A Space Imaging Concept Based on a 4-meter Spun-Cast Borosilicate Monolithic Primary Mirror

DTIC Science & Technology

2010-06-01

borosilicate monolithic primary mirror 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Steve West, S.H... Mirror Technology Days, Boulder, Colorado, USA, 7-9 June 2010. 14. ABSTRACT The goal of this effort is to produce the largest monolithic telescope...capable of being lifted by a Delta IV or Atlas V EELV to 500 km. A strategy using a 4 m borosilicate mirror is proposed. A preliminary architecture was

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.

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.

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

TiO2 induced structural modifications in Cs containing borosilicate glasses: Raman and infrared studies

NASA Astrophysics Data System (ADS)

Pandey, M.; Banerjee, D.; Sudarsan, V.; Kshirsagar, R. J.

2018-04-01

Effect of TiO2 addition in Cs containing Sodium-borosilicate glasses is studied using Raman and infrared spectroscopic techniques. As revealed from infrared and Raman studies, TiO2 does not form segregated phase, but instead enters into the borosilicate network. It is further observed that TiO2 addition results in modifications of the borate and silicate structural units by transforming into tetraborates and metasilicate structural units. These structural modifications are responsible for Cs immobilization, leach rate and chemical durability of these glasses.

Evaluation of alloy 690 process pot at the contact with borosilicate melt pool during vitrification of high-level nuclear waste

NASA Astrophysics Data System (ADS)

Sengupta, Pranesh; Kaushik, C. P.; Kale, G. B.; Das, D.; Raj, K.; Sharma, B. P.

2009-08-01

Understanding the material behaviour under service conditions is essential to enhance the life span of alloy 690 process pot used in vitrification of high-level nuclear waste. During vitrification process, interaction of alloy 690 with borosilicate melt takes place for substantial time period. Present experimental studies show that such interactions may result in Cr carbide precipitation along grain boundaries, Cr depletion in austenitic matrix and intergranular attack close to alloy 690/borosilicate melt pool interfaces. Widths of Cr depleted zone within alloy 690 is found to follow kinetics of the type x = 10.9 × 10 -6 + 1 × 10 -8t1/2 m. Based on the experimental results it is recommended that compositional modification of alloy 690 process pot adjacent to borosilicate melt pool need to be considered seriously for any efforts towards reduction and/or prevention of process pot failures.

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.

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.

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

Evaluation of Diffuse Reflection Infrared Spectrometry for End-of-Shift Measurement of α-quartz in Coal Dust Samples

PubMed Central

Miller, Arthur L.; Murphy, Nathaniel C.; Bayman, Sean J.; Briggs, Zachary P.; Kilpatrick, Andrew D.; Quinn, Courtney A.; Wadas, Mackenzie R.; Cauda, Emanuele G.; Griffiths, Peter R.

2015-01-01

The inhalation of toxic substances is a major threat to the health of miners, and dust containing respirable crystalline silica (α-quartz) is of particular concern, due to the recent rise in cases of coal workers’ pneumoconiosis and silicosis in some U.S. mining regions. Currently, there is no field-portable instrument that can measure airborne α-quartz and give miners timely feedback on their exposure. The U.S. National Institute for Occupational Safety and Health (NIOSH) is therefore conducting studies to investigate technologies capable of end-of-shift or real-time measurement of airborne quartz. The present study focuses on the potential application of Fourier transform infrared (FT-IR) spectrometry conducted in the diffuse reflection (DR) mode as a technique for measuring α-quartz in respirable mine dust. A DR accessory was used to analyze lab-generated respirable samples of Min-U-Sil 5 (which contains more than 90% α-quartz) and coal dust, at mass loadings in the ranges of 100–600 μg and 600–5300 μg, respectively. The dust samples were deposited onto three different types of filters, borosilicate fiberglass, nylon, and polyvinyl chloride (PVC). The reflectance, R, was calculated by the ratio of a blank filter and a filter with deposited mine dust. Results suggest that for coal and pure quartz dusts deposited on 37 mm PVC filters, measurements of −log R correlate linearly with known amounts of quartz on filters, with R2 values of approximately 0.99 and 0.94, respectively, for samples loaded up to ~4000 μg. Additional tests were conducted to measure quartz in coal dusts deposited onto the borosilicate fiberglass and nylon filter media used in the NIOSH-developed Personal Dust Monitor (PDM). The nylon filter was shown to be amenable to DR analysis, but quantification of quartz is more accurate when the filter is “free,” as opposed to being mounted in the PDM filter holder. The borosilicate fiberglass filters were shown to produce excessive interference, making quartz quantification impossible. It was concluded that, while the DR/FT-IR method is potentially useful for on-filter measurement of quartz in dust samples, the use of PVC filters produced the most accurate results. PMID:25636081

Evaluation of Diffuse Reflection Infrared Spectrometry for End-of-Shift Measurement of α-quartz in Coal Dust Samples.

PubMed

Miller, Arthur L; Murphy, Nathaniel C; Bayman, Sean J; Briggs, Zachary P; Kilpatrick, Andrew D; Quinn, Courtney A; Wadas, Mackenzie R; Cauda, Emanuele G; Griffiths, Peter R

2015-01-01

The inhalation of toxic substances is a major threat to the health of miners, and dust containing respirable crystalline silica (α-quartz) is of particular concern, due to the recent rise in cases of coal workers' pneumoconiosis and silicosis in some U.S. mining regions. Currently, there is no field-portable instrument that can measure airborne α-quartz and give miners timely feedback on their exposure. The U.S. National Institute for Occupational Safety and Health (NIOSH) is therefore conducting studies to investigate technologies capable of end-of-shift or real-time measurement of airborne quartz. The present study focuses on the potential application of Fourier transform infrared (FT-IR) spectrometry conducted in the diffuse reflection (DR) mode as a technique for measuring α-quartz in respirable mine dust. A DR accessory was used to analyze lab-generated respirable samples of Min-U-Sil 5 (which contains more than 90% α-quartz) and coal dust, at mass loadings in the ranges of 100-600 μg and 600-5300 μg, respectively. The dust samples were deposited onto three different types of filters, borosilicate fiberglass, nylon, and polyvinyl chloride (PVC). The reflectance, R, was calculated by the ratio of a blank filter and a filter with deposited mine dust. Results suggest that for coal and pure quartz dusts deposited on 37 mm PVC filters, measurements of -log R correlate linearly with known amounts of quartz on filters, with R(2) values of approximately 0.99 and 0.94, respectively, for samples loaded up to ∼4000 μg. Additional tests were conducted to measure quartz in coal dusts deposited onto the borosilicate fiberglass and nylon filter media used in the NIOSH-developed Personal Dust Monitor (PDM). The nylon filter was shown to be amenable to DR analysis, but quantification of quartz is more accurate when the filter is "free," as opposed to being mounted in the PDM filter holder. The borosilicate fiberglass filters were shown to produce excessive interference, making quartz quantification impossible. It was concluded that, while the DR/FT-IR method is potentially useful for on-filter measurement of quartz in dust samples, the use of PVC filters produced the most accurate results.

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

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.

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.

Immobilized TiO2 on glass spheres applied to heterogeneous photocatalysis: photoactivity, leaching and regeneration process.

PubMed

Cunha, Deivisson Lopes; Kuznetsov, Alexei; Achete, Carlos Alberto; Machado, Antonio Eduardo da Hora; Marques, Marcia

2018-01-01

Heterogeneous photocatalysis using titanium dioxide as catalyst is an attractive advanced oxidation process due to its high chemical stability, good performance and low cost. When immobilized in a supporting material, additional benefits are achieved in the treatment. The purpose of this study was to develop a simple protocol for impregnation of TiO 2 -P25 on borosilicate glass spheres and evaluate its efficiency in the photocatalytic degradation using an oxidizable substrate (methylene blue), in a Compound Parabolic Concentrator (CPC) reactor. The assays were conducted at lab-scale using radiation, which simulated the solar spectrum. TiO 2 leaching from the glass and the catalyst regeneration were both demonstrated. A very low leaching ratio (0.03%) was observed after 24 h of treatment, suggesting that deposition of TiO 2 resulted in good adhesion and stability of the photocatalyst on the surface of borosilicate. This deposition was successfully achieved after calcination of the photocatalyst at 400 °C (TiO 2 -400 °C). The TiO 2 film was immobilized on glass spheres and the powder was characterized by scanning electron microscopy (SEM), X-ray diffraction and BET. This characterization suggested that thermal treatment did not introduce substantial changes in the measured microstructural characteristics of the photocatalyst. The immobilized photocatalyst degraded more than 96% of the MB in up to 90 min of reaction. The photocatalytic activity decreased after four photocatalytic cycles, but it was recovered by the removal of contaminants adsorbed on the active sites after washing in water under UV-Vis irradiation. Based on these results, the TiO 2 -400 °C coated on glass spheres is potentially a very attractive option for removal of persistent contaminants present in the environment.

Immobilized TiO2 on glass spheres applied to heterogeneous photocatalysis: photoactivity, leaching and regeneration process

PubMed Central

Kuznetsov, Alexei; Achete, Carlos Alberto; Machado, Antonio Eduardo da Hora; Marques, Marcia

2018-01-01

Heterogeneous photocatalysis using titanium dioxide as catalyst is an attractive advanced oxidation process due to its high chemical stability, good performance and low cost. When immobilized in a supporting material, additional benefits are achieved in the treatment. The purpose of this study was to develop a simple protocol for impregnation of TiO2-P25 on borosilicate glass spheres and evaluate its efficiency in the photocatalytic degradation using an oxidizable substrate (methylene blue), in a Compound Parabolic Concentrator (CPC) reactor. The assays were conducted at lab-scale using radiation, which simulated the solar spectrum. TiO2 leaching from the glass and the catalyst regeneration were both demonstrated. A very low leaching ratio (0.03%) was observed after 24 h of treatment, suggesting that deposition of TiO2 resulted in good adhesion and stability of the photocatalyst on the surface of borosilicate. This deposition was successfully achieved after calcination of the photocatalyst at 400 °C (TiO2-400 °C). The TiO2 film was immobilized on glass spheres and the powder was characterized by scanning electron microscopy (SEM), X-ray diffraction and BET. This characterization suggested that thermal treatment did not introduce substantial changes in the measured microstructural characteristics of the photocatalyst. The immobilized photocatalyst degraded more than 96% of the MB in up to 90 min of reaction. The photocatalytic activity decreased after four photocatalytic cycles, but it was recovered by the removal of contaminants adsorbed on the active sites after washing in water under UV-Vis irradiation. Based on these results, the TiO2-400 °C coated on glass spheres is potentially a very attractive option for removal of persistent contaminants present in the environment. PMID:29527416

Mechanical Strength and Broadband Transparency Improvement of Glass Wafers via Surface Nanostructures.

PubMed

Kumar, Amarendra; Kashyap, Kunal; Hou, Max T; Yeh, J Andrew

2016-06-17

In this study, we mechanically strengthened a borosilicate glass wafer by doubling its bending strength and simultaneously enhancing its transparency using surface nanostructures for different applications including sensors, displays and panels. A fabrication method that combines dry and wet etching is used for surface nanostructure fabrication. Specifically, we improved the bending strength of plain borosilicate glass by 96% using these surface nanostructures on both sides. Besides bending strength improvement, a limited optical transmittance enhancement of 3% was also observed in the visible light wavelength region (400-800 nm). Both strength and transparency were improved by using surface nanostructures of 500 nm depth on both sides of the borosilicate glass without affecting its bulk properties or the glass manufacturing process. Moreover, we observed comparatively smaller fragments during the breaking of the nanostructured glass, which is indicative of strengthening. The range for the nanostructure depth is defined for different applications with which improvements of the strength and transparency of borosilicate glass substrate are obtained.

Mechanical Strength and Broadband Transparency Improvement of Glass Wafers via Surface Nanostructures

PubMed Central

Kumar, Amarendra; Kashyap, Kunal; Hou, Max T.; Yeh, J. Andrew

2016-01-01

In this study, we mechanically strengthened a borosilicate glass wafer by doubling its bending strength and simultaneously enhancing its transparency using surface nanostructures for different applications including sensors, displays and panels. A fabrication method that combines dry and wet etching is used for surface nanostructure fabrication. Specifically, we improved the bending strength of plain borosilicate glass by 96% using these surface nanostructures on both sides. Besides bending strength improvement, a limited optical transmittance enhancement of 3% was also observed in the visible light wavelength region (400–800 nm). Both strength and transparency were improved by using surface nanostructures of 500 nm depth on both sides of the borosilicate glass without affecting its bulk properties or the glass manufacturing process. Moreover, we observed comparatively smaller fragments during the breaking of the nanostructured glass, which is indicative of strengthening. The range for the nanostructure depth is defined for different applications with which improvements of the strength and transparency of borosilicate glass substrate are obtained. PMID:27322276

Low-weight, low-cost, low-cycle time, replicated glass mirrors

NASA Astrophysics Data System (ADS)

Egerman, Robert; De Smitt, Steven; Strafford, David

2010-07-01

ITT has patented and continues to develop processes to fabricate low-cost borosilicate mirrors that can be used for both ground and space-based optical telescopes. Borosilicate glass is a commodity and is the material of choice for today's flat-panel televisions and monitors. Supply and demand has kept its cost low compared to mirror substrate materials typically found in telescopes. The current technology development is on the path to having the ability to deliver imaging quality optics of up to 1m (scalable to 2m) in diameter in three weeks. For those applications that can accommodate the material properties of borosilicate glasses, this technology has the potential to revolutionize ground and space-based astronomy. ITT Corporation has demonstrated finishing a planar, 0.6m borosilicate, optic to <100 nm-rms. This paper will provide an historical overview of the development in this area with an emphasis on recent technology developments to fabricate a 0.6m parabolic mirror under NASA Earth Science Technology Office (ESTO) grant #NNX09AD61G.

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.

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.

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.

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.

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...

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, L.J.H.; Singh, P.; Ruka, R.J.; Vasilow, T.R.; Bratton, R.J.

1997-11-11

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators. 4 figs.

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, Lewis J. H.; Singh, Prabhakar; Ruka, Roswell J.; Vasilow, Theodore R.; Bratton, Raymond J.

1997-01-01

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators.

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

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

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.

High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated

Additive manufacturing of borosilicate glass (Conference Presentation)

NASA Astrophysics Data System (ADS)

Luo, Junjie; Goldstein, Jonathan T.; Urbas, Augustine M.; Bristow, Douglas A.; Landers, Robert G.; Kinzel, Edward C.

2017-02-01

Glasses including have significant scientific and engineering applications including optics, communications, electronics, and hermetic seals. This paper investigates a filament fed process for Additive Manufacturing (AM) of borosilicate glasses. Compared to soda-lime glasses, borosilicate glasses have improved coefficient of thermal expansion (CTE) and are widely used because of thermal shock resistance. In this work, borosilicate glass filaments are fed into a CO2 laser generated melt pool, smoothly depositing material onto the workpiece. Single tracks are printed to explore the effects that different process parameters have on the morphology of printed glass as well as the residual stress trapped in the glass. The transparency of glass allows residual stress to be measured using a polariscope. The effect of the substrate as well and substrate temperature are analyzed. We show that if fracture due to thermal shock can be avoided during deposition, then the residual stress can be relieved with an annealing step, removing birefringence. When combined with progress toward avoiding bubble entrapment in printed glass, we show the AM approach has the potential to produce high quality optically transparent glass for optical applications.

Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations.

PubMed

Deng, Lu; Du, Jincheng

2018-01-14

Borosilicate glasses form an important glass forming system in both glass science and technologies. The structure and property changes of borosilicate glasses as a function of thermal history in terms of cooling rate during glass formation and simulation system sizes used in classical molecular dynamics (MD) simulation were investigated with recently developed composition dependent partial charge potentials. Short and medium range structural features such as boron coordination, Si and B Q n distributions, and ring size distributions were analyzed to elucidate the effects of cooling rate and simulation system size on these structure features and selected glass properties such as glass transition temperature, vibration density of states, and mechanical properties. Neutron structure factors, neutron broadened pair distribution functions, and vibrational density of states were calculated and compared with results from experiments as well as ab initio calculations to validate the structure models. The results clearly indicate that both cooling rate and system size play an important role on the structures of these glasses, mainly by affecting the 3 B and 4 B distributions and consequently properties of the glasses. It was also found that different structure features and properties converge at different sizes or cooling rates; thus convergence tests are needed in simulations of the borosilicate glasses depending on the targeted properties. The results also shed light on the complex thermal history dependence on structure and properties in borosilicate glasses and the protocols in MD simulations of these and other glass materials.

Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Deng, Lu; Du, Jincheng

2018-01-01

Borosilicate glasses form an important glass forming system in both glass science and technologies. The structure and property changes of borosilicate glasses as a function of thermal history in terms of cooling rate during glass formation and simulation system sizes used in classical molecular dynamics (MD) simulation were investigated with recently developed composition dependent partial charge potentials. Short and medium range structural features such as boron coordination, Si and B Qn distributions, and ring size distributions were analyzed to elucidate the effects of cooling rate and simulation system size on these structure features and selected glass properties such as glass transition temperature, vibration density of states, and mechanical properties. Neutron structure factors, neutron broadened pair distribution functions, and vibrational density of states were calculated and compared with results from experiments as well as ab initio calculations to validate the structure models. The results clearly indicate that both cooling rate and system size play an important role on the structures of these glasses, mainly by affecting the 3B and 4B distributions and consequently properties of the glasses. It was also found that different structure features and properties converge at different sizes or cooling rates; thus convergence tests are needed in simulations of the borosilicate glasses depending on the targeted properties. The results also shed light on the complex thermal history dependence on structure and properties in borosilicate glasses and the protocols in MD simulations of these and other glass materials.

