bogoliubov (GB) along with Percus-Yevick hard sphere reference system and Gajjar's model potential. The local field correction function proposed by Taylor is applied to introduce the exchange and correlation effects in the study of thermodynamics of these metals. The present results in comparison with available theoretical and experimental are found to be in good agreement and confirm the ability of the model potential.

Synthesis and luminescent properties of the novel poly(ethylene-co-acrylic acid) films based on surface modification with lanthanide (Eu3+, Tb3+) complexes

NASA Astrophysics Data System (ADS)

Wu, Yuewen; Chu, Yang; Yu, Zhenjiang; Hao, Haixia; Wu, Qingyao; Xie, Hongde

2017-10-01

Two kinds of novel fluorescent films have been successfully synthesized by surface modification on the poly(ethylene-co-acrylic acid) films using the lanthanide (Eu3+, Tb3+) complexes. The process consists of three steps: conversion of carboxylic acid groups on the surface of the poly(ethylene-co-acrylic acid) films to acid chloride groups, synthesis of the lanthanide complexes bearing amino groups, and amidation to form the modified films. To characterize the modified films, Fourier transform infrared, thermogravimetric analysis, static water contact angle measurements and photoluminescence tests have been employed. Fourier transform infrared verifies the successful preparation of the lanthanide complexes and the modified poly(ethylene-co-acrylic acid) films. These films can emit strong characteristic red and green light under UV light excitation. In addition, the films both have short lifetime (1.14 ms and 1.21 ms), high thermal stability (Td = 408 °C and 411 °C) and, compared with unmodified ones, increased hydrophilicity. All these results suggest that the modified films have potential application as luminescent materials under high temperature.

Recent advances in enhanced luminescence upconversion of lanthanide-doped NaYF4 phosphors

NASA Astrophysics Data System (ADS)

Kumar, Deepak; Verma, Kartikey; Verma, Shefali; Chaudhary, Babulal; Som, Sudipta; Sharma, Vishal; Kumar, Vijay; Swart, Hendrik C.

2018-04-01

NaYF4 is regarded as the best upconversion (UC) matrix owing to its low phonon energy, more chemical stability, and a superior refractive index. This review reports on the various synthesis techniques of lanthanide-doped NaYF4 phosphors for UC application. The UC intensity depends on different properties of the matrix and those are discussed in detail. Plasmon-enhanced luminescence UC of the lanthanide-doped NaYF4 core-shells structure is discussed based on a literature survey. The present review provides the information about how the UC intensity can be enhanced. The idea about the UC is then deliberately used for versatile applications such as luminescent materials, display devices, biomedical imaging and different security appliances. In addition, the present review demonstrates the recent trends of NaYF4 UC materials in solar cell devices. The role of NaYF4 phosphor to eradicate the spectral variance among the incident solar spectrum, semiconductor as well as the sub-band gap nature of the semiconductor materials is also discussed in detail. Considering the fact that the research status on NaYF4 phosphor for photovoltaic application is now growing, the present review is therefore very important to the researchers. More importantly, this may promote more interesting research platforms to investigate the realistic use of UC nanophosphors as spectral converters for solar cells.

The Emergence of a Lanthanide-rich Kilonova Following the Merger of Two Neutron Stars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanvir, N. R.; Levan, A. J.; González-Fernández, C.

Here, we report the discovery and monitoring of the near-infrared counterpart (AT2017gfo) of a binary neutron-star merger event detected as a gravitational wave source by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo (GW170817) and as a short gamma-ray burst by Fermi Gamma-ray Burst Monitor (GBM) and Integral SPI-ACS (GRB 170817A). The evolution of the transient light is consistent with predictions for the behavior of a "kilonova/macronova" powered by the radioactive decay of massive neutron-rich nuclides created via r-process nucleosynthesis in the neutron-star ejecta. In particular, evidence for this scenario is found from broad features seen in Hubble Space Telescope infrared spectroscopy, similar to those predicted for lanthanide-dominated ejecta, and the much slower evolution in the near-infraredmore » $${K}_{{\\rm{s}}}$$-band compared to the optical. This indicates that the late-time light is dominated by high-opacity lanthanide-rich ejecta, suggesting nucleosynthesis to the third r-process peak (atomic masses $$A\\approx 195$$). This discovery thus confirms that neutron-star mergers produce kilo-/macronovae and that they are at least a major—if not the dominant—site of rapid neutron capture nucleosynthesis in the universe.« less

The Emergence of a Lanthanide-rich Kilonova Following the Merger of Two Neutron Stars

DOE PAGES

Tanvir, N. R.; Levan, A. J.; González-Fernández, C.; ...

2017-10-16

Here, we report the discovery and monitoring of the near-infrared counterpart (AT2017gfo) of a binary neutron-star merger event detected as a gravitational wave source by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo (GW170817) and as a short gamma-ray burst by Fermi Gamma-ray Burst Monitor (GBM) and Integral SPI-ACS (GRB 170817A). The evolution of the transient light is consistent with predictions for the behavior of a "kilonova/macronova" powered by the radioactive decay of massive neutron-rich nuclides created via r-process nucleosynthesis in the neutron-star ejecta. In particular, evidence for this scenario is found from broad features seen in Hubble Space Telescope infrared spectroscopy, similar to those predicted for lanthanide-dominated ejecta, and the much slower evolution in the near-infraredmore » $${K}_{{\\rm{s}}}$$-band compared to the optical. This indicates that the late-time light is dominated by high-opacity lanthanide-rich ejecta, suggesting nucleosynthesis to the third r-process peak (atomic masses $$A\\approx 195$$). This discovery thus confirms that neutron-star mergers produce kilo-/macronovae and that they are at least a major—if not the dominant—site of rapid neutron capture nucleosynthesis in the universe.« less

Sensing temperature via downshifting emissions of lanthanide-doped metal oxides and salts. A review

NASA Astrophysics Data System (ADS)

Dramićanin, Miroslav D.

2016-12-01

Temperature is important because it has an effect on even the tiniest elements of daily life and is involved in a broad spectrum of human activities. That is why it is the most commonly measured physical quantity. Traditional temperature measurements encounter difficulties when used in some emerging technologies and environments, such as nanotechnology and biomedicine. The problem may be alleviated using optical techniques, one of which is luminescence thermometry. This paper reviews the state of luminescence thermometry and presents different temperature read-out schemes with an emphasis on those utilizing the downshifting emission of lanthanide-doped metal oxides and salts. The read-out schemes for temperature include those based on measurements of spectral characteristics of luminescence (band positions and shapes, emission intensity and ratio of emission intensities), and those based on measurements of the temporal behavior of luminescence (lifetimes and rise times). This review (with 140 references) gives the basics of the fundamental principles and theory that underlie the methods presented, and describes the methodology for the estimation of their performance. The major part of the text is devoted to those lanthanide-doped metal oxides and salts that are used as temperature probes, and to the comparison of their performance and characteristics.

A multifunctional chemical sensor based on a three-dimensional lanthanide metal-organic framework

NASA Astrophysics Data System (ADS)

Du, Pei-Yao; Liao, Sheng-Yun; Gu, Wen; Liu, Xin

2016-12-01

A 3D lanthanide MOF with formula [Sm2(abtc)1.5(H2O)3(DMA)]·H2O·DMA (1) has been successfully synthesized via solvothermal method. Luminescence studies reveal that 1 exhibits dual functional detection benzyl alcohol and benzaldehyde among different aromatic molecules. In addition, 1 displays a turn-on luminescence sensing with respect to ethanol among different alcohol molecules, which suggests that 1 is also a promising luminescent probe for high selective sensing of ethanol.

Engineering Encodable Lanthanide-Binding Tags (LBTs) into Loop Regions of Proteins

PubMed Central

Barthelmes, Katja; Reynolds, Anne M.; Peisach, Ezra; Jonker, Hendrik R. A.; DeNunzio, Nicholas J.; Allen, Karen N.; Imperiali, Barbara; Schwalbe, Harald

2011-01-01

Lanthanide-binding-tags (LBTs) are valuable tools for investigation of protein structure, function, and dynamics by NMR spectroscopy, X-ray crystallography and luminescence studies. We have inserted LBTs into three different loop positions (denoted L, R, and S) of the model protein interleukin-1β and varied the length of the spacer between the LBT and the protein (denoted 1-3). Luminescence studies demonstrate that all nine constructs bind Tb3+ tightly in the low nanomolar range. No significant change in the fusion protein occurs from insertion of the LBT, as shown by two X-ray crystallographic structures of the IL1β-S1 and IL1β-L3 constructs and for the remaining constructs by comparing 1H-15N-HSQC NMR spectra with wild-type IL1β. Additionally, binding of LBT-loop IL1β proteins to their native binding partner in vitro remains unaltered. X-ray crystallographic phasing was successful using only the signal from the bound lanthanide. Large residual dipolar couplings (RDCs) could be determined by NMR spectroscopy for all LBT-loop-constructs and revealed that the LBT-2 series were rigidly incorporated into the interleukin-1β structure. The paramagnetic NMR spectra of loop-LBT mutant IL1β-R2 were assigned and the Δχ tensor components were calculated based on RDCs and pseudocontact shifts (PCSs). A structural model of the IL1β-R2 construct was calculated using the paramagnetic restraints. The current data provide support that encodable LBTs serve as versatile biophysical tags when inserted into loop regions of proteins of known structure or predicted via homology modelling. PMID:21182275

Complexation of Sn{sub 2}Se{sub 6} with lanthanide(III) centers influenced by ethylene polyamines: Solvothermal syntheses, crystal structures, and optical properties of lanthanide selenidostannates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Chunying; Wang, Fang; Chen, Ruihong

Lanthanide selenidostannates (H{sub 3}O){sub n}[Ce(tepa)(μ-1κ{sup 2}:2κ{sup 2}-Sn{sub 2}Se{sub 6})]{sub n} (1), [(Yb(tepa)(μ-OH)){sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})]{sub n}·nH{sub 2}O (2), [Htrien]{sub 2}[(Ln(trien)(tren)){sub 2}(μ-1κ:2κ-Sn{sub 2}Se{sub 6})][Sn{sub 2}Se{sub 6}] (Ln=Ce(3), Nd(4)) and [(Yb(dien){sub 2}){sub 2}(μ-OH){sub 2}]Sn{sub 2}Se{sub 6} (5) were solvothermally prepared in different ethylene polyamines. The Sn{sub 2}Se{sub 6} unit connects [Ce(tepa)]{sup 3+} and [(Yb(tepa)(μ-OH)){sub 2}]{sup 4+} fragments with tetradentate μ-1κ{sup 2}Se{sup 1},Se{sup 2}:2κ{sup 2}Se{sup 5},Se{sup 6} and bidentate μ-1κSe{sup 1}:2κSe{sup 5} bridging coordination modes in tepa, to form polymers 1 and 2, respectively. It joins two [Ln(trien)(tren)]{sup 3+} fragments as a μ-1κSe{sup 1}:2κSe{sup 5} ligand to form binuclear complexes 3 and 4more » in trien. Unlike the Sn{sub 2}Se{sub 6} units in 1–4 that bind with Ln(III) centers as Se-donor ligands, the Sn{sub 2}Se{sub 6} unit in 5 exists as a discrete ion. The syntheses of 1–5 show that the ethylene polyamines play an important role in the complexation of Sn{sub 2}Se{sub 6} ligand with Ln(III) centers. Compounds 1–5 exhibit optical band gaps in the range of 2.09–2.42 eV, which are influenced by the complexation of Sn{sub 2}Se{sub 6} with Ln(III) centers. - Graphical abstract: New lanthanide complexes concerning the Sn{sub 2}Se{sub 6} ligand were solvothermally prepared, and the effect of ethylene polyamines on the complexation of Sn{sub 2}Se{sub 6} with Ln(III) centers are observed. Highlights: • Lanthanide complexes concerning the selenidostannates have been solvothermally prepared in different ethylene polyamines. • A tetradentate μ-1κ{sup 2}Se{sup 1},Se{sup 2}:2κ{sup 2}Se{sup 5},Se{sup 6} and a bidentate μ-1κSe{sup 1}:2κSe{sup 5} bridging coordination modes for the Sn{sub 2}Se{sub 6} ligand is obtained. • The complexation of the Sn{sub 2}Se{sub 6} ligand with Ln

Structural properties of liquid lanthanides using charge hard sphere reference system

NASA Astrophysics Data System (ADS)

Thakora, P. B.; Sonvane, Y. A.; Patel, H. P.; Gajjar, P. N.; Jani, A. R.

2012-06-01

In the present paper Charge Hard Sphere (CHS) system is employed to investigate the structural properties like long wavelength limit S(0), isothermal compressibility (χT) and coordination number n for some liquid lanthanides viz.: La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu. Our well established parameter free model potential is used to describe the electron-ion interaction alongwith sarkar et al. dielectric function. From the present results, it is seen that good agreement between present results and available experimental data have been achieved. At last, we establish the applicability of our parameter free model potential and CHS method to account such structural properties.

Lanthanide complexes with 2-(tosylamino)benzylidene-N-benzoylhydrazone, which exhibit high NIR emission.

PubMed

Utochnikova, V V; Kovalenko, A D; Burlov, A S; Marciniak, L; Ananyev, I V; Kalyakina, A S; Kurchavov, N A; Kuzmina, N P

2015-07-28

New NIR emitting materials were found among the lanthanide complexes with 2-(tosylamino)benzylidene-N-benzoylhydrazone. Complexes of Nd(3+), Er(3+) and Yb(3+), as well as Eu(3+), Gd(3+) and Lu(3+), were synthesized for the first time. Owing to the absence of vibration quenching the ytterbium complex was found to exhibit a photoluminescence quantum yield of 1.4%. Since the sensitization efficiency was calculated to be 55%, the losses in the quantum yield are probably due to Yb-Yb resonant energy transfer.

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

NASA Astrophysics Data System (ADS)

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

2015-05-01

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 21 helical chains. While the Nd(III) ions are bridged through μ2-HIDC2- 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.

Lanthanide binding and IgG affinity construct: Potential applications in solution NMR, MRI, and luminescence microscopy

PubMed Central

Barb, Adam W; Ho, Tienhuei Grace; Flanagan-Steet, Heather; Prestegard, James H

2012-01-01

Paramagnetic lanthanide ions when bound to proteins offer great potential for structural investigations that utilize solution nuclear magnetic resonance spectroscopy, magnetic resonance imaging, or optical microscopy. However, many proteins do not have native metal ion binding sites and engineering a chimeric protein to bind an ion while retaining affinity for a protein of interest represents a significant challenge. Here we report the characterization of an immunoglobulin G-binding protein redesigned to include a lanthanide binding motif in place of a loop between two helices (Z-L2LBT). It was shown to bind Tb3+ with 130 nM affinity. Ions such as Dy3+, Yb3+, and Ce3+ produce paramagnetic effects on NMR spectra and the utility of these effects is illustrated by their use in determining a structural model of the metal-complexed Z-L2LBT protein and a preliminary characterization of the dynamic distribution of IgG Fc glycan positions. Furthermore, this designed protein is demonstrated to be a novel IgG-binding reagent for magnetic resonance imaging (Z-L2LBT:Gd3+ complex) and luminescence microscopy (Z-L2LBT: Tb3+ complex). PMID:22851279

Lanthanide-Containing Polymer Microspheres by Multiple-Stage Dispersion Polymerization for Highly Multiplexed Bioassays

PubMed Central

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

2009-01-01

We describe the synthesis and characterization of metal-encoded polystyrene microspheres by multiple-stage dispersion polymerization with diameters on the order of 2 µm and a very narrow size distribution. Different lanthanides were loaded into these microspheres through the addition of a mixture of LnCl3 salts and excess acrylic acid or acetoacetylethyl methacrylate (AAEM) dissolved in ethanol to the reaction after about 10% conversion of styrene, i.e., well after the particle nucleation stage was complete. Individual microspheres contain ca. 106 – 108 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 anti-mouse IgG bearing a metal-chelating polymer with Pr. PMID:19807075

Dinuclear lanthanide complexes based on amino alcoholate ligands: Structure, magnetic and fluorescent properties

NASA Astrophysics Data System (ADS)

Sun, Gui-Fang; Zhang, Cong-Ming; Guo, Jian-Ni; Yang, Meng; Li, Li-Cun

2017-05-01

Two binuclear lanthanide complexes [Ln2(hfac)6(HL)2] (LnIII = Dy(1), Tb(2); hfac = hexafluoroacetylacetonate, HL = (R)-2-amino-2-phenylethanol) have been successfully obtained by using amino alcoholate ligand. In two complexes, the Ln(III) ions are bridged by two alkoxido groups from HL ligands, resulting in binuclear complexes. The variable-temperature magnetic susceptibility studies indicate that there exists ferromagnetic interaction between two Ln(III) ions. Frequency dependent out-of-phase signals are observed for complex 1, suggesting SMM type behavior. Complexes 1 and 2 display intensely characteristic luminescent properties.

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

DOE PAGES

Demir, Selvan; Brune, Nicholas K.; Van Humbeck, Jeffrey F.; ...

2016-04-08

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, Sr 2+, Fe 3+, Nd 3+, and Am 3+, from aqueous solutionsmore » 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. Finally, recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.« less

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

PubMed Central

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

Lanthanide-doped NaGdF4 core-shell nanoparticles for non-contact self-referencing temperature sensors.

PubMed

Zheng, Shuhong; Chen, Weibo; Tan, Dezhi; Zhou, Jiajia; Guo, Qiangbing; Jiang, Wei; Xu, Cheng; Liu, Xiaofeng; Qiu, Jianrong

2014-06-07

We report that non-contact self-referencing temperature sensors can be realized with the use of core-shell nanostructures. These lanthanide-based nanothermometers (NaGdF4:Yb(3+)/Tm(3+)@Tb(3+)/Eu(3+)) exhibit higher sensitivity in a wide range from 125 to 300 K based on two emissions of Tb(3+) at 545 nm and Eu(3+) at 615 nm under near-infrared laser excitation.

Thermodynamic Studies to Support Actinide/Lanthanide Separations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Linfeng

2016-09-04

Thermodynamic data on the complexation of Np(V) with HEDTA in a wide pH region were re-modeled by including a dimeric complex species, (NpO 2) 2(OH) 2L 2 6- where L 3- stands for the fully deprotonated HEDTA ligand and better fits were achieved for the spectrophotometric data. The presence of the dimeric complex species in high pH region was verified for the first time by the EXAFS experiments at Stanford Synchrotron Radiation Laboratory (SSRL).

Lanthanide complexes as luminogenic probes to measure sulfide levels in industrial samples.

PubMed

Thorson, Megan K; Ung, Phuc; Leaver, Franklin M; Corbin, Teresa S; Tuck, Kellie L; Graham, Bim; Barrios, Amy M

2015-10-08

A series of lanthanide-based, azide-appended complexes were investigated as hydrogen sulfide-sensitive probes. Europium complex 1 and Tb complex 3 both displayed a sulfide-dependent increase in luminescence, while Tb complex 2 displayed a decrease in luminescence upon exposure to NaHS. The utility of the complexes for monitoring sulfide levels in industrial oil and water samples was investigated. Complex 3 provided a sensitive measure of sulfide levels in petrochemical water samples (detection limit ∼ 250 nM), while complex 1 was capable of monitoring μM levels of sulfide in partially refined crude oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Coumarin Derivative Directly Coordinated to Lanthanides Acts as an Excellent Antenna for UV-Vis and Near-IR Emission.

PubMed

Guzmán-Méndez, Óscar; González, Federico; Bernès, Sylvain; Flores-Álamo, Marcos; Ordóñez-Hernández, Javier; García-Ortega, Héctor; Guerrero, Joselin; Qian, Wenjie; Aliaga-Alcalde, Nuria; Gasque, Laura

2018-02-05

A chelating coumarin-derived ligand sensitizes all emitting lanthanide ions in the solid state and gives high absolute quantum yields for ethanol solutions of complexes of Sm, Eu, Tb, and Dy, above 20% for the last two. Crystal structures of these four complexes are [Ln(Cum) 3 (H 2 O)(X)]·X where X = MeOH or EtOH.

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

DOE PAGES

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

2017-05-10

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

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

PubMed

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.

Pyrolytic synthesis and luminescence of porous lanthanide Eu-MOF.

PubMed

Jin, Guangya; Liu, Zhijian; Sun, Hongfa; Tian, Zhiyong

2016-02-01

A lanthanide metal coordination polymer [Eu2(BDC)3(DMSO)(H2O)] was synthesized by the reaction of europium oxide with benzene-1,3-dicarboxylic acid (H2BDC) in a mixed solution of dimethyl sulfoxide (DMSO) and water under hydrothermal conditions. The crystal structure of Eu2(BDC)3(DMSO)(H2O) was characterized by X-ray diffraction (XRD). Thermo-gravimetric analysis of Eu2(BDC)3(DMSO)(H2O) indicated that coordinated DMSO and H2O molecules could be removed to create Eu2(BDC)3(DMSO)(H2O)-py with permanent microporosity, which was also verified by powder XRD (PXRD) and elemental analysis. Both Eu2(BDC)3(DMSO)(H2O) and Eu2(BDC)3(DMSO)(H2O)-py showed mainly Eu-based luminescence and had characteristic emissions in the range 550-700 nm. Copyright © 2015 John Wiley & Sons, Ltd.

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

NASA Astrophysics Data System (ADS)

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.

Lanthanide co-doped paramagnetic spindle-like mesocrystals for imaging and autophagy induction

NASA Astrophysics Data System (ADS)

Xu, Yun-Jun; Lin, Jun; Lu, Yang; Zhong, Sheng-Liang; Wang, Lei; Dong, Liang; Wu, Ya-Dong; Peng, Jun; Zhang, Li; Pan, Xiao-Feng; Zhou, Wei; Zhao, Yang; Wen, Long-Ping; Yu, Shu-Hong

2016-07-01

We synthesized two novel lanthanide doped spindle-like mesocrystals, YF3:Ce,Eu,Gd and YF3:Ce,Tb,Gd (abbreviated as YEG and YTG mesospindles, respectively). Both of them possess paramagnetic and fluorescent properties, and their excellent cyto-compatibility and low haemolysis are further confirmed. Therefore, they could act as dual mode contrast agents for magnetic resonance imaging (MRI) and fluorescence imaging. Furthermore, YEG and YTG mesospindles induce dose and time dependent autophagy by activating the PI3K signaling pathway. The autophagy induced by YEG and YTG mesocrystals is confirmed by enhanced autophagosome formation, normal cargo degradation, and no disruption of lysosomal function. This work is important to illustrate how rare-earth mesocrystals affect the autophagic pathway, indicating the potential of the YEG and YTG mesospindles in diagnosis and therapy.We synthesized two novel lanthanide doped spindle-like mesocrystals, YF3:Ce,Eu,Gd and YF3:Ce,Tb,Gd (abbreviated as YEG and YTG mesospindles, respectively). Both of them possess paramagnetic and fluorescent properties, and their excellent cyto-compatibility and low haemolysis are further confirmed. Therefore, they could act as dual mode contrast agents for magnetic resonance imaging (MRI) and fluorescence imaging. Furthermore, YEG and YTG mesospindles induce dose and time dependent autophagy by activating the PI3K signaling pathway. The autophagy induced by YEG and YTG mesocrystals is confirmed by enhanced autophagosome formation, normal cargo degradation, and no disruption of lysosomal function. This work is important to illustrate how rare-earth mesocrystals affect the autophagic pathway, indicating the potential of the YEG and YTG mesospindles in diagnosis and therapy. Electronic supplementary information (ESI) available: Size distribution, HRTEM image and additional cellular data. See DOI: 10.1039/c6nr03171d

A Systematic Study on the Generation of Multimetallic Lanthanide Fullerene ions by Laser Ablation Mass Spectrometry.