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.

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 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

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

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.

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.

Monte Carlo simulations of coupled diffusion and surface reactions during the aqueous corrosion of borosilicate glasses

DOE PAGES

Kerisit, Sebastien; Pierce, Eric M.; Ryan, Joseph V.

2014-09-19

Borosilicate nuclear waste glasses develop complex altered layers as a result of coupled processes such as hydrolysis of network species, condensation of Si species, and diffusion. However, diffusion has often been overlooked in Monte Carlo models of the aqueous corrosion of borosilicate glasses. Therefore, in this paper three different models for dissolved Si diffusion in the altered layer were implemented in a Monte Carlo model and evaluated for glasses in the compositional range (75 - x) mol% SiO 2 (12.5 + x/2) mol% B 2O 3 and (12.5 + x/2) mol% Na 2O, where 0 ≤ x ≤ 20%, andmore » corroded in static conditions at a surface-area-to-volume ratio of 1000 m -1. The three models considered instantaneous homogenization (M1), linear concentration gradients (M2), and concentration profiles determined by solving Fick's 2nd law using a finite difference method (M3). Model M3 revealed that concentration profiles in the altered layer are not linear and show changes in shape and magnitude as corrosion progresses, unlike those assumed in model M2. Furthermore, model M3 showed that, for borosilicate glasses with a high forward dissolution rate compared to the diffusion rate, the gradual polymerization and densification of the altered layer is significantly delayed compared to models M1 and M2. Finally, models M1 and M2 were found to be appropriate models only for glasses with high release rates such as simple borosilicate glasses with low ZrO 2 content.« less

Rhenium Solubility in Borosilicate Nuclear Waste Glass: Implications for the Processing and Immobilization of Technetium-99

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

McCloy, John S.; Riley, Brian J.; Goel, Ashutosh

2012-10-26

The immobilization of 99Tc in a suitable host matrix has proved to be an arduous task for the researchers in nuclear waste community around the world. At the Hanford site in Washington State, the total amount of 99Tc in low-activity waste (LAW) is ~1300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility/retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of the similarity between theirmore » ionic radii and other chemical aspects. The glasses containing Re (0 – 10,000 ppm by mass) were synthesized in vacuum-sealed quartz ampoules in order to minimize the loss of Re by volatilization during melting at 1000 °C. The rhenium was found to predominantly exist as Re (VII) in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) with inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of crystalline inclusions that were detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). The implications of these results on the immobilization of 99Tc from radioactive wastes in borosilicate glasses have been discussed.« 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...

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.

Nanoindentation of the pristine and irradiated forms of a sodium borosilicate glass: Insights from molecular dynamics simulations

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

Kilymis, D. A.; Ispas, S., E-mail: simona.ispas-crouzet@umontpellier.fr; Delaye, J.-M.

2016-07-28

We have carried out classical molecular dynamics simulations in order to get insight into the atomistic mechanisms of the deformation during nanoindentation of the pristine and irradiated forms of a sodium borosilicate glass. In terms of the glass hardness, we have found that the primary factor affecting the decrease of hardness after irradiation is depolymerization rather than free volume, and we argue that this is a general trend applicable to other borosilicate glasses with similar compositions. We have analyzed the changes of the short- and medium-range structures under deformation and found that the creation of oxygen triclusters is an importantmore » mechanism in order to describe the deformation of highly polymerized borosilicate glasses and is essential in the understanding of the folding of large rings under stress. We have equally found that the less polymerized glasses present a higher amount of relative densification, while the analysis of bond-breaking during the nanoindentation has showed that shear flow is more likely to appear around sodium atoms. The results provided in this study can be proven to be useful in the interpretation of experimental results.« less

Continuous-wave laser-induced glass fiber generation

NASA Astrophysics Data System (ADS)

Nishioka, Nobuyasu; Hidai, Hirofumi; Matsusaka, Souta; Chiba, Akira; Morita, Noboru

2017-09-01

Pulsed-laser-induced glass fiber generation has been reported. We demonstrate a novel glass fiber generation technique by continuous-wave laser illumination and reveal the generation mechanism. In this technique, borosilicate glass, metal foil, and a heat insulator are stacked and clamped by a jig as the sample. Glass fibers are ejected from the side surface of the borosilicate glass by laser illumination of the sample from the borosilicate glass side. SEM observation shows that nanoparticles are attached on the glass fibers. High-speed imaging reveals that small bubbles are formed at the side surface of the borosilicate glass and the bursting of the bubble ejects the fibers. The temperature at the fiber ejection point is estimated to be 1220 K. The mechanism of the fiber ejection includes the following steps: the metal thin foil heated by the laser increases the temperature of the surrounding glass by heat conduction. Since the absorption coefficient of the glass is increased by increasing the temperature, the glass starts to absorb the laser irradiation. The heated glass softens and bubbles form. When the bubble bursts, molten glass and gas inside the bubble scatter into the air to generate the glass fibers.

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

Effect of barium on diffusion of sodium in borosilicate glass.

PubMed

Mishra, R K; Kumar, Sumit; Tomar, B S; Tyagi, A K; Kaushik, C P; Raj, Kanwar; Manchanda, V K

2008-08-15

Diffusion coefficients of sodium in barium borosilicate glasses having varying concentration of barium were determined by heterogeneous isotopic exchange method using (24)Na as the radiotracer for sodium. The measurements were carried out at various temperatures (748-798 K) to obtain the activation energy (E(a)) of diffusion. The E(a) values were found to increase with increasing barium content of the glass, indicating that introduction of barium in the borosilicate glass hinders the diffusion of alkali metal ions from the glass matrix. The results have been explained in terms of the electrostatic and structural factors, with the increasing barium concentration resulting in population of low energy sites by Na(+) ions and, plausibly, formation of more tight glass network. The leach rate measurements on the glass samples show similar trend.

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

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

Laser Fabrication and Characterization of Adhesive-Free Joints for Encapsulation of Biomedical Implant Devices

DTIC Science & Technology

2005-01-01

excitation sources should be helpful in overcoming this problem. CONCLUSIONS Biocompatible joints between polyimide and titanium-coated borosilicate...Technology, 46025 Port St., Plymouth, MI 48170, U.S.A. ABSTRACT Laser-fabricated joints of sub-millimeter widths between biocompatible , dissimilar materials...method of a very promising system, polyimide /titanium-coated borosilicate glass, and present and discuss results from characterization of such laser

Stress Wave and Damage Propagation in Transparent Laminates at Elevated Temperatures

DTIC Science & Technology

2010-03-01

materials like Starphire (a registered trademark of PPG Industries, Pittsburgh, PA) soda - lime glass , borosilicate glass , fused silica , and the...in transparent armor materials like Starphire soda - lime glass , borosilicate glass , fused silica , and the transparent ceramic AlON.1 Since...transparent ceramic AlON. Since transparent armor consists of glass laminates with polymer interlayer and backing, the influence of interlayer type and

Radiation response of cubic mesoporous silicate and borosilicate thin films

NASA Astrophysics Data System (ADS)

Manzini, Ayelén; Alurralde, Martín; Luca, Vittorio

2018-01-01

The radiation response has been studied of cubic mesoporous silicate and borosilicate thin films having different boron contents prepared using the block copolymer template Brij 58 and the dip coating technique. The degree of pore ordering of the films was analysed using low-angle X-ray diffraction and film thickness measured by X-ray reflectivity. For films calcined at 350 °C, the incorporation of boron resulted in a reproducible oscillatory variation in the d-spacing and intensity of the primary reflection as a function of boron content. A clear peak was observed in the d-spacing at 5-10 mol% boron incorporation. For borosilicate films of a given composition an overall suppression of d-spacing was observed as a function of aging time relative to films that did not contain boron. This was ascribed to a slow condensation process. The films were irradiated in pile with neutrons and with iodine ions at energies of 180 keV and 70 MeV. Neutron irradiation of the silicate thin films for periods up to 30 days and aged for 400 days resulted in little reduction in either d-spacing or intensity of the primary low-angle X-ray reflection indicating that the films retained their mesopore ordering. In contrast borosilicate films for which the B (n, α) reaction was expected to result in enhanced displacement damage showed much larger variations in X-ray parameters. For these films short irradiation times resulted in a reduction of the d-spacing and intensity of the primary reflections considerably beyond that observed through aging. It is concluded that prolonged neutron irradiation and internal α irradiation have only a small, although measurable, impact on mesoporous borosilicate thin films increasing the degree of condensation and increasing unit cell contraction. When these borosilicate films were irradiated with iodine ions, more profound changes occurred. The pore ordering of the films was significantly degraded when low energy ions were used. In some cases the degree of damage was such that no low-angle reflection could be observed. This degradation of pore ordering was confirmed in scanning electron microscopy images of the irradiated films.

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

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.

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.

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.

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.

Separation of actinides from lanthanides utilizing molten salt electrorefining

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

Grimmett, D.L.; Fusselman, S.P.; Roy, J.J.

1996-10-01

TRUMP-S (TRansUranic Management through Pyropartitioning Separation) is a pyrochemical process being developed to separate actinides form fission products in nuclear waste. A key process step involving molten salt electrorefining to separate actinides from lanthanides has been studied on a laboratory scale. Electrorefining of U, Np, Pu, Am, and lanthanide mixtures from molten cadmium at 450 C to a solid cathode utilizing a molten chloride electrolyte resulted in > 99% removal of actinides from the molten cadmium and salt phases. Removal of the last few percent of actinides is accompanied by lowered cathodic current efficiency and some lanthanide codeposition. Actinide/lanthanide separationmore » ratios on the cathode are ordered U > Np > Pu > Am and are consistent with predictions based on equilibrium potentials.« less

RHENIUM SOLUBILITY IN BOROSILICATE NUCLEAR WASTE GLASS IMPLICATIONS FOR THE PROCESSING AND IMMOBILIZATION OF TECHNETIUM-99 (AND SUPPORTING INFORMATION WITH GRAPHICAL ABSTRACT)

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

AA KRUGER; A GOEL; CP RODRIGUEZ

2012-08-13

The immobilization of 99Tc in a suitable host matrix has proved a challenging task for researchers in the nuclear waste community around the world. At the Hanford site in Washington State in the U.S., the total amount of 99Tc in low-activity waste (LAW) is {approx} 1,300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility and retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW sodium borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant becausemore » of previously established similarities in ionic radii and other chemical aspects. The glasses containing target Re concentrations varying from 0 to10,000 ppm by mass were synthesized in vacuum-sealed quartz ampoules to minimize the loss of Re by volatilization during melting at 1000 DC. The rhenium was found to be present predominantly as Re7 + in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be {approx}3,000 ppm (by mass) using inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of alkali perrhenate crystalline inclusions detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). Assuming justifiably substantial similarities between Re7 + and Tc 7+ behavior in this glass system, these results implied that the processing and immobilization of 99Tc from radioactive wastes should not be limited by the solubility of 99Tc in borosilicate LAW glasses.« less

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

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…

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 of lanthanides that could support sufficient enzymatic activities to support specific metabolisms, and so far, no other redox proteins involved in lanthanide-dependent methanotrophy have been demonstrated. The research presented here provides enzyme activity-level data on lanthanide-dependent methanotrophy in a model methanotroph. Additionally, we identify a second protein important for lanthanide-dependent metabolism in this organism, XoxG(4), a novel cytochrome. XoxG(4) appears to have multiple functions in methanotrophy, one function as an electron acceptor from XoxF and another function remaining unknown. On the basis of the dramatic phenotype of the XoxG(4) mutant, this function must be crucial for methanotrophy.« less

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 of lanthanides that could support sufficient enzymatic activities to support specific metabolisms, and so far, no other redox proteins involved in lanthanide-dependent methanotrophy have been demonstrated. The research presented here provides enzyme activity-level data on lanthanide-dependent methanotrophy in a model methanotroph. Additionally, we identify a second protein important for lanthanide-dependent metabolism in this organism, XoxG(4), a novel cytochrome. XoxG(4) appears to have multiple functions in methanotrophy, one function as an electron acceptor from XoxF and another function remaining unknown. On the basis of the dramatic phenotype of the XoxG(4) mutant, this function must be crucial for methanotrophy.« less

Second generation large area microchannel plate flat panel phototubes

NASA Astrophysics Data System (ADS)

Ertley, C. D.; Siegmund, O. H. W.; Jelinsky, S. R.; Tedesco, J.; Minot, M. J.; O'Mahony, A.; Craven, C. A.; Popecki, M.; Lyashenko, A. V.; Foley, M. R.

2016-07-01

Very large (20 cm × 20 cm) flat panel phototubes are being developed which employ novel microchannel plates (MCPs). The MCPs are manufactured using borosilicate microcapillary arrays which are functionalized by the application of resistive and secondary emissive layers using atomic layer deposition (ALD). This allows the operational parameters to be set by tailoring sequential ALD deposition processes. The borosilicate substrates are robust, including the ability to be produced in large formats (20 cm square). ALD MCPs have performance characteristics (gain, pulse amplitude distributions, and imaging) that are equivalent or better than conventional MCPs. They have low intrinsic background (0.045 events cm-2 sec-1)., high open area ratios (74% for the latest generation of borosilicate substrates), and stable gain during >7 C cm-2 charge extraction after preconditioning (vacuum bake and burn-in). The tube assemblies use a pair of 20 cm × 20 cm ALD MCPs comprised of a borosilicate entrance window, a proximity focused bialkali photocathode, and a strip-line readout anode. The second generation design employs an all glass body with a hot indium seal and a transfer photocathode. We have achieved >20% quantum efficiency and good gain uniformity over the 400 cm2 field of view, spatial resolution of <1 cm and obtained event timing accuracy of close to 100 ps FWHM.

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.

“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands

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

“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands

DOE PAGES

Ellis, Ross J.; Brigham, Derek M.; Delmau, Laetitia; ...

2016-11-23

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

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.

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 not only for MDH genes but also the subsequent formaldehyde oxidation pathways and respiratory chain, which might be due to the direct oxidation of methanol to formate by XoxF. In addition, a considerable number of genes of unknown function, including AT-rich genes, were found to be upregulated in the presence of lanthanides. This study provides first insights into the specific reaction of methylotrophic bacteria to the presence of lanthanides, emphasizing the biological relevance of this trace metal. PMID:29404411

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 not only for MDH genes but also the subsequent formaldehyde oxidation pathways and respiratory chain, which might be due to the direct oxidation of methanol to formate by XoxF. In addition, a considerable number of genes of unknown function, including AT-rich genes, were found to be upregulated in the presence of lanthanides. This study provides first insights into the specific reaction of methylotrophic bacteria to the presence of lanthanides, emphasizing the biological relevance of this trace metal.

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…

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.

Impact Experiments into Borosilicate Glass at Three Scale Sizes

DTIC Science & Technology

2009-11-01

DEDF and soda - lime glass during rod impact. Shock Compression in Condensed Matter–2005 (Furnish MD, Elert M, Russell TP, and White CT, Eds.) AIP Conf...in a float soda - lime silicate glass . Int. J. Appl. Glass Sci., to be submitted (2009). 18. Chocron S, Dannemann KA, Nicholls AE, and Anderson CE Jr...UNCLASSIFIED UNCLASSIFIED Impact Experiments into Borosilicate Glass at Three Scale Sizes Charles E. Anderson, Jr. Carl E. Weiss Sidney Chocron

Effect of Loading Rate and Surface Conditions on Flexural Strength of Borosilicate Glass

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

Nie, X; Chen, Wayne; Wereszczak, Andrew A

2009-01-01

This study evaluates the loading rate and surface condition dependence of the flexural strength of a borosilicate glass. The glass specimens are subjected to three different surface treatments before four-point bending tests to study the effect of surface flaws. Quasistatic (Material Test System 810) and dynamic (Kolsky bar) experiments are performed at loading rates ranging from 0.7 to 4 x 10{sup 6} MPa/s. The results show that the flexural strength of the borosilicate glass has a strong dependence on the loading rate. A chemically etched surface produces an enhanced flexural strength by about an order of magnitude. Scanning electron microscopymore » images on fracture surfaces indicate that the failure is governed by different types of flaws under different surface treatment conditions. Edge failure is also identified for samples possessing high flexural strength.« less

Alkali borosilicate glass by fly ash from a coal-fired power plant.

PubMed

Park, Jong Soo; Taniguchi, Shoji; Park, Young Jun

2009-01-01

The possibility of using coal fly ash as a silica source for alkali borosilicate glass was investigated. Alkali borosilicate glasses were prepared from the coal fly ash mixed with 30 wt.% reagents composed of Na(2)O and B(2)O(3) by susceptor-induction heating. Their densities ranged from 2.24 to 2.55 g cm(-3) and decreased as the amount of B(2)O(3) addition increased. However, the Vickers microhardness showed a different tendency with the density since the glass network connectivity improved by boron anomaly, which was identified by a nuclear magnetic resonance analysis. The Vickers microhardness of the glass product, with the addition of 15 wt.% B(2)O(3) and 15 wt.% Na(2)O, was about 4030 MPa. Furthermore, the changes in microstructure were consistent with those in the chemical stability by the toxicity characteristic leaching procedure (TCLP).

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.

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.

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 effect. • In solid-state structures of compounds 9-11, no lanthanide ions were observed. • This study provides a means of separating lanthanides cations.« less

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

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.

There Is Still Room for Improvement: Presentation of a Neutral Borosilicate Glass with Improved Chemical Stability for Parenteral Packaging.

PubMed

Boltres, Bettine; Tratzky, Stephan; Kass, Christof; Eichholz, Rainer; Naß, Peter

2016-01-01

For pharmaceutical parenteral packaging the glass compositions have always been either Type I borosilicate or Type III soda-lime glass. As both the compositions and certain chemical and physical properties are mandated by international standards, there has not been room for any changes. However, by applying only minor adjustments, a borosilicate glass was developed that showed improved chemical stability. The chemical composition is still in the range of currently used borosilicate glasses, which makes it a Type I glass according to all current pharmacopeia. A study was performed on glass vials comparing the new glass with the standard FIOLAX(®) and two other publicly available glasses. In an extraction study with water at 121 °C the new glass showed the highest chemical stability with the lowest amount of extractables. In an accelerated ageing study, which was done with water, phosphate, and carbonate buffer at 40 °C for 12 months, the new glass also proved to have the lowest amount of leachables. In this article the new glass and the results from the studies are presented, showing the reader how much of an effect can be attained with only minor adjustments if the scientific fundamentals are clear. The pharmaceutical market has been quite constant and risk-oriented due to the high impact on the safety of the patient. As any change necessitates a complicated change process, this has, in consequence, lead the industry to resist changing the parenteral primary packaging material for decades. The main glasses have either been Type I borosilicate or Type III soda-lime glass. On the other hand, a combination of improved inspection systems and the development of more sensitive biologically based drugs has elevated the standards for parental packaging materials. For example, the measurement of extractables and leachables from the packaging material steadily came into focus. In this article, a new glass is presented that still belongs to the group of Type I borosilicate glasses according to all pharmacopeia. However, with some minor adjustments in the chemical composition it was possible to increase the chemical stability measurably. To prove this several studies were performed, of which the extraction study with water at 121 °C and the accelerated ageing study with water, phosphate, and carbonate buffer at 40 °C for 12 months are presented here. © PDA, Inc. 2016.

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.

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.

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, our data suggest that M. extorquens AM1 has a mechanism to regulate which MeDH is transcribed, depending on the presence or absence of lanthanides. While the mechanism controlling differential regulation is not yet understood, further research into how methylotrophs obtain and use lanthanides will facilitate their cultivation in the laboratory and their use as a biomining and biorecycling strategy for recovery of these commercially valuable rare-earth elements. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

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 methylotrophs. Further, our data suggest that M. extorquens AM1 has a mechanism to regulate which MeDH is transcribed, depending on the presence or absence of lanthanides. While the mechanism controlling differential regulation is not yet understood, further research into how methylotrophs obtain and use lanthanides will facilitate their cultivation in the laboratory and their use as a biomining and biorecycling strategy for recovery of these commercially valuable rare-earth elements. PMID:26833413

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.

Comparison of hardness variation of ion irradiated borosilicate glasses with different projected ranges

NASA Astrophysics Data System (ADS)

Sun, M. L.; Peng, H. B.; Duan, B. H.; Liu, F. F.; Du, X.; Yuan, W.; Zhang, B. T.; Zhang, X. Y.; Wang, T. S.

2018-03-01

Borosilicate glass has potential application for vitrification of high-level radioactive waste, which attracts extensive interest in studying its radiation durability. In this study, sodium borosilicate glass samples were irradiated with 4 MeV Kr17+ ion, 5 MeV Xe26+ ion and 0.3 MeV P+ ion, respectively. The hardness of irradiated borosilicate glass samples was measured with nanoindentation in continuous stiffness mode and quasi continuous stiffness mode, separately. Extrapolation method, mean value method, squared extrapolation method and selected point method are used to obtain hardness of irradiated glass and a comparison among these four methods is conducted. The extrapolation method is suggested to analyze the hardness of ion irradiated glass. With increasing irradiation dose, the values of hardness for samples irradiated with Kr, Xe and P ions dropped and then saturated at 0.02 dpa. Besides, both the maximum variations and decay constants for three kinds of ions with different energies are similar indicates the similarity behind the hardness variation in glasses after irradiation. Furthermore, the hardness variation of low energy P ion irradiated samples whose range is much smaller than those of high energy Kr and Xe ions, has the same trend as that of Kr and Xe ions. It suggested that electronic energy loss did not play a significant role in hardness decrease for irradiation of low energy ions.

Relaxation dynamics of dysprosium(III) single molecule magnets.

PubMed

Guo, Yun-Nan; Xu, Gong-Feng; Guo, Yang; Tang, Jinkui

2011-10-21

Over the past decade, lanthanide compounds have become of increasing interest in the field of Single Molecule Magnets (SMMs) due to the large inherent anisotropy of the metal ions. Heavy lanthanide metal systems, in particular those containing the dysprosium(III) ion, have been extensively employed to direct the formation of a series of SMMs. Although remarkable progress is being made regarding the synthesis and characterization of lanthanide-based SMMs, the understanding and control of the relaxation dynamics of strongly anisotropic systems represents a formidable challenge, since the dynamic behaviour of lanthanide-based SMMs is significantly more complex than that of transition metal systems. This perspective paper describes illustrative examples of pure dysprosium(III)-based SMMs, published during the past three years, showing new and fascinating phenomena in terms of magnetic relaxation, aiming at shedding light on the features relevant to modulating relaxation dynamics of polynuclear lanthanide SMMs. This journal is © The Royal Society of Chemistry 2011

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.

The TRUSPEAK Concept: Combining CMPO and HDEHP for Separating Trivalent Lanthanides from the Transuranic Elements

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

Lumetta, Gregg J.; Gelis, Artem V.; Braley, Jenifer C.

2013-04-08

Combining octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl-phosphine oxide (CMPO) and bis-(2-ethylhexyl) phosphoric acid (HDEHP) into a single process solvent for separating transuranic elements from liquid high-level waste is explored. Co-extraction of americium and the lanthanide elements from nitric acid solution is possible with a solvent mixture consisting of 0.1-M CMPO plus 1-M HDEHP in n-dodecane. Switching the aqueous-phase chemistry to a citrate-buffered solution of diethylene triamine pentaacetic acid (DTPA) allows for selective stripping of americium, separating it from the lanthanide elements. Potential strategies for managing molybdenum and zirconium (both of which co-extract with americium and the lanthanides) have been developed. The work presented here demonstratesmore » the feasibility of combining CMPO and HDEHP into a single extraction solvent for recovering americium from high-level waste and its separation from the lanthanides.« less

Enhancing Patient Safety through the Use of a Pharmaceutical Glass Designed To Prevent Cracked Containers.

PubMed

Schaut, Robert A; Hoff, Kyle C; Demartino, Steven E; Denson, William K; Verkleeren, Ronald L

2017-01-01

An essential role of packaging material for the storage and delivery of drug products is to provide adequate protection against contamination and loss of sterility. This is especially important for parenteral containers, as lack of sterility or contamination can result in serious adverse events including death. Nonetheless, cracked parenteral containers are an important source of container integrity failures for injectable drugs and pose a serious risk for patients. Despite significant investments in inspection technology, each year many injectable drugs are investigated and recalled for sterility risks associated with cracked borosilicate containers. Multiple studies and the many difficulties in detection of cracked containers suggest that the magnitude of the public health risk is even larger than the recall rate would suggest. Here we show that the root cause of cracked parenteral containers (low internal energy following annealing) is inherent to the glasses currently used for primary packaging of the majority of injectable drugs. We also describe a strengthened aluminosilicate glass that has been designed to prevent cracks in parenteral containers through the use of an engineered stress profile in the glass. Laboratory tests that simulate common filling line damage events show that the strengthened aluminosilicate glass is highly effective at preventing cracks. Significant safety benefits have been demonstrated in other industries from the use of special stress profiles in glass components to mitigate failure modes that may result in harm to humans. Those examples combined with the results described here suggest that a significant improvement in patient safety can be achieved through the use of strengthened aluminosilicate glass for parenteral containers. LAY ABSTRACT: Cracks are small cuts or gaps in a container which provide a pathway for liquid, gas, or microbes through a glass container. When these defects are introduced to conventional glass containers holding injectable medicines, the affected drug can pose serious risks to the patient receiving that medication. Specifically, the drug product may become less effective or even non-sterile, which could lead to bloodstream infections and, in some cases, death. This article presents a review of some previously documented cases of cracked glass containers that led to patient infections and deaths. Following a survey of common crack locations in glass vials, lab-based methods for replicating these cracks are presented. These methods are then used to compare the fracture response of vials made from conventional borosilicate glass and strengthened aluminosilicate glass. The results show that stable cracks are essentially prevented (at least 31 times less likely to occur) in the strengthened aluminosilicate glass containers (relative to conventional borosilicate glass). This improvement in safety is similar to improvements already engineered into other glass product designs by utilizing stored strain energy to mitigate certain failure modes. © PDA, Inc. 2017.

The separation of lanthanides and actinides in supercritical fluid carbon dioxide

DOE PAGES

Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; ...

2015-10-28

Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

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.

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.

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.

A computational approach to predicting ligand selectivity for the size-based separation of trivalent lanthanides

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

Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

An accurate description of solvation effects for trivalent lanthanide ions is a main stumbling block to the qualitative prediction of selectivity trends along the lanthanide series. In this work, we propose a simple model to describe the differential effect of solvation in the competitive binding of a ligand by lanthanide ions by including weakly co-ordinated counterions in the complexes of more than a +1 charge. The success of the approach to quantitatively reproduce selectivities obtained from aqueous phase complexation studies demonstrates its potential for the design and screening of new ligands for efficient size-based separation.

A computational approach to predicting ligand selectivity for the size-based separation of trivalent lanthanides

DOE PAGES

Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

2016-06-20

An accurate description of solvation effects for trivalent lanthanide ions is a main stumbling block to the qualitative prediction of selectivity trends along the lanthanide series. In this work, we propose a simple model to describe the differential effect of solvation in the competitive binding of a ligand by lanthanide ions by including weakly co-ordinated counterions in the complexes of more than a +1 charge. The success of the approach to quantitatively reproduce selectivities obtained from aqueous phase complexation studies demonstrates its potential for the design and screening of new ligands for efficient size-based separation.

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.

Formation and corrosion of a 410 SS/ceramic composite

NASA Astrophysics Data System (ADS)

Chen, X.; Ebert, W. L.; Indacochea, J. E.

2016-11-01

This study addressed 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 using a single waste form. A representative composite material 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 available Zr reacted with lanthanide oxides to generate lanthanide zirconates, which combined with the unreacted lanthanide oxides to form a porous ceramic network that filled with alloy to produce a composite puck. Alloy present in excess of the pore volume of the ceramic generated a metal bead on top of the puck. The alloys in the composite and forming the bead were both mixtures of martensite grains and ferrite grains bearing carbide precipitates; FeCrMo intermetallic phases also precipitated at ferrite grain boundaries within the composite puck. Micrometer-thick regions of ferrite surrounding the carbides were sensitized and corroded preferentially in electrochemical tests. The lanthanide oxides dissolved chemically, but the lanthanide zirconates did not dissolve and are suitable host phases. The presence of oxide phases did not affect corrosion of the neighboring alloy phases.

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

Ding, Ling; Zhong, Jie-Cen; Qiu, Xing-Tai

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

Fabrication of the LSST monolithic primary-tertiary mirror

NASA Astrophysics Data System (ADS)

Tuell, Michael T.; Martin, Hubert M.; Burge, James H.; Ketelsen, Dean A.; Law, Kevin; Gressler, William J.; Zhao, Chunyu

2012-09-01

As previously reported (at the SPIE Astronomical Instrumentation conference of 2010 in San Diego1), the Large Synoptic Survey Telescope (LSST) utilizes a three-mirror design in which the primary (M1) and tertiary (M3) mirrors are two concentric aspheric surfaces on one monolithic substrate. The substrate material is Ohara E6 borosilicate glass, in a honeycomb sandwich configuration, currently in production at The University of Arizona’s Steward Observatory Mirror Lab. We will provide an update to the status of the mirrors and metrology systems, which have advanced from concepts to hardware in the past two years. In addition to the normal requirements for smooth surfaces of the appropriate prescriptions, the alignment of the two surfaces must be accurately measured and controlled in the production lab, reducing the degrees of freedom needed to be controlled in the telescope. The surface specification is described as a structure function, related to seeing in excellent conditions. Both the pointing and centration of the two optical axes are important parameters, in addition to the axial spacing of the two vertices. This paper details the manufacturing process and metrology systems for each surface, including the alignment of the two surfaces. M1 is a hyperboloid and can utilize a standard Offner null corrector, whereas M3 is an oblate ellipsoid, so it has positive spherical aberration. The null corrector is a phase-etched computer-generated hologram (CGH) between the mirror surface and the center-of-curvature. Laser trackers are relied upon to measure the alignment and spacing as well as rough-surface metrology during looseabrasive grinding.

Ultrapure glass optical waveguide development in microgravity by the sol-gel process

NASA Technical Reports Server (NTRS)

Mukherjee, S. P.

1980-01-01

The alkali-borosilicate system was selected as the glass system for the preparation of ultrapure low loss glasses suitable for optical communication. The effect of different oxide contents on the absorption loss was critically reviewed. One composition was chosen to develop the gel preparation procedure in the alkali-borosilicate system. In addition, several procedures for the preparation of gels based on two different approaches were developed. The influence of different preparation parameters were investigated qualitatively. Several conclusions are drawn from the results.

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

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers.

PubMed

Du, H S; Wood, D J; Elshani, S; Wai, C M

1993-02-01

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.

SEM and AFM Studies of Two-Phase Magnetic Alkali Borosilicate Glasses

PubMed Central

Tomkovich, M.; Nacke, B.; Filimonov, A.; Alekseeva, O.; Vanina, P.; Nizhankovskii, V.

2017-01-01

The morphology and composition of four types of two-phase alkali borosilicate glasses with magnetic atoms prepared by inductive melting have been studied. The results of scanning electron microscopy point to uniform distribution of Na, Si, and O atoms in these samples while magnetic iron atoms form ball-shaped agglomerates. The magnetic properties of these agglomerates have been confirmed by magnetic force microscopy. Atomic force microscopy had shown that in these samples two different morphological structures, drop-like and dendrite net, are formed. The formation of dendrite-like structure is a necessary condition for production of porous magnetic glasses. The obtained results allow us to optimize the melting and heat treatment processes leading to production of porous alkali borosilicate glasses with magnetic properties. The first results for nanocomposite materials on the basis of magnetic glasses containing the embedded ferroelectrics KH2PO4 demonstrate the effect of applied magnetic field on the ferroelectric phase transition. PMID:28428976

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

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

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.

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.

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.

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.

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

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

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch modemore » frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.« less

The magnetic properties of a magnetic detector using oxidized amorphous Co 95- xFe 5(BSi) x alloys

NASA Astrophysics Data System (ADS)

Ahn, S. J.; Kim, C. K.; Kim, S. J.; Choi, D. K.; O'Handley, R. C.

2000-07-01

A comparative oxidation study of several amorphous Co 75- xFe 5(BSi) 20+ x alloys was carried out. Reentrant magnetization behavior and field-induced anisotropy which are of a critical importance for a magnetic detector were obtained after oxidation of the amorphous Co-rich ribbons. During this oxidation, the ribbons develop surface oxides which are primarily nonmagnetic borosilicate or a combination of borosilicate and magnetic oxides such CoO or FeO. Beneath this lies a 100-1000 Å thick Co-rich magnetic alloy which may be either HCP or FCC in its crystal structure. The thickness of the Co-crystallized layer is determined by the type of the surface oxides. The oxidation products such as appear to affect the reentrant magnetization behavior of Co-rich amorphous alloys significantly. We have determined the amount of metalloids (a critical concentration of B and Si) which is necessary to form a continuous layer of the most thermodynamically stable oxide, in our case borosilicate, on the surface. We also observed that there is a good correlation between reentrant magnetization and the thickness of Co layer. The best reentrant M- H loop for the magnetic detector was obtained in ribbons with a surface borate-rich borosilicate since it ensures conditions such as (1) metalloid depletion in the substrate and (2) formation of oxygen impurity faults in Co grains that are required for strong reentrant magnetization behavior.

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 symmetry structures. As a result, through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.« less

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 structures. Through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.

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 symmetry structures. As a result, through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.« less

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.

SEPARATION OF EUROPIUM FROM OTHER LANTHANIDE RAE EARTHS BY SOLVENT EXTRACTION

DOEpatents

Peppard, D.F.; Horwitz, E.P.; Mason, G.W.