PubMed

Wang, Yiyun; Ma, LiFu; Mu, Lei; Ren, Juan; Kong, Xianglei

2018-06-01

Laser ablation masss spectromety has been previously proved to be a powerful tool for studying endohedro metallofullerene (EMF) ions. Our previous study showed the possiblity of forming multi-metallofullerene ions containg more than six metal atoms for La, Y and Lu. Thus, it is important to conduct a systematic study on the generation of multi-metallofullerenes and their distribuitons for all lanthanide elements. Experiments were performed on a 7.0 T Fourier transform ion cyclotron resonance (FT ICR) mass spectrometer. Laser ablation mass spectra were obtained by laser irradiation on mixtures of graphene and MCl 3 on a stainless steel plate, applying a 355 nm Nd: YAG laser with a typical energy of 2.5 mJ/pulse. Reaction test experiments were performed by introducing O 2 into the FT ICR cell with a pulse valve. Multi-metallofullerene ions Ce2-4C2m+, Pr2-4C2m+, Gd2-4C2m+, Nd3C2m+, Dy2-3C2m+, Tb2-7C2m+, Ho2-6C2m+ were observed in the mass spectra. For metal Sm and Eu, no multi-metallofullerene ion was observed. No reaction with O 2 was observed in the reaction experiments, verifying that these species had endohedral structures. For the observed series of multi-metallofullerene ions, tri-metallofullerene ions dominated their mass spectra. The results were further compared with previously generated EMF ions for La, Er, Tm, Yb and Lu. Endohedral lanthanide metallofullerene ions were generated by laser ablation of graphene and the corresponding metal salts MCl 3 (M = Ce, Pr, Nd, Gd, Tb, Dy and Ho) and studied with a FT ICR mass spectrometer. Typically, multi-metallofullerene ions of TbnC2m+2≤n≤780≤2m≤176, Ho6C2m+2≤n≤674≤2m≤162 were observed. The results show that the formation of multi-EMF ions containing lanthanides that have +3 and +4 oxidation states is easier than those containing +2 oxidation states in the process of laser ablation. This article is protected by copyright. All rights reserved.

Coordination geometries of solvated lanthanide(II) ions: Molecular structures of the cationic species [(DIME)[sub 3]Ln][sup 2+] (DIME = diethylene glycol dimethyl ether; Ln[sup 2+] = Sm, Yb), [(DIME)[sub 2]Yb(CH[sub 3]CN)[sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

White, J.P. III; Deng, H.; Boyd, E.P.

1994-04-13

The first lanthanide(II) cationic species with coordination numbers 7,8, and 9 have been structurally characterized. Mercury amalgams of the elemental lanthanides (Ln(Hg) where Ln = Sm, Eu, Yb) cleanly reduce Mn[sub 2](CO)[sub 10] and Co[sub 2](CO)[sub 8] in polydentate ethers to [Mn(CO)[sub 5

Polymer-based lanthanide luminescent sensor for detection of the hydrolysis product of the nerve agent Soman in water.

PubMed

Jenkins, A L; Uy, O M; Murray, G M

1999-01-15

The techniques of molecular imprinting and sensitized lanthanide luminescence have been combined to create the basis for a sensor that can selectively measure the hydrolysis product of the nerve agent Soman in water. The sensor functions by selectively and reversibly binding the phosphonate hydrolysis product of this agent to a functionality-imprinted copolymer possessing a coordinatively bound luminescent lanthanide ion, Eu3+. Instrumental support for this device is designed to monitor the appearance of a narrow luminescence band in the 610-nm region of the Eu3+ spectrum that results when the analyte is coordinated to the copolymer. The ligand field shifted luminescence was excited using 1 mW of the 465.8-nm line of an argon ion laser and monitored via an optical fiber using a miniature spectrometer. For this configuration, the limit of detection for the hydrolysis product is 7 parts per trillion (ppt) in solution with a linear range from 10 ppt to 10 ppm. Chemical and spectroscopic selectivities have been combined to reduce the likelihood of false positive analyses. Chemically analogous organophosphorus pesticides tested against the sensor have been shown to not interfere with determination.

True-coincidence correction when using an LEPD for the determination of the lanthanides in the environment via k0-based INAA.

PubMed

Freitas, M C; De Corte, F

1994-01-01

As part of a recent study on the environmental effects caused by the operation of a coal-fired power station at Sines, Portugal, k0-based instrumental neutron activation analysis (INAA) was used for the determination of the lanthanides (and also of tantalum and uranium) in plant leaves and lichens. In view of the accuracy and sensitivity of the determinations, it was advantageous to make use of a low-energy photon detector (LEPD). To begin with, in the present article, a survey is given of the former developments leading to user-friendly procedures for detection efficiency calibration of the LEPD and for correction for true-coincidence (cascade summing) effects. As a continuation of this, computer coincidence correction factors are now tabulated for the relevant low-energetic gamma-rays of the analytically interesting lanthanide, tantalum, and uranium radionuclides. Also the 140.5-keV line of 99Mo/99mTc is included, molybdenum being the comparator chosen when counting using an LEPD.

Sparkle model for AM1 calculation of lanthanide complexes: improved parameters for europium.

PubMed

Rocha, Gerd B; Freire, Ricardo O; Da Costa, Nivan B; De Sá, Gilberto F; Simas, Alfredo M

2004-04-05

In the present work, we sought to improve our sparkle model for the calculation of lanthanide complexes, SMLC,in various ways: (i) inclusion of the europium atomic mass, (ii) reparametrization of the model within AM1 from a new response function including all distances of the coordination polyhedron for tris(acetylacetonate)(1,10-phenanthroline) europium(III), (iii) implementation of the model in the software package MOPAC93r2, and (iv) inclusion of spherical Gaussian functions in the expression which computes the core-core repulsion energy. The parametrization results indicate that SMLC II is superior to the previous version of the model because Gaussian functions proved essential if one requires a better description of the geometries of the complexes. In order to validate our parametrization, we carried out calculations on 96 europium(III) complexes, selected from Cambridge Structural Database 2003, and compared our predicted ground state geometries with the experimental ones. Our results show that this new parametrization of the SMLC model, with the inclusion of spherical Gaussian functions in the core-core repulsion energy, is better capable of predicting the Eu-ligand distances than the previous version. The unsigned mean error for all interatomic distances Eu-L, in all 96 complexes, which, for the original SMLC is 0.3564 A, is lowered to 0.1993 A when the model was parametrized with the inclusion of two Gaussian functions. Our results also indicate that this model is more applicable to europium complexes with beta-diketone ligands. As such, we conclude that this improved model can be considered a powerful tool for the study of lanthanide complexes and their applications, such as the modeling of light conversion molecular devices.

Recovery of transplutonium elements from nuclear reactor waste

DOEpatents

Campbell, David O.; Buxton, Samuel R.

1977-05-24

A method of separating actinide values from nitric acid waste solutions resulting from reprocessing of irradiated nuclear fuels comprises oxalate precipitation of the major portion of actinide and lanthanide values to provide a trivalent fraction suitable for subsequent actinide/lanthanide partition, exchange of actinide and lanthanide values in the supernate onto a suitable cation exchange resin to provide an intermediate-lived raffinate waste stream substantially free of actinides, and elution of the actinide values from the exchange resin. The eluate is then used to dissolve the trivalent oxalate fraction prior to actinide/lanthanide partition or may be combined with the reprocessing waste stream and recycled.

Multicolor Luminescence from Conjugates of Genetically Encoded Elastin-like Polymers and Terpyridine-Lanthanides

DOE PAGES

Ghosh, Koushik; Balog, Eva Rose M.; Kahn, Jennifer L.; ...

2015-08-20

Functional hybrid materials with optically active metal-ligand moieties embedded within a polymer matrix have a great potential in (bio)materials science, including applications in light-emitting diode devices. Here, we report a simple strategy to incorporate terpyridine derivatives into the side chains of elastin-like polymers (ELPs). The further binding of trivalent lanthanide ions with the terpyridine ligands generated an array of photoluminescence ranging from the visible to the near-infrared regions. Lastly, as thin films, these ELP-based optical materials also exhibited distinct morphologies that depend upon the temperature of the aqueous solutions from which the hybrid polymers were spin coated or drop cast.

Structural Effects of Lanthanide Dopants on Alumina

PubMed Central

Patel, Ketan; Blair, Victoria; Douglas, Justin; Dai, Qilin; Liu, Yaohua; Ren, Shenqiang; Brennan, Raymond

2017-01-01

Lanthanide (Ln3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO3, Ln2O3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. The delay in phase transition (θ → α), and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. This study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications. PMID:28059121

Structural Effects of Lanthanide Dopants on Alumina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, Ketan; Blair, Victoria; Douglas, Justin

Lanthanide (Ln 3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO3, Ln2O3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. The delay in phase transition (θ → α), and alteration of powder morphology,more » particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. This study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.« less

Hysteresis in Lanthanide Aluminum Oxides Observed by Fast Pulse CV Measurement

PubMed Central

Zhao, Chun; Zhao, Ce Zhou; Lu, Qifeng; Yan, Xiaoyi; Taylor, Stephen; Chalker, Paul R.

2014-01-01

Oxide materials with large dielectric constants (so-called high-k dielectrics) have attracted much attention due to their potential use as gate dielectrics in Metal Oxide Semiconductor Field Effect Transistors (MOSFETs). A novel characterization (pulse capacitance-voltage) method was proposed in detail. The pulse capacitance-voltage technique was employed to characterize oxide traps of high-k dielectrics based on the Metal Oxide Semiconductor (MOS) capacitor structure. The variation of flat-band voltages of the MOS structure was observed and discussed accordingly. Some interesting trapping/detrapping results related to the lanthanide aluminum oxide traps were identified for possible application in Flash memory technology. After understanding the trapping/detrapping mechanism of the high-k oxides, a solid foundation was prepared for further exploration into charge-trapping non-volatile memory in the future. PMID:28788225

Unclonable Security Codes Designed from Multicolor Luminescent Lanthanide-Doped Y2O3 Nanorods for Anticounterfeiting.

PubMed

Kumar, Pawan; Nagpal, Kanika; Gupta, Bipin Kumar

2017-04-26

The duplicity of important documents has emerged as a serious problem worldwide. Therefore, many efforts have been devoted to developing easy and fast anticounterfeiting techniques with multicolor emission. Herein, we report the synthesis of multicolor luminescent lanthanide-doped Y 2 O 3 nanorods by hydrothermal method and their usability in designing of unclonable security codes for anticounterfeiting applications. The spectroscopic features of nanorods are probed by photoluminescence spectroscopy. The Y 2 O 3 :Eu 3+ , Y 2 O 3 :Tb 3+ , and Y 2 O 3 :Ce 3+ nanorods emit hypersensitive red (at 611 nm), strong green (at 541 nm), and bright blue (at 438 nm) emissions at 254, 305, and 381 nm, respectively. The SEM and TEM/HRTEM results reveal that these nanorods have diameter and length in the range of 80-120 nm and ∼2-5 μm, respectively. The two-dimensional spatially resolved photoluminescence intensity distribution in nanorods is also investigated by using confocal photoluminescence microscopic technique. Further, highly luminescent unclonable security codes are printed by a simple screen printing technique using luminescent ink fabricated from admixing of lanthanide doped multicolor nanorods in PVC medium. The prospective use of these multicolor luminescent nanorods provide a new opportunity for easily printable, highly stable, and unclonable multicolor luminescent security codes for anti-counterfeiting applications.

New anion-templated 3D heterobimetallic open frameworks based on lanthanide-carboxylate layers and copper pillars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Yunwu; Wang Yonghui; Li Yangguang

2008-06-15

A series of new three-dimensional (3D) lanthanide-transition metal (4f-3d) heterobimetallic open frameworks, [Ln{sub 2}(1,2-bdc){sub 2}(H{sub 2}O){sub 2} Cu(inic){sub 2}](ClO{sub 4}) (Ln=Eu (1), Tb (2), Nd (3) and Sm (4); 1,2-bdc=1,2-benzenedicarboxylate; Hinic=isonicotinic acid) have been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction analysis. Compounds 1-4 are isostructural. They possess a new anion-templated 3D heterobimetallic open framework, which is observed for the first time in the {l_brace}Ln/TM/bdc/inic{r_brace} (TM=transition metal) system. Compounds 1 and 2 exhibit the characteristic fluorescent properties of Eu(III) and Tb(III), respectively. - Graphical abstract: A series of new anion-templated 3D heterobimetallic open frameworkmore » based on the lanthanide-carboxylate layers and copper(I)-inic pillars, [Ln{sub 2}(1,2-bdc){sub 2}(H{sub 2}O){sub 2}Cu(inic){sub 2}](ClO{sub 4}) (Ln=Eu (1), Tb (2), Nd (3) and Sm (4); 1,2-bdc=1,2-benzenedicarboxylate; Hinic=isonicotinic acid), have been hydrothermally synthesized and structurally characterized, among which compounds 1 and 2 exhibit good fluorescent properties.« less

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

NASA Astrophysics Data System (ADS)

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.

Actinide extraction methods

DOEpatents

Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

2010-09-21

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

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

NASA Astrophysics Data System (ADS)

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.

Rydberg series in the lanthanides and actinides observed by stepwise laser excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worden, E.F.; Solarz, R.W.; Paisner, J.A.

1977-05-18

The techniques of stepwise laser excitation were applied to obtain Ryberg series in the lanthanides and in uranium. The methods employed circumvent many of the experimental difficulties inherent in conventional absorption spectrosopy of these heavy atoms with very complex spectra. The Rydberg series observed have allowed the determination of accurate ionization limits. The values in eV are: Ce, 5.5387(4);Nd, 5.5250(6); Sm, 5.6437(10); Eu, 5.6704(3); Gd, 6.1502(6); Tb, 5.8639(6); Dy, 5.9390(6); Ho, 6.0216(6); Er 6.1077(6); U, 6.1941(5). A comparison of the f/sup n/s/sup 2/-f/sup n/s ionization limits as a function of n with theoretical calculations is made.

Lanthanide-cyclodextrin complexes as probes for elucidating optical purity by NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wenzel, T.J.; Bogyo, M.S.; Lebeau, E.L.

1994-06-01

A multidentate ligand is bonded to cyclodextrins by the reaction of diethylenetriaminepentaacetic dianhydride with 6-mono- and 2-mono(ethylenediamine) derivatives of cyclodextrin. Adding Dy(III) to the cyclodextrin derivatives enhances the enantiomeric resolution in the [sup 1]H NMR spectra of carbionoxamine maleate, doxylamine succinate, pheniramine maleate, propranolol hydrochloride, and tryptophan. The enhancement is more pronounced with the secondary derivative. The Dy(III)-induced shifts can be used to elucidate the geometry of cyclodextrin-substrate inclusion complexes. Lanthanide-induced shifts are reported for complexes of aspartame, tryptophan, propranolol, and 1-anilino-8-naphthalenesulfonate with cyclodextrins, and the relative magnitudes of the shifts agree with previously reported structures of the complexes. 37more » refs., 9 figs., 5 tabs.« less

Separation of americium from europium using 3,3'-dimethoxy-phenyl-bis-1,2,4-triazinyl-2,6-pyridine

DOE PAGES

Hill, Talon G.; Chin, Ai Lin; Tai, Serene; ...

2017-03-22

Development of liquid-liquid separation processes for the effective removal of the minor actinide Am(III) from used nuclear fuel using ligand-based strategies continues to be an area of significant research focus. The current investigation demonstrates the efficacy of a nitrogen-based bis-triazinyl pyridine (BTP) derivative to selectively extract Am(III) from nitric acid solutions containing light lanthanides. The performance of 3,3’-dimethoxy-phenyl-bis-1,2,4-triazinyl-2,6- pyridine (MOB-BTP) was compared to that of a camphor substituted BTP (CA-BTP). The results of this investigation demonstrate the novel 3,3’-methoxy-BTP extractant dissolved in a polar diluent was a more efficient extractant for Am(III) at a lower concentration than CA-BTP under comparablemore » conditions.« less

Separation of americium from europium using 3,3'-dimethoxy-phenyl-bis-1,2,4-triazinyl-2,6-pyridine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hill, Talon G.; Chin, Ai Lin; Tai, Serene

Development of liquid-liquid separation processes for the effective removal of the minor actinide Am(III) from used nuclear fuel using ligand-based strategies continues to be an area of significant research focus. The current investigation demonstrates the efficacy of a nitrogen-based bis-triazinyl pyridine (BTP) derivative to selectively extract Am(III) from nitric acid solutions containing light lanthanides. The performance of 3,3’-dimethoxy-phenyl-bis-1,2,4-triazinyl-2,6- pyridine (MOB-BTP) was compared to that of a camphor substituted BTP (CA-BTP). The results of this investigation demonstrate the novel 3,3’-methoxy-BTP extractant dissolved in a polar diluent was a more efficient extractant for Am(III) at a lower concentration than CA-BTP under comparablemore » conditions.« less

High-resolution electron spectroscopy of lanthanide (Ce, Pr, and Nd) complexes of cyclooctatetraene: the role of 4f electrons.

PubMed

Kumari, Sudesh; Roudjane, Mourad; Hewage, Dilrukshi; Liu, Yang; Yang, Dong-Sheng

2013-04-28

Cerium, praseodymium, and neodymium complexes of 1,3,5,7-cyclooctatetraene (COT) complexes were produced in a laser-vaporization metal cluster source and studied by pulsed-field ionization zero electron kinetic energy spectroscopy and quantum chemical calculations. The computations included the second-order Møller-Plesset perturbation theory, the coupled cluster method with single, double, and perturbative triple excitations, and the state-average complete active space self-consistent field method. The spectrum of each complex exhibits multiple band systems and is assigned to ionization of several low-energy electronic states of the neutral complex. This observation is different from previous studies of M(COT) (M = Sc, Y, La, and Gd), for which a single band system was observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field, and the number of the low-energy states increases rapidly with increasing number of the metal 4f electrons. On the other hand, the 4f electrons have a small effect on the geometries and vibrational frequencies of these lanthanide complexes.

Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry.

PubMed

Kautenburger, Ralf; Beck, Horst Philipp

2007-08-03

For the long-term storage of radioactive waste, detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is necessary. Humic acid (HA) can play an important role in the immobilisation or mobilisation of metal ions due to complexation and colloid formation. Therefore, we investigate the complexation behavior of HA and its influence on the migration or retardation of selected lanthanides (europium and gadolinium as homologues of the actinides americium and curium). Two independent speciation techniques, ultrafiltration and capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) have been compared for the study of Eu and Gd interaction with (purified Aldrich) HA. The degree of complexation of Eu and Gd in 25 mg l(-1) Aldrich HA solutions was determined with a broad range of metal loading (Eu and Gd total concentration between 10(-6) and 10(-4) mol l(-1)), ionic strength of 10 mM (NaClO4) and different pH-values. From the CE-ICP-MS electropherograms, additional information on the charge of the Eu species was obtained by the use of 1-bromopropane as neutral marker. To detect HA in the ICP-MS and separate between HA complexed and non complexed metal ions in the CE-ICP-MS, we have halogenated the HA with iodine as ICP-MS marker.

The interaction of human serum albumin with selected lanthanide and actinide ions: Binding affinities, protein unfolding and conformational changes.

PubMed

Ali, Manjoor; Kumar, Amit; Kumar, Mukesh; Pandey, Badri N

2016-04-01

Human serum albumin (HSA), the most abundant soluble protein in blood plays critical roles in transportation of biomolecules and maintenance of osmotic pressure. In view of increasing applications of lanthanides- and actinides-based materials in nuclear energy, space, industries and medical applications, the risk of exposure with these metal ions is a growing concern for human health. In present study, binding interaction of actinides/lanthanides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] with HSA and its structural consequences have been investigated. Ultraviolet-visible, Fourier transform-infrared, Raman, Fluorescence and Circular dichroism spectroscopic techniques were applied to study the site of metal ions interaction, binding affinity determination and the effect of metal ions on protein unfolding and HSA conformation. Results showed that these metal ions interacted with carbonyl (CO..:)/amide(N..-H) groups and induced exposure of aromatic residues of HSA. The fluorescence analysis indicated that the actinide binding altered the microenvironment around Trp214 in the subdomain IIA. Binding affinity of U(VI) to HSA was slightly higher than that of Th(IV). Actinides and Ce(IV) altered the secondary conformation of HSA with a significant decrease of α-helix and an increase of β-sheet, turn and random coil structures, indicating a partial unfolding of HSA. A correlation was observed between metal ion's ability to alter HSA conformation and protein unfolding. Both cationic effects and coordination ability of metal ions seemed to determine the consequences of their interaction with HSA. Present study improves our understanding about the protein interaction of these heavy ions and their impact on its secondary structure. In addition, binding characteristics may have important implications for the development of rational antidote for the medical management of health effects of actinides and lanthanides. Copyright © 2016 Elsevier

Lipophilic ternary complexes in liquid-liquid extraction of trivalent lanthanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lumetta, Gregg J.; Levitskaia, Tatiana G.; Latesky, Stanley

2012-03-01

The formation of ternary complexes between lanthanide ions [Nd(III) or Eu(III)], octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO), and bis-(2-ethylhexyl)phosphoric acid (HDEHP) was probed by liquid-liquid extraction and spectroscopic techniques. Equilibrium modeling of data for the extraction of Nd(III) or Eu(III) from lactic acid media into n-dodecane solutions of CMPO and HDEHP indicates the predominant extracted species are of the type [Ln(AHA){sub 2}(A)] and [Ln(CMPO)(AHA){sub 2}(A)], where Ln = Nd or Eu and A represents the DEHP{sup -} anion. FTIR (for both Eu and Nd) and visible spectrophotometry (in the case of Nd) indicate the formation of the [Ln(CMPO)(A){sup 3}] complexes when CMPO ismore » added to n-dodecane solutions of the LnA{sub 3} compounds. Both techniques indicate a stronger propensity of CMPO to complex Nd(III) versus Eu(III).« less

Calix[4]arenes as selective extracting agents. An NMR dynamic and conformational investigation of the lanthanide(III) and thorium(IV) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, B.; Jacques, V.; Shivanyuk, A.

The lanthanide and Th{sup 4+} complexes with calix[4]arene ligands substituted either on the narrow or at the wide rim by four coordinating groups behave totally differently as shown by an NMR investigation of the dia- and paramagnetic complexes. Solutions of complexes were prepared by reacting anhydrous metal perchlorate salts with the ligands in dry acetonitrile (CAUTION). Relaxation time T{sub 1} titrations of acetonitrile solutions of Gd{sup 3+} by calixarenes indicate that ligands substituted on the narrow rim form stable 1:1 complexes whether they feature four amide groups (1) or four phosphine oxide functions. In contrast, a ligand substituted by fourmore » (carbamoylmethyl)-diphenylphosphine oxide moieties on the wide rim (3) and its derivatives form polymeric species even at a 1:1 ligand/metal concentration ratio. Nuclear magnetic relaxation dispersion (NMRD) curves (relaxation rates 1/T{sub 1} vs magnetic field strength) of Gd{sup 3+}, Gd{sup 3+}{center_dot}1 and Gd{sup 3+}{center_dot}3 perchlorates in acetonitrile are analyzed by an extended version of the Solomon-Bloembergen-Morgan equations. A comparison of the calculated rotational correlation times {tau}{sub r} shows that ligand 3 forms oligomeric Gd{sup 3+} species. The chelates of ligand 1 are axially symmetric (C{sub 4} symmetry), and the paramagnetic shifts induced by the Yb{sup 3+} ion are accounted for quantitatively. The addition of water or of nitrate ions does not modify the geometry of the complex. The metal chelates of 3 and its derivatives adopt a C{sub 2} symmetry, and the paramagnetic shifts are interpreted on a semiquantitative basis only. Water and NO{sub 3}{sup {minus}} ions completely labilize the complexes of the heavy lanthanides. The very high selectivity of ligand 3 through the lanthanide series stems from a complex interplay of factors.« less

Unique (3,8)-connected lanthanide arenedisulfonate metal-organic frameworks containing benzimidazole-5,6-dicarboxylic acid co-ligand: Syntheses, structures and luminescence

NASA Astrophysics Data System (ADS)

Sun, Yan-Qiong; Liu, Qi; Zhong, Jie-Cen; Pan, Qun-Feng; Chen, Yi-Ping

2013-10-01

Two isostructural 3D lanthanide arenedisulfonate metal-organic frameworks (MOFs) [Ln(Hbidc)(nds)0.5(H2O)]n(Ln=Eu(1), La(2)) have been successfully synthesized by the hydrothermal reaction of lanthanide oxide with 2,6-naphthalenedisulfonate sodium (Na2nds) and an auxiliary ligand, 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc). The two complexes are both constructed from 2D [Ln(Hbidc)]+ double layers pillared by nds2- ligands to generate 3D (3, 8)-connected open-framework structures with 1D long narrow channels running along the a axis. From topological point of view, the 3D framework is a (3, 8)-connected tfz-d net. The weak interactions including N-H⋯O, O-H⋯O hydrogen bonds and π-π stacking are observed in 1. The 2D IR correlation spectroscopy was applied to study the molecular interactions induced by thermal perturbation. The emission spectra of 1 exhibit the characteristic transition of 5D0→7FJ(J=0-4) of Eu(III).

4f fine-structure levels as the dominant error in the electronic structures of binary lanthanide oxides.

PubMed

Huang, Bolong

2016-04-05

The ground-state 4f fine-structure levels in the intrinsic optical transition gaps between the 2p and 5d orbitals of lanthanide sesquioxides (Ln2 O3 , Ln = La…Lu) were calculated by a two-way crossover search for the U parameters for DFT + U calculations. The original 4f-shell potential perturbation in the linear response method were reformulated within the constraint volume of the given solids. The band structures were also calculated. This method yields nearly constant optical transition gaps between Ln-5d and O-2p orbitals, with magnitudes of 5.3 to 5.5 eV. This result verifies that the error in the band structure calculations for Ln2 O3 is dominated by the inaccuracies in the predicted 4f levels in the 2p-5d transition gaps, which strongly and non-linearly depend on the on-site Hubbard U. The relationship between the 4f occupancies and Hubbard U is non-monotonic and is entirely different from that for materials with 3d or 4d orbitals, such as transition metal oxides. This new linear response DFT + U method can provide a simpler understanding of the electronic structure of Ln2 O3 and enables a quick examination of the electronic structures of lanthanide solids before hybrid functional or GW calculations. © 2015 Wiley Periodicals, Inc.

Synthesis, structure, and luminescent properties of microporous lanthanide metal-organic frameworks with inorganic rod-shaped building units.

PubMed

Guo, Xiaodan; Zhu, Guangshan; Sun, Fuxing; Li, Zhongyue; Zhao, Xiaojun; Li, Xiaotian; Wang, Hanchang; Qiu, Shilun

2006-03-20

A series of microporous lanthanide metal-organic frameworks, Tb3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(H2O) (1) and Ln3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(C2H5OH)(0.5)(H2O)(0.5) [Ln = Dy (2), Ho (3), Er (4)], have been synthesized by the reaction of the lanthanide metal ion (Ln3+) with 1,4-benzenedicarboxylic acid and triethylenetetramine in a mixed solution of N,N'-dimethylformamide (DMF), water, and C(2)H(5)OH. X-ray diffraction analyses reveal that they are extremely similar in structure and crystallized in triclinic space group P. An edge-sharing metallic dimer and 4 metallic monomers assemble with 18 carboxylate groups to form discrete inorganic rod-shaped building units [Ln6(CO2)18], which link to each other through phenyl groups to lead to three-dimensional open frameworks with approximately 4 x 6 A rhombic channels along the [0,-1,1] direction. A water sorption isotherm proves that guest molecules in the framework of complex 1 can be removed to create permanent microporosity and about four water molecules per formula unit can be adsorbed into the micropores. These complexes exhibit blue fluorescence, and complex 1 shows a Tb3+ characteristic emission in the range of 450-650 nm.

Structural Effects of Lanthanide Dopants on Alumina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, Ketan; Blair, Victoria; Douglas, Justin

Lanthanide (Ln 3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO 3, Ln 2O 3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. In addition, the delay in phase transition (θ → α),more » and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. Lastly, this study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.« less

Ultrasmall lanthanide-doped nanoparticles as multimodal platforms

NASA Astrophysics Data System (ADS)

Yust, Brian G.; Pedraza, Francisco J.; Sardar, Dhiraj K.

2014-03-01

Recently, there has been a great amount of interest in nanoparticles which are able to provide a platform with high contrast for multiple imaging modalities in order to advance the tools available to biomedical researchers and physicians. However, many nanoparticles do not have ideal properties to provide high contrast in different imaging modes. In order to address this, ultrasmall lanthanide doped oxide and fluoride nanoparticles with strong NIR to NIR upconversion fluorescence and a strong magnetic response for magnetic resonance imaging (MRI) have been developed. Specifically, these nanoparticles incorporate gadolinium, dysprosium, or a combination of both into the nano-crystalline host to achieve the magnetic properties. Thulium, erbium, and neodymium codopants provide the strong NIR absorption and emission lines that allow for deeper tissue imaging since near infrared light is not strongly absorbed or scattered by most tissues within this region. This also leads to better image quality and lower necessary excitation intensities. As a part of the one pot synthesis, these nanoparticles are coated with peg, pmao, or d-glucuronic acid to make them water soluble, biocompatible, and bioconjugable due to the available carboxyl or amine groups. Here, the synthesis, morphological characterization, magnetic response, NIR emission, and the quantum yield will be discussed. Cytotoxicity tested through cell viability at varying concentrations of nanoparticles in growth media will also be discussed.

Structural Effects of Lanthanide Dopants on Alumina

DOE PAGES

Patel, Ketan; Blair, Victoria; Douglas, Justin; ...

2017-01-06

Lanthanide (Ln 3+) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO 3, Ln 2O 3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. In addition, the delay in phase transition (θ → α),more » and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. Lastly, this study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.« less

NMR Spectroscopy Using a Chiral Lanthanide Shift Reagent to Assess the Optical Purity of 1-Phenylethylamine

NASA Astrophysics Data System (ADS)

Viswanathan, Tito; Toland, Alan

1995-10-01

Enantiomeric forms of 1-phenylethylamine cannot be distinguished by 1H or 13C-NMR because the groups attached to the stereocenter are in an enantiopic environment. However, the chemical shifts of the protons in the groups attached to the stereocenter can be differentially altered to appear as distinct peaks in the NMR spectrum. This is accomplished by the use of a commercially available chiral lanthanide shift reagent, Yb(tfC)3. The NMR spectrum after the addition of a chiral shift reagent allows one to assess the optical purity of the sample.

Biocompatible and high-performance amino acids-capped MnWO4 nanocasting as a novel non-lanthanide contrast agent for X-ray computed tomography and T1-weighted magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Dong, Kai; Liu, Zhen; Liu, Jianhua; Huang, Sa; Li, Zhenhua; Yuan, Qinghai; Ren, Jinsong; Qu, Xiaogang

2014-01-01

In the present work, a novel non-lanthanide dual-modality contrast agent, manganese tungstate (MnWO4), has been successfully constructed by a facile and versatile hydrothermal route. With the merits of a high atomic number and a well-positioned K-edge energy of tungsten, our well-prepared non-lanthanide nanoprobes provide a higher contrast efficacy than routine iodine-based agents in clinics. Additionally, the presence of Mn in these nanoparticles endow them with excellent T1-weighted MR imaging capabilities. As an alternative to T2-weighted MRI and CT dual-modality contrast agents, the nanoprobes can provide a positive contrast signal, which prevents confusion with the dark signals from hemorrhage and blood clots. To the best of our knowledge, this is the first report that a non-lanthanide imaging nanoprobe is applied for CT and T1-weighted MRI simultaneously. Moreover, comparing with gadolinium-based T1-weighted MRI and CT dual-modality contrast agents that were associated with nephrogenic systemic fibrosis (NSF), our contrast agents have superior biocompatibility, which is proved by a detailed study of the pharmacokinetics, biodistribution, and in vivo toxicology. Together with excellent dispersibility, high biocompatibility and superior contrast efficacy, these nanoprobes provide detailed and complementary information from dual-modality imaging over traditional single-mode imaging and bring more opportunities to the new generation of non-lanthanide nanoparticulate-based contrast agents.In the present work, a novel non-lanthanide dual-modality contrast agent, manganese tungstate (MnWO4), has been successfully constructed by a facile and versatile hydrothermal route. With the merits of a high atomic number and a well-positioned K-edge energy of tungsten, our well-prepared non-lanthanide nanoprobes provide a higher contrast efficacy than routine iodine-based agents in clinics. Additionally, the presence of Mn in these nanoparticles endow them with excellent T1

Photoluminescent lanthanide-organic bilayer networks with 2,3-pyrazinedicarboxylate and oxalate.

PubMed

Soares-Santos, Paula C R; Cunha-Silva, Luís; Paz, Filipe A Almeida; Ferreira, Rute A S; Rocha, João; Carlos, Luís D; Nogueira, Helena I S

2010-04-05

The hydrothermal reaction between lanthanide nitrates and 2,3-pyrazinedicarboxylic acid led to a new series of two-dimensional (2D) lanthanide-organic frameworks: [Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)](n) [where 2,3-pzdc(2-) = 2,3-pyrazinedicarboxylate, ox(2-) = oxalate, and Ln(III) = Ce, Nd, Sm, Eu, Gd, Tb, or Er]. The structural details of these materials were determined by single-crystal X-ray diffraction (for Ce(3+) and Nd(3+)) that revealed the formation of a layered structure. Cationic monolayers of {(infinity)(2)[Ln(2,3-pzdc)(H(2)O)](+)} are interconnected via the ox(2-) ligand leading to the formation of neutral (infinity)(2)[Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)] bilayer networks; structural cohesion of the crystalline packing is reinforced by the presence of highly directional O-H...O hydrogen bonds between adjacent bilayers. Under the employed hydrothermal conditions 2,3-pyrazinedicarboxylic acid can be decomposed into ox(2-) and 2-pyrazinecarboxylate (2-pzc(-)), as unequivocally proved by the isolation of the discrete complex [Tb(2)(2-pzc)(4)(ox)(H(2)O)(6)].10H(2)O. Single-crystal X-ray diffraction of this latter complex revealed its co-crystallization with an unprecedented (H(2)O)(16) water cluster. Photoluminescence measurements were performed for the Nd(3+), Sm(3+), Eu(3+), and Tb(3+) compounds which show, under UV excitation at room temperature, the Ln(3+) characteristic intra-4f(N) emission peaks. The energy level of the triplet states of 2,3-pyrazinedicarboxylic acid (18939 cm(-1)) and oxalic acid (24570 cm(-1)) was determined from the 12 K emission spectrum of the Gd(3+) compound. The (5)D(0) and (5)D(4) lifetime values (0.333 +/- 0.006 and 0.577 +/- 0.017 ms) and the absolute emission quantum yields (0.13 +/- 0.01 and 0.05 +/- 0.01) were determined for the Eu(3+) and Tb(3+) compounds, respectively. For the Eu(3+) compound the energy transfer efficiency arising from the ligands' excited states was estimated (0.93 +/- 0.01).

Record high magnetic ordering temperature in a lanthanide at extreme pressure

DOE PAGES

Lim, J.; Fabbris, G.; Haskel, D.; ...

2017-11-07

Today's best permanent magnet materials, SmCo 5 and Nd 2Fe 14B, could likely be made signi fi cantly more powerful were it not necessary to dilute the strong magnetism of the rare earth ions (Sm, Nd) with the 3 d transition elements (Fe, Co). Since the rare-earth metals order magnetically at relatively low temperatures T o <= 292 K, transition elements must be added to bring T o to temperatures well above ambient. Under pressure T o (P) for the neighboring lanthanides Gd, Tb, and Dy follows a notably nonmonotonic, but nearly identical, dependence to similar to 60 GPa. Atmore » higher pressures, however, Tb and Dy exhibit highly anomalous behavior, T o for Dy soaring to temperatures well above ambient. In conclusion, we suggest that this anomalously high magnetic ordering temperature is an heretofore unrecognized feature of the Kondo lattice state.« less

Record high magnetic ordering temperature in a lanthanide at extreme pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, J.; Fabbris, G.; Haskel, D.

Today's best permanent magnet materials, SmCo 5 and Nd 2Fe 14B, could likely be made signi fi cantly more powerful were it not necessary to dilute the strong magnetism of the rare earth ions (Sm, Nd) with the 3 d transition elements (Fe, Co). Since the rare-earth metals order magnetically at relatively low temperatures T o <= 292 K, transition elements must be added to bring T o to temperatures well above ambient. Under pressure T o (P) for the neighboring lanthanides Gd, Tb, and Dy follows a notably nonmonotonic, but nearly identical, dependence to similar to 60 GPa. Atmore » higher pressures, however, Tb and Dy exhibit highly anomalous behavior, T o for Dy soaring to temperatures well above ambient. In conclusion, we suggest that this anomalously high magnetic ordering temperature is an heretofore unrecognized feature of the Kondo lattice state.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ellis, Ross J.; Brigham, Derek M.; Delmau, Laetitia

The subtle energetic differences underpinning adjacent lanthanide discrimination are explored with diglycolamide ligands. Our approach converges liquid–liquid extraction experiments with solution-phase X-ray absorption spectroscopy (XAS) and density functional theory (DFT) simulations, spanning the lanthanide series. The homoleptic [(DGA)3Ln]3+ complex was confirmed in the organic extractive solution by XAS, and this was modeled using DFT. An interplay between steric strain and coordination energies apparently gives rise to a nonlinear trend in discriminatory lanthanide ion complexation across the series. Our results highlight the importance of optimizing chelate molecular geometry to account for both coordination interactions and strain energies when designing new ligandsmore » for efficient adjacent lanthanide separation for rare-earth refining.« less

Solid Electrolyte Materials for use in Lithium-water Primary Batteries And the Synthesis and Characterization of Lanthanide Orthoferrite Magnetic Nanomaterials

NASA Astrophysics Data System (ADS)

Cook, Clifford Corlin

This thesis was developed in two parts with the overall goals of this work being (1) synthesize and develop solid electrolyte materials for use in a lithium-water battery and (2) synthesize and characterize ternary magnetic nanomaterials. Lithium metal in combination with water is a highly attractive power source due to its high specific energy. Because of the vigorous nature of the reaction between lithium and water, many obstacles must be overcome in order to harness the energy that this system is capable of producing. Parasitic reactions must be controlled so as not to passivate the lithium or consume it totally. In addition, production of hydrogen gas that accompanies both the electrochemical and parasitic reactions can present a serious challenge. As a result it is difficult to maintain high voltage and control the current density in these systems. In order to overcome these obstacles we have developed composite membranes of various lithium-ion conducting solid electrolytes and polymers. Lithium-ion conducting solid electrolytes are known to achieve ionic conductance as high as 10-3 S/cm2. Utilizing these materials in conjunction with polymers, we have created hydrophobic membranes that allow us to limit the parasitic reactions and maintain low cell impedance. Lanthanide orthoferrite materials are technologically important classes of magnetic materials. They have found application in magneto-optical devices as well as in magnetic recording devices. We have explored the syntheses and magnetic properties of nanocrystalline materials. The synthesis of the nanomaterials was done by co-reduction of lanthanide, Ln3+, and iron, Fe 3+, cations with alkalide solution producing the Ln-Fe alloy of the desired stoichiometry. Removal of the byproducts and oxidization of the alloy was accomplished by washing the product with aerated water. Presented herein, several nanoscale lanthanide orthoferrite materials (LnFeO3, Ln = Gd, Tb, Er, Tm, Sm, Dy, Ho, and La) have been

ICP-MS Analysis of Lanthanide-Doped Nanoparticles as a Non-Radiative, Multiplex Approach to Quantify Biodistribution and Blood Clearance

PubMed Central

Crayton, Samuel H.; Elias, Andrew; Al-Zaki, Ajlan; Cheng, Zhiliang; Tsourkas, Andrew

2011-01-01

Recent advances in material science and chemistry have led to the development of nanoparticles with diverse physicochemical properties, e.g. size, charge, shape, and surface chemistry. Evaluating which physicochemical properties are best for imaging and therapeutic studies is challenging not only because of the multitude of samples to evaluate, but also because of the large experimental variability associated with in vivo studies (e.g. differences in tumor size, injected dose, subject weight, etc.). To address this issue, we have developed a lanthanide-doped nanoparticle system and analytical method that allows for the quantitative comparison of multiple nanoparticle compositions simultaneously. Specifically, superparamagnetic iron oxide (SPIO) with a range of different sizes and charges were synthesized, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy (ICP-MS) was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood samples and the resected tumor and organs. The method proved generalizable to other nanoparticle platforms, including dendrimers, liposomes, and polymersomes. This approach provides a simple, cost-effective, and non-radiative method to quantitatively compare tumor localization, biodistribution, and blood clearance of more than 10 nanoparticle compositions simultaneously, removing subject-to-subject variability. PMID:22100983

Scalable Direct Writing of Lanthanide-Doped KMnF3 Perovskite Nanowires into Aligned Arrays with Polarized Up-Conversion Emission.

PubMed

Shi, Shuo; Sun, Ling-Dong; Xue, Ying-Xian; Dong, Hao; Wu, Ke; Guo, Shi-Chen; Wu, Bo-Tao; Yan, Chun-Hua

2018-05-09

The use of one-dimensional nano- and microstructured semiconductor and lanthanide materials is attractive for polarized-light-emission studies. Up-conversion emission from single-nanorod or anisotropic nanoparticles with a degree of polarization has also been discussed. However, microscale arrays of nanoparticles, especially well-aligned one-dimensional nanostructures as well as their up-conversion polarization characterization, have not been investigated yet. Herein, we present a novel and facile paradigm for preparing highly aligned arrays of lanthanide-doped KMnF 3 (KMnF 3 :Ln) perovskite nanowires, which are good candidates for polarized up-conversion emission studies. These perovskite nanowires, with a width of 10 nm and length of a few micrometers, are formed through the oriented attachment of KMnF 3 :Ln nanocubes along the [001] direction. By the employment of KMnF 3 :Ln nanowire gel as nanoink, a direct-writing method is developed to obtain diverse types of aligned patterns from the nanoscale to the wafer scale. Up-conversion emissions from the highly aligned nanowire arrays are polarized along the array direction with a polarization degree up to 60%. Taking advantage of microscopic nanowire arrays, these polarized up-conversion emissions should offer potential applications in light or information transportation.

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

PubMed

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

2018-05-05

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. Copyright © 2018. Published by Elsevier B.V.

Bonding in gold-rare earth [Au2M] (M = Eu, Yb, Lu) ions. A strong covalent gold-lanthanide bond

NASA Astrophysics Data System (ADS)

Páez-Hernández, Dayán; Muñoz-Castro, Alvaro; Arratia-Perez, Ramiro

2017-09-01

The electronic structure and bonding nature of a series of intermetallic gold-lanthanide [Au2Ln] molecules, where Ln = Eu, Yb, Lu is predicted via the DFT and CASSCF/CASPT2 calculations. The 2c-2e bond model shows a good description of the intermetallic bonding which have a large covalent component with important contribution from bonding interaction between the 6s-Au and the 6s-Ln shell of orbitals.

Interactions of Plutonium and Lanthanides with Ordered Mesoporous Materials

NASA Astrophysics Data System (ADS)

Parsons-Moss, Tashi

Ordered mesoporous materials are porous solids with a regular, patterned structure composed of pores between 2 and 50 nm wide. Such materials have attracted much attention in the past twenty years because the chemistry of their synthesis allows control of their unique physicochemical properties, which can be tuned for a variety of applications. Generally, ordered mesoporous materials have very high specific surface areas and pore volumes, and offer unique structures that are neither crystalline nor amorphous. The large tunable interface provided by ordered mesoporous solids may be advantageous in applications involving sequestration, separation, or detection of actinides and lanthanides in solution. However, the fundamental chemical interactions of actinides and lanthanides must be understood before applications can be implemented. This dissertation focuses primarily on the fundamental interactions of plutonium with organically modified mesoporous silica, as well as several different porous carbon materials, both untreated and chemically oxidized. A method for functionalizing mesoporous silica by self assembly and molecular grafting of functional organosilane ligands was optimized for the 2D-hexagonal ordered mesoporous silica known as SBA-15 (Santa Barbara amorphous silica). Four different organically-modified silica materials were synthesized and characterized with several techniques. To confirm that covalent bonds were formed between the silane anchor of the ligand and the silica substrate, functionalized silica samples were analyzed with 29Si nuclear magnetic resonance spectroscopy. Infrared spectroscopy was used in combination with 13C and 31P nuclear magnetic resonance spectroscopy to verify the molecular structures of the ligands after they were synthesized and grafted to the silica. The densities of the functional silane ligands on the silica surface were estimated using thermogravimetric analysis. Batch sorption experiments were conducted with solutions of

Photoluminescence and Coordination Behaviour of Lanthanide Complexes of Tris (Aminomethyl)Ethane-5-Oxine in Aqueous Solution.