1963-02-12

This patent deals with a process of separating europium from other lanthanides present in aqueous hydrochloric or sulfuric acid solutions. The europium is selectively reduced to the divalent state with a divalent chromium salt formed in situ from chromium(III) salt plus zinc amalgam. The other trivalent lanthanides are then extracted away from the divalent europium with a nitrogen-flushed phosphoric acid ester or a phosphonic acid ester. (AEC)

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.

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

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.

Effect of X-ray irradiation on the optical absorption of СdSe1-xTex nanocrystals embedded in borosilicate glass

NASA Astrophysics Data System (ADS)

Prymak, M. V.; Azhniuk, Yu. M.; Solomon, A. M.; Krasilinets, V. M.; Lopushansky, V. V.; Bodnar, I. V.; Gomonnai, A. V.; Zahn, D. R. T.

2012-07-01

The effect of X-ray irradiation on the optical absorption spectra of CdSe1-xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature.

Study of the Accelerating Channel Wall Property Influence on the Hall Thruster Discharge Characteristics

DTIC Science & Technology

2004-11-01

Hall thruster characteristics there was prepared Hall thruster model of the SPT-100 type for these experiments and there were manufactured the required discharge chamber parts (rings) made of the Russian BN-SiO2 (borosil) ceramics and of the Russian AIN-BN (ABN) and Western ABN ceramics having secondary electron emission yield (SEEY) different from that one for borosil. These parts were replaceable during experiments. Thruster model was equipped by set of the near wall probes mounted at external discharge chamber wall. There was made characterization

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 3

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

Cunnane, J.C.; Bates, J.K.; Bradley, C.R.

1994-03-01

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II.

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.

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

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

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).

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

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-.

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

Low Velocity Sphere Impact of a Borosilicate Glass

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

Morrissey, Timothy G; Ferber, Mattison K; Wereszczak, Andrew A

2012-05-01

This report summarizes US Army TARDEC sponsored work at Oak Ridge National Laboratory (ORNL) involving low velocity (< 30 m/s or < 65 mph) ball impact testing of Borofloat borosilicate glass, and is a follow-up to a similar study completed by the authors on Starphire soda-lime silicate glass last year. The response of the borosilicate glass to impact testing at different angles was also studied. The Borofloat glass was supplied by the US Army Research Laboratory and its tin-side was impacted or indented. The intent was to better understand low velocity impact response in the Borofloat. Seven sphere materials weremore » used whose densities bracket that of rock: borosilicate glass, soda-lime silicate glass, silicon nitride, aluminum oxide, zirconium oxide, carbon steel, and a chrome steel. A gas gun or a ball-drop test setup was used to produce controlled velocity delivery of the spheres against the glass tile targets. Minimum impact velocities to initiate fracture in the Borofloat were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the seven sphere-Borofloat-target combinations. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) BS glass responded similarly to soda-lime silicate glass when spherically indented but quite differently under sphere impact conditions; (2) Frictional effects contributed to fracture initiation in BS glass when it spherically indented. This effect was also observed with soda-lime silicate glass; (3) The force necessary to initiate fracture in BS glass under spherical impact decreases with increasing elastic modulus of the sphere material. This trend is opposite to what was observed with soda-lime silicate glass. Friction cannot explain this trend and the authors do not have a legitimate explanation for it yet; (4) The force necessary to initiate contact-induced fracture is higher under dynamic conditions than under quasi-static conditions. That difference decreases with increasing elastic modulus mismatch between the sphere material and borosilicate This trend was opposite in soda-lime silicate glass; (5) Fracture in borosilicate glass occurs at lower velocities (i.e., easier) at 24{sup o} than at 0{sup o} (orthogonal) and 46{sup o} of impact for the same probability of failure. Though not analyzed yet, this suggests that a convolution of kinetic energy and friction is contributing to that trend; (6) There is a subtle indication there was intra-tile differences in spherical indentation RCIF. This likely is not a material property nor exclusive to borosilicate glass, rather, it is a statistical response of a combination of local, surface-located flaw and imposed tensile stress. Understanding of the surface flaw population and flaw positioning can likely enable prediction of spherical indentation RCIF; and (7) Contact-induced fracture did not initiate in the Borofloat BS for impact kinetic energies up to {approx} 20 mJ. For kinetic energies between {approx} 20-150 mJ, fracture sometimes initiated. Contact-induced fracture would always occur for impact energies > 150 mJ. The energy values, and their boundaries, were much lower for BS glass than they were for soda-lime silicate glass.« 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

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.

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.

Separations of actinides, lanthanides and other metals

DOEpatents

Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

1995-01-01

An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

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

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.

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.

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.

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.

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.

Modelling the sulfate capacity of simulated radioactive waste borosilicate glasses

DOE PAGES

Bingham, Paul A.; Vaishnav, Shuchi; Forder, Sue D.; ...

2016-11-10

In this paper, the capacity of simulated high-level radioactive waste borosilicate glasses to incorporate sulfate has been studied as a function of glass composition. Combined Raman, 57Fe Mössbauer and literature evidence supports the attribution of coordination numbers and oxidation states of constituent cations for the purposes of modelling, and results confirm the validity of correlating sulfate incorporation in multicomponent borosilicate radioactive waste glasses with different models. A strong compositional dependency is observed and this can be described by an inverse linear relationship between incorporated sulfate (mol% SO 4 2-) and total cation field strength index of the glass, Σ(z/a 2),more » with a high goodness-of-fit (R 2 ≈ 0.950). Similar relationships are also obtained if theoretical optical basicity, Λ th (R 2 ≈ 0.930) or non-bridging oxygen per tetrahedron ratio, NBO/T (R 2 ≈ 0.919), are used. Finally, results support the application of these models, and in particular Σ(z/a 2), as predictive tools to aid the development of new glass compositions with enhanced sulfate capacities.« less

Modelling the sulfate capacity of simulated radioactive waste borosilicate glasses

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

Bingham, P. A.; Vaishnav, S.; Forder, S. D.

2017-02-01

The capacity of simulated high-level radioactive waste borosilicate glasses to incorporate sulfate has been studied as a function of glass composition. Combined Raman, 57Fe Mössbauer and literature evidence supports the attribution of coordination numbers and oxidation states of constituent cations for the purposes of modelling, and results confirm the validity of correlating sulfate incorporation in multicomponent borosilicate radioactive waste glasses with different models. A strong compositional dependency is observed and this can be described by an inverse linear relationship between incorporated sulfate (mol% SO 4 2-) and total cation field strength index of the glass, Σ(z/a 2), with a highmore » goodness-of-fit (R 2 ≈ 0.950). Similar relationships are also obtained if theoretical optical basicity, Λ th (R 2 ≈ 0.930) or non-bridging oxygen per tetrahedron ratio, NBO/T (R 2 ≈ 0.919), are used. Results support the application of these models, and in particular Σ(z/a 2), as predictive tools to aid the development of new glass compositions with enhanced sulfate capacities.« less

Optical testing of the LSST combined primary/tertiary mirror

NASA Astrophysics Data System (ADS)

Tuell, Michael T.; Martin, Hubert M.; Burge, James H.; Gressler, William J.; Zhao, Chunyu

2010-07-01

The Large Synoptic Survey Telescope (LSST) utilizes a three-mirror design in which the primary (M1) and tertiary (M3) mirrors are two concentric aspheric surfaces on one monolithic substrate. The substrate material is Ohara E6 borosilicate glass, in a honeycomb sandwich configuration, currently in production at The University of Arizona's Steward Observatory Mirror Lab. In addition to the normal requirements for smooth surfaces of the appropriate prescriptions, the alignment of the two surfaces must be accurately measured and controlled in the production lab. Both the pointing and centration of the two optical axes are important parameters, in addition to the axial spacing of the two vertices. This paper describes the basic metrology systems for each surface, with particular attention to the alignment of the two surfaces. These surfaces are aspheric enough to require null correctors for each wavefront. Both M1 and M3 are concave surfaces with both non-zero conic constants and higher-order terms (6th order for M1 and both 6th and 8th orders for M3). M1 is hyperboloidal and can utilize a standard Offner null corrector. M3 is an oblate ellipsoid, so has positive spherical aberration. We have chosen to place a phase-etched computer-generated hologram (CGH) between the mirror surface and the center-of-curvature (CoC), whereas the M1 null lens is beyond the CoC. One relatively new metrology tool is the laser tracker, which is relied upon to measure the alignment and spacings. A separate laser tracker system will be used to measure both surfaces during loose abrasive grinding and initial polishing.

Spectroscopic determination of thermal impulse in sub-second heating events using lanthanide-doped oxide precursors and phenomenological modeling

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

Anderson, Benjamin R., E-mail: branderson@wsu.edu; Gunawidjaja, Ray; Price, Patrick

2016-08-28

Using a mixture of crystalline-Ho:ZrO{sub 2}, precursor-Dy:Y{sub 2}O{sub 3}, and precursor-Eu:ZrO{sub 2} nanoparticles we develop thermal impulse sensors capable of measuring equivalent isothermal temperatures and durations during a heating event, with response times of <100 ms, and a temperature range of at least 673 K to 1173 K. In order to determine the temperature and duration from the sensors after the heating event we measure the sensors' fluorescence spectrum, which is then compared with lab based calibration data. By using two precursor materials with different reaction kinetics we are able to extract both temperature and duration. Based on blind sample testing we findmore » that the sensors and calculation method are accurate for measuring temperature and duration, but currently suffer a lack of precision due to difficulties in producing homogeneously heated samples.« less

Final acceptance testing of the LSST monolithic primary/tertiary mirror

NASA Astrophysics Data System (ADS)

Tuell, Michael T.; Burge, James H.; Cuerden, Brian; Gressler, William; Martin, Hubert M.; West, Steven C.; Zhao, Chunyu

2014-07-01

The Large Synoptic Survey Telescope (LSST) is a three-mirror wide-field survey telescope with the primary and tertiary mirrors on one monolithic substrate1. This substrate is made of Ohara E6 borosilicate glass in a honeycomb sandwich, spin cast at the Steward Observatory Mirror Lab at The University of Arizona2. Each surface is aspheric, with the specification in terms of conic constant error, maximum active bending forces and finally a structure function specification on the residual errors3. There are high-order deformation terms, but with no tolerance, any error is considered as a surface error and is included in the structure function. The radii of curvature are very different, requiring two independent test stations, each with instantaneous phase-shifting interferometers with null correctors. The primary null corrector is a standard two-element Offner null lens. The tertiary null corrector is a phase-etched computer-generated hologram (CGH). This paper details the two optical systems and their tolerances, showing that the uncertainty in measuring the figure is a small fraction of the structure function specification. Additional metrology includes the radii of curvature, optical axis locations, and relative surface tilts. The methods for measuring these will also be described along with their tolerances.

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.

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.

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

Morphology and Magnetic Properties of Ferriferous Two-Phase Sodium Borosilicate Glasses

PubMed Central

Naberezhnov, Alexander; Porechnaya, Nadezda; Nizhankovskii, Viktor; Filimonov, Alexey; Nacke, Bernard

2014-01-01

This contribution is devoted to the study of morphology and magnetic properties of sodium borosilicate glasses with different concentrations (15, 20, and 25 wt.%) of α-Fe2O3 in an initial furnace charge. These glasses were prepared by a melt-quenching method. For all glasses a coexistence of drop-like and two-phase interpenetrative structures is observed. The most part of a drop structure is formed by self-assembling iron oxides particles. All types of glasses demonstrate the magnetic properties and can be used for preparation of porous magnetic matrices with nanometer through dendrite channel structure. PMID:25162045

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.

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.

Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides

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

Jensen, Mark P.; Chiarizia, Renato; Ulicki, Joseph S.

2015-02-27

The sterically constrained, macrocyclic, aqueous soluble ligand N,N'-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2BP18C6) was investigated for separating americium from curium and all the lanthanides by solvent extraction. Pairing H2BP18C6, which favors complexation of larger f-element cations, with acidic organophosphorus extractants that favor extraction of smaller f-element cations, such as bis-(2-ethylhexyl)phosphoric acid (HDEHP) or (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]), created solvent extraction systems with good Cm/Am selectivity, excellent trans-lanthanide selectivity (Kex,Lu/Kex,La = 108), but poor selectivity for Am against the lightest lanthanides. However, using an organic phase containing both a neutral extractant, N,N,N’,N’-tetra(2-ethylhexyl)diglycolamide (TEHDGA), and HEH[EHP] enabled rejection of the lightest lanthanides during loading ofmore » the organic phase from aqueous nitric acid, eliminating their interference in the americium stripping stages. In addition, although it is a macrocyclic ligand, H2BP18C6 does not significantly impede the mass transfer kinetics of the HDEHP solvent extraction system« less

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.

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.

Transfer of tracers and pesticides in lab scale wetland systems: the role of vegetation

NASA Astrophysics Data System (ADS)

Durst, R.; Imfeld, G.; Lange, J.

2012-04-01

Surface wetlands can collect contaminated runoff from urban or agricultural catchments and have intrinsic physical, chemical and biological retention and removal processes useful for mitigating contaminants, including pesticides, and thus limiting the contamination of aquatic ecosystems. Yet little is known about the transfer of pesticides between wetlands collecting pesticides runoff and groundwater, and the subsequent threat of groundwater contamination. In particular, the influence of wetland vegetation and related processes during pesticide transfer is largely unknown. Here we evaluate the transfer of the widely used herbicide Isoproturon (IPU) and the fungicide Metalaxyl (MTX) with that of Uranine (UR) and Sulphorhodamine (SRB) in a vegetated and a non-vegetated lab-scale wetland. UR and SRB had successfully served as a reference for pesticides in surface wetlands. We filled two 65 cm long and 15 cm diameter borosilicate columns with sediment cores from a wetland, one without and one with vegetation (Phragmites australis, Cav.). When a constant flow-through rate of 0.33 ml min-1 was reached, tracers and pesticides were injected simultaneously and continuously. The hydrological mass balance and tracer concentrations were measured daily at the outlet of the lab-scale wetland. Samples for pesticides and hydrochemical analyses were collected biweekly. The lab-scale wetlands were covered to limit evaporation and light decay of injected compounds. The reactive transfer of compounds in the vegetated and non-vegetated lab-scale wetland was compared based on breakthrough curves (BTC's) and model parameters of the lumped parameter model CXTFIT. The hydrologic balance revealed that the intensity of transpiration and hence plant activity in the lab-scale wetlands progressively decreased and then apparently ceased after about eight days following continuous pesticide injection. In this first phase, no significant difference in the hydrologic balances could be observed between the vegetated and the non-vegetated column. In a second phase, vegetation transpiration progressively increased, as inferred from lower volumes of effluent water in the vegetated system. Overall, the behavior of pesticides and tracers, as inferred from the BTC's, were similar. This suggests that fluorescent tracers may be used as a reference for pesticides when studying the surface-groundwater interface. Both pesticides and tracers showed larger recovery rates (UR: 81.7 to 78.6%; SRB: 65.6 to 55.9%; IPU: 76.6 to 79.7%; MTX: 39.5 to 37.5%) and lower retention in the vegetated system. We attribute this finding to preferential flow paths along plant roots. Overall, our study suggests that wetland vegetation and rhizosheric processes may have a dual role in wetland pollutant transfer: while wetland vegetation may enhance retention and bio-degradation of contaminants in surface water, it may also generate preferential flow paths and hence facilitate pollutant transfer to groundwater. Acknowledgment: This study has been funded by the European Union (INTERREG) in the framework of the PhytoRet Project.

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

Emission analysis of Tb3+ -and Sm3+ -ion-doped (Li2 O/Na2 O/K2 O) and (Li2 O + Na2 O/Li2 O + K2 O/K2 O + Na2 O)-modified borosilicate glasses.

PubMed

Naveen Kumar Reddy, B; Sailaja, S; Thyagarajan, K; Jho, Young Dahl; Sudhakar Reddy, B

2018-05-01

Four series of borosilicate glasses modified by alkali oxides and doped with Tb 3+ and Sm 3+ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B 2 O 3 + 10SiO 2 + 5MgO + R + 0.5(Tb 2 O 3 /Sm 2 O 3 ) [where R = 10(Li 2 O /Na 2 O/K 2 O) for series A and C, and R = 5(Li 2 O + Na 2 O/Li 2 O + K 2 O/K 2 O + Na 2 O) for series B and D]. The X-ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the 5 D 4 → 7 F 5 (543 nm) transition of the Tb 3+ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm 3+ ions with the series C and D glasses showed strong reddish-orange emission at 600 nm ( 4 G 5/2 → 6 H 7/2 ) with an excitation wavelength λ exci = 404 nm ( 6 H 5/2 → 4 F 7/2 ). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb 3+ and Sm 3+ ions was studied to optimize the potential alkali-oxide-modified borosilicate glass. Copyright © 2017 John Wiley & Sons, Ltd.

A space imaging concept based on a 4m structured spun-cast borosilicate monolithic primary mirror

NASA Astrophysics Data System (ADS)

West, S. C.; Bailey, S. H.; Bauman, S.; Cuerden, B.; Granger, Z.; Olbert, B. H.

2010-07-01

Lockheed Martin Corporation (LMC) tasked The University of Arizona Steward Observatory (UASO) to conduct an engineering study to examine the feasibility of creating a 4m space telescope based on mature borosilicate technology developed at the UASO for ground-based telescopes. UASO has completed this study and concluded that existing launch vehicles can deliver a 4m monolithic telescope system to a 500 km circular orbit and provide reliable imagery at NIIRS 7-8. An analysis of such an imager based on a lightweight, high-performance, structured 4m primary mirror cast from borosilicate glass is described. The relatively high CTE of this glass is used to advantage by maintaining mirror shape quality with a thermal figuring method. Placed in a 290 K thermal shroud (similar to the Hubble Space Telescope), the orbit averaged figure surface error is 6nm rms when earth-looking. Space-looking optical performance shows that a similar thermal conditioning scheme combined with a 270 K shroud achieves primary mirror distortion of 10 nm rms surface. Analysis shows that a 3-point bipod mount will provide launch survivability with ample margin. The primary mirror naturally maintains its shape at 1g allowing excellent end-to-end pre-launch testing with e.g. the LOTIS 6.5m Collimator. The telescope includes simple systems to measure and correct mirror shape and alignment errors incorporating technologies already proven on the LOTIS Collimator. We have sketched a notional earth-looking 4m telescope concept combined with a wide field TMA concept into a DELTA IV or ATLAS 552 EELV fairing. We have combined an initial analysis of launch and space performance of a special light-weighted honeycomb borosilicate mirror (areal density 95 kg/m2) with public domain information on the existing launch vehicles.

Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions.

PubMed

Huang, Wenhai; Day, Delbert E; Kittiratanapiboon, Kanisa; Rahaman, Mohamed N

2006-07-01

Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37 degrees Celsius. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO(2) with B(2)O(3). Higher B(2)O(3) content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO(2) in a Na-depleted core. The concentration of Na(+) in the phosphate solution increased with reaction time whereas the PO(4) (3-) concentration decreased, both reaching final limiting values at a rate that increased with the B(2)O(3) content of the glass. However, the Ca(2+) concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K(2)HPO(4) and K(2)CO(3) produced a carbonate-substituted HA but the presence of the K(2)CO(3) had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process.

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

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.

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

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

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.

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.

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.

Structural investigations of bismuth lead borosilicate glasses under the influence of gamma irradiation through ultrasonic studies

NASA Astrophysics Data System (ADS)

Bootjomchai, Cherdsak; Laopaiboon, Jintana; Laopaiboon, Raewat

2012-04-01

The ultrasonic velocity measurements for different compositions of irradiated bismuth lead borosilicate glasses xBi2O3-(50-x)PbO-20B2O3-30SiO2 (x=2, 4, 6, 8, and 10 mol.%) were performed at room temperature using pulse-echo technique. Densities of glass samples were measured by Archimedes' principle using n-hexane as the immersion liquid. The results from the studies show that ultrasonic velocity, elastic moduli, Poisson's ratio, microhardness, and the Debye temperature increase with increasing bismuth oxide content and increasing gamma-radiation dose (3-12 Gy).

Interaction of water vapor with silicate glass surfaces: Mass-spectrometric investigations

NASA Astrophysics Data System (ADS)

Kudriavtsev, Yu.; Asomoza-Palacio, R.; Manzanilla-Naim, L.

2017-05-01

The secondary ion mass-spectroscopy technique was used to study the results of hydration of borosilicate, aluminosilicate, and soda-lime silicate glasses in 1H2 18O water vapor containing 97% of the isotope 18O. It is shown that hydration of the surface of the soda-lime silicate glass occurs as a result of the ion-exchange reaction with alkali metals. In the case of borosilicate and aluminosilicate glasses, water molecules decompose on the glass surface, with the observed formation of hydrogenated layer in the glass being the result of a solid-state chemical reaction—presumably, with the formation of hydroxides from aluminum and boron oxides.

The thermal degradation of 5 alpha (H)-cholestane during closed-system pyrolysis

NASA Astrophysics Data System (ADS)

Abbott, Geoffrey D.; Bennett, Barry; Stuart Fetch, G.

1995-06-01

Involatile hydrocarbons were identified following the heating of 5α(H)-cholestane in water with reaction vessel walls composed of 316 grade stainless steel and borosilicate glass. These analyses were compared with the hydrocarbon product compositions from closed-system pyrolysis experiments with no added water. Unsaturated hydrocarbons dominate their saturated counterparts following hydrous pyrolysis in both stainless steel-316 and borosilicate glass. In the absence of added water the converse is true in that saturated components dominate the hydrocarbon mixture. Backbone rearrangement in the steroid nucleus leading to spirosterene formation was only observed under aqueous conditions in both borosilicate glass and stainless steel-316 vessels. These comparisons demonstrate that water, as opposed to reaction vessel surface catalytic effects, plays a central role in mediating hydrocarbon degradation during closed-system hydrous pyrolysis. 5α(H)-cholestane degradation under aqueous conditions is a complex composite of dissociative and rearrangement processes. These include (I) carbon-carbon bond cleavage in the sidechains as well as the ring system, (2) dehydrogenation, and (3) backbone rearrangement. These laboratory experiments provide a product description of the involatile hydrocarbons which will be the basis for a mechanistic study of 5α(H)-cholestane degradation in hot water.

A new potential for radiation studies of borosilicate glass

NASA Astrophysics Data System (ADS)

Alharbi, Amal F.; Jolley, Kenny; Smith, Roger; Archer, Andrew J.; Christie, Jamieson K.

2017-02-01

Borosilicate glass containing 70 mol% SiO2 and 30 mol% B2O3 is investigated theoretically using fixed charge potentials. An existing potential parameterisation for borosilicate glass is found to give good agreement for the bond angle and bond length distributions compared to experimental values but the optimal density is 30% higher than experiment. Therefore the potential parameters are refitted to give an optimal density of 2.1 g/cm3, in line with experiment. To determine the optimal density, a series of random initial structures are quenched at a rate of 5 × 1012 K/s using constant volume molecular dynamics. An average of 10 such quenches is carried out for each fixed volume. For each quenched structure, the bond angles, bond lengths, mechanical properties and melting points are determined. The new parameterisation is found to give the density, bond angles, bond lengths and Young's modulus comparable with experimental data, however, the melting points and Poisson's ratio are higher than the reported experimental values. The displacement energy thresholds are computed to be similar to those determined with the earlier parameterisation, which is lower than those for ionic crystalline materials.

High-impact resistance optical sensor windows

NASA Astrophysics Data System (ADS)

Askinazi, Joel; Ceccorulli, Mark L.; Goldman, Lee

2011-06-01

Recent field experience with optical sensor windows on both ground and airborne platforms has shown a significant increase in window fracturing from foreign object debris (FOD) impacts and as a by-product of asymmetrical warfare. Common optical sensor window materials such as borosilicate glass do not typically have high impact resistance. Emerging advanced optical window materials such as aluminum oxynitride offer the potential for a significant improvement in FOD impact resistance due to their superior surface hardness, fracture toughness and strength properties. To confirm the potential impact resistance improvement achievable with these emerging materials, Goodrich ISR Systems in collaboration with Surmet Corporation undertook a set of comparative FOD impact tests of optical sensor windows made from borosilicate glass and from aluminum oxynitride. It was demonstrated that the aluminum oxynitride windows could withstand up to three times the FOD impact velocity (as compared with borosilicate glass) before fracture would occur. These highly encouraging test results confirm the utility of this new highly viable window solution for use on new ground and airborne window multispectral applications as well as a retrofit to current production windows. We believe that this solution can go a long way to significantly reducing the frequency and life cycle cost of window replacement.

Estimating rock and slag wool fiber dissolution rate from composition.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-12-01

A method was tested for calculating the dissolution rate constant in the lung for a wide variety of synthetic vitreous silicate fibers from the oxide composition in weight percent. It is based upon expressing the logarithm of the dissolution rate as a linear function of the composition and using a different set of coefficients for different types of fibers. The method was applied to 29 fiber compositions including rock and slag fibers as well as refractory ceramic and special-purpose, thin E-glass fibers and borosilicate glass fibers for which in vivo measurements have been carried out. These fibers had dissolution rates that ranged over a factor of about 400, and the calculated dissolution rates agreed with the in vivo values typically within a factor of 4. The method presented here is similar to one developed previously for borosilicate glass fibers that was accurate to a factor of 1.25. The present coefficients work over a much broader range of composition than the borosilicate ones but with less accuracy. The dissolution rate constant of a fiber may be used to estimate whether disease would occur in animal inhalation or intraperitoneal injection studies of that fiber.

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.

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.

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

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

1962-08-14

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

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.

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

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.

A Post-synthetic Modification of II–VI Nanoparticles to Create Tb3+ and Eu3+ Luminophores

PubMed Central

Mukherjee, Prasun; Sloan, Robin F.; Shade, Chad M.; Waldeck, David H.; Petoud, Stéphane

2013-01-01

We describe a novel method for creating luminescent lanthanide-containing nanoparticles in which the lanthanide cations are sensitized by the semiconductor nanoparticle’s electronic excitation. In contrast to previous strategies, this new approach creates such materials by addition of external salt to a solution of fully formed nanoparticles. We demonstrate this post-synthetic modification for the lanthanide luminescence sensitization of two visible emitting lanthanides (Ln), Tb3+ and Eu3+ ions, through ZnS nanoparticles in which the cations were added post-synthetically as external Ln(NO3)3·xH2O salt to solutions of ZnS nanoparticles. The post-synthetically treated ZnS nanoparticle systems display Tb3+ and Eu3+ luminescence intensities that are comparable to those of doped Zn(Ln)S nanoparticles, which we reported previously (J. Phys. Chem. A, 2011, 115, 4031–4041). A comparison with the synthetically doped systems is used to contrast the spatial distribution of the lanthanide ions, bulk versus surface localized. The post-synthetic strategy described in this work is fundamentally different from the synthetic incorporation (doping) approach and offers a rapid and less synthetically demanding protocol for Tb3+:ZnS and Eu3+:ZnS luminophores, thereby facilitating their use in a broad range of applications. PMID:23997842

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.

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

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

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.

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.

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.

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.

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.

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

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.

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.

Actinide and lanthanide separation process (ALSEP)

DOEpatents

Guelis, Artem V.

2013-01-15

The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

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.

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

Method and Apparatus for Detecting and Quantifying Bacterial Spores on a Surface

NASA Technical Reports Server (NTRS)

Ponce, Adrian (Inventor)

2017-01-01

A method and an apparatus for detecting and quantifying bacterial spores on a surface. In accordance with the method: a matrix including lanthanide ions is provided on the surface containing the bacterial spores; functionalized aromatic molecules are released from the bacterial spores on the surface; a complex of the lanthanide ion and the aromatic molecule is formed on the surface; the complex of the lanthanide ion and the aromatic molecule is excited to generate a characteristic luminescence of the complex on the surface; and the bacterial spores exhibiting the luminescence of the complex on the surface are detected and quantified.

Method and apparatus for detecting and quantifying bacterial spores on a surface

NASA Technical Reports Server (NTRS)

Ponce, Adrian (Inventor)

2009-01-01

A method and an apparatus for detecting and quantifying bacterial spores on a surface. In accordance with the method: a matrix including lanthanide ions is provided on the surface containing the bacterial spores; functionalized aromatic molecules are released from the bacterial spores on the surface; a complex of the lanthanide ion and the aromatic molecule is formed on the surface; the complex of the lanthanide ion and the aromatic molecule is excited to generate a characteristic luminescence of the complex on the surface; and the bacterial spores exhibiting the luminescence of the complex on the surface are detected and quantified.

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.

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.

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.

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.

Manufacture of large glass honeycomb mirrors. [for astronomical telescopes

NASA Technical Reports Server (NTRS)

Angel, J. R. P.; Hill, J. M.

1982-01-01

The problem of making very large glass mirrors for astronomical telescopes is examined, and the advantages of honeycomb mirrors made of borosilicate glass are discussed. Thermal gradients in the glass that degrade the figure of thick borosilicate mirrors during use can be largely eliminated in a honeycomb structure by internal ventilation (in air) or careful control of the radiation environment (in space). It is expected that ground-based telescopes with honeycomb mirrors will give better images than those with solid mirrors. Materials, techniques, and the experience that has been gained making trial mirrors and test castings as part of a program to develop 8-10-m-diameter lightweight mirrors are discussed.

Investigating the effect of V2O5 addition on sodium barium borosilicate glasses

NASA Astrophysics Data System (ADS)

Halder, Rumu; Sengupta, Pranesh; Sudarsan, V.; Kaushik, C. P.; Dey, G. K.

2016-05-01

V2O5 doped sodium barium borosilicate glasses were characterized by photoluminescence spectroscopy and electron probe microanalyzer (EPMA). The glass remains homogeneous for lower concentration of V2O5 but a phase separation is observed when V2O5 doping is increased beyond 5 mol%. Detailed microanalysis reveals that the phase separated glass consists of a phase containing V, Ba and Si and a separate Si rich phase within the glass matrix. The luminescence study demonstrated that at low concentration the vanadium mainly interacts with the structural units of B/Si while at higher concentrations, V-O-V/ V-O- Na+/Ba2+ linkages are formed.

Color centers of a borosilicate glass induced by 10 MeV proton, 1.85 MeV electron and 60Co-γ ray

NASA Astrophysics Data System (ADS)

Du, Jishi; Wu, Jiehua; Zhao, Lili; Song, Lixin

2013-05-01

Optical absorption spectra, electron paramagnetic resonance (EPR) spectra, Raman spectra of a borosilicate glass after irradiation by 10 MeV proton, 1.85 MeV electron and 60Co-γ ray were studied. The process of irradiation inducing color centers in the glass was discussed. The band gap of the glass before and after 60Co-γ ray irradiation was studied using Mott and Davis's theory, and it was found that calculated change of the band gap introduced a paradox, because Mott and Davis's theory on the band gap cannot be adopted in the study on the irradiated glass.

Electron irradiation induced phase separation in a sodium borosilicate glass

NASA Astrophysics Data System (ADS)

Sun, K.; Wang, L. M.; Ewing, R. C.; Weber, W. J.

2004-06-01

Electron irradiation induced phase separation in a sodium borosilicate glass was studied in situ by analytical electron microscopy. Distinctly separate phases that are rich in boron and silicon formed at electron doses higher than 4.0 × 10 11 Gy during irradiation. The separated phases are still in amorphous states even at a much high dose (2.1 × 10 12 Gy). It indicates that most silicon atoms remain tetrahedrally coordinated in the glass during the entire irradiation period, except some possible reduction to amorphous silicon. The particulate B-rich phase that formed at high dose was identified as amorphous boron that may contain some oxygen. Both ballistic and ionization processes may contribute to the phase separation.

Rare earth element concentrations in dissolved and acid available particulate forms for eastern UK rivers

NASA Astrophysics Data System (ADS)

Neal, C.

2007-01-01

Variations in concentration of yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm) and gadolinium (Gd) among rivers of eastern England and the border with Scotland are described in relation to the dissolved (<0.45 µM) fraction and acid-available particulate (AAP) fractions. The rivers cover a range of rural, agricultural and urban/industrial environments. Yttrium and the lanthanides show significant levels of both dissolved and acid-available particulate forms (typically about 40% in the dissolved form). For the dissolved phase, Y and the lanthanides are linearly correlated with each other and with iron: most of this dissolved component may be in a micro-particulate/colloidal form. The Y and lanthanide relationships show marked scatter and there are anomalously high La concentrations at times for the rivers Great Ouse, Thames and Wear that are probably linked to pollutant sources. For the Ouse, and especially for one of its tributaries, the Swale, relatively high Sm concentrations are probably associated with mineralisation within the catchment and contamination of the associated flood plain. For the AAP components, there are strong linear relationships with Y and the lanthanides across all the rivers. There is also a strong link between these AAP associated REE and AAP iron, although the scatter is greater and the industrial rivers have a lower lanthanide to iron ratio, probably due to iron-rich contaminants.

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

Novel Flourescent Sensors for the Detection of Organic Molecules in Extraterrestrial Samples

NASA Astrophysics Data System (ADS)

Adkin, Roy C.; Bruce, James I.; Pearson, Victoria K.