PubMed

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.

Highly Luminescent Lanthanide Complexes of 1 Hydroxy-2-pyridinones

DOE Office of Scientific and Technical Information (OSTI.GOV)

University of California, Berkeley; Lawrence National Laboratory; Raymond, Kenneth

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 photophysicalmore » 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.« less

Paramagnetic Nanocrystals: Remarkable Lanthanide-Doped Nanoparticles with Varied Shape, Size, and Composition.

PubMed

Holmberg, Rebecca J; Aharen, Tomoko; Murugesu, Muralee

2012-12-20

Magnetic nanoparticles have been developed in recent years with applications in unique and crucial areas such as biomedicine, data storage, environmental remediation, catalysis, and so forth. NaYF4 nanoparticles were synthesized and isolated with lanthanide dopant percentages, confirmed by ICP-OES measurements, of Er, Yb, Tb, Gd, and Dy that were in agreement with the targeted ratios. SEM images showed a distinct variation in particle size and shape with dopant type and percentage. HRTEM and XRD studies confirmed the particles to be crystalline, possessing both α and β phases. Magnetic measurements determined that all of the nanoparticles were paramagnetic and did not exhibit a blocking temperature from 2 to 300 K. The multifunctional properties of these nanoparticles make them suitable for many applications, such as multimodal imaging probes, up-conversion fluorescent markers, as well as MRI contrast agents.

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.

PubMed

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.

Activation barriers for series of exothermic homologous reactions. VI. Reactions of lanthanide and transition metal atoms.

NASA Astrophysics Data System (ADS)

Blue, Alan S.; Fontijn, Arthur

2001-09-01

Semiempirical configuration interaction (SECI) theory to predict activation barriers, E, as given by k(T)=ATn exp(-E(RT), has been applied to homologous series of lanthanide (LN) and transition metal (TM) atom oxidation reactions. This was achieved by considering as homologous series reactions of elements differing only by the number of electrons in one subshell. Comparison between SECI and experimental results leads to an average deviation for the LN+N2O reactions of 0.66 kJ mol-1, and up to 5.5 kJ mol-1 for other series. Thirty-one activation barriers are reported.

Extraction of water and speciation of trivalent lanthanides and americium in organophosphorus extractants

DOE PAGES

Gullekson, Brian J.; Breshears, Andrew T.; Brown, M. Alex; ...

2016-11-29

Complexes of the trivalent lanthanides and Am with di-2-ethylhexylphosphoric acid (HDEHP) dissolved in an aliphatic diluent were probed with UV–vis, X-ray absorption fine structure, and time-resolved fluorescence spectroscopy while the water concentration was determined by Karl Fischer titrations. In particular, our work focuses on the Nd-hypersensitive UV–vis absorbance region to identify the cause of changing absorbance values at 570 and 583 nm in relation to the pseudooctahedral Nd environment when coordinated with three HDEHP dimers. In contrast to recently reported interpretations, we establish that while impurities have an effect on this electronic transition band, a high water content can causemore » distortion of the pseudooctahedral symmetry of the six-coordinate Nd, resembling the reported spectra of the seven-coordinate Nd compounds. Extended X-ray absorption fine structure analysis of the Nd in high-concentration HDEHP solutions also points to an increase in the coordination number from 6 to 7. The spectral behavior of other lanthanides (Pr, Ho, Sm, and Er) and Am III as a function of the HDEHP concentration suggests that water coordination with the metal likely depends on the metal’s effective charge. Fluorescence data using lifetime studies and excitation and emission spectra support the inclusion of water in the Eu coordination sphere. Further, the role of the effective charge was confirmed by a comparison of the Gibbs free energies of six- and seven-coordinate La-HDEHP–H 2O and Lu-HDEHP–H 2O complexes using density functional theory. In contrast, HEH[EHP], the phosphonic acid analogue of HDEHP, exhibits a smaller capacity for water, and the electronic absorption spectra of Nd or Am appear to be unchanged, although the Pr spectra show a noticeable change in intensity as a function of the water content. As a result, electronic absorption extinction coefficients of Am III, Nd III, Pr III, Sm III, Er III, and Ho III as a function of the

Extraction of water and speciation of trivalent lanthanides and americium in organophosphorus extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gullekson, Brian J.; Breshears, Andrew T.; Brown, M. Alex

Complexes of the trivalent lanthanides and Am with di-2-ethylhexylphosphoric acid (HDEHP) dissolved in an aliphatic diluent were probed with UV–vis, X-ray absorption fine structure, and time-resolved fluorescence spectroscopy while the water concentration was determined by Karl Fischer titrations. In particular, our work focuses on the Nd-hypersensitive UV–vis absorbance region to identify the cause of changing absorbance values at 570 and 583 nm in relation to the pseudooctahedral Nd environment when coordinated with three HDEHP dimers. In contrast to recently reported interpretations, we establish that while impurities have an effect on this electronic transition band, a high water content can causemore » distortion of the pseudooctahedral symmetry of the six-coordinate Nd, resembling the reported spectra of the seven-coordinate Nd compounds. Extended X-ray absorption fine structure analysis of the Nd in high-concentration HDEHP solutions also points to an increase in the coordination number from 6 to 7. The spectral behavior of other lanthanides (Pr, Ho, Sm, and Er) and Am III as a function of the HDEHP concentration suggests that water coordination with the metal likely depends on the metal’s effective charge. Fluorescence data using lifetime studies and excitation and emission spectra support the inclusion of water in the Eu coordination sphere. Further, the role of the effective charge was confirmed by a comparison of the Gibbs free energies of six- and seven-coordinate La-HDEHP–H 2O and Lu-HDEHP–H 2O complexes using density functional theory. In contrast, HEH[EHP], the phosphonic acid analogue of HDEHP, exhibits a smaller capacity for water, and the electronic absorption spectra of Nd or Am appear to be unchanged, although the Pr spectra show a noticeable change in intensity as a function of the water content. As a result, electronic absorption extinction coefficients of Am III, Nd III, Pr III, Sm III, Er III, and Ho III as a function of the

The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce J. Mincher; Guiseppe Modolo; Strephen P. Mezyk

2009-01-01

Solvent extraction is the most commonly used process scale separation technique for nuclear applications and it benefits from more than 60 years of research and development and proven experience at the industrial scale. Advanced solvent extraction processes for the separation of actinides and fission products from dissolved nuclear fuel are now being investigated worldwide by numerous groups (US, Europe, Russia, Japan etc.) in order to decrease the radiotoxic inventories of nuclear waste. While none of the advanced processes have yet been implemented at the industrial scale their development studies have sometimes reached demonstration tests at the laboratory scale. Most ofmore » the partitioning strategies rely on the following four separations: 1. Partitioning of uranium and/or plutonium from spent fuel dissolution liquors. 2. Separation of the heat generating fission products such as strontium and cesium. 3. Coextraction of the trivalent actinides and lanthanides. 4. Separation of the trivalent actinides from the trivalent lanthanides. Tributylphosphate (TBP) in the first separation is the basis of the PUREX, UREX and COEX processes, developed in Europe and the US, whereas monoamides as alternatives for TBP are being developed in Japan and India. For the second separation, many processes were developed worldwide, including the use of crown-ether extractants, like the FPEX process developed in the USA, and the CCD-PEG process jointly developed in the USA and Russia for the partitioning of cesium and strontium. In the third separation, phosphine oxides (CMPOs), malonamides, and diglycolamides are used in the TRUEX, DIAMEX and the ARTIST processes, respectively developed in US, Europe and Japan. Trialkylphosphine oxide(TRPO) developed in China, or UNEX (a mixture of several extractants) jointly developed in Russia and the USA allow all actinides to be co-extracted from acidic radioactive liquid waste. For the final separation, soft donor atom-containing ligands

Synthesis, crystal structure, optical and thermal properties of lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho).

PubMed

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.

Pushing the sensitivity envelope of lanthanide-based magnetic resonance imaging (MRI) contrast agents for molecular imaging applications.

PubMed

Aime, Silvio; Castelli, Daniela Delli; Crich, Simonetta Geninatti; Gianolio, Eliana; Terreno, Enzo

2009-07-21

range of nanosized carriers (micelles, liposomes, microemulsions, and the like, as well as biological structures such as apoferritin and lipoproteins) properly loaded with Gd-based chelates. Furthermore, the sensitivity of Gd-based agents can be markedly affected either by their interactions with biological structures or by their cellular localization. For CEST agents, a huge sensitivity enhancement has been obtained by using the water molecules contained in the inner cavity of liposomes as the exchangeable source of protons for magnetization transfer. Several "tricks" (for example, the use of multimeric lanthanide(III) shift reagents, changes in the shape of the liposome container, and so forth) have been devised to improve the chemical shift separation between the intraliposomal water and the "bulk" water resonances. Overall, excellent sensitivity enhancements have been obtained for both classes of agents, enabling their use in MR molecular imaging applications.

Nuclear Magnetic Resonance Shift Reagents: Abnormal 13C Shifts Produced by Complexation of Lanthanide Chelates with Saturated Amines and n-Butyl Isocyanide

PubMed Central

Marzin, Claude; Leibfritz, Dieter; Hawkes, Geoffrey E.; Roberts, John D.

1973-01-01

Lanthanide-induced shfits of 13C nuclear magnetic resonances are reported for several amines and n-butyl isocyanide. Contact contributions to such shifts, especially of β carbons, are clearly important for the chelates of Eu+3 and Pr+3. The importance of contact terms is shown to change in a rather predictable manner with the structure of the amine. PMID:16592062

ICP-MS analysis of lanthanide-doped nanoparticles as a non-radiative, multiplex approach to quantify biodistribution and blood clearance.

PubMed

Crayton, Samuel H; Elias, Drew R; Al Zaki, Ajlan; Cheng, Zhiliang; Tsourkas, Andrew

2012-02-01

Recent advances in material science and chemistry have led to the development of nanoparticles with diverse physicochemical properties, e.g. size, charge, shape, and surface chemistry. Evaluating which physicochemical properties are best for imaging and therapeutic studies is challenging not only because of the multitude of samples to evaluate, but also because of the large experimental variability associated with in vivo studies (e.g. differences in tumor size, injected dose, subject weight, etc.). To address this issue, we have developed a lanthanide-doped nanoparticle system and analytical method that allows for the quantitative comparison of multiple nanoparticle compositions simultaneously. Specifically, superparamagnetic iron oxide (SPIO) with a range of different sizes and charges were synthesized, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy (ICP-MS) was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood samples and the resected tumor and organs. The method proved generalizable to other nanoparticle platforms, including dendrimers, liposomes, and polymersomes. This approach provides a simple, cost-effective, and non-radiative method to quantitatively compare tumor localization, biodistribution, and blood clearance of more than 10 nanoparticle compositions simultaneously, removing subject-to-subject variability. Copyright © 2011 Elsevier Ltd. All rights reserved.

Structure factor and radial distribution function of some liquid lanthanides using charged hard sphere

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

2017-05-01

The structure factor S(q) and radial distribution function g(r) play vital role to study the various structural properties like electronic, dynamic, magnetic etc. The present paper deals with the structural studies of foresaid properties using our newly constructed parameter free model potential with the Charged Hard Sphere (CHS) approximation. The local field correction due to Sarkar et al. is used to incorporate exchange and correlation among the conduction electrons in dielectric screening. Here we report the S(q) and g(r) for some liquid lanthanides viz: La, Ce, Pr, Nd and Eu. Present computed results are compared with the available experimental data. Lastly we found that our parameter free model potential successfully explains the structural propertiesof4fliquidlanthanides.

Bimetallic lanthanide amido complexes as highly active initiators for the ring-opening polymerization of lactides.

PubMed

Sun, Song; Nie, Kun; Tan, Yufang; Zhao, Bei; Zhang, Yong; Shen, Qi; Yao, Yingming

2013-02-28

A series of neutral bimetallic lanthanide amido complexes supported by rigid phenylene bridged bis(β-diketiminate) ligands were synthesized, and their catalytic behavior for the polymerization of L-lactide and rac-lactide was explored. The amine elimination reaction of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with PARA-H(2), [PARA-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(para-phenylene)] in a 2:1 molar ratio in THF at 25 °C afforded the corresponding bimetallic lanthanide amido complexes PARA-{Ln[N(SiMe(3))(2)](2)}(2) [Ln = Nd(1), Sm(2), Y(3)] in high isolated yields. Similar reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with META-H(2), [META-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(meta-phenylene)] at 90 °C in toluene for about 48 h gave META-{Nd[N(SiMe(3))(2)](2)}(2) (4). Complexes 1-4 were well characterized by elemental analysis, IR spectroscopy, and their definitive structures were confirmed by an X-ray crystal structure analysis. The coordination environment and coordination geometry around the metal atoms are similar in these complexes. Each of the metal atoms is four-coordinated with two nitrogen atoms from the N,N-chelating β-diketiminate unit, and two nitrogen atoms from two (Me(3)Si)(2)N- groups to form a distorted tetrahedron. These complexes can serve as highly active initiators for L-lactide polymerization in toluene. In addition, they also showed high activity towards rac-lactide polymerization in THF at room temperature, giving heterotactic-enriched polymers (P(r) ≈ 0.70), and complex 4 displays obviously higher activity in comparison with complex 1.

Synthesis and Characterization of Monodisperse Core-shell Lanthanide Upconversion Nanoparticles NaYF4: Yb,Tm/SiO2

NASA Astrophysics Data System (ADS)

Manurung, R. V.; Wiranto, G.; Hermida, I. D. P.

2018-05-01

Lanthanide up-converting luminescent nanoparticles (UCNPs) are exciting and promising materials for optical bioimaging, biosensor and theranostic due to their unique and advantageous optical and chemical properties. The UCNPs absorb low energy near-infrared (NIR) light and emit high-energy shorter wavelength photons (visible light). Their unique features allow them to overcome various problems associated with conventional imaging probes such as photostability, lack of toxicity, and to provide versatility for creating nanoplatforms with both imaging and therapeutic modalities. This paper reports synthesis and characterization of core-shell structured of NaYF4:Yb,Tm/SiO2 microspheres. The synthesis of lanthanide upconversion nanoparticles NaYF4:Yb,Tm was prepared by thermal decomposition process which involves dissolving organic precursors in high-boiling-point solvents oleic acid (OA) and octadecene (ODE). After that, the NaYF4:Yb,Tm phosphors was coated by silica via reverse microemulsion process to obtain core-shell structured NaYF4:Yb,Tm/SiO2. Scanning electron microscopy, transmission electron microscopy, specific area electron diffraction, and photoluminescence were applied to characterize these samples. The obtained core-shell structured NaYF4:Yb,Tm/SiO2 phosphors exhibit a perfect cubic morphology with narrow size distribution and smooth surface. Upon IR excitation at 980 nm, the NaYF4:Yb,Tm/SiO2 samples exhibit whitish blue upconversion (UC) luminescence, respectively. These phosphors show potential applications in the displaying on biological fields and biosensing.

A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carter, Korey P.; Pope, Simon J. A.; Cahill, Christopher L.

Fifteen new lanthanide p-chlorobenzoic acid complexes, [PrL3(terpy)(H2O)]2 (1), [LnL3(terpy)(H2O)]2 (Ln = Nd (2), Sm (3), and Eu (4)), and [LnL3(terpy)(H2O)] (Ln = Sm (3'), Eu (4'), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11), Lu (12), and Y (13); HL: p-chlorobenzoic acid; terpy: 2,2':6',2''-terpyridine), have been synthesized hydrothermally at varying temperatures and structurally characterized by single crystal and powder X-ray diffraction. The series is comprised of binuclear molecular units (Pr–Eu) that give way to mononuclear molecular complexes (Sm–Y) as the lanthanide contraction takes effect. All fifteen complexes feature a tridentate terpyridine ligand, p-chlorobenzoic acidmore » ligands exhibiting multiple binding modes, bidentate, bridging bidentate, and monodentate, and a bound water molecule. Binuclear complexes 1–4 are stitched together via intermolecular interactions: aromatic–aromatic interactions for 1, halogen•••halogen interactions for 2–4, to form 1D chains. Mononuclear complexes 3', 4', and 5–13 utilize supramolecular hydrogen and halogen bonding to form 2D sheets. Visible and near-IR solid state luminescence studies were performed on complexes 2, 3, 3', 4, 4', 6, 7 and 11 and the characteristic visible luminescence of Sm(III), Eu(III), Tb(III), and Dy(III) was exhibited. The near-IR spectra of the Nd(III) and Yb(III) complexes exhibit weak characteristic luminescence, showing that terpy can act as a sensitizing chromophore in these systems.« less

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst.

PubMed

de Souza, Viviane P; Oliveira, Cristiane K; de Souza, Thiago M; Menezes, Paulo H; Alves, Severino; Longo, Ricardo L; Malvestiti, Ivani

2016-11-16

Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

Would the solvent effect be the main cause of band shift in the theoretical absorption spectrum of large lanthanide complexes?

NASA Astrophysics Data System (ADS)

Freire, Ricardo O.; Rodrigues, Nailton M.; Rocha, Gerd B.; Gimenez, Iara F.; da Costa Junior, Nivan B.

2011-06-01

As most reactions take place in solution, the study of solvent effects on relevant molecular properties - either by experimental or theoretical methods - is crucial for the design of new processes and prediction of technological properties. In spite of this, only few works focusing the influence of the solvent nature specifically on the spectroscopic properties of lanthanide complexes can be found in the literature. The present work describes a theoretical study of the solvent effect on the prediction of the absorption spectra for lanthanide complexes, but other possible relevant factors have been also considered such as the molecular geometry and the excitation window used for interaction configuration (CI) calculations. The [Eu(ETA) 2· nH 2O] +1 complex has been chosen as an ideal candidate for this type of study due to its small number of atoms (only 49) and also because the absorption spectrum exhibits a single band. Two Monte Carlo simulations were performed, the first one considering the [Eu(ETA) 2] +1 complex in 400 water molecules, evidencing that the complex presents four coordinated water molecules. The second simulation considered the [Eu(ETA) 2·4H 2O] +1 complex in 400 ethanol molecules, in order to evaluate the solvent effect on the shift of the maximum absorption in calculated spectra, compared to the experimental one. Quantum chemical studies were also performed in order to evaluate the effect of the accuracy of calculated ground state geometry on the prediction of absorption spectra. The influence of the excitation window used for CI calculations on the spectral shift was also evaluated. No significant solvent effect was found on the prediction of the absorption spectrum for [Eu(ETA) 2·4H 2O] +1 complex. A small but significant effect of the ground state geometry on the transition energy and oscillator strength was also observed. Finally it must be emphasized that the absorption spectra of lanthanide complexes can be predicted with great accuracy

The New Element Americium (Atomic Number 95)

DOE R&D Accomplishments Database

Seaborg, G.T.; James, R.A.; Morgan, L.O.

1948-01-01

Several isotopes of the new element 95 have been produced and their radiations characterized. The chemical properties of this tripositive element are similar to those of the typical tripositive lanthanide rare-earth elements. Element 95 is different from the latter in the degree and rate of formation of certain compounds of the complex ion type, which makes possible the separation of element 95 from the lanthanide rare-earths. The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series.

PIXE analysis of tumors and localization behavior of a lanthanide in nude mice

NASA Astrophysics Data System (ADS)

Chang, Pei-Jiun; Yang, Czau-Siung; Chou, Ming-Ji; Wei, Chau-Chin; Hsu, Chu-Chung; Wang, Chia-Yu

1984-04-01

We have used particle induced X-ray emission (PIXE) to analyze the elemental compositions and uptakes of a lanthanide, yttrium in this report, in tumors and normal tissues of nude mice. A small amount of yttrium nitrate was injected into nude mice with tumors. Samples of normal and malignant tissues taken from these mice were bombarded by the 2 MeV proton beam from a 3 MeV Van de Graaff accelerator with a Ge detector system to determine the relative elemental compositions of tissues and the relative concentrations of yttrium taken up by these tissues. We found that the uptakes of yttrium by tumors were at least five times more than those by normal tissues. Substantial differences were often observed between the trace element weight (or concentration) pattern of the cancerous and normal tissues. The present result is compared with human tissues.

Lanthanide Fluorobenzoates as Bio-Probes: a Quest for the Optimal Ligand Fluorination Degree.

PubMed

Kalyakina, Alena S; Utochnikova, Valentina V; Bushmarinov, Ivan S; Le-Deygen, Irina M; Volz, Daniel; Weis, Patrick; Schepers, Ute; Kuzmina, Natalia P; Bräse, Stefan

2017-10-20

The thorough study of fluorinated benzoates of lanthanides (Eu, Tb, Nd, Er, Yb, Gd, La, Lu) is reported. Their composition in single crystal and powder state revealed two predominant structural motifs. An in-depth luminescence study has been performed on the reported fluorobenzoates, showing, that terbium and europium complexes in solid state possess high luminescence intensity with the quantum yield of up to 69 %. High solubility in most organic solvents, as well as in water, combined with the high luminescence intensity in water solution and non-toxicity allowed the testing of europium complexes as bioprobes in cellulo. Among all tested fluorobenzoates, europium 2-fluorobenzoate dihydrate combined the best luminescent properties, thermodynamic stability, aqueous solubility, and non-toxicity, and was shown to be a viable bio-marker. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two novel 2D lanthanide sulfate frameworks: Syntheses, structures, and luminescence properties

NASA Astrophysics Data System (ADS)

Li, Zhong-Yi; Zhang, Chi; Zhang, Fu-Li; Zhang, Fu-Qiang; Zhang, Xiang-Fei; Li, Su-Zhi; Cao, Guang-Xiu; Zhai, Bin

2016-03-01

Two novel lanthanide-sulfate compounds, [Ln2(SO4)3(H2O)8] (Ln = Tb (1) and Dy (2)), have been synthesized under hydrothermal reactions. X-ray crystal structure analyses reveal that 1 and 2 are isomorphous and crystallize in monoclinic C2/c pace group, showing a layered structure. The layers bear a rare quasi-honeycomb metal arrangement, which is fastened by μ3 = η1:η1:η1 and μ2 = η1:η1 sulfates. If assigning the μ3 = η1:η1:η1 sulfate as a 3-connected node and the Ln3+ ion as a 4-connected node, the network can be rationalized as a binodal (3,4)-connected V2O5 topology with a Schäfli symbol of (42·63·8) (42·6). In addition, the infrared, thermogravimetric analysis and luminescent properties were also studied. Complexes 1 and 2 exhibit outstanding thermal stability and characteristic terbium and dysprosium luminescence.