2015-04-01

Organic compounds in extraterrestrial samples have mostly been elucidated by destructive analytical techniques therefore information regarding spatial relationships between minerals and organic species is lost. Minerals form under specific chemical and physical conditions so organic compounds associated with these minerals are likely to have formed under the same conditions. It is therefore possible to infer in which cosmological provinces their chemical evolution took place. We will describe progress towards developing fluorescent sensors that may resolve spatial discrimination. Lanthanide elements such as europium and terbium produce well defined line-like, high intensity and long lived fluorescent emissions. Interactions with organic molecules may alter the luminescent emission characteristics. The lanthanide atom needs to be rendered chemically inert but must remain susceptible to these organic molecule interactions. An organic ligand must be employed to attain this. DOTA (1,4,7,10-tetraazacyclododecanetetracetic acid) was chosen as a plausible organic ligand because its structure, a tetra-substituted cyclen ring, and ability to chelate are well characterized. It is also commercially available. Fluorescent lanthanide-DOTA complexes are used in many biological and analytical imaging applications so it is logical to investigate their applicability to fluorimetric analysis of extraterrestrial organics. Lanthanide-DOTA complexes are very stable because the lanthanide metal atom is enveloped within the DOTA structure. Experimental procedures were designed to investigate lanthanide/analyte interactions and their effect upon fluorescent emissions. A range of compounds were chosen giving a good representation of the organics identified in extraterrestrial samples and whether they may to interact with the lanthanide metal ion. An Europium-DOTA baseline fluorescent spectrum was obtained and compared against Europium-DOTA/analyte mixtures of a range of concentrations resembling those present in extraterrestrial samples. Upon collation and analysis of results a much reduced set of analytes were chosen for experimentation with Terbium-DOTA. Results showed no change in fluorescent intensity or emission spectrum for any of the analytes at the concentrations found in extraterrestrial samples (μM to nM). This could be due to no interaction at any concentration of analyte or there is an intrinsic limit of detection. Experiments were carried out at equimolar concentration with fewer analytes. It was found that here was an increase in fluorescent intensity for some analytes and decrease for others (e.g. adenine and ornithine, respectively). There was no discernible trend in behaviour according to analyte structure or how they might interact as a result. Attention has now turned to the tris-substituted cyclen ring, DO3A, which could afford improved scope for interaction. DOTA is an unsuitable ligand to use for the sensor. Experimentation has shown that neither lanthanide-DOTA complexes exhibited a change in fluorescent spectrum; the ligand requires modification not the choice of lanthanide. We will present results from the development and preliminary testing of the DO3A sensor.

RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

EPA Science Inventory

Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

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.

Pyrolytic carbon-coated nuclear fuel

DOEpatents

Lindemer, Terrence B.; Long, Jr., Ernest L.; Beatty, Ronald L.

1978-01-01

An improved nuclear fuel kernel having at least one pyrolytic carbon coating and a silicon carbon layer is provided in which extensive interaction of fission product lanthanides with the silicon carbon layer is avoided by providing sufficient UO.sub.2 to maintain the lanthanides as oxides during in-reactor use of said fuel.

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 series of water-soluble acidic 1,3-propanediaminetetraacetato lanthanides [Ln(1,3-H{sub 3}pdta)(H{sub 2}O){sub 5}]n·2Cl{sub n}·3nH{sub 2}O have been converted to their 2D and 3D lanthanides, which are active for the catalytic conversion of ester hydrolysis. - Highlights: • Novel acidic propanediaminetetraacetato lanthanides. • Water-soluble 1D coordination polymers. • Acidic conditions are suitable for the isolations of lanthanide complexes in different structures. • 1 and 5 show good catalytic activity to ester hydrolysis. • Europium coordination polymers 13 and 20 give visible fluorescence.« less

Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form. [Yucca Mountain Project

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

Smith, D.K.

1990-01-01

Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300{degrees}C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surfacemore » reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 {degrees}C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs.« less

Glass viscosity calculation based on a global statistical modelling approach

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

Fluegel, Alex

2007-02-01

A global statistical glass viscosity model was developed for predicting the complete viscosity curve, based on more than 2200 composition-property data of silicate glasses from the scientific literature, including soda-lime-silica container and float glasses, TV panel glasses, borosilicate fiber wool and E type glasses, low expansion borosilicate glasses, glasses for nuclear waste vitrification, lead crystal glasses, binary alkali silicates, and various further compositions from over half a century. It is shown that within a measurement series from a specific laboratory the reported viscosity values are often over-estimated at higher temperatures due to alkali and boron oxide evaporation during the measurementmore » and glass preparation, including data by Lakatos et al. (1972) and the recently published High temperature glass melt property database for process modeling by Seward et al. (2005). Similarly, in the glass transition range many experimental data of borosilicate glasses are reported too high due to phase separation effects. The developed global model corrects those errors. The model standard error was 9-17°C, with R^2 = 0.985-0.989. The prediction 95% confidence interval for glass in mass production largely depends on the glass composition of interest, the composition uncertainty, and the viscosity level. New insights in the mixed-alkali effect are provided.« less

Optical and structural investigation on sodium borosilicate glasses doped with Cr2O3

NASA Astrophysics Data System (ADS)

Ebrahimi, E.; Rezvani, M.

2018-02-01

In this work, Sodium borosilicate glasses with chemical composition of 60% SiO2-20% B2O3-20%Na2O doped with different contents of Cr2O3 were prepared by melting-quenching method. Physical, structural and optical properties of glasses were investigated by studying density and molar volume, Fourier Transform Infrared (FT-IR) Spectra and UV-visible absorption spectroscopy. The results showed an increase in density of glasses with the increase of Cr2O3 that can be due to addition of oxide with high molar mass. The optical absorption spectra of un-doped glass reveals UV absorption due to trace iron impurities with no visible band however Cr2O3 doped glasses shows absorption in visible range that are characteristic. Increasing of Cr3 + ions in the glassy microstructure of samples provides a semiconducting character to Sodium borosilicate glass by reducing the direct and indirect optical band gaps of glass samples from 3.79 to 2.59 (ev) and 3.36 to 2.09 (ev), respectively. These changes could be attributed to the role of Cr3 + ions as the network former which asserts improvement of semiconducting behavior in presence of Cr2O3.

Optical and structural investigation on sodium borosilicate glasses doped with Cr2O3.

PubMed

Ebrahimi, E; Rezvani, M

2018-02-05

In this work, Sodium borosilicate glasses with chemical composition of 60% SiO 2 -20% B 2 O 3 -20%Na 2 O doped with different contents of Cr 2 O 3 were prepared by melting-quenching method. Physical, structural and optical properties of glasses were investigated by studying density and molar volume, Fourier Transform Infrared (FT-IR) Spectra and UV-visible absorption spectroscopy. The results showed an increase in density of glasses with the increase of Cr 2 O 3 that can be due to addition of oxide with high molar mass. The optical absorption spectra of un-doped glass reveals UV absorption due to trace iron impurities with no visible band however Cr 2 O 3 doped glasses shows absorption in visible range that are characteristic. Increasing of Cr 3+ ions in the glassy microstructure of samples provides a semiconducting character to Sodium borosilicate glass by reducing the direct and indirect optical band gaps of glass samples from 3.79 to 2.59 (ev) and 3.36 to 2.09 (ev), respectively. These changes could be attributed to the role of Cr 3+ ions as the network former which asserts improvement of semiconducting behavior in presence of Cr 2 O 3 . Copyright © 2017. Published by Elsevier B.V.

Rhenium solubility in borosilicate nuclear waste glass: implications for the processing and immobilization of technetium-99.

PubMed

McCloy, John S; Riley, Brian J; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J; Rodriguez, Carmen P; Hrma, Pavel; Kim, Dong-Sang; Lukens, Wayne W; Kruger, Albert A

2012-11-20

The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.

Large Binocular Telescope project

NASA Astrophysics Data System (ADS)

Hill, John M.; Salinari, Piero

2003-02-01

The Large Binocular Telescope (LBT) Project is a collaboration between institutions in Arizona, Germany, Italy, and Ohio. The first of two 8.4-meter borosilicate honeycomb primary mirrors for LBT is being polished at the Steward Observatory Mirror Lab this year. The second of the two 8.4-meter mirror blanks waits its turn in the polishing queue. The baseline optical configuration of LBT includes adaptive infrared secondaries of a Gregorian design. The F/15 secondaries are undersized to provide a low thermal background focal plane which is unvignetted over a 4-arcminute diameter field-of-view. These adaptive secondary mirrors with 672 voice-coil actuators are now in the early stages of fabrication. The interferometric focus combining the light from the two 8.4-meter primaries will reimage the two folded Gregorian focal planes to three central locations for phased array imaging. The telescope elevation structure accommodates swing arm spiders which allow rapid interchange of the various secondary and tertiary mirrors as well as prime focus cameras. The telescope structure accommodates installation of a vacuum bell jar for aluminizing the primary mirrors in-situ on the telescope. The telescope structure was fabricated and pre-assembled in Italy by Ansaldo-Camozzi in Milan. The structure was disassembled, packed and shipped to Arizona. The enclosure was built on Mt. Graham and is ready for telescope installation.

Nanoscale Ex-Situ Thermal Impulse Sensors for Structural Fire Forensics.

PubMed

Anderson, Benjamin R; Gese, Natalie; Gunawidjaja, Ray; Eilers, Hergen

2017-01-01

We develop nanoscale ex situ thermal impulse (i.e., the temperature and duration of a heating event) sensors for structural fire forensics using a mixture of two lanthanide-doped oxide precursors (precursor Eu:ZrO 2 and precursor Dy:Y 2 O 3 ) that undergo irreversible phase changes when heated. These changes are probed using photoluminescence (PL) spectroscopy with the PL spectra being dependent on the thermal impulse (TI) experienced by the sensors. By correlating the PL spectra to different in-lab TIs, we are able to produce a spectroscopic calibration for our sensors. This calibration allows us to determine an unknown TI of a heating event using only the PL spectrum of the heated TI sensors. In this study, we report on the calibration of these sensors for isothermal heating durations up to 600 s and isothermal temperatures up to 1273 K. Using this calibration, we also demonstrate their ability to determine an unknown TI and demonstrate their functionality when dispersed into paint, which is heated in the presence of drywall.

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.

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.

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).

Comparing the 2,2'-Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium

DOE PAGES

Cross, Justin N.; Macor, Joseph A.; Bertke, Jeffery A.; ...

2016-09-15

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear-fuel cycles. Here in this paper, we describe the preparation of (NBu 4)Am[S 2P( tBu 2C 12H 6)] 4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., Nd III) and an isoelectronic one (Eu III). The results include the first measurement of an Am-S bond length, with a mean value of 2.921(9) Å, by single-crystal X-ray diffraction. Comparison with the Eu III and Nd III complexes revealed subtle electronic differences between the complexes of Am III and the lanthanides.

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.

Electrochemical corrosion of a noble metal-bearing alloy-oxide composite

DOE PAGES

Chen, X.; Ebert, W. L.; Indacochea, J. E.

2017-04-27

The effects of added Ru and Pd on the microstructure and electrochemical behaviour of a composite material made by melting those metals with AISI 410 stainless steel, Zr, Mo, and lanthanide oxides were assessed using electrochemical and microscopic methods Furthermore, the lanthanide oxides reacted with Zr to form durable lanthanide zirconates and Mo alloyed with steel to form FeMoCr intermetallics. The noble metals alloyed with the steel to provide solid solution strengthening and inhibit carbide/nitride formation. In a passive film formed during electrochemical tests in acidic NaCl solution, but became less effective as corrosion progressed and regions over the intermetallicsmore » eventually failed.« less

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

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.

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.

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.

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.

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

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.

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.

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].

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

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 concentrated more metal than was made available by the lake water extraction of soil and less metal than was made available by the nitric acid extraction of soil.« less

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.

Synthesis and Characterization of Europium(III) and Terbium(III) Complexes: An Advanced Undergraduate Inorganic Chemistry Experiment

ERIC Educational Resources Information Center

Swavey, Shawn

2010-01-01

Undergraduate laboratories rarely involve lanthanide coordination chemistry. This is unfortunate in light of the ease with which many of these complexes are made and the interesting and instructive photophysical properties they entail. The forbidden nature of the 4f transitions associated with the lanthanides is overcome by incorporation of…

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.

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.

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.

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.

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.

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

Wetting of single crystal mullite by borosilicate and yttrium-aluminosilicate glasses and wetting phenomena of steels containing aluminum and titanium

NASA Astrophysics Data System (ADS)

Eldred, Benjamin Todd

This dissertation consists of two major sections. The first section concerns the wetting of single crystal mullite by borosilicate and yttrium-aluminosilicate glasses. The borosilicate glass showed poor wetting and interacted only moderately with the substrate. The yttrium-aluminosilicate glass interacted strongly with mullite and showed very good wetting. Balanced chemical equations between each glass and mullite were derived from EDS data. Wetting was found to be dependent on the crystallographic orientation of the substrate, in agreement with previous studies of the surface energy of mullite. The second section concerns the wetting phenomena of steels containing aluminum and titanium. A modified sessile drop technique was used to investigate the wetting of steels containing aluminum and/or titanium as a function of furnace atmosphere. It was found that the steel chemistry and furnace atmosphere had little effect on wetting except in the case of a particular ultra-low carbon steel containing both aluminum and titanium. This steel was found to show significantly lower contact angles than any other steel tested when it was in an atmosphere of pure hydrogen. As nitrogen was added to the atmosphere, the contact angle increased monotonically and irreversibly. The interaction between aluminum, titanium, and nitrogen is explained in terms of first-order interaction coefficients available in thermodynamic literature.

An Experimental Investigation of the Long-Term Stability of Triple-Point-of-Water Cells

NASA Astrophysics Data System (ADS)

Hill, K. D.

2014-04-01

Contamination of triple-point-of-water (TPW) cells by the chemical components of the borosilicate glass that contains the water is now widely recognized as the principal contributor to long-term drift of the cell temperature. To add to the available experimental data, a comparison of 24 TPW cells of various ages (from 10 years to 59 years), manufacturers (NRC, Jarrett, Isotech), and materials (borosilicate glass and fused quartz) was undertaken in 2013. Twelve cells from this group were compared to one another in 1997. By comparing the current inter-cell temperature differences to those determined 16 years earlier, it was found that some cells have remained stable, others have become colder (as might be expected from ongoing dissolution of the glass), and one or two show an apparent increase in temperature that seems anomalous. Also included among the 24 cells are five cells of borosilicate glass and five of fused quartz that were purchased 10 years ago. By comparing the relative temperature differences among this group of borosilcate and fused-quartz-encapsulated cells to the values obtained when they were last compared 6 years ago, it was found that the average temperature of the borosilcate group of cells decreases by , in reasonable agreement with an average drift of suggested 12 years ago. It was concluded that fused quartz is the superior container for TPW cells.

Wettability measurement under high P-T conditions using X-ray imaging with application to the brine-supercritical CO2 system

NASA Astrophysics Data System (ADS)

Chaudhary, Kuldeep; Guiltinan, Eric J.; Cardenas, M. Bayani; Maisano, Jessica A.; Ketcham, Richard A.; Bennett, Philip C.

2015-09-01

We present a new method for measuring wettability or contact angle of minerals at reservoir pressure-temperature conditions using high-resolution X-ray computed tomography (HRXCT) and radiography. In this method, a capillary or a narrow slot is constructed from a mineral or a rock sample of interest wherein two fluids are allowed to form an interface that is imaged using X-rays. After some validation measurements at room pressure-temperature conditions, we illustrate this method by measuring the contact angle of CO2-brine on quartz, muscovite, shale, borosilicate glass, polytetrafluoroethylene (PTFE or Teflon), and polyether ether ketone (PEEK) surfaces at 60-71°C and 13.8-22.8 MPa. At reservoir conditions, PTFE and PEEK surfaces were found to be CO2-wet with contact angles of 140° and 127°, respectively. Quartz and muscovite were found to be water-wet with contact angles of 26° and 58°, respectively, under similar conditions. Borosilicate glass-air-brine at room conditions showed strong water-wet characteristics with a contact angle of 9°, whereas borosilicate glass-CO2-brine at 13.8 MPa and 60°C showed a decrease in its water-wetness with contact angle of 54°. This method provides a new application for X-ray imaging and an alternative to other methods.

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.

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.

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.

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.

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.

Radiometric evaluation of diglycolamide resins for the chromatographic separation of actinium from fission product lanthanides

DOE PAGES

Radchenko, Valery; Mastren, Tara; Meyer, Catherine A. L.; ...

2017-07-20

Actinium-225 is a potential Targeted Alpha Therapy (TAT) isotope. It can be generated with high energy (≥ 100 MeV) proton irradiation of thorium targets. The main challenge in the chemical recovery of 225Ac lies in the separation from thorium and many fission by-products most importantly radiolanthanides. We recently developed a separation strategy based on a combination of cation exchange and extraction chromatography to isolate and purify 225Ac. In this study, actinium and lanthanide equilibrium distribution coefficients and column elution behavior for both TODGA (N,N,N',N'-tetra- n-octyldiglycolamide) and TEHDGA (N,N,N',N'-tetrakis-2-ethylhexyldiglycolamide) were determined. Density functional theory (DFT) calculations were performed and were inmore » agreement with experimental observations providing the foundation for understanding of the selectivity for Ac and lanthanides on different DGA (diglycolamide) based resins. The results of Gibbs energy (ΔG aq) calculations confirm significantly higher selectivity of DGA based resins for Ln III over Ac III in the presence of nitrate. As a result, DFT calculations and experimental results reveal that Ac chemistry cannot be predicted from lanthanide behavior under comparable circumstances.« less

Erbium concentration anomaly as an indicator of nuclear activity: Focus on Natural waters in the Chernobyl exclusion zone.