Measuring lanthanide concentrations in molten salt using laser-induced breakdown spectroscopy (LIBS).

PubMed

Weisberg, Arel; Lakis, Rollin E; Simpson, Michael F; Horowitz, Leo; Craparo, Joseph

2014-01-01

The versatility of laser-induced breakdown spectroscopy (LIBS) as an analytical method for high-temperature applications was demonstrated through measurement of the concentrations of the lanthanide elements europium (Eu) and praseodymium (Pr) in molten eutectic lithium chloride-potassium chloride (LiCl-KCl) salts at a temperature of 500 °C. Laser pulses (1064 nm, 7 ns, 120 mJ/pulse) were focused on the top surface of the molten salt samples in a laboratory furnace under an argon atmosphere, and the resulting LIBS signals were collected using a broadband Echelle-type spectrometer. Partial least squares (PLS) regression using leave-one-sample-out cross-validation was used to quantify the concentrations of Eu and Pr in the samples. The root mean square error of prediction (RMSEP) for Eu was 0.13% (absolute) over a concentration range of 0-3.01%, and for Pr was 0.13% (absolute) over a concentration range of 0-1.04%.

Nanoparticles speckled by ready-to-conjugate lanthanide complexes for multimodal imaging

NASA Astrophysics Data System (ADS)

Biju, Vasudevanpillai; Hamada, Morihiko; Ono, Kenji; Sugino, Sakiko; Ohnishi, Takashi; Shibu, Edakkattuparambil Sidharth; Yamamura, Shohei; Sawada, Makoto; Nakanishi, Shunsuke; Shigeri, Yasushi; Wakida, Shin-Ichi

2015-09-01

Multimodal and multifunctional contrast agents receive enormous attention in the biomedical imaging field. Such contrast agents are routinely prepared by the incorporation of organic molecules and inorganic nanoparticles (NPs) into host materials such as gold NPs, silica NPs, polymer NPs, and liposomes. Despite their non-cytotoxic nature, the large size of these NPs limits the in vivo distribution and clearance and inflames complex pharmacokinetics, which hinder the regulatory approval for clinical applications. Herein, we report a unique method that combines magnetic resonance imaging (MRI) and fluorescence imaging modalities together in nanoscale entities by the simple, direct and stable conjugation of novel biotinylated coordination complexes of gadolinium(iii) to CdSe/ZnS quantum dots (QD) and terbium(iii) to super paramagnetic iron oxide NPs (SPION) but without any host material. Subsequently, we evaluate the potentials of such lanthanide-speckled fluorescent-magnetic NPs for bioimaging at single-molecule, cell and in vivo levels. The simple preparation and small size make such fluorescent-magnetic NPs promising contrast agents for biomedical imaging.

A series of novel lanthanide complexes with 2-bromine-5-methoxybenzoic acid and 2,2‧-bipyridine: Syntheses, crystal structures, and luminescent properties

NASA Astrophysics Data System (ADS)

Zhao, Qing-Qing; Zhu, Min-Min; Ren, Ning; Zhang, Jian-Jun

2017-12-01

Six new lanthanide complexes [Ln(2-Br-5-MOBA)3(2,2‧-DIPY)]2 (Ln = Nd(1), Eu(2), Gd(3), Tb(4), Ho(5), Er(6); 2-Br-5-MOBA = 2-bromine-5-methoxybenzoate; 2,2‧-DIPY = 2,2‧-bipyridine) have been successfully synthesized and characterized. The complexes 1-5 are isostructural and nine-coordinated by the single-crystal X-ray diffraction analyses, while the complex 6 is eight-coordinated. The difference of crystal structure may be the result of the lanthanide contraction effect. The binuclear units were further assembled into 1D, 2D, 3D supramolecular structures by the π-π stacking and Csbnd H⋯O hydrogen bonding interactions. The thermal decomposition mechanism of complexes 1-6 was studied by TG analysis and further authenticated by TG/DSC-FTIR techniques. The solid-state luminescence properties of complexes 2 and 4 were investigated at room temperature. The results indicate that complexes 2 and 4 show characteristic emission of Eu3+ ion and Tb3+ ion, respectively. What's more, the title complexes have good antibacterial activities against Candida albicans.

Influence of deformed surface diffuseness on alpha decay half-lives of actinides and lanthanides

NASA Astrophysics Data System (ADS)

Dahmardeh, S.; Alavi, S. A.; Dehghani, V.

2017-07-01

By using semiclassical WKB method and taking into account the Bohr-Sommerfeld quantization condition, the alpha decay half-lives of some deformed lanthanide (with 151 ≤ A ≤ 160 and 66 ≤ Z ≤ 73) and rare-earth nuclei (with 217 ≤ A ≤ 261 and 92 ≤ Z ≤ 104) have been calculated. The effective potential has been considered as sum of deformed Woods-Saxon nuclear potential, deformed Coulomb potential, and centrifugal potential. The influence of deformed surface diffuseness on the potential barrier, transmission coefficient at each angle, assault frequency, and alpha decay half-lives has been investigated. Good agreement between calculated half-lives with deformed surface diffuseness and experiment is observed. Relative differences between calculated half-lives with deformed surface diffuseness and with constant surface diffuseness were significant.

Chiral Silver-Lanthanide Metal-Organic Frameworks Comprised of One-Dimensional Triple Right-Handed Helical Chains Based on [Ln7(μ3-OH)8]13+ Clusters.

PubMed

Guo, Yan; Zhang, Lijuan; Muhammad, Nadeem; Xu, Yan; Zhou, Yunshan; Tang, Fang; Yang, Shaowei

2018-02-05

Three new isostructural chiral silver-lanthanide heterometal-organic frameworks [Ag 3 Ln 7 (μ 3 -OH) 8 (bpdc) 6 (NO 3 ) 3 (H 2 O) 6 ](NO 3 )·2H 2 O [Ln = Eu (1), Tb (2, Sm (3); H 2 bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid] based on heptanuclear lanthanide clusters [Ln 7 (μ 3 -OH) 8 ] 13+ comprised of one-dimensional triple right-handed helical chains were hydrothermally synthesized. Various means such as UV-vis spectroscopy, IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric/differential thermal analysis were used to characterize the compounds, wherein compound 3 was crystallographically characterized. In the structure of compound 3, eight μ 3 -OH - groups link seven Sm 3+ ions, forming a heptanuclear cluster, [Sm 7 (μ 3 -OH) 8 ] 13+ , and the adjacent [Sm 7 (μ 3 -OH) 8 ] 13+ clusters are linked by the carboxylic groups of bpdc 2- ligands, leading to the formation of a one-dimensional triple right-handed helical chain. The adjacent triple right-handed helical chains are further joined together by coordinating the pyridyl N atoms of the bpdc 2- ligands with Ag + , resulting in a chiral three-dimensional silver(I)-lanthanide(III) heterometal-organic framework with one-dimensional channels wherein NO 3 - anions and crystal lattice H 2 O molecules are trapped. The compounds were studied systematically with respect to their photoluminescence properties and energy-transfer mechanism, and it was found that H 2 bpdc (the energy level for the triplet states of the ligand H 2 bpdc is 21505 cm -1 ) can sensitize Eu 3+ luminescence more effectively than Tb 3+ and Sm 3+ luminescence because of effective energy transfer from bpdc 2- to Eu 3+ under excitation in compound 1.

Active caspase-1 induces plasma membrane pores that precede pyroptotic lysis and are blocked by lanthanides#

PubMed Central

Russo, Hana M.; Rathkey, Joseph; Boyd-Tressler, Andrea; Katsnelson, Michael A.; Abbott, Derek W.; Dubyak, George R.

2016-01-01

Canonical inflammasome activation induces a caspase-1/gasdermin D (Gsdmd) dependent lytic cell death called pyroptosis which promotes anti-microbial host defense but may contribute to sepsis. The nature of the caspase-1-dependent change in plasma membrane (PM) permeability during pyroptotic progression remains incompletely defined. We assayed propidium2+ (Pro2+) influx kinetics during NLRP3 or Pyrin inflammasome activation in murine bone marrow-derived macrophages (BMDM) as an indicator of this PM permeabilization. BMDM were characterized by rapid Pro2+ influx after initiation of NLRP3 or Pyrin inflammasomes by nigericin or C. difficile toxin B (TcdB), respectively. No Pro2+ uptake in response to nigericin or TcdB was observed in Caspase-1−/− or ASC−/− BMDM. The cytoprotectant glycine profoundly suppressed nigericin and TcdB-induced lysis but not Pro2+ influx. The absence of Gsdmd expression resulted in suppression of nigericin-stimulated Pro2+ influx and pyroptotic lysis. Extracellular La3+ and Gd3+ rapidly and reversibly blocked the induced Pro2+ influx and markedly delayed pyroptotic lysis without limiting upstream inflammasome assembly and caspase-1 activation. Thus, caspase-1 driven pyroptosis requires induction of initial pre-lytic pores in the PM that are dependent on Gsdmd expression. These PM pores also facilitated the efflux of cytosolic ATP and influx of extracellular Ca2+. Although lanthanides and Gsdmd deletion both suppressed PM pore activity and pyroptotic lysis, robust IL-1β release was observed in lanthanide-treated BMDM but not in Gsdmd-deficient cells. This suggests roles for Gsdmd in both passive IL-1β release secondary to pyroptotic lysis and in non-lytic/non-classical IL-1β export. PMID:27385778

Lanthanide luminescent displacement assays: the sensing of phosphate anions using Eu(III)-cyclen-conjugated gold nanoparticles in aqueous solution.

PubMed

Massue, Julien; Quinn, Susan J; Gunnlaugsson, Thorfinnur

2008-06-04

1.Eu, a cyclen based Eu(III)-thiol conjugate, was incorporated onto the surface of water-soluble gold nanoparticles to give AuNP-1.Eu. The self-assembly between AuNP-1.Eu and the antenna 2 resulted in the formation of the highly luminescent lanthanide system, AuNP-1.Eu-2, at pH 7.4. The sensing of flavin monophosphate 3 is demonstrated, whereby 3 displaced the antenna 2 in AuNP-1.Eu-2, resulting in the formation of AuNP-1.Eu-3 and quenching of the Eu(III) emission.

Functionalisation of lanthanide complexes via microwave-enhanced Cu(I)-catalysed azide-alkyne cycloaddition.

PubMed

Szíjjártó, Csongor; Pershagen, Elias; Borbas, K Eszter

2012-07-07

Cu(I)-catalysed azide-alkyne cycloaddition reactions were used to functionalise lanthanide(III)-complexes (Ln; La, Eu and Tb) incorporating alkyne or azide reactive groups. Microwave irradiation significantly accelerated the reactions, enabling full conversion to the triazole products in some cases in 5 min. Alkyl and aryl azides and alkyl and aryl alkynes could all serve as coupling partners. These reaction conditions proved efficient for cyclen-tricarboxylates and previously unreactive cyclen-tris-primary amide chelates. The synthesis of heterobimetallic (Eu/Tb, EuTb17 and Eu/La, EuLa17) and heterotrimetallic (Eu/La/Eu) complexes was achieved in up to 60% isolated yield starting from coumarin 2-appended alkynyl complexes Tb16 or La16 and an azido-Eu complex Eu4, and bis-alkynyl La-complex La5 and Eu4, respectively. EuTb17 displayed dual Eu(III) and Tb(III)-emission upon antenna-centred excitation.

Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

PubMed

Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

2015-04-13

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling the magnetic properties of lanthanide complexes: relationship of the REC parameters with Pauling electronegativity and coordination number.

PubMed

Baldoví, José J; Gaita-Ariño, Alejandro; Coronado, Eugenio

2015-07-28

In a previous study, we introduced the Radial Effective Charge (REC) model to study the magnetic properties of lanthanide single ion magnets. Now, we perform an empirical determination of the effective charges (Zi) and radial displacements (Dr) of this model using spectroscopic data. This systematic study allows us to relate Dr and Zi with chemical factors such as the coordination number and the electronegativities of the metal and the donor atoms. This strategy is being used to drastically reduce the number of free parameters in the modeling of the magnetic and spectroscopic properties of f-element complexes.

Extending lifetimes of lanthanide-based near-infrared emitters (Nd, Yb) in the millisecond range through Cr(III) sensitization in discrete bimetallic edifices.

PubMed

Imbert, Daniel; Cantuel, Martine; Bünzli, Jean-Claude G; Bernardinelli, Gérald; Piguet, Claude

2003-12-24

A [Cr(alpha,alpha'-diimine)3]3+ chromophore is used as a donor for sensitizing NdIII and YbIII near-infrared (NIR) emitters in the heterobimetallic helicates [LnCrIIIL3]6+. The intramolecular CrIII --> LnIII energy transfer process controls the population of the lanthanide-centered emitting levels, thus leading to unprecedented extension of the NIR luminescence decay times in the millisecond range for Nd and Yb ions incorporated in coordination complexes.

Unexpected magnetism, and transport properties in mixed lanthanide compound

NASA Astrophysics Data System (ADS)

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 <=30 kOe, and a clear Griffiths-like phase behavior at <1 kOe. The compound also exhibits an asymmetry of hysteresis loop, or exchange bias (EB) effect after 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.

Spectroscopic studies on the lanthanide sensitized luminescence and chemiluminescence properties of fluoroquinolone with different structure.

PubMed

Sun, Chunyan; Ping, Hong; Zhang, Minwei; Li, Hongkun; Guan, Fengrui

2011-11-01

Lanthanide sensitized luminescence and chemiluminescence (CL) are of great importance because of the unique spectral properties, such as long lifetime, large Stokes shifts, and narrow emission bands characteristic to lanthanide ions (Ln(3+)). With the fluoroquinolone (FQ) compounds including enoxacin (ENX), norfloxacin (NFLX), lomefloxacin (LMFX), fleroxacin (FLRX), ofloxacin (OFLX), rufloxacin (RFX), gatifloxacin (GFLX) and sparfloxacin (SPFX), the luminescence and CL properties of Tb(3+)-FQ and Eu(3+)-FQ complexes have been investigated in this contribution. Ce(4+)-SO(3)(2-) in acidic conditions was taken as the CL system and sensitized CL intensities of Tb(3+)-FQ and Eu(3+)-FQ complexes were determined by flow-injection analysis. The luminescence and CL spectra of Tb(3+)-FQ complexes show characteristic peaks of Tb(3+) at 490 nm, 545 nm, 585 nm and 620 nm. Complexes of Tb(3+)-ENX, Tb(3+)-NFLX, Tb(3+)-LMFX and Tb(3+)-FLRX display relatively strong emission intensity compared with Tb(3+)-OFLX, Tb(3+)-RFX, Tb(3+)-GFLX and Tb(3+)-SPFX. Quite weak peaks with unique characters of Eu(3+) at 590 nm and 617 nm appear in the luminescence and CL spectra of Eu(3+)-ENX, but no notable sensitized luminescence and CL of Eu(3+) could be observed when Eu(3+) is added into other FQ. The distinct differences on emission intensity of Tb(3+)-FQ and Eu(3+)-FQ might originate from the different energy gap between the triplet levels of FQ and the excited levels of the Ln(3+). The different sensitized luminescence and CL signals among Tb(3+)-FQ complexes could be attributed to different optical properties and substituents of these FQ compounds. The detailed mechanism involved in the luminescence and CL properties of Tb(3+)-FQ and Eu(3+)-FQ complexes has been investigated by analyzing the luminescence and CL spectra, quantum yields, and theoretical calculation results. Copyright © 2011 Elsevier B.V. All rights reserved.

Development of a ratiometric time-resolved luminescence sensor for pH based on lanthanide complexes.

PubMed

Liu, Mingjing; Ye, Zhiqiang; Xin, Chenglong; Yuan, Jingli

2013-01-25

Time-resolved luminescence bioassay technique using lanthanide complexes as luminescent probes/sensors has shown great utilities in clinical diagnostics and biotechnology discoveries. In this work, a novel terpyridine polyacid derivative that can form highly stable complexes with lanthanide ions in aqueous media, (4'-hydroxy-2,2':6',2''-terpyridine-6,6''-diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu(3+) and Tb(3+) complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA-Eu(3+) is strongly dependent on the pH values in weakly acidic to neutral media (pK(a) = 5.8, pH 4.8-7.5), while that of HTTA-Tb(3+) is pH-independent. This unique luminescence response allows the mixture of HTTA-Eu(3+) and HTTA-Tb(3+) (the HTTA-Eu(3+)/Tb(3+) mixture) to be used as a ratiometric luminescence sensor for the time-resolved luminescence detection of pH with the intensity ratio of its Tb(3+) emission at 540 nm to its Eu(3+) emission at 610 nm, I(540 nm)/I(610 nm), as a signal. Moreover, the UV absorption spectrum changes of the HTTA-Eu(3+)/Tb(3+) mixture at different pHs (pH 4.0-7.0) also display a ratiometric response to the pH changes with the ratio of absorbance at 290 nm to that at 325 nm, A(290 nm)/A(325 nm), as a signal. This feature enables the HTTA-Eu(3+)/Tb(3+) mixture to have an additional function for the pH detection with the absorption spectrometry technique. For loading the complexes into the living cells, the acetoxymethyl ester of HTTA was synthesized and used for loading HTTA-Eu(3+) and HTTA-Tb(3+) into the cultured HeLa cells. The luminescence imaging results demonstrated the practical utility of the new sensor for the time-resolved luminescence cell imaging application. Copyright © 2012 Elsevier B.V. All rights reserved.

Rare-earth organic frameworks involving three types of architecture tuned by the lanthanide contraction effect: hydrothermal syntheses, structures and luminescence.

PubMed

Deng, Zhao-Peng; Kang, Wei; Huo, Li-Hua; Zhao, Hui; Gao, Shan

2010-07-21

The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) () for type I, {[Ln(apca)(ox)(H(2)O)(2)].H(2)O}(n) (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D "snowflake" chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex exhibits strong blue emission and complex exhibits characteristic luminescence of Eu(3+).

Strategies for Optimizing Water-Exchange Rates of Lanthanide-Based Contrast Agents for Magnetic Resonance Imaging

PubMed Central

Siriwardena-Mahanama, Buddhima N.; Allen, Matthew J.

2013-01-01

This review describes recent advances in strategies for tuning the water-exchange rates of contrast agents for magnetic resonance imaging (MRI). Water-exchange rates play a critical role in determining the efficiency of contrast agents; consequently, optimization of water-exchange rates, among other parameters, is necessary to achieve high efficiencies. This need has resulted in extensive research efforts to modulate water-exchange rates by chemically altering the coordination environments of the metal complexes that function as contrast agents. The focus of this review is coordination-chemistry-based strategies used to tune the water-exchange rates of lanthanide(III)-based contrast agents for MRI. Emphasis will be given to results published in the 21st century, as well as implications of these strategies on the design of contrast agents. PMID:23921796

Lanthanide-based oxides and silicates for high-kappa gate dielectric applications

NASA Astrophysics Data System (ADS)

Jur, Jesse Stephen

The ability to improve performance of the high-end metal oxide semiconductor field effect transistor (MOSFET) is highly reliant on the dimensional scaling of such a device. In scaling, a decrease in dielectric thickness results in high current leakage between the electrode and the substrate by way of direct tunneling through the gate dielectric. Observation of a high leakage current when the standard gate dielectric, SiO2, is decreased below a thickness of 1.5 nm requires engineering of a replacement dielectric that is much more scalable. This high-kappa dielectric allows for a physically thicker oxide, reducing leakage current. Integration of select lanthanide-based oxides and silicates, in particular lanthanum oxide and silicate, into MOS gate stack devices is examined. The quality of the high-kappa dielectrics is monitored electrically to determine properties such as equivalent oxide thickness, leakage current density and defect densities. In addition, analytical characterization of the dielectric and the gate stack is provided to examine the materialistic significance to the change of the electrical properties of the devices. In this work, lanthanum oxide films have been deposited by thermal evaporation on to a pre-grown chemical oxide layer on silicon. It is observed that the SiO2 interfacial layer can be consumed by a low-temperature reaction with lanthanum oxide to produce a high-quality silicate. This is opposed to depositing lanthanum oxide directly on silicon, which can possibly favor silicide formation. The importance of oxygen regulation in the surrounding environment of the La2O3-SiO2 reaction-anneal is observed. By controlling the oxygen available during the reaction, SiO2 growth can be limited to achieve high stoichiometric ratios of La2O 3 to SiO2. As a result, MOS devices with an equivalent oxide thickness (EOT) of 5 A and a leakage current density of 5.0 A/cm 2 are attained. This data equals the best value achieved in this field and is a

Brilliant Sm, Eu, Tb and Dy chiral lanthanide complexes withstrong circularly polarized luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petoud, Stephane; Muller, Gilles; Moore, Evan G.

The synthesis, characterization and luminescent behavior of trivalent Sm, Eu, Dy and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g{sub lum}, recorded for the Eu(III) complexmore » is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.« less

Investigation of heavy-ion fusion with deformed surface diffuseness: Actinide and lanthanide targets

NASA Astrophysics Data System (ADS)

Alavi, S. A.; Dehghani, V.

2017-05-01

By using a deformed Broglia-Winther nuclear interaction potential in the framework of the WKB method, the near- and above-barrier heavy-ion-fusion cross sections of 16O with some lanthanides and actinides have been calculated. The effect of deformed surface diffuseness on the nuclear interaction potential, the effective interaction potential at distinct angle, barrier position, barrier height, cross section at each angles, and fusion cross sections of 16O+147Sm,150Nd,154Sm , and 166Er and 16O+232Th,238U,237Np , and 248Cm have been studied. The differences between the results obtained by using deformed surface diffuseness and those obtained by using constant surface diffuseness were noticeable. Good agreement between experimental data and theoretical calculation with deformed surface diffuseness were observed for 16O+147Sm,154Sm,166Er,238U,237Np , and 248Cm reactions. It has been observed that deformed surface diffuseness plays a significant role in heavy-ion-fusion studies.

Strong exchange and magnetic blocking in N₂³⁻-radical-bridged lanthanide complexes.

PubMed

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).

Syntheses, structures and properties of 3D inorganic-organic hybrid frameworks constructed from lanthanide polymer and Keggin-type tungstosilicate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao Yuanzhe; College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, Hebei 050016; Xu Yanqing, E-mail: xyq@bit.edu.c

2010-05-15

Inorganic-organic hybrid frameworks, namely [Ce(H{sub 2}O){sub 3}(pdc)]{sub 4}[SiW{sub 12}O{sub 40}].6H{sub 2}O 1, [M(H{sub 2}O){sub 4}(pdc)]{sub 4}[SiW{sub 12}O{sub 40}].2H{sub 2}O (M=Ce for 2a, La for 2b, Nd for 2c; H{sub 2}pdc=pyridine-2,6-dicarboxylic acid) were assembled through incorporation of Keggin-type heteropolyanion [SiW{sub 12}O{sub 40}]{sup 4-} within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition. Single-crystal X-ray analyses of these crystals reveal that compound 1 presents 3D pillar-layered framework with the [SiW{sub 12}O{sub 40}]{sup 4-} anions located on the square voids of the two-dimensional Ce-pdc bilayer. Compounds 2a-c are isostructural and constructed from 3D Ln-pdc-based metal-organic framework (MOF) incorporating noncoordinatingmore » guests Keggin structure [SiW{sub 12}O{sub 40}]{sup 4-}. Solid-state properties of compounds 1 and 2a-c such as thermal stability and photoluminescence have been further investigated. - Graphical abstract: Two types of new inorganic-organic hybrid frameworks through incorporation of Keggin-type heteropolyanion [SiW{sub 12}O{sub 40}]{sup 4-} within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition were successfully assembled. Solid-state properties of compounds 1 and 2a such as thermal stability and photoluminescence have been further investigated.« less

Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions

DOE PAGES

Brown, Jessie L.; Davis, Benjamin L.; Scott, Brian L.; ...

2015-12-25

Dissolution of LnI 3 (Ln = La, Ce) in acetonitrile (MeCN) results in the highly soluble solvates LnI 3(MeCN) 5 [Ln = La (1), Ce (2)] in good yield. The ionic complex [La(MeCN) 9][LaI 6] (4), containing a rare homoleptic La 3+ cation and anion, was also isolated as a minor product. Extending this chemistry to NdI 3 results in the consistent formation of the complex ionic structure [Nd(MeCN) 9] 2[NdI 5(MeCN)][NdI 6][I] (3), which contains an unprecedented pentaiodide lanthanoid anion. Also described is the synthesis, isolation, and structural characterization of several homoleptic early-lanthanide MeCN solvates with noncoordinating anions, namely,more » [Ln(MeCN) 9][AlCl 4] 3 [Ln = La (5), Ce (6), Nd (7)]. Notably, complex 6 is the first homoleptic cerium MeCN solvate reported to date. All reported complexes were structurally characterized by X-ray crystallography, as well as by IR spectroscopy and CHN elemental analysis. Furthermore, complexes 1–3 were also characterized by thermogravimetric analysis coupled with mass spectrometry to further elucidate their bulk composition in the solid-state.« less

Plasmon-Induced Selective Enhancement of Green Emission in Lanthanide-Doped Nanoparticles.

PubMed

Zhang, Weina; Li, Juan; Lei, Hongxiang; Li, Baojun

2017-12-13

By introducing an 18 nm thick Au nanofilm, selective enhancement of green emission from lanthanide-doped (β-NaYF 4 :Yb 3+ /Er 3+ ) upconversion nanoparticles (UCNPs) is demonstrated. The Au nanofilm is deposited on a microfiber surface by the sputtering method and then covered with the UCNPs. The plasma on the surface of the Au nanofilm can be excited by launching a 980 nm wavelength laser beam into the microfiber, resulting in an enhancement of the local electric field and a strong thermal effect. A 36-fold luminescence intensity enhancement of the UCNPs at 523 nm is observed, with no obvious reduction in the photostability of the UCNPs. Further, the intensity ratios of the emissions at 523-545 nm and at 523-655 nm are enhanced with increasing pump power, which is attributed to the increasing plasmon-induced thermal effect. Therefore, the fabricated device is further demonstrated to exhibit an excellent ability in temperature sensing. By controlling the pump power and the UCNP concentration, a wide temperature range (325-811 K) and a high temperature resolution (0.035-0.046 K) are achieved in the fabricated device.

Fast and background-free three-dimensional (3D) live-cell imaging with lanthanide-doped upconverting nanoparticles.

PubMed

Jo, Hong Li; Song, Yo Han; Park, Jinho; Jo, Eun-Jung; Goh, Yeongchang; Shin, Kyujin; Kim, Min-Gon; Lee, Kang Taek

2015-12-14

We report on the development of a three-dimensional (3D) live-cell imaging technique with high spatiotemporal resolution using lanthanide-doped upconverting nanoparticles (UCNPs). It employs the sectioning capability of confocal microscopy except that the two-dimensional (2D) section images are acquired by wide-field epi-fluorescence microscopy. Although epi-fluorescence images are contaminated with the out-of-focus background in general, the near-infrared (NIR) excitation used for the excitation of UCNPs does not generate any autofluorescence, which helps to lower the background. Moreover, the image blurring due to defocusing was naturally eliminated in the image reconstruction process. The 3D images were used to investigate the cellular dynamics such as nuclear uptake and single-particle tracking that require 3D description.

New anion-templated 3D heterobimetallic open frameworks based on lanthanide-carboxylate layers and copper pillars

NASA Astrophysics Data System (ADS)

Li, Yun-Wu; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

2008-06-01

A series of new three-dimensional (3D) lanthanide-transition metal (4 f-3 d) heterobimetallic open frameworks, [ Ln2(1,2-bdc) 2(H 2O) 2 Cu(inic) 2](ClO 4) ( Ln=Eu (1), Tb (2), Nd (3) and Sm (4); 1,2-bdc=1,2-benzenedicarboxylate; Hinic=isonicotinic acid) have been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction analysis. Compounds 1-4 are isostructural. They possess a new anion-templated 3D heterobimetallic open framework, which is observed for the first time in the { Ln/ TM/bdc/inic} ( TM=transition metal) system. Compounds 1 and 2 exhibit the characteristic fluorescent properties of Eu(III) and Tb(III), respectively.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

NASA Astrophysics Data System (ADS)

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.

Scanning two-photon microscopy with upconverting lanthanide nanoparticles via Richardson-Lucy deconvolution.

PubMed

Gainer, Christian F; Utzinger, Urs; Romanowski, Marek

2012-07-01

The use of upconverting lanthanide nanoparticles in fast-scanning microscopy is hindered by a long luminescence decay time, which greatly blurs images acquired in a nondescanned mode. We demonstrate herein an image processing method based on Richardson-Lucy deconvolution that mitigates the detrimental effects of their luminescence lifetime. This technique generates images with lateral resolution on par with the system's performance, ∼1.2  μm, while maintaining an axial resolution of 5 μm or better at a scan rate comparable with traditional two-photon microscopy. Remarkably, this can be accomplished with near infrared excitation power densities of 850 W/cm(2), several orders of magnitude below those used in two-photon imaging with molecular fluorophores. By way of illustration, we introduce the use of lipids to coat and functionalize these nanoparticles, rendering them water dispersible and readily conjugated to biologically relevant ligands, in this case epidermal growth factor receptor antibody. This deconvolution technique combined with the functionalized nanoparticles will enable three-dimensional functional tissue imaging at exceptionally low excitation power densities.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes.

PubMed

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

2017-02-03

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.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

PubMed Central

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.

2017-01-01

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. PMID:28155857

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).

PubMed

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.

Potentiometric study of binary complexes of 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride with some lanthanide ions in aqueous and mixed solutions

NASA Astrophysics Data System (ADS)

Sharma, S. S.; Kadia, M. V.

2014-12-01

The complexation of lanthanide ions (Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Gd3+, Tb3+, and Dy3+) with 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride was studied at different temperatures and different ionic strengths in aqueous solutions by Irving-Rossotti pH titration technique. Stepwise calculation, PKAS and BEST Fortran IV computer programs were used for determination of proton-ligand and metal-ligand stability constants. The formation of species like MA, MA2, and MA(OH) is considered in SPEPLOT. Thermodynamic parameters of complex formation (Δ G, Δ H, and Δ S) are also evaluated. Negative Δ G and Δ H values indicate that complex formation is favourable in these experimental conditions. The stability of complexes is also studied at in different solvent-aqueous (vol/vol). The stability series of lanthanide complexes has shown to have the "gadolinium break." Stability of complexes decreases with increase in ionic strength and temperature. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained.

Separation of 103Ru from a proton irradiated thorium matrix: A potential source of Auger therapy radionuclide 103mRh

PubMed Central

Hopkins, Philip D.; Engle, Jonathan W.; Weidner, John W.; Copping, Roy; Brugh, Mark; Nortier, F. Meiring; Birnbaum, Eva R.; John, Kevin D.

2017-01-01

Ruthenium-103 is the parent isotope of 103mRh (t1/2 56.1 min), an isotope of interest for Auger electron therapy. During the proton irradiation of thorium targets, large amounts of 103Ru are generated through proton induced fission. The development of a two part chemical separation process to isolate 103Ru in high yield and purity from a proton irradiated thorium matrix on an analytical scale is described herein. The first part employed an anion exchange column to remove cationic actinide/lanthanide impurities along with the majority of the transition metal fission products. Secondly, an extraction chromatographic column utilizing diglycolamide functional groups was used to decontaminate 103Ru from the remaining impurities. This method resulted in a final radiochemical yield of 83 ± 5% of 103Ru with a purity of 99.9%. Additionally, measured nuclear reaction cross sections for the formation of 103Ru and 106Ru via the 232Th(p,f)103,106Ru reactions are reported within. PMID:29272318

Brilliant Sm, Eu, Tb, and Dy Chiral Lanthanide Complexes with Strong Circularly Polarized Luminescence

PubMed Central

Petoud, Stéphane; Muller, Gilles; Moore, Evan G.; Xu, Jide; Sokolnicki, Jurek; Riehl, James P.; Le, Uyen N.; Cohen, Seth M.; Raymond, Kenneth N.

2009-01-01

The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, glum, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments. PMID:17199285

Synthesis, characterization and anticancer activities of two lanthanide(III) complexes with a nicotinohydrazone ligand

NASA Astrophysics Data System (ADS)

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.

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks.

PubMed

Marinho, Maria Vanda; Reis, Daniella O; Oliveira, Willian X C; Marques, Lippy F; Stumpf, Humberto O; Déniz, Mariadel; Pasán, Jorge; Ruiz-Pérez, Catalina; Cano, Joan; Lloret, Francesc; Julve, Miguel

2017-02-20

In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln 2 (2,5-pzdc) 3 (H 2 O) 4 ]·6H 2 O} n [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er 2 (2,5-pzdc) 3 (H 2 O) 4 ]·5H 2 O} n (5). Single-crystal X-ray diffraction on 1-5 reveals that they crystallize in the triclinic system, P1̅ space group with the series 1-4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc 2- dianions acting as two- and fourfold connectors, building a binodal 4,4-connected (4·6 4 8)(4 2 6 2 8 2 )-mog network. The photophysical properties of the Nd(III) (3) and Eu(III) (4) complexes exhibit sensitized photoluminescence in the near-infrared and visible regions, respectively. The photoluminescence intensity and lifetime of 4 were very sensitive due to the luminescence quenching of the 5 D 0 level by O-H oscillators of four water molecules in the first coordination sphere leading to a quantum efficiency of 11%. Variable-temperature magnetic susceptibility measurements for 1-5 reveal behaviors as expected for the ground terms of the magnetically isolated rare-earth ions [ 2 F 5/2 , 2 H 4 , 4 I 9/2 , 7 F 0 , and 4 I 15/2 for Ce(III), Pr(III), Nd(III), Eu(III), and Er(III), respectively] with M J = 0 (2 and 4) and ±1/2 (1, 3, and 5). Q-band electron paramagnetic resonance measurements at low temperature corroborate these facts. Frequency-dependent alternating-current magnetic susceptibility signals under external direct-current fields in the range of 100-2500 G were observed for the Kramers ions of 1, 3, and 5, indicating slow magnetic relaxation (single-ion magnet) behavior. In these compounds, τ -1 decreases with decreasing temperature at any magnetic field, but no Arrhenius law can simulate such

Two Series of Homodinuclear Lanthanide Complexes: Greatly Enhancing Energy Barriers through Tuning Terminal Solvent Ligands in Dy2 Single-Molecule Magnets.

PubMed

Qin, Yaru; Zhang, Haifeng; Sun, Hao; Pan, Yangdan; Ge, Yu; Li, Yahong; Zhang, Yi-Quan

2017-11-02

The utilization of 2-ethoxy-6-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol (H 2 L) as a chelating ligand, in combination with the employment of alcohols (EtOH and MeOH) as auxiliary ligands, in 4 f-metal chemistry afforded two series of dinuclear lanthanide complexes of compositions [Ln 2 L 2 (NO 3 ) 2 (EtOH) 2 ] (Ln=Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7)) and [Ln 2 L 2 (NO 3 ) 2 (MeOH) 2 ] (Ln=Sm (8), Eu (9), Gd (10), Tb (11), Dy (12), Ho (13), Er (14)). The structures of 1-14 were determined by single-crystal X-ray crystallography. Complexes 1-7 are isomorphous. The two lanthanide(III) ions in 1-7 are doubly bridged by two deprotonated aminophenoxide oxygen atoms of two μ 2 :η 0 :η 1 :η 2 :η 1 :η 1 :η 0 -L 2- ligands. One nitrogen atom, two oxygen atoms of the NO 3 - anion, two methoxide oxygen atoms of two ligand sets, and one oxygen atom of the terminally coordinated EtOH molecule complete the distorted dodecahedron geometry of each lanthanide(III) ion. Compounds 8-14 are isomorphous and their structures are similar to those of 1-7. The slight difference between 1-7 and 8-14 stems from purposefully replacing the EtOH ligands in 1-7 with MeOH in 8-14. Direct-current magnetic susceptibility studies in the 2-300 K range reveal weak antiferromagnetic interactions for 3, 4, 7, 10, 11, and 14, and ferromagnetic interactions at low temperature for 5, 6, 12, and 13. Complexes 5 and 12 exhibit single-molecule magnet (SMM) behavior with energy barriers of 131.3 K for 5 and 198.8 K for 12. The energy barrier is significantly enhanced by dexterously regulating the terminal ligands. To rationalize the observed difference in the magnetic behavior, complete-active-space self-consistent field (CASSCF) calculations were performed on two Dy 2 complexes. Subtle variation in the angle between the magnetic axes and the vector connecting two dysprosium(III) ions results in a weaker influence on the tunneling gap of individual dysprosium(III) ions

Designer Diamonds: Applications in Iron-based Superconductors and Lanthanides

NASA Astrophysics Data System (ADS)

Vohra, Yogesh

2013-06-01

This talk will focus on the recent progress in the fabrication of designer diamond anvils as well as scientific applications of these diamonds in static high pressure research. The two critical parameters that have emerged in the microwave plasma chemical vapor deposition of designer diamond anvils are (1) the precise [100] alignment of the starting diamond substrate and (2) balancing the competing roles of parts per million levels of nitrogen and oxygen in the diamond growth plasma. The control of these parameters results in the fabrication of high quality designer diamonds with culet size in excess of 300 microns in diameter. The three different applications of designer diamond anvils will be discussed (1) simultaneous electrical resistance and crystal structure measurements using a synchrotron source on Iron-based superconductors with data on both electron and hole doped BaFe2As2 materials and other novel superconducting materials (2) high-pressure high-temperature melting studies on metals using eight-probe Ohmic heating designer diamonds and (3) high pressure low temperature studies on magnetic behavior of 4f-lanthanide metals using four-probe electrical resistance measurements and complementary neutron diffraction studies on a spallation neutron source. Future opportunities in boron-doped conducting designer diamond anvils as well as fabrication of two-stage designer diamonds for ultra high pressure experiments will also be presented. This work was supported by the Department of Energy (DOE) - National Nuclear Security Administration (NNSA) under Grant No. DE-FG52-10NA29660.

Deciphering three beneficial effects of 2,2'-bipyridine-N,N'-dioxide on the luminescence sensitization of lanthanide(III) hexafluoroacetylacetonate ternary complexes.

PubMed

Eliseeva, Svetlana V; Pleshkov, Dmitry N; Lyssenko, Konstantin A; Lepnev, Leonid S; Bünzli, Jean-Claude G; Kuzmina, Natalia P

2011-06-06

Lanthanide hexafluoroacetylacetonate ternary complexes with 2,2'-bipyridine-N,N'-dioxide, [Ln(hfa)(3)(bpyO2)], were synthesized for Ln = Eu, Gd, Tb, and Lu and fully characterized by elemental, thermal, and mass-spectrometric analyses. The X-ray crystal structure of [Eu(hfa)(3)(bpyO2)]·0.5C(6)H(6) reveals an octa-coordinate metal ion lying in a severely distorted trigonal dodecahedron geometry; the Eu-O distances lie in the range 2.36-2.44 Å with no significant difference between hfa(-) and bpyO2. A detailed comparative photophysical investigation has been carried out to determine the exact influence of the introduction of bpyO2 in the inner coordination sphere of the metal ion in replacement of the two water molecules in [Ln(hfa)(3)(H(2)O)(2)]. While this replacement is detrimental for Tb, it leads to a 15-fold increase in the overall quantum yield for Eu. This large improvement originates from (i) a better sensitization efficiency, the ancillary ligand being responsible for 3/4 of the energy transfer, (ii) elimination of nonradiative deactivation pathways through harmonics of O-H vibrations, and (iii) reduction in the radiative lifetime. The latter influence is rarely documented, but it accounts here for a ≈25% increase in the intrinsic quantum yield, so that more attention should be given to this parameter when designing highly luminescent lanthanide complexes. © 2011 American Chemical Society

Formation and corrosion of a 410 SS/ceramic composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, X.; Ebert, W. L.; Indacochea, J. E.

This study evaluates the possible use of alloy/ceramic composite waste forms to immobilize metallic and oxide waste streams generated during the electrochemical reprocessing of spent reactor fuel in a single waste form. A representative composite material AOC410 was made to evaluate the microstructure and corrosion behavior at alloy/ceramic interfaces by reacting 410 stainless steel with Zr, Mo, and a mixture of lanthanide oxides. Essentially all of the Zr reacted with lanthanide oxides to form lanthanide zirconate, which combined with the remaining lanthanide oxides to form a porous ceramic network encapsulated by alloy as a composite puck. Excess alloy formed amore » metal bead on top of the composite. The alloys in the composite and bead were both mixture of martensite grains and ferrite grains with carbide precipitates. FeCrMo intermetallic phases also precipitated in the ferrite grains in the composite part. Ferrite surrounding carbides was sensitized and the least corrosion resistant in electrochemical corrosion tests conducted in an acidic brine electrolyte; ferrite neighboring martensite grains and intermetallics corroded galvanically. The lanthanide oxide domains dissolved chemically, but lanthanide zirconate domains did not dissolve. The presence of oxide phases did not affect corrosion of the neighboring alloy phases. These results suggest the longterm corrosion of a composite waste form can be evaluated by using separate material degradation models for the alloy and ceramic phases.« less

Ionic liquid assisted microwave synthesis route towards color-tunable luminescence of lanthanide- doped BiPO 4

DOE PAGES

Cybinska, Joanna; Lorbeer, Chantal; Mudring, Anja -Verena

2015-07-08

Ln 3+-doped (Ln=Sm, Eu, Tb, Dy) nanoparticles of BiPO 4 with a particle size below 10 nm were synthesized in a straightforward manner from the appropriate mixture of the respective metal acetates and the task-specific ionic liquids choline or butylammonium dihydrogen-phosphate by conversion in a laboratory microwave (120 °C, 10 min). The ionic liquid acts not only as a solvent and microwave susceptor, but also as the reaction partner and nanoparticle stabilizer. The materials were thoroughly characterized not only with respect to their optical properties but also by PXRD, FT-IR, TEM techniques. Furthermore, depending on the lanthanide, the nanomaterial showsmore » intense luminescence of different colors such as: orange (Sm 3+), red (Eu 3+), green (Tb 3+) or even white (Dy 3+).« less

Two- and three-dimensional lanthanide-organic frameworks constructed using 1-hydro-6-oxopyridine-3-carboxylate and oxalate ligands.

PubMed

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.

Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity.

PubMed

Ji, Wen-Xin; Xu, Wei; Schwarz, W H Eugen; Wang, Shu-Guang

2015-03-15

Lanthanide trihalide molecules LnX3 (X = F, Cl, Br, I) were quantum chemically investigated, in particular detail for Ln = Lu (lutetium). We applied density functional theory (DFT) at the nonrelativistic and scalar and SO-coupled relativistic levels, and also the ab initio coupled cluster approach. The chemically active electron shells of the lanthanide atoms comprise the 5d and 6s (and 6p) valence atomic orbitals (AO) and also the filled inner 4f semivalence and outer 5p semicore shells. Four different frozen-core approximations for Lu were compared: the (1s(2) -4d(10) ) [Pd] medium core, the [Pd+5s(2) 5p(6) = Xe] and [Pd+4f(14) ] large cores, and the [Pd+4f(14) +5s(2) 5p(6) ] very large core. The errors of LuX bonding are more serious on freezing the 5p(6) shell than the 4f(14) shell, more serious upon core-freezing than on the effective-core-potential approximation. The LnX distances correlate linearly with the AO radii of the ionic outer shells, Ln(3+) -5p(6) and X(-) -np(6) , characteristic for dominantly ionic Ln(3+) -X(-) binding. The heavier halogen atoms also bind covalently with the Ln-5d shell. Scalar relativistic effects contract and destabilize the LuX bonds, spin orbit coupling hardly affects the geometries but the bond energies, owing to SO effects in the free atoms. The relativistic changes of bond energy BE, bond length Re , bond force k, and bond stretching frequency vs do not follow the simple rules of Badger and Gordy (Re ∼BE∼k∼vs ). The so-called degeneracy-driven covalence, meaning strong mixing of accidentally near-degenerate, nearly nonoverlapping AOs without BE contribution is critically discussed. © 2015 Wiley Periodicals, Inc.

Tuning the autophagy-inducing activity of lanthanide-based nanocrystals through specific surface-coating peptides

NASA Astrophysics Data System (ADS)

Zhang, Yunjiao; Zheng, Fang; Yang, Tianlong; Zhou, Wei; Liu, Yun; Man, Na; Zhang, Li; Jin, Nan; Dou, Qingqing; Zhang, Yong; Li, Zhengquan; Wen, Long-Ping

2012-09-01

The induction of autophagy on exposure of cells to a variety of nanoparticles represents both a safety concern and an application niche for engineered nanomaterials. Here, we show that a short synthetic peptide, RE-1, identified by means of phage display, binds to lanthanide (LN) oxide and upconversion nanocrystals (UCN), forms a stable coating layer on the nanoparticles’ surface, and effectively abrogates their autophagy-inducing activity. Furthermore, RE-1 peptide variants exhibit a differentially reduced binding capability, and correspondingly, a varied ability to reduce the autophagic response. We also show that the addition of an arginine-glycine-aspartic acid (RGD) motif to RE-1 enhances autophagy for LN UCN through the interaction with integrins. RE-1 and its variants provide a versatile tool for tuning material-cell interactions to achieve the desired level of autophagy, and may prove useful for the various diagnostic and therapeutic applications of LN-based nanomaterials and nanodevices.