PubMed

Plausinaitis, Deivis; Prokopchik, Aleksandr; Karaliunas, Algimantas; Bohdan, Leonid; Balashevska, Yuliya

2018-04-15

This study focused on measurement of lanthanides in surface water (SW) and ground water (GW) samples from the Chernobyl Exclusion Zone. Results showed that the total lanthanide concentration in SW ranges from 500 to 1100ngL -1 and is about 10 times lower than the GW concentration. The normalized patterns of lanthanide concentrations increase from lighter elements to heavier lanthanides. Concurrently, concentration anomalies of Ce, Eu, and Er are visible. The Er anomaly is the most noticeable and exceeds the theoretical calculation by about 13 times. The Ce and Eu anomalies are likely related to the variety of oxidation states of these elements. Meanwhile, the cause of the Er anomaly is not completely clear, but is likely related to the Chernobyl Nuclear Power Plant accident, since increased concentrations correlate with the distribution of contamination in the zone. 137 Cs activity measurements partially confirm this hypothesis. Simultaneously, there is a relationship between the positive Er anomaly and increase in 235 U concentrations. However, there is no reliable information in the literature that indicates that Er was used in the Chernobyl Nuclear Power Plant before the reactor accident. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Enhancing multiphoton upconversion through energy clustering at sublattice level

NASA Astrophysics Data System (ADS)

Wang, Juan; Deng, Renren; MacDonald, Mark A.; Chen, Bolei; Yuan, Jikang; Wang, Feng; Chi, Dongzhi; Andy Hor, Tzi Sum; Zhang, Peng; Liu, Guokui; Han, Yu; Liu, Xiaogang

2014-02-01

The applications of lanthanide-doped upconversionnanocrystals in biological imaging, photonics, photovoltaics and therapeutics have fuelled a growing demand for rational control over the emission profiles of the nanocrystals. A common strategy for tuning upconversion luminescence is to control the doping concentration of lanthanide ions. However, the phenomenon of concentration quenching of the excited state at high doping levels poses a significant constraint. Thus, the lanthanide ions have to be stringently kept at relatively low concentrations to minimize luminescence quenching. Here we describe a new class of upconversion nanocrystals adopting an orthorhombic crystallographic structure in which the lanthanide ions are distributed in arrays of tetrad clusters. Importantly, this unique arrangement enables the preservation of excitation energy within the sublattice domain and effectively minimizes the migration of excitation energy to defects, even in stoichiometric compounds with a high Yb3+ content (calculated as 98 mol%). This allows us to generate an unusual four-photon-promoted violet upconversion emission from Er3+ with an intensity that is more than eight times higher than previously reported. Our results highlight that the approach to enhancing upconversion through energy clustering at the sublattice level may provide new opportunities for light-triggered biological reactions and photodynamic therapy.

Radiometric evaluation of diglycolamide resins for the chromatographic separation of actinium from fission product lanthanides

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

Radchenko, Valery; Mastren, Tara; Meyer, Catherine A. L.

Actinium-225 is a potential Targeted Alpha Therapy (TAT) isotope. It can be generated with high energy (≥ 100 MeV) proton irradiation of thorium targets. The main challenge in the chemical recovery of 225Ac lies in the separation from thorium and many fission by-products most importantly radiolanthanides. We recently developed a separation strategy based on a combination of cation exchange and extraction chromatography to isolate and purify 225Ac. In this study, actinium and lanthanide equilibrium distribution coefficients and column elution behavior for both TODGA (N,N,N',N'-tetra- n-octyldiglycolamide) and TEHDGA (N,N,N',N'-tetrakis-2-ethylhexyldiglycolamide) were determined. Density functional theory (DFT) calculations were performed and were inmore » agreement with experimental observations providing the foundation for understanding of the selectivity for Ac and lanthanides on different DGA (diglycolamide) based resins. The results of Gibbs energy (ΔG aq) calculations confirm significantly higher selectivity of DGA based resins for Ln III over Ac III in the presence of nitrate. As a result, DFT calculations and experimental results reveal that Ac chemistry cannot be predicted from lanthanide behavior under comparable circumstances.« less

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.

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.

Coupling Influences SMM Properties for Pure 4 f Systems.

PubMed

Zhang, Xuejing; Liu, Shuang; Vieru, Veacheslav; Xu, Na; Gao, Chen; Wang, Bing-Wu; Shi, Wei; Chibotaru, Liviu F; Gao, Song; Cheng, Peng; Powell, Annie K

2018-04-20

Increasing both the energy barrier for magnetization reversal and the coercive field of the hysteresis loop are significant challenges in the field of single-molecule magnets (SMMs). Coordination geometries of lanthanide ions and magnetic interactions between lanthanide ions are both important for guiding the magnetic behavior of SMMs. We report a high energy barrier of 657 K (457 cm -1 ) in a diamagnetic-ion-diluted lanthanide chain compound with a constrained bisphenoid symmetry (D 2d ); this energy barrier is substantially higher than the barrier of 567 K (394 cm -1 ) of the non-diluted chain compound with intrachain ferromagnetic interactions. Although intrachain magnetic interaction lowers the energy barrier for magnetization reversal, it can greatly enhance the coercive fields and zero-field remanence of the hysteresis loops, which is crucial for the rational design of high-performance SMMs. Factors related to the coordination sphere of the lanthanide center, which govern the high magnetic relaxation barriers through the second excited Kramer's doublets and the magnetic interactions that affect the hysteresis loops, were revealed through ab initio calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Commercial Ion Exchange Resin Vitrification in Borosilicate Glass

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

Cicero-Herman, C.A.; Workman, P.; Poole, K.

1998-05-01

Bench-scale studies were performed to determine the feasibility of vitrification treatment of six resins representative of those used in the commercial nuclear industry. Each resin was successfully immobilized using the same proprietary borosilicate glass formulation. Waste loadings varied from 38 to 70 g of resin/100 g of glass produced depending on the particular resin, with volume reductions of 28 percent to 68 percent. The bench-scale results were used to perform a melter demonstration with one of the resins at the Clemson Environmental Technologies Laboratory (CETL). The resin used was a weakly acidic meth acrylic cation exchange resin. The vitrification processmore » utilized represented a approximately 64 percent volume reduction. Glass characterization, radionuclide retention, offgas analyses, and system compatibility results will be discussed in this paper.« less

Investigating the effect of V{sub 2}O{sub 5} addition on sodium barium borosilicate glasses

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

Halder, Rumu, E-mail: rumuhalder24feb@gmail.com; Sengupta, Pranesh; Dey, G. K.

2016-05-23

V{sub 2}O{sub 5} doped sodium barium borosilicate glasses were characterized by photoluminescence spectroscopy and electron probe microanalyzer (EPMA). The glass remains homogeneous for lower concentration of V{sub 2}O{sub 5} but a phase separation is observed when V{sub 2}O{sub 5} doping is increased beyond 5 mol%. Detailed microanalysis reveals that the phase separated glass consists of a phase containing V, Ba and Si and a separate Si rich phase within the glass matrix. The luminescence study demonstrated that at low concentration the vanadium mainly interacts with the structural units of B/Si while at higher concentrations, V-O-V/ V-O{sup −} Na{sup +}/Ba{sup 2+} linkagesmore » are formed.« less

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

PubMed

Stone-Weiss, Nicholas; Pierce, Eric M; Youngman, Randall E; Gulbiten, Ozgur; Smith, Nicholas J; Du, Jincheng; Goel, Ashutosh

2018-01-01

The past decade has witnessed a significant upsurge in the development of borate and borosilicate based resorbable bioactive glasses owing to their faster degradation rate in comparison to their silicate counterparts. However, due to our lack of understanding about the fundamental science governing the aqueous corrosion of these glasses, most of the borate/borosilicate based bioactive glasses reported in the literature have been designed by "trial-and-error" approach. With an ever-increasing demand for their application in treating a broad spectrum of non-skeletal health problems, it is becoming increasingly difficult to design advanced glass formulations using the same conventional approach. Therefore, a paradigm shift from the "trial-and-error" approach to "materials-by-design" approach is required to develop new-generations of bioactive glasses with controlled release of functional ions tailored for specific patients and disease states, whereby material functions and properties can be predicted from first principles. Realizing this goal, however, requires a thorough understanding of the complex sequence of reactions that control the dissolution kinetics of bioactive glasses and the structural drivers that govern them. While there is a considerable amount of literature published on chemical dissolution behavior and apatite-forming ability of potentially bioactive glasses, the majority of this literature has been produced on silicate glass chemistries using different experimental and measurement protocols. It follows that inter-comparison of different datasets reveals inconsistencies between experimental groups. There are also some major experimental challenges or choices that need to be carefully navigated to unearth the mechanisms governing the chemical degradation behavior and kinetics of boron-containing bioactive glasses, and to accurately determine the composition-structure-property relationships. In order to address these challenges, a simplified borosilicate based model melt-quenched bioactive glass system has been studied to depict the impact of thermal history on its molecular structure and dissolution behavior in water. It has been shown that the methodology of quenching of the glass melt impacts the dissolution rate of the studied glasses by 1.5×-3× depending on the changes induced in their molecular structure due to variation in thermal history. Further, a recommendation has been made to study dissolution behavior of bioactive glasses using surface area of the sample - to - volume of solution (SA/V) approach instead of the currently followed mass of sample - to - volume of solution approach. The structural and chemical dissolution data obtained from bioactive glasses following the approach presented in this paper can be used to develop the structural descriptors and potential energy functions over a broad range of bioactive glass compositions. Realizing the goal of designing third generation bioactive glasses requires a thorough understanding of the complex sequence of reactions that control their rate of degradation (in physiological fluids) and the structural drivers that control them. In this article, we have highlighted some major experimental challenges and choices that need to be carefully navigated in order to unearth the mechanisms governing the chemical dissolution behavior of borosilicate based bioactive glasses. The proposed experimental approach allows us to gain a new level of conceptual understanding about the composition-structure-property relationships in these glass systems, which can be applied to attain a significant leap in designing borosilicate based bioactive glasses with controlled dissolution rates tailored for specific patient and disease states. Copyright © 2017 Acta Materialia Inc. All rights reserved.

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

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.

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.

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.

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.

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 functionalization, multiple (double or triple) luminescent centers were created with different luminescent bands in the visible region. Because of the different luminescent natures of the lanthanide ions, MOF linkers, and other species (organic dyes or carbon dots), they display different responses to sensing species. Currently, using these strategies, we have utilized a dual-response luminescent probe to realize chemical sensing of different types of cations (Fe 3+ /Fe 2+ , Hg 2+ , and Cd 2+ ), anions (Cr 2 O 7 2- /CrO 4 - and CO 3 2- ), molecules (volatile organic compounds and O 2 ), special air pollutants (formaldehyde), and biomarkers of food spoilage as well as pH and temperature. Additionally, we have achieved triple-luminescence-response sensing of ions (Ag + , Hg 2+ , and S 2- ) in complicated aqueous environments, which was developed using a logic operation.

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 redox conditions that favour Ce+3, Th+4, and U+4 instead of higher oxidation states. The absence of any cations other than those deliberately added permits positive control of cation mixtures in starting materials. The synthetic pathway—condensation of POx units--provides ideal conditions for the homogeneous distribution of cations including those with different charges. We present the results of synthesis, elemental analysis and imaging by XRF and SEM-EDX for mixed lanthanide-actinide phosphate 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.

Alternate method of source preparation for alpha spectrometry: No electrodeposition, no hydrofluoric acid

DOE PAGES

Kurosaki, Hiromu; Mueller, Rebecca J.; Lambert, Susan B.; ...

2016-07-15

An alternate method of preparing actinide alpha counting sources was developed in place of electrodeposition or lanthanide fluoride micro-precipitation. The method uses lanthanide hydroxide micro-precipitation to avoid the use of hazardous hydrofluoric acid. Lastly, it provides a quicker, simpler, and safer way of preparing actinide alpha counting sources in routine, production-type laboratories that process many samples daily.

Extended electron energy loss fine structure simulation of the local boron environment in sodium aluminoborosilicate glasses containing gadolinium

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

Qian, Morris; Li, Hong; Li, Liyu

Gadolinium can be dissolved in sodium-alumino-borosilicate glasses up to 47 wt% in a baseline borosilicate glass (mol%) 20 B2O3, 5 Al2O3, 60 SiO2,and 20 Na2O. Understanding of Gd dissolution in borosilicate melts is important in glass formulation optimization. Electron energy loss fine structure (ELFS) spectroscopy is chosen, which provides well resolved local atomic structure information for both amorphous and crystalline materials with high sensitivity to low Z elements such as Al, B, Na, O, and Si where the x-ray absorption fine structure (XAFS) technique faces experimental difficulty. In this study, we report our results of boron K-edge ELFS study. Twomore » borosilicate glass samples with 30 and 47 mass% Gd2O3, B20Gd30 and B20Gd47were chosen for B K-edge ELFS study. EEL spectra were acquired on a Philips 430 TEM equipped with Gatan PEELS system 666 and EL/P 2.1 software with Custom function AcqLong. The ELFS data analysis was performed using UWELFS, UWXAFS and FEFF software. From our Gd solubility study, the local structure of Gd in the borate environment possibly resembles double chain structure found in crystalline Gd(BO2)3 as proposed by Chakraborty et al. The B/Gd ratio's in both glasses are smaller then 3, which means the excess Gd atoms in the Si-sites would be 17 and 60 mol% of the total Gd atoms, respectively according to the model, yet the local environment of borate sites saturated with Gd should be remained. To verity above hypothesis, the double chain structure model was applied to fit boron K-edge. The model was shown to well fit experimental boron K-edge EELS spectra for both glasses with some degree of distance distortion which is understandable in amorphous structure. Therefore, it is very likely that Gd stabilized in borate sites has a local structure resembling the double chain Gd(BO2)3 structure as proposed by our solubility study and literature.« less

Synthesis and characterization of nanotubes from misfit compounds (LnS)1+yTaS2 (Ln= Pr, Sm, Gd, Yb).

PubMed

Tenne, Reshef; Serra, Marco; Stolovas, Dalit; Houben, Lothar; Popovitz-Biro, Ronit; Pinkas, Iddo; Kampmann, Felix; Maultzsch, Janina; Joselevich, Ernesto

2018-06-06

The synthesis and characterization of nanotubes from the misfit layered compounds (MLC) (LnS)1+yTaS2 (shortly denoted as LnS-TaS2) (Ln= Pr, Sm, Gd and Yb), not reported before, are described (the bulk compound YbS-LaS2 was not documented before). Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) show that the interlayer spacing along the c-axis decrease with increasing atomic number of the lanthanide atom, suggesting tighter interaction between the LnS layer and the TaS2 for the late lanthanides. The Raman spectra of the tubules were studied and compared to the bulk MLC compounds. Like bulk MLC, the Raman spectra can be divided into the low frequency modes (110-150 cm-1) of the LnS lattice and the high frequency (250-400 cm-1) of the TaS2 lattice. The Raman spectra indicate that the vibrational lattice modes of the strained layers in the tubes are stiffer than those in the bulk compounds. Furthermore, the modes of the late lanthanides are higher in energy compared with the earlier lanthanides, suggesting larger charge transfer between the LnS and the TaS2 layers for the late lanthanides. Polarized Raman measurements showed the expected binodal intensity profile (antenna effect). The intensity ratio of the Raman signal showed that the E2g mode of TaS2 is more sensitive to the light polarization effect than its A1g mode. These nanotubes are expected to reveal interesting low temperature quasi-1D transport behavior. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In vivo three-dimensional molecular imaging with Biosensor Imaging of Redundant Deviation in Shifts (BIRDS) at high spatiotemporal resolution.

PubMed

Coman, Daniel; de Graaf, Robin A; Rothman, Douglas L; Hyder, Fahmeed

2013-11-01

Spectroscopic signals which emanate from complexes between paramagnetic lanthanide (III) ions (e.g. Tm(3+)) and macrocyclic chelates (e.g. 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate, or DOTMA(4-)) are sensitive to physiology (e.g. temperature). Because nonexchanging protons from these lanthanide-based macrocyclic agents have relaxation times on the order of a few milliseconds, rapid data acquisition is possible with chemical shift imaging (CSI). Thus, Biosensor Imaging of Redundant Deviation in Shifts (BIRDS) which originate from nonexchanging protons of these paramagnetic agents, but exclude water proton detection, can allow molecular imaging. Previous two-dimensional CSI experiments with such lanthanide-based macrocyclics allowed acquisition from ~12-μL voxels in rat brain within 5 min using rectangular encoding of k space. Because cubical encoding of k space in three dimensions for whole-brain coverage increases the CSI acquisition time to several tens of minutes or more, a faster CSI technique is required for BIRDS to be of practical use. Here, we demonstrate a CSI acquisition method to improve three-dimensional molecular imaging capabilities with lanthanide-based macrocyclics. Using TmDOTMA(-), we show datasets from a 20 × 20 × 20-mm(3) field of view with voxels of ~1 μL effective volume acquired within 5 min (at 11.7 T) for temperature mapping. By employing reduced spherical encoding with Gaussian weighting (RESEGAW) instead of cubical encoding of k space, a significant increase in CSI signal is obtained. In vitro and in vivo three-dimensional CSI data with TmDOTMA(-), and presumably similar lanthanide-based macrocyclics, suggest that acquisition using RESEGAW can be used for high spatiotemporal resolution molecular mapping with BIRDS. Copyright © 2013 John Wiley & Sons, Ltd.