Four one-dimensional lanthanide-phenylacetate polymers exhibiting luminescence and magnetic cooling/spin-glass behavior.

PubMed

Li, Zhong-Yi; Xu, Ya-Lan; Zhang, Xiang-Fei; Zhai, Bin; Zhang, Fu-Li; Zhang, Jian-Jun; Zhang, Chi; Li, Su-Zhi; Cao, Guang-Xiu

2017-12-21

Four isostructural lanthanide coordination polymers with a phenylacetate (PAA - ) ligand, [Ln(PAA) 3 (H 2 O)] n (Ln = Eu (1); Gd (2); Tb (3); Dy (4)), were synthesized under hydrothermal conditions. Complexes 1-4 display a one-dimensional (1D) wave chain structure bridged by the carboxylate of the PAA - ligand, which was generated via the in situ decarboxylation of phenylmalonic acid. Magnetic studies suggest the presence of ferromagnetic LnLn coupling in the 1D chain of 1-4. Meanwhile, 2 has a significant cryogenic magnetocaloric effect with the maximum -ΔS m of 26.73 at 3 K and 7 T, and 3 and 4 show interesting spin-glass behavior, which is rarely reported for Ln-containing complexes. Additionally, the solid-state photophysical properties of 1 and 3 display strong characteristic Eu 3+ and Tb 3+ photoluminescence emission in the visible region, indicating that Eu- and Tb-based luminescence are sensitized by the effective energy transfer from the ligand to the metal centers.

Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Rational Design and Development of Lanthanide-Doped NaYF4@CdS-Au-RGO as Quaternary Plasmonic Photocatalysts for Harnessing Visible-Near-Infrared Broadband Spectrum.

PubMed

Kumar, Ajay; Reddy, Kumbam Lingeshwar; Kumar, Suneel; Kumar, Ashish; Sharma, Vipul; Krishnan, Venkata

2018-05-09

Utilization of the total solar spectrum efficiently for photocatalysis has remained a huge challenge for a long time. However, designing a system by rationally combining nanocomponents with complementary properties, such as upconversion nanoparticles, semiconductors, plasmonic metals, and carbonaceous support, offers a promising route for efficient utilization of solar energy by harnessing the broadband spectrum. In this work, a series of novel quaternary plasmonic photocatalysts comprising of lanthanide-doped NaYF 4 @CdS (UC) core-shell nanostructures decorated with Au nanoparticles (Au NPs) supported on reduced graphene oxide (RGO) nanosheets were prepared using the multistep hydrothermal method. The different components of the prepared nanocomposites could be efficiently employed to utilize both the visible and near-infrared (NIR) regions. Specifically in this work, the utility of these quaternary nanocomposites for photocatalytic degradation of a colorless pharmaceutical pollutant, ciprofloxacin, under visible and NIR light irradiations has been demonstrated. In comparison to bare counterparts, our quaternary nanocomposites exhibit an enhanced photocatalytic activity attributable to the synergistic effect of different components arranged in such a way that favors harnessing energy from the broad spectral region and efficient charge separation. The combination of upconversion and plasmonic properties along with the advantages of a carbonaceous support can provide new physical insights for further development of photocatalysts, which could utilize the broadband spectrum.

Microparticle Separation by Cyclonic Separation

NASA Astrophysics Data System (ADS)

Karback, Keegan; Leith, Alexander

2017-11-01

The ability to separate particles based on their size has wide ranging applications from the industrial to the medical. Currently, cyclonic separators are primarily used in agriculture and manufacturing to syphon out contaminates or products from an air supply. This has led us to believe that cyclonic separation has more applications than the agricultural and industrial. Using the OpenFoam computational package, we were able to determine the flow parameters of a vortex in a cyclonic separator in order to segregate dust particles to a cutoff size of tens of nanometers. To test the model, we constructed an experiment to separate a test dust of various sized particles. We filled a chamber with Arizona test dust and utilized an acoustic suspension technique to segregate particles finer than a coarse cutoff size and introduce them into the cyclonic separation apparatus where they were further separated via a vortex following our computational model. The size of the particles separated from this experiment will be used to further refine our model. Metropolitan State University of Denver, Colorado University of Denver, Dr. Randall Tagg, Dr. Richard Krantz.

Preparation, structure, and luminescence of dinuclear lanthanide complexes of a novel imine-amine phenolate macrocycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matthews, K.D.; Kahwa, I.A.; Williams, D.J.

1994-03-30

Metal-free condensation of 2,6-diformyl-p-cresol with 3,6-dioxa-1,8-octanediamine followed by reduction with sodium tetrahydroborate and addition of lanthanide(III) nitrate salts, in that order, yield (slowly) crystalline dinuclear complexes of a novel imine-amine phenolate macrocycle 2. The decacoordination geometry of the identical Pr[sup 3+] ions in a C[sub 2v] 4A,6B-extended dodecahedron made up of two bidentate NO[sub 3]-ions, two phenolate and two either oxygens, and one imine and one amine nitrogens. Dinuclear lanthanide complexes of 2 appear to be more stable than those of the totally reduced chelate 2 in alcoholic media. The Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]-OH and (La[sub 0.97]Tb[sub 0.03])[submore » 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH compounds exhibit strong Tb[sup 3+] ([sup 5]D[sub 4] [yields] [sup 7]F[sub J]) emission sensitized by the single state of 2 at both 77 and 295 K. No Tb[sup 3+]-Tb[sup 3+] self-quenching or N-H trapping effects are observed at 77 K (decay rate is 598 s[sup [minus]1]); the coordination cavities of 2 are therefore potentially good hosts for Tb[sup 3+] in luminescent diagnostic agents. At room temperature the complex decay kinetics of Tb[sup 3+] in Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH are similar to those of Tb[sub 2]1(NO[sub 3])[sub 4][center dot]H[sub 2]O. But for the dilute complex, (La[sub 0.97]-Tb[sub 0.03])[sub 2]2(NO[sub 3])[sub 4][center dot]1.35CH[sub 3]OH, unusual thermal equilibration of the ligand triplet and Tb[sup 3+] [sup 5]D[sub 4] states occurs at room temperature; the ligand-to-Tb[sup 3+] energy-transfer rate is [approx]4.36 x 10[sup 4] s[sup [minus]1], while Tb[sup 3+]-to-ligand back-energy-transfer is [approx]7.1 x 10[sup 4] s[sup [minus]1].« less

Lanthanide and transition metal complexes of bioactive coumarins: molecular modeling and spectroscopic studies.

PubMed

Georgieva, I; Mihaylov, Tz; Trendafilova, N

2014-06-01

The present paper summarizes theoretical and spectroscopic investigations on a series of active coumarins and their lanthanide and transition metal complexes with application in medicine and pharmacy. Molecular modeling as well as IR, Raman, NMR and electronic spectral simulations at different levels of theory were performed to obtain important molecular descriptors: total energy, formation energy, binding energy, stability, conformations, structural parameters, electron density distribution, molecular electrostatic potential, Fukui functions, atomic charges, and reactive indexes. The computations are performed both in gas phase and in solution with consideration of the solvent effect on the molecular structural and energetic parameters. The investigations have shown that the advanced computational methods are reliable for prediction of the metal-coumarin binding mode, electron density distribution, thermodynamic properties as well as the strength and nature of the metal-coumarin interaction (not experimentally accessible) and correctly interpret the experimental spectroscopic data. Known results from biological tests for cytotoxic, antimicrobial, anti-fungal, spasmolytic and anti-HIV activities on the studied metal complexes are reported and discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

Self-assembly of 2-aldehyde-8-hydroxyquinolinate-based lanthanide complexes and NIR luminescence

NASA Astrophysics Data System (ADS)

Zhang, Meiqi; Li, Hongfeng; Chen, Peng; Sun, Wenbin; Zhang, Lei; Yan, Pengfei

2015-02-01

Self-assembly reaction of 2-aldehyde-8-hydroxyquinoline, tris(hydroxymethyl)aminomethane and LnCl3ṡ6H2O affords a series of mononuclear lanthanide complexes Ce(baho)2·Et2O (1) (H2baho = 2,8-bis(2-(8-hydroxylquinolinyl))-1-aza-5-hydroxymethyl-3,7-dioxabicyclo[3.3.0]octane), Dy(nhm)2Cl·0.5H2O (2) and Ln(nhm)2Cl·0.5C6H14 (Ln = Ho (3), Er (4), Yb (5) and Hnhm = N-(2-(8-hydroxylquinolinyl)methylene)(trishydroxymethyl)methylamine. The crystal structures have been determined by X-ray crystallographic analysis, and the tetravalence of Ce in 1 has been proven by XPS. Interestingly, the positive charge of Ce4+ ion in 1 is neutralized by two deprotonated baho2- ligands, while two deprotonated nhm- ligands and one Cl- compensate the positive charge of Ln3+ ions in 2-5. Complex 5 exhibit essential NIR luminescence of Yb3+ ion with lifetime of 17.64 μs in solid and 9.96 μs in CH3OH solution.

Features of the Thermodynamics of Trivalent Lanthanide/Actinide Distribution Reactions by Tri-n-Octylphosphine Oxide and Bis(2-EthylHexyl) Phosphoric Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » 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.« less

Impurity doping: a novel strategy for controllable synthesis of functional lanthanide nanomaterials.

PubMed

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.

Mesoporous stilbene-based lanthanide metal organic frameworks: synthesis, photoluminescence and radioluminescence characteristics.

PubMed

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.

Review Article: Overview of lanthanide pnictide films and nanoparticles epitaxially incorporated into III-V semiconductors

DOE PAGES

Bomberger, Cory C.; Lewis, Matthew R.; Vanderhoef, Laura R.; ...

2017-03-30

The incorporation of lanthanide pnictide nanoparticles and films into III-V matrices allows for semiconductor composites with a wide range of potential optical, electrical, and thermal properties, making them useful for applications in thermoelectrics, tunnel junctions, phototconductive switches, and as contact layers. The similarities in crystal structures and lattice constants allow them to be epitaxially incorporated into III-V semiconductors with low defect densities and high overall film quality. A variety of growth techniques for these composites with be discussed, along with their growth mechanisms and current applications, with a focus on more recent developments. Results obtained from molecular beam epitaxy filmmore » growth will be highlighted, although other growth techniques will be mentioned. Optical and electronic characterization along with the microscopy analysis of these composites is presented to demonstrate influence of nanoinclusion composition and morphology on the resulting properties of the composite material.« less

Review Article: Overview of lanthanide pnictide films and nanoparticles epitaxially incorporated into III-V semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bomberger, Cory C.; Lewis, Matthew R.; Vanderhoef, Laura R.

The incorporation of lanthanide pnictide nanoparticles and films into III-V matrices allows for semiconductor composites with a wide range of potential optical, electrical, and thermal properties, making them useful for applications in thermoelectrics, tunnel junctions, phototconductive switches, and as contact layers. The similarities in crystal structures and lattice constants allow them to be epitaxially incorporated into III-V semiconductors with low defect densities and high overall film quality. A variety of growth techniques for these composites with be discussed, along with their growth mechanisms and current applications, with a focus on more recent developments. Results obtained from molecular beam epitaxy filmmore » growth will be highlighted, although other growth techniques will be mentioned. Optical and electronic characterization along with the microscopy analysis of these composites is presented to demonstrate influence of nanoinclusion composition and morphology on the resulting properties of the composite material.« less

Designing lanthanide-doped nanocrystals with both up- and down-conversion luminescence for anti-counterfeiting

NASA Astrophysics Data System (ADS)

Liu, Yanlan; Ai, Kelong; Lu, Lehui

2011-11-01

The widespread forgery in all kinds of paper documents and certificates has become a real threat to society. Traditional fluorescent anti-counterfeiting materials generally exhibit unicolor display and suffer greatly from substitution, thus leading to a poor anti-counterfeiting effect. In this work, unseen but significant enhanced blue down-conversion emission from oleic acid-stabilized lanthanide-doped fluoride nanocrystals is first present and the mechanism is proposed and validated. This not only endows these nanocrystals with dual-mode fluorescence, but also offers a simplified synthesis approach for dual-mode fluorescent nanocrystals involving no further complicated assembly or coating procedures, unlike the traditional methods. Furthermore, by changing the host/dopant combination or the content of dopant, these nanocrystals can exhibit simultaneously multicolor up-conversion emission under excitation at near-infrared light and unalterable blue down-conversion emission under ultraviolet light. A preliminary investigation of their anti-counterfeiting performance has been made, and the results indicate that this color tuning capability and high concealment makes these nanocrystals behave in a similar way to chameleons and can provide a strengthened and more reliable anti-counterfeiting effect.The widespread forgery in all kinds of paper documents and certificates has become a real threat to society. Traditional fluorescent anti-counterfeiting materials generally exhibit unicolor display and suffer greatly from substitution, thus leading to a poor anti-counterfeiting effect. In this work, unseen but significant enhanced blue down-conversion emission from oleic acid-stabilized lanthanide-doped fluoride nanocrystals is first present and the mechanism is proposed and validated. This not only endows these nanocrystals with dual-mode fluorescence, but also offers a simplified synthesis approach for dual-mode fluorescent nanocrystals involving no further complicated

Slow magnetic relaxation and luminescence properties in lanthanide(iii)/anil complexes.

PubMed

Maniaki, Diamantoula; Mylonas-Margaritis, Ioannis; Mayans, Julia; Savvidou, Aikaterini; Raptopoulou, Catherine P; Bekiari, Vlasoula; Psycharis, Vassilis; Escuer, Albert; Perlepes, Spyros P

2018-05-22

The initial use of anils, i.e. bidentate Schiff bases derived from the condensation of anilines with salicylaldehyde or its derivatives, in 4f-metal chemistry is described. The 1 : 1 reactions between Ln(NO3)3·xH2O (Ln = lanthanide) or Y(NO3)3·6H2O and N-(5-bromosalicylidene)aniline (5BrsalanH) in MeCN has provided access to complexes [Ln(NO3)3(5BrsalanH)2(H2O)]·MeCN (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) and [Y(NO3)3(5BrsalanH)2(H2O)]·MeCN, respectively, in good yields. The structures of the isomorphous complexes with Ln = Pr(1·MeCN), Sm(3·MeCN), Gd(5·MeCN), Dy(7·MeCN) and Er(9·MeCN) have been determined by single-crystal X-ray crystallography. The other complexes were proven to be isostructural with the fully structurally characterized compounds based on elemental analyses, IR spectra, unit cell determinations and powder X-ray patterns. The 9-coordinate LnIII centre in the [Ln(NO3)3(5BrsalanH)2(H2O)] molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the organic ligands and one oxygen atom from the aquo ligand. The 5BrsalanH molecules behave as monodentate O-donors; the acidic H atom is clearly located on the imino N atom and thus the formally neutral ligands adopt an extremely rare coordination mode participating in the zwitterionic form. The coordination polyhedra defined by the nine donor atoms around the LnIII centres are best described as spherical capped square antiprisms. Various intermolecular interactions build the crystal structures and Hirshfeld surface analysis was applied to evaluate the magnitude of interactions between the molecules. Solid-state IR and UV/VIS data are discussed in terms of structural features. 1H NMR data prove that the diamagnetic [Y(NO3)3(5BrsalanH)2(H2O)] complex decomposes in DMSO. Combined dc and ac magnetic susceptibility, as well as magnetization data for 7 suggest that this complex shows field-induced slow magnetic relaxation. Two

Lanthanide-Doped KLu2F7 Nanoparticles with High Upconversion Luminescence Performance: A Comparative Study by Judd-Ofelt Analysis and Energy Transfer Mechanistic Investigation

NASA Astrophysics Data System (ADS)

Xu, Dekang; Li, Anming; Yao, Lu; Lin, Hao; Yang, Shenghong; Zhang, Yueli

2017-02-01

The development, design and the performance evaluation of rare-earth doped host materials is important for further optical investigation and industrial applications. Herein, we successfully fabricate KLu2F7 upconversion nanoparticles (UCNPs) through hydrothermal synthesis by controlling the fluorine-to-lanthanide-ion molar ratio. The structural and morphological results show that the samples are orthorhombic-phase hexagonal-prisms UCNPs, with average side length of 80 nm and average thickness of 110 nm. The reaction time dependent crystal growth experiment suggests that the phase transformation is a thermo-dynamical process and the increasing F-/Ln3+ ratio favors the formation of the thermo-dynamical stable phase - orthorhombic KLu2F7 structure. The upconversion luminescence (UCL) spectra display that the orthorhombic KLu2F7:Yb/Er UCNPs present stronger UCL as much as 280-fold than their cubic counterparts. The UCNPS also display better UCL performance compared with the popular hexagonal-phase NaREF4 (RE = Y, Gd). Our mechanistic investigation, including Judd-Ofelt analysis and time decay behaviors, suggests that the lanthanide tetrad clusters structure at sublattice level accounts for the saturated luminescence and highly efficient UCL in KLu2F7:Yb/Er UCNPs. Our research demonstrates that the orthorhombic KLu2F7 is a promising host material for UCL and can find potential applications in lasing, photovoltaics and biolabeling techniques.

The chemistry of TALSPEAK: A review of the science

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, Kenneth L.

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) inmore » 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+. Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving

The chemistry of TALSPEAK: A review of the science

DOE PAGES

Nash, Kenneth L.

2014-11-13

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) inmore » 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+. Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving

Dual roles of f electrons in mixing Al 3 p character into d -orbital conduction bands for lanthanide and actinide dialuminides

DOE PAGES

Altman, Alison B.; Pemmaraju, C. D.; Alayoglu, Selim; ...

2018-01-15

Correlated electron phenomena in lanthanide and actinide materials are driven by a complex interplay between the f and d orbitals. Here in this study, aluminum K-edge x-ray absorption spectroscopy and density functional theory calculations are used to evaluate the electronic structure of the dialuminides, MAl 2 (M = Ce, Sm, Eu, Yb, Lu, U, and Pu). The results show how the energy and occupancy of the 4f or 5f orbitals impacts mixing of Al 3p character into the 5d or 6d conduction bands, which has implications for understanding the magnetic and structural properties of correlated electron systems.

Effect of HEH[EHP] impurities on the ALSEP solvent extraction process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holfeltz, Vanessa E.; Campbell, Emily L.; Peterman, Dean R.

In solvent extraction processes, organic phase impurities can negatively impact separation factors, hydrolytic performance, and overall system robustness. This affects the process-level viability of a separation concept and necessitates knowledge of the behavior and mechanisms to control impurities in the solvent. The most widespread way through which impurities are introduced into a system is through impure extractants and/or diluents used to prepare the solvent, and often development of new purification schemes to achieve the desired level of purity is needed. In this work, the acidic extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])—proposed for application in extractive processes aimed at separating trivalentmore » minor actinides from lanthanides and other fission products—is characterized with respect to its common impurities and their impact on Am(III) stripping in the Actinide Lanthanide SEParation (ALSEP) system. To control impurities in HEH[EHP], existing purification technologies commonly applied for the acidic organophosphorus reagents are reviewed, and a new method specific to HEH[EHP] purification is presented.« less

Rationally designed mineralization for selective recovery of the rare earth elements

NASA Astrophysics Data System (ADS)

Hatanaka, Takaaki; Matsugami, Akimasa; Nonaka, Takamasa; Takagi, Hideki; Hayashi, Fumiaki; Tani, Takao; Ishida, Nobuhiro

2017-05-01

The increasing demand for rare earth (RE) elements in advanced materials for permanent magnets, rechargeable batteries, catalysts and lamp phosphors necessitates environmentally friendly approaches for their recovery and separation. Here, we propose a mineralization concept for direct extraction of RE ions with Lamp (lanthanide ion mineralization peptide). In aqueous solution containing various metal ions, Lamp promotes the generation of RE hydroxide species with which it binds to form hydrophobic complexes that accumulate spontaneously as insoluble precipitates, even under physiological conditions (pH ~6.0). This concept for stabilization of an insoluble lanthanide hydroxide complex with an artificial peptide also works in combination with stable scaffolds like synthetic macromolecules and proteins. Our strategy opens the possibility for selective separation of target metal elements from seawater and industrial wastewater under mild conditions without additional energy input.

Rationally designed mineralization for selective recovery of the rare earth elements.

PubMed

Hatanaka, Takaaki; Matsugami, Akimasa; Nonaka, Takamasa; Takagi, Hideki; Hayashi, Fumiaki; Tani, Takao; Ishida, Nobuhiro

2017-05-26

The increasing demand for rare earth (RE) elements in advanced materials for permanent magnets, rechargeable batteries, catalysts and lamp phosphors necessitates environmentally friendly approaches for their recovery and separation. Here, we propose a mineralization concept for direct extraction of RE ions with Lamp (lanthanide ion mineralization peptide). In aqueous solution containing various metal ions, Lamp promotes the generation of RE hydroxide species with which it binds to form hydrophobic complexes that accumulate spontaneously as insoluble precipitates, even under physiological conditions (pH ∼6.0). This concept for stabilization of an insoluble lanthanide hydroxide complex with an artificial peptide also works in combination with stable scaffolds like synthetic macromolecules and proteins. Our strategy opens the possibility for selective separation of target metal elements from seawater and industrial wastewater under mild conditions without additional energy input.

Challenges in the Search for Magnetic Coupling in 3d/4f Materials: Syntheses, Structures, and Magnetic Properties of the Lanthanide Copper Heterobimetallic Compounds, RE 2 Cu(TeO 3 ) 2 (SO 4 ) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Jian; Chai, Ping; Diefenbach, Kariem

2014-03-03

Twelve new lanthanide copper heterobimetallic compounds, RE2Cu(TeO3)2(SO4)2 (RE = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), with two different structural topologies, have been prepared by hydrothermal treatment. Both structure types crystallize in the triclinic space group, Pmore » $$\\bar{1}$$, but the unit cell parameters and structures are quite different. The earlier RE2Cu(TeO3)2(SO4)2 (RE = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Tm) share a common structural motif consisting of edge-sharing LnO8 chains and [Cu(TeO3)2(SO4)2]6– units. The later lanthanide version (Yb and Lu) is composed of edge-sharing LnO7 dimers bridged by similar [Cu(TeO3)2(SO4)2]6– units. The change in the structure type can be attributed to the decreasing ionic radii of the lanthanides. The compounds containing RE3+ ions with diamagnetic ground states (Y3+ and Eu3+) exhibit antiferromagnetic ordering at 12.5 K and 15 K, respectively, owing to the magnetic exchange between Cu2+ moments. No magnetic phase transition was observed in all the other phases. The lack of magnetic ordering is attributed to the competing magnetic interactions caused by the presence of paramagnetic RE3+ ions. The magnetism data suggests that substantial 3d–4f coupling only occurs in the Yb analogue.« less

Direct observation of the discrete energy spectrum of two lanthanide-based single-chain magnets by far-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Haas, Sabrina; Heintze, Eric; Zapf, Sina; Gorshunov, Boris; Dressel, Martin; Bogani, Lapo

2014-05-01

The far-infrared optical transmission has been studied for two lanthanide-based single-chain magnets DyPhOPh and TbPhOPh in the frequency range between 3 and 80 cm-1. The spectra were acquired at temperatures between 2 and 80 K and magnetic fields up to 6 T. Based on their magnetic field dependence in DyPhOPh two of the observed absorption lines are identified as transitions inside the crystal field split Dy3+ ground multiplet 6H15/2, coupled to the neighboring spins. In TbPhOPh one transition was observed inside the crystal-field-split Tb3+ ground multiplet 7F6. The results allow a spectroscopic investigation of the role of single-ion anisotropy and exchange in Glauber dynamics.

Preparation and luminescent properties of lanthanide (Eu3+ and Tb3+) complexes grafted to 3-aminopropyltriethoxysilane by covalent bonds

NASA Astrophysics Data System (ADS)

Zhang, Wenjun; Wang, Haiyan

2015-12-01

A novel precursor PMA-Si was synthesized by modifying 1,2,4,5-benzene-tetracarboxylic acid (PMA) with 3-aminopropyltriethoxysilane (APTES). Then the hybrids were prepared by PMA-Si coordinating to lanthanide ions (Eu3+ and Tb3+) in sol-gel process. In order to improve luminescent efficiency, 1,10-Phenanthroline (Phen) was introduced to the system as the second ligand. As-prepared compounds in sol condition were coated on quartz plates to form a layer of thin film, which was different from other similar hybrids. The properties of the hybrids were characterized by FT-IR, fluorescence spectra, TG and SEM. The results showed that the obtained materials enhanced thermal stability, mechanical resistances, waterproofness as well as machining properties.

Separation of 103Ru from a proton irradiated thorium matrix: A potential source of Auger therapy radionuclide 103mRh

DOE PAGES

Mastren, Tara; Radchenko, Valery; Hopkins, Philip D.; ...

2017-12-22

Ruthenium-103 is the parent isotope of 103mRh (t1/2 56.1 min), an isotope of interest for Auger electron therapy. During the proton irradiation of thorium targets, large amounts of 103Ru are generated through proton induced fission. Furthermore, the development of a two part chemical separation process to isolate 103Ru in high yield and purity from a proton irradiated thorium matrix on an analytical scale is described herein. The first part employed an anion exchange column to remove cationic actinide/lanthanide impurities along with the majority of the transition metal fission products. Secondly, an extraction chromatographic column utilizing diglycolamide functional groups was usedmore » to decontaminate 103Ru from the remaining impurities. This method then resulted in a final radiochemical yield of 83 ± 5% of 103Ru with a purity of 99.9%. Additionally, measured nuclear reaction cross sections for the formation of 103Ru and 106Ru via the 232Th(p,f) 103,106Ru reactions are reported within.« less

Network dimensionality and ligand flexibility in lanthanide terephthalate hydrates

NASA Astrophysics Data System (ADS)

Zehnder, Ralph A.; Renn, Robert A.; Pippin, Ethan; Zeller, Matthias; Wheeler, Kraig A.; Carr, Jason A.; Fontaine, Nick; McMullen, Nathan C.

2011-01-01

Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd 2(TP) 3(H 2O) 4( 1), Er 2(TP) 3(H 2O) 4( 2), Yb 2(TP) 3(H 2O) 2( 3), Yb 2(TP) 3(H 2O) 6( 4), and Yb 2(TP) 3(H 2O) 8·2H 2O ( 5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1- 5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H 2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra.

Refractive Index Tuning of Hybrid Materials for Highly Transmissive Luminescent Lanthanide Particle-Polymer Composites.

PubMed

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.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

PubMed

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

A Series of Lanthanide Selenidogermanates: The First Coexistence of Three Types of Selenidogermanate Units in the Same Architecture.

PubMed

Tang, Shimei; Zhou, Jian; Zou, Hua-Hong; Liu, Xing; Zhang, Li

2018-02-05

A series of lanthanide selenidogermanates, (H 2 peha)[Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ]{[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )}[Ge 2 Se 6 ]Cl 2 [Ln = Y (1a) and Er (1b); peha = pentaethylenexamine, tepa = tetraethylenepentamine], [Sm 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (2), [Ho 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (3), and [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n (4), were made under solvothermal conditions. Compounds 1a and 1b contain a protonated H 2 peha 2+ ion, the complex cation [Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ] 2+ , a [Ge 2 Se 6 ] 4- anion, free Cl - ions, and a {[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )} 2+ cation constructed by two unsaturated [Ln 2 (μ-OH) 2 (tepa) 2 Cl] 3+ groups connecting via the trans terminal Se atoms of the [Ge 2 Se 6 ] 4- anion, which provides the first example of an organic decorated lanthanide selenidogermanate cation. Both compounds 2 and 3 contain one-dimensional chains [Ln 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n constructed by a combination of unsaturated complex cations [Ln 2 (μ-OH) 2 (tepa) 2 ] 4+ and [Ge 2 Se 6 ] 4- anions, but their stacking patterns of neutral chains are different. Compound 4 contains one-dimensional chain [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n , where three different selenidogermanate units acting as bridging ligands connect unsaturated [Ce(tepa)] 3+ ions. Compound 4 represents the first example of the coexistence of three different selenidogermanate anions in the same architecture. Their optical properties are studied, and the magnetic properties of compounds 1b and 2-4 are also investigated.

Rationally designed mineralization for selective recovery of the rare earth elements

PubMed Central

Hatanaka, Takaaki; Matsugami, Akimasa; Nonaka, Takamasa; Takagi, Hideki; Hayashi, Fumiaki; Tani, Takao; Ishida, Nobuhiro

2017-01-01

The increasing demand for rare earth (RE) elements in advanced materials for permanent magnets, rechargeable batteries, catalysts and lamp phosphors necessitates environmentally friendly approaches for their recovery and separation. Here, we propose a mineralization concept for direct extraction of RE ions with Lamp (lanthanide ion mineralization peptide). In aqueous solution containing various metal ions, Lamp promotes the generation of RE hydroxide species with which it binds to form hydrophobic complexes that accumulate spontaneously as insoluble precipitates, even under physiological conditions (pH ∼6.0). This concept for stabilization of an insoluble lanthanide hydroxide complex with an artificial peptide also works in combination with stable scaffolds like synthetic macromolecules and proteins. Our strategy opens the possibility for selective separation of target metal elements from seawater and industrial wastewater under mild conditions without additional energy input. PMID:28548098

The behavior and importance of lactic acid complexation in Talspeak extraction systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grimes, Travis S.; Nilsson, Mikael; Nash, Kenneth L.

2008-07-01

Advanced partitioning of spent nuclear fuel in the UREX +la process relies on the TALSPEAK process for separation of fission-product lanthanides from trivalent actinides. The classic TALSPEAK utilizes an aqueous medium of both lactic acid and diethylenetriaminepentaacetic acid and the extraction reagent di(2-ethylhexyl)phosphoric acid in an aromatic diluent. In this study, the specific role of lactic acid and the complexes involved in the extraction of the trivalent actinides and lanthanides have been investigated using {sup 14}C-labeled lactic acid. Our results show that lactic acid partitions between the phases in a complex fashion. (authors)

First quadruple-glycine bridging mono-lanthanide-substituted borotungstate hybrids.

PubMed

Liu, Jiancai; Yu, Jing; Han, Qing; Wen, Yue; Chen, Lijuan; Zhao, Junwei

2016-10-18

A class of novel organic-inorganic hybrid lanthanide (Ln)-substituted Keggin-type borotungstates K 4 Na 4 H 4 [Ln 2 (gly) 4 (α-BW 11 O 39 ) 2 ]·23H 2 O [Ln = Ce 3+ (1), Pr 3+ (2), Nd 3+ (3), Sm 3+ (4), Eu 3+ (5), Tm 3+ (6); gly = glycine] have been synthesized from the reaction of K 8 [BW 11 O 39 H]·13H 2 O, NaAc·6H 2 O and Ln(NO 3 ) 3 ·6H 2 O by employing gly ligands as structure-stabilizing agents in the conventional aqueous solution system and structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The common prominent structural feature of isomorphic 1-6 is that all of them consist of two mono-Ln-substituted Keggin [Ln(α-BW 11 O 39 )] 6- fragments linked by four gly ligands, furnishing an intriguing dimeric assembly of the quadruple-gly-connective mono-Ln-substituted borotungstate, in which each carboxylic oxygen atom from gly ligands is bound to Ln 3+ cations in the μ 2 -O or μ 3 -O mode. To the best of our knowledge, 1-6 represent the first examples of inorganic-organic hybrid Ln-substituted borotungstates functionalized by quadruple amino acid bridges. The solid-state photoluminescence properties of 3-5 have been determined at ambient temperature and the photoluminescence emission spectra exhibit the characteristic emission bands derived from Ln 3+ centers. The thermostability of 1-6 has been studied and the thermal decomposition procedure of 3 has been comprehensively investigated with the assistance of variable-temperature PXRD patterns and variable-temperature IR spectra. Furthermore, magnetic susceptibility measurements of 1, 2 and 4 have been conducted.

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

PubMed

Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

2016-08-15

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Shape of intrinsic alpha pulse height spectra in lanthanide halide scintillators

NASA Astrophysics Data System (ADS)

Wolszczak, W.; Dorenbos, P.

2017-06-01

Internal contamination with actinium-227 and its daughters is a serious drawback in low-background applications of lanthanide-based scintillators. In this work we showed the important role of nuclear γ de-excitations on the shape of the internal alpha spectrum measured in scintillators. We calculated with Bateman equations the activities of contamination isotopes and the time evolution of actinium-227 and its progenies. Next, we measured the intrinsic background spectra of LaBr3(Ce), LaBr3(Ce,Sr) and CeBr3 with a digital spectroscopy technique, and we analyzed them with a pulse shape discrimination method (PSD) and a time-amplitude analysis. Finally, we simulated the α background spectrum with Geant4 tool-kit, consequently taking into account complex α-γ-electron events, the α / β ratio dependence on the α energy, and the electron/γ nonproportionality. We found that α-γ mixed events have higher light yield than expected for alpha particles alone, which leads to overestimation of the α / β ratio when it is measured with internal 227Th and 223Ra isotopes. The time-amplitude analysis showed that the α peaks of 219Rn and 215Po in LaBr3(Ce) and LaBr3(Ce,Sr) are not symmetric. We compared the simulation results with the measured data and provided further evidence of the important role of mixed α-γ-electron events for understanding the shape of the internal α spectrum in scintillators.

4f and 5d energy levels of the divalent and trivalent lanthanide ions in M{sub 2}Si{sub 5}N{sub 8} (M=Ca, Sr, Ba)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kate, O.M. ten, E-mail: o.m.tenkate@tudelft.nl; Energy Materials and Devices, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5600MB Eindhoven; Zhang, Z.

Optical data of Sm, Tb and Yb doped Ca{sub 2}Si{sub 5}N{sub 8} and Sr{sub 2}Si{sub 5}N{sub 8} phosphors that have been prepared by solid-state synthesis, are presented. Together with luminescence data from literature on Ce{sup 3+} and Eu{sup 2+} doping in the M{sub 2}Si{sub 5}N{sub 8} (M=Ca, Sr, Ba) hosts, energy level schemes were constructed showing the energy of the 4f and 5d levels of all divalent and trivalent lanthanide ions relative to the valence and conduction band. The schemes were of great help in interpreting the optical data of the lanthanide doped phosphors and allow commenting on the valencemore » stability of the ions, as well as the stability against thermal quenching of the Eu{sup 2+}d-f emission. Tb{sup 3+} substitutes on both a high energy and a low energy site in Ca{sub 2}Si{sub 5}N{sub 8}, due to which excitation at 4.77 eV led to emission from both the {sup 5}D{sub 3} and {sup 5}D{sub 4} levels, while excitation at 4.34 eV gave rise to mainly {sup 5}D{sub 4} emission. Doping with Sm resulted in typical Sm{sup 3+}f-f line absorption, as well as an absorption band around 4.1 eV in Ca{sub 2}Si{sub 5}N{sub 8} and 3.6 eV in Sr{sub 2}Si{sub 5}N{sub 8} that could be identified as the Sm{sup 3+} charge transfer band. Yb on the other hand was incorporated in both the divalent and the trivalent state in Ca{sub 2}Si{sub 5}N{sub 8}. - Graphical abstract: Energy level schemes showing the 4f ground states of the trivalent ( Black-Down-Pointing-Small-Triangle ) and divalent ( Black-Up-Pointing-Small-Triangle ) lanthanide ions and lowest energy 5d states of the trivalent ({nabla}) and divalent ({Delta}) ions with respect to the valence and conduction bands of Ca{sub 2}Si{sub 5}N{sub 8} (left) and Sr{sub 2}Si{sub 5}N{sub 8} (right). Highlights: Black-Right-Pointing-Pointer Construction of energy level schemes of all lanthanides within the M{sub 2}Si{sub 5}N{sub 8} hosts. Black-Right-Pointing-Pointer Construction was done by analyzing existing as well as new

Genetic algorithm based approach to investigate doped metal oxide materials: Application to lanthanide-doped ceria

NASA Astrophysics Data System (ADS)

Hooper, James; Ismail, Arif; Giorgi, Javier B.; Woo, Tom K.

2010-06-01

A genetic algorithm (GA)-inspired method to effectively map out low-energy configurations of doped metal oxide materials is presented. Specialized mating and mutation operations that do not alter the identity of the parent metal oxide have been incorporated to efficiently sample the metal dopant and oxygen vacancy sites. The search algorithms have been tested on lanthanide-doped ceria (L=Sm,Gd,Lu) with various dopant concentrations. Using both classical and first-principles density-functional-theory (DFT) potentials, we have shown the methodology reproduces the results of recent systematic searches of doped ceria at low concentrations (3.2% L2O3 ) and identifies low-energy structures of concentrated samarium-doped ceria (3.8% and 6.6% L2O3 ) which relate to the experimental and theoretical findings published thus far. We introduce a tandem classical/DFT GA algorithm in which an inexpensive classical potential is first used to generate a fit gene pool of structures to enhance the overall efficiency of the computationally demanding DFT-based GA search.

Amine-functionalized lanthanide-doped zirconia nanoparticles: optical spectroscopy, time-resolved fluorescence resonance energy transfer biodetection, and targeted imaging.

PubMed

Liu, Yongsheng; Zhou, Shanyong; Tu, Datao; Chen, Zhuo; Huang, Mingdong; Zhu, Haomiao; Ma, En; Chen, Xueyuan

2012-09-12

Ultrasmall inorganic oxide nanoparticles doped with trivalent lanthanide ions (Ln(3+)), a new and huge family of luminescent bioprobes, remain nearly untouched. Currently it is a challenge to synthesize biocompatible ultrasmall oxide bioprobes. Herein, we report a new inorganic oxide bioprobe based on sub-5 nm amine-functionalized tetragonal ZrO(2)-Ln(3+) nanoparticles synthesized via a facile solvothermal method and ligand exchange. By utilizing the long-lived luminescence of Ln(3+), we demonstrate its application as a sensitive time-resolved fluorescence resonance energy transfer (FRET) bioprobe to detect avidin with a record-low detection limit of 3.0 nM. The oxide nanoparticles also exhibit specific recognition of cancer cells overexpressed with urokinase plasminogen activator receptor (uPAR, an important marker of tumor biology and metastasis) and thus may have great potentials in targeted bioimaging.

Redox-activated MRI contrast agents based on lanthanide and transition metal ions.

PubMed

Tsitovich, Pavel B; Burns, Patrick J; McKay, Adam M; Morrow, Janet R

2014-04-01

The reduction/oxidation (redox) potential of tissue is tightly regulated in order to maintain normal physiological processes, but is disrupted in disease states. Thus, the development of new tools to map tissue redox potential may be clinically important for the diagnosis of diseases that lead to redox imbalances. One promising area of chemical research is the development of redox-activated probes for mapping tissue through magnetic resonance imaging (MRI). In this review, we summarize several strategies for the design of redox-responsive MRI contrast agents. Our emphasis is on both lanthanide(III) and transition metal(II/III) ion complexes that provide contrast either as T1 relaxivity MRI contrast agents or as paramagnetic chemical exchange saturation transfer (PARACEST) contrast agents. These agents are redox-triggered by a variety of chemical reactions or switches including redox-activated thiol groups, and heterocyclic groups that interact with the metal ion or influence properties of other ancillary ligands. Metal ion centered redox is an approach which is ripe for development by coordination chemists. Redox-triggered metal ion approaches have great potential for creating large differences in magnetic properties that lead to changes in contrast. An attractive feature of these agents is the ease of fine-tuning the metal ion redox potential over a biologically relevant range. Copyright © 2014 Elsevier Inc. All rights reserved.

New reversed phase-high performance liquid chromatographic method for selective separation of yttrium from all rare earth elements employing nitrilotriacetate complexes in anion exchange mode.

PubMed

Dybczyński, Rajmund S; Kulisa, Krzysztof; Pyszynska, Marta; Bojanowska-Czajka, Anna

2015-03-20

Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group. Copyright © 2015 Elsevier B.V. All rights reserved.

Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection.

PubMed

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.

BHHST: An improved lanthanide chelate for time-resolved fluorescence applications

NASA Astrophysics Data System (ADS)

Connally, Russell; Jin, Dayong; Piper, James

2005-04-01

The detection of the waterborne pathogens Giardia lamblia and Cryptosporidium parvum in environmental water bodies requires concentration of large volumes of water due to the low dose required for infection. The highly concentrated (10,000-fold) water sample is often rich in strongly autofluorescent algae, organic debris and mineral particles that can obscure immunofluorescently labeled (oo)cysts during analysis. Time-resolved fluorescence techniques exploit the long fluorescence lifetimes of lanthanide chelates (ms) to differentiate target fluorescence from background autofluorescence (ns). Relatively simple instrumentation can be used to enhance the signal-to-noise ratio (S/N) of labelled target. Time-resolved fluorescence techniques exploit the large difference in lifetime by briefly exciting fluorescence from the sample using a pulsed excitation source. Capture of the resulting fluorescence emission is delayed until the more rapidly decaying autofluorescence has faded beyond detection, whereon the much stronger and slower fading emission from labelled target is collected. BHHCT is a tetradentate beta-diketone chelate that is activated to bind with protein (antibody) as the chlorosulfonate. The high activity of this residue makes conjugations difficult to control and can lead to the formation of unstable immunoconjugates. To overcome these limitations a 5-atom hydrophylic molecular tether was attached to BHHCT via the chlorosulfonate and the BHHCT derivative was then activated to bind to proteins as the succinimide. The new compound (BHHST) could be prepared in high purity and was far more stable than the chlorosulfonate on storage. A high activity immunocojugate was prepared against Cryptosporidium that yielded an 8-fold increase in SNR using a lab-built time-resolved fluorescence microscope.

Study on separation of minor actinides from HLLW with new extractant of TODGA-DHOA/Kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Guo-an; Zhu, Wen-bin; Li, Feng-feng

2013-07-01

The extraction behavior of U, Np, Pu, Am, rare earth elements and Sr from nitric acid solutions by TODGA/dodecan, DHOA/dodecane and TODGA-DHOA/dodecane were investigated, respectively. Based on experimental results, a separation process was proposed for minor actinide isolation from high level liquid waste (HLLW): the TODGA-DHOA/kerosene system. The multi-stage counter-current cascade experiments were carried out for the purpose by 0.1 mol/l TODGA-1.0 mol/l DHOA/kerosene with miniature mixer- settler contactor rigs (8 stages for extraction, 6 stages for scrubbing, 8 stages for first stripping, 8 stages for second stripping). The results show that the recovery efficiencies of the actinides and lanthanidesmore » are more than 99.9%, whereas less than 1% Sr was extracted by 0.1 mol/l TODGA - 1.0 mol/l DHOA/kerosene. The stripping efficiencies of U, Np and Pu are more than 95% in the first stripping step by 0.5 mol/l HNO{sub 3} + 0.5 mol/l AHA(aceto-hydroxamic acid), all of the remained actinides and lanthanides can be stripped by 0.01 mol/l HNO{sub 3} in the second stripping step. 99% Sr was extracted by 0.1 mol/l TODGA/kerosene, so Sr can be recovered efficiently directly from the raffinate by 0.1 mol/l TODGA/kerosene. (authors)« less

A Coordination Chemistry Approach to Fine-Tune the Physicochemical Parameters of Lanthanide Complexes Relevant to Medical Applications.

PubMed

Le Fur, Mariane; Molnár, Enikő; Beyler, Maryline; Kálmán, Ferenc K; Fougère, Olivier; Esteban-Gómez, David; Rousseaux, Olivier; Tripier, Raphaël; Tircsó, Gyula; Platas-Iglesias, Carlos

2018-03-02

The geometric features of two pyclen-based ligands possessing identical donor atoms but different site organization have a profound impact in their complexation properties toward lanthanide ions. The ligand containing two acetate groups and a picolinate arm arranged in a symmetrical fashion (L1) forms a Gd 3+ complex being two orders of magnitude less stable than its dissymmetric analogue GdL2. Besides, GdL1 experiences a much faster dissociation following the acid-catalyzed mechanism than GdL2. On the contrary, GdL1 exhibits a lower exchange rate of the coordinated water molecule compared to GdL2. These very different properties are related to different strengths of the Gd-ligand bonds associated to steric effects, which hinder the coordination of a water molecule in GdL2 and the binding of acetate groups in GdL1. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benker, Dennis; Delmau, Laetitia Helene; Dryman, Joshua Cory

This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results ofmore » tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.« less

Lanthanide-doped NaScF4 nanoprobes: crystal structure, optical spectroscopy and biodetection

NASA Astrophysics Data System (ADS)

Ai, Yu; Tu, Datao; Zheng, Wei; Liu, Yongsheng; Kong, Jintao; Hu, Ping; Chen, Zhuo; Huang, Mingdong; Chen, Xueyuan

2013-06-01

Trivalent lanthanide ions (Ln3+)-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 Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal decomposition method. The biotinylated NaScF4:Er3+/Yb3+ 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:Ln3+ 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.Trivalent lanthanide ions (Ln3+)-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 Sc3+ with crystallographic site symmetry of C1, which was verified by high-resolution photoluminescence spectroscopy of Eu3+ at low temperature (10 K). Furthermore, monodisperse and size-controllable NaScF4:Ln3+ NPs were synthesized via a facile thermal