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

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

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

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

China's rare-earth industry

USGS Publications Warehouse

Tse, Pui-Kwan

2011-01-01

Introduction China's dominant position as the producer of over 95 percent of the world output of rare-earth minerals and rapid increases in the consumption of rare earths owing to the emergence of new clean-energy and defense-related technologies, combined with China's decisions to restrict exports of rare earths, have resulted in heightened concerns about the future availability of rare earths. As a result, industrial countries such as Japan, the United States, and countries of the European Union face tighter supplies and higher prices for rare earths. This paper briefly reviews China's rare-earth production, consumption, and reserves and the important policies and regulations regarding the production and trade of rare earths, including recently announced export quotas. The 15 lanthanide elements-lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium (atomic numbers 57-71)-were originally known as the rare earths from their occurrence in oxides mixtures. Recently, some researchers have included two other elements-scandium and yttrium-in their discussion of rare earths. Yttrium (atomic number 39), which lies above lanthanum in transition group III of the periodic table and has a similar 3+ ion with a noble gas core, has both atomic and ionic radii similar in size to those of terbium and dysprosium and is generally found in nature with lanthanides. Scandium (atomic number 21) has a smaller ionic radius than yttrium and the lanthanides, and its chemical behavior is intermediate between that of aluminum and the lanthanides. It is found in nature with the lanthanides and yttrium. Rare earths are used widely in high-technology and clean-energy products because they impart special properties of magnetism, luminescence, and strength. Rare earths are also used in weapon systems to obtain the same properties.

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.

ULTRASONIC NEUTRON DOSIMETER

DOEpatents

Truell, R.; de Klerk, J.; Levy, P.W.

1960-02-23

A neutron dosimeter is described which utilizes ultrasonic waves in the megacycle region for determination of the extent of neutron damage in a borosilicate glass through ultrasonic wave velocity and attenuation measurements before and after damage.

Fabrication and characterization of a cell electrostimulator device combining physical vapor deposition and laser ablation

NASA Astrophysics Data System (ADS)

Aragón, Angel L.; Pérez, Eliseo; Pazos, Antonio; Bao-Varela, Carmen; Nieto, Daniel

2017-08-01

In this work we present the process of fabrication and optimization of a prototype of a cell electrostimulator device for medical application combining physical vapor deposition and laser ablation. The fabrication of the first prototype begins with a deposition of a thin layer of 200 nm of aluminium on a borosilicate glass substrate using physical vapor deposition (PVD). In the second stage the geometry design of the electrostimulator is made in a CAD-like software available in a Nd:YVO4 Rofin Power line 20E, operating at the fundamental wavelength of 1064 nm and 20 ns pulse width. Choosing the proper laser parameters the negative of the electrostimulator desing is ablated. After that the glass is assembled between two polycarbonate sheets and a thick sheet of polydimethylsiloxane (PDMS). The PDMS sheet has a round hole in where cells are placed. There is also included a thin soda-lime silicate glass (100 μm) between the electrostimulator and the PMDS to prevent the cells for being in contact with the electric circuit. In order to control the electrical signal applied to the electrostimulator is used a digital I/O device from National Instruments (USB-6501) which provides 5 V at the output monitored by a software programmed in LabVIEW. Finally, the optical and electrical characterization of the cell electrostimulator device is presented.

La-oxides as tracers for PuO{sub 2} to simulate contaminated aerosol behavior

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

Meyer, L.C.; Newton, G.J.; Cronenberg, A.W.

1994-04-01

An analytical and experimental study was performed on the use of lanthanide oxides (La-oxides) as surrogates for plutonium oxides (PuO{sub 2}) during simulated buried waste retrieval. This study determined how well the La-oxides move compared to PuO{sub 2} in aerosolized soils during retrieval scenarios. As part of the analytical study, physical properties of La-oxides and PuO{sub 2}, such as molecular diameter, diffusivity, density, and molecular weight are compared. In addition, an experimental study was performed in which Idaho National Engineering Laboratory (INEL) soil, INEL soil with lanthanides, and INEL soil with plutonium were aerosolized and collected in filters. Comparison ofmore » particle size distribution parameters from this experimental study show similarity between INEL soil, INEL soil with lanthanides, and INEL soil with plutonium.« less

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.

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.

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

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

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.

Research on graphite reinforced glass matrix composites

NASA Technical Reports Server (NTRS)

Bacon, J. F.; Prewo, K. M.; Thompson, E. R.

1978-01-01

A composite that can be used at temperatures up to 875 K with mechanical properties equal or superior to graphite fiber reinforced epoxy composites is presented. The composite system consist of graphite fiber, uniaxially or biaxially, reinforced borosilicate glass. The mechanical and thermal properties of such a graphite fiber reinforced glass composite are described, and the system is shown to offer promise as a high performance structural material. Specific properties that were measured were: a modified borosilicate glass uniaxially reinforced by Hercules HMS graphite fiber has a three-point flexural strength of 1030 MPa, a four-point flexural strength of 964 MPa, an elastic modulus of 199 GPa and a failure strain of 0.0052. The preparation and properties of similar composites with Hercules HTS, Celanese DG-102, Thornel 300 and Thornel Pitch graphite fibers are also described.

Optical waveguides in magneto-optical glasses fabricated by proton implantation

NASA Astrophysics Data System (ADS)

Liu, Chun-Xiao; Li, Yu-Wen; Zheng, Rui-Lin; Fu, Li-Li; Zhang, Liao-Lin; Guo, Hai-Tao; Zhou, Zhi-Guang; Li, Wei-Nan; Lin, She-Bao; Wei, Wei

2016-11-01

Planar waveguides in magneto-optical glasses (Tb3+-doped aluminum borosilicate glasses) have been produced by a 550-keV proton implantation at a dose of 4.0×1016 ions/cm2 for the first time to our knowledge. After annealing at 260 °C for 1.0 h, the dark-mode spectra and near-field intensity distributions are measured by the prism-coupling and end-face coupling methods. The damage profile, refractive index distribution and light propagation mode of the planar waveguide are numerically calculated by SRIM 2010, RCM and FD-BPM, respectively. The effects of implantation on the structural and optical properties are investigated by Raman and absorption spectra. It suggests that the proton-implanted Tb3+-doped aluminum borosilicate glass waveguide is a good candidate for a waveguide isolator in optical fiber communication and all-optical communication.

Incorporation and distribution of rhenium in a borosilicate glass melt heat treated in a sealed ampoule

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

Kim, Dong-Sang; Schweiger, Michael J.

2013-07-25

We investigated a mass balance of rhenium (used as a surrogate for technetium-99) in a borosilicate glass that was mixed with excess Re source (KReO4) beyond its solubility and heat treated in a vacuum-sealed fused silica ampoule. Distribution of Re in the bulk of the glass, in a salt phase formed on the melt surface, and in condensate material deposited on the ampoule wall was evaluated to understand the Re migration into different phases during the reaction between the molten glass and KReO4. The information gained from this study will contribute to an effort to understand the mechanism of technetiummore » retention in or escape from glass melt during early stages of glass batch melting, which is a goal of the present series of studies.« less

Aluminum elution and precipitation in glass vials: effect of pH and buffer species.

PubMed

Ogawa, Toru; Miyajima, Makoto; Wakiyama, Naoki; Terada, Katsuhide

2015-02-01

Inorganic extractables from glass vials may cause particle formation in the drug solution. In this study, the ability of eluting Al ion from borosilicate glass vials, and tendencies of precipitation containing Al were investigated using various pHs of phosphate, citrate, acetate and histidine buffer. Through heating, all of the buffers showed that Si and Al were eluted from glass vials in ratios almost the same as the composition of borosilicate glass, and the amounts of Al and Si from various buffer solutions at pH 7 were in the following order: citrate > phosphate > acetate > histidine. In addition, during storage after heating, the Al concentration at certain pHs of phosphate and acetate buffer solution decreased, suggesting the formation of particles containing Al. In citrate buffer, Al did not decrease in spite of the high elution amount. Considering that the solubility profile of aluminum oxide and the Al eluting profile of borosilicate glass were different, it is speculated that Al ion may be forced to leach into the buffer solution according to Si elution on the surface of glass vials. When Al ions were added to the buffer solutions, phosphate, acetate and histidine buffer showed a decrease of Al concentration during storage at a neutral range of pHs, indicating the formation of particles containing Al. In conclusion, it is suggested that phosphate buffer solution has higher possibility of forming particles containing Al than other buffer solutions.

Wettability measurement under high P-T conditions using X-ray imaging with application to the brine-supercritical CO 2 system: WETTABILITY MEASUREMENT USING X-RAY

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

Chaudhary, Kuldeep; Guiltinan, Eric J.; Cardenas, M. Bayani

2015-08-30

We present a new method for measuring wettability or contact angle of minerals at reservoir pressure-temperature conditions using high-resolution X-ray computed tomography (HRXCT) and radiography. In this method, a capillary or a narrow slot is constructed from a mineral or a rock sample of interest wherein two fluids are allowed to form an interface that is imaged using X-rays. After some validation measurements at room pressure-temperature conditions, we illustrate this method by measuring the contact angle of CO 2-brine on quartz, muscovite, shale, borosilicate glass, polytetrafluoroethylene (PTFE or Teflon), and polyether ether ketone (PEEK) surfaces at 60–71°C and 13.8–22.8 MPa.more » At reservoir conditions, PTFE and PEEK surfaces were found to be CO 2-wet with contact angles of 140° and 127°, respectively. Quartz and muscovite were found to be water-wet with contact angles of 26° and 58°, respectively, under similar conditions. Borosilicate glass-air-brine at room conditions showed strong water-wet characteristics with a contact angle of 9°, whereas borosilicate glass-CO 2-brine at 13.8 MPa and 60°C showed a decrease in its water-wetness with contact angle of 54°. This method provides a new application for X-ray imaging and an alternative to other methods.« less

Comprehensive studies of the Ag+ effect on borosilicate glass ceramics containing Ag nanoparticles and Er-doped hexagonal NaYF4 nanocrystals: morphology, structure, and 2.7 μm emission

NASA Astrophysics Data System (ADS)

Liu, Qunhuo; Tian, Ying; Tang, Wenhua; Jing, Xufeng; Zhang, Junjie; Xu, Shiqing

2018-05-01

In this work, we have performed a comprehensive investigation of the Ag+ concentration effect on the morphological, thermal, structural, and mid-infrared emission properties of novel oxyfluoride borosilicate glasses and glass ceramics containing both Ag nanoparticles and erbium-doped hexagonal NaYF4 nanocrystals. The effect of Ag+ ions on the glass forming and crystallization processes was discussed in detail by glass structural analysis. It was found that the Ag+ concentration can affect the distribution of Na+ ion and bridge oxygen in boron-rich and silicon-rich phases, which induced the transformation between BO3 triangles and BO4 tetrahedra during crystallization process. In addition, there was a turning point when the doped Ag+ ion concentration reached its solubility in the borosilicate glass. Furthermore, the enhancement of the 2.7 μm emission and the reduction of the lifetime of the 4I13/2 level were observed both in glasses and in glass ceramics, and its origin was revealed by qualitative and quantitative analyses of the Er3+-Ag nanoparticles (localized electric field enhancement) and Er3+-Er3+ (nonradiative resonance energy transfer) interactions within glasses and glass ceramics. Moreover, the high lifetime of the 4I11/2 level (2.12 ms) and the peak emission cross section in 2.7 μm (6.8×10-21 cm2) suggested that the prepared glass ceramics have promising mid-infrared laser applications.

Fabrication of Silicon Nitride Dental Core Ceramics with Borosilicate Veneering material

NASA Astrophysics Data System (ADS)

Wananuruksawong, R.; Jinawath, S.; Padipatvuthikul, P.; Wasanapiarnpong, T.

2011-10-01

Silicon nitride (Si3N4) ceramic is a great candidate for clinical applications due to its high fracture toughness, strength, hardness and bio-inertness. This study has focused on the Si3N4 ceramic as a dental core material. The white Si3N4 was prepared by pressureless sintering at relative low sintering temperature of 1650 °C in nitrogen atmosphere. The coefficient of thermal expansion (CTE) of Si3N4 ceramic is lower than that of Zirconia and Alumina ceramic which are popular in this field. The borosilicate glass veneering was employed due to its compatibility in thermal expansion. The sintered Si3N4 specimens represented the synthetic dental core were paintbrush coated by a veneer paste composed of borosilicate glass powder (<150 micrometer, Pyrex) with 5 wt% of zirconia powder (3 wt% Y2O3 - partial stabilized zirconia) and 30 wt% of polyvinyl alcohol (5 wt% solution). After coating the veneer on the Si3N4 specimens, the firing was performed in electric tube furnace between 1000-1200°C. The veneered specimens fired at 1100°C for 15 mins show good bonding, smooth and glossy without defect and crazing. The veneer has thermal expansion coefficient as 3.98×10-6 °C-1, rather white and semi opaque, due to zirconia addition, the Vickers hardness as 4.0 GPa which is closely to the human teeth.

Effects of optical dopants and laser wavelength on atom probe tomography analyses of borosilicate glasses

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

Lu, Xiaonan; Schreiber, Daniel K.; Neeway, James J.

Atom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub-nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass (international simple glass). A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with amore » green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality such as compositional accuracy and total ions collected, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material’s optical properties.« less

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.

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.

How does ytterbium chloride interact with DMPC bilayers? A computational and experimental study.

PubMed

Gonzalez, Miguel A; Barriga, Hanna M G; Richens, Joanna L; Law, Robert V; O'Shea, Paul; Bresme, Fernando

2017-03-29

Lanthanide salts have been studied for many years, primarily in Nuclear Magnetic Resonance (NMR) experiments of mixed lipid-protein systems and more recently to study lipid flip-flop in model membrane systems. It is well recognised that lanthanide salts can influence the behaviour of both lipid and protein systems, however a full molecular level description of lipid-lanthanide interactions is still outstanding. Here we present a study of lanthanide-bilayer interactions, using molecular dynamics computer simulations, fluorescence electrostatic potential experiments and nuclear magnetic resonance. Computer simulations reveal the microscopic structure of DMPC lipid bilayers in the presence of Yb 3+ , and a surprising ability of the membranes to adsorb significant concentrations of Yb 3+ without disrupting the overall membrane structure. At concentrations commonly used in NMR experiments, Yb 3+ ions bind strongly to 5 lipids, inducing a small decrease of the area per lipid and a slight increase of the ordering of the aliphatic chains and the bilayer thickness. The area compressibility modulus increases by a factor of two, with respect to the free-salt case, showing that Yb 3+ ions make the bilayer more rigid. These modifications of the bilayer properties should be taken into account in the interpretation of NMR experiments.

1,2-Hydroxypyridonates as Contrast Agents for Magnetic ResonanceImaging: TREN-1,2-HOPO

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

Jocher, Christoph J.; Moore, Evan G.; Xu, Jide

2007-05-08

1,2-Hydroxypyridinones (1,2-HOPO) form very stable lanthanide complexes that may be useful as contrast agents for Magnetic Resonance Imaging (MRI). X-ray diffraction of single crystals established that the solid state structures of the Eu(III) and the previously reported [Inorg. Chem. 2004, 43, 5452] Gd(III) complex are identical. The recently discovered sensitizing properties of 1,2-HOPO chelates for Eu(III) luminescence allow direct measurement of the number if water molecules in the metal complex. Fluorescence measurements of the Eu(III) complex corroborate that in solution two water molecules coordinate the lanthanide (q = 2) as proposed from the analysis of NMRD profiles. In addition, fluorescencemore » measurements have verified the anion binding interactions of lanthanide TREN-1,2-HOPO complexes in solution, studied by relaxivity, revealing only very weak oxalate binding (K{sub A} = 82.7 {+-} 6.5 M{sup -1}). Solution thermodynamic studies of the metal complex and free ligand have been carried out using potentiometry, spectrophotometry and fluorescence spectroscopy. The metal ion selectivity of TREN-1,2-HOPO supports the feasibility of using 1,2-HOPO ligands for selective lanthanide binding [pGd = 19.3 (2); pZn = 15.2 (2), pCa = 8.8 (3)].« 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.

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.

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

Analysis of the isomer ratios of polymethylated-DOTA complexes and the implications on protein structural studies

PubMed Central

Opina, Ana Christina L.; Strickland, Madeleine; Lee, Yong-Sok; Tjandra, Nico; Byrd, R. Andrew; Swenson, Rolf E.; Vasalatiy, Olga

2016-01-01

A rigidified and symmetrical polymethylated 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) ligand bearing four SSSS methyl groups in both the tetraaza ring and the acetate arms (SSSS-SSSS-M4DOTMA) was prepared. The isomer ratio of SSSS-SSSS-M4DOTMA complexed with a series of lanthanide ions was carefully investigated using RP-HPLC and NMR. A square antiprismatic (SAP) configuration was exclusively observed for the early lanthanides, while the twisted square antiprismatic (TSAP) geometry was preferred as the lanthanide ion size decreases. The late lanthanides preferentially adopted the TSAP geometry. One of the pendant arms was modified with a pyridyl disulfide group (SSSS-SSSS-M8SPy) for cysteine attachment and displayed a similar isomer trend as the parent compound, Ln-SSSS-SSSS-M4DOTMA. Covalent attachment to the ubiquitin S57C mutant showed resonances whose intensities are in agreement with the isomeric population observed by HPLC. Furthermore, the NOE experiments combined with quantum chemical calculations have unequivocally demonstrated that the SAP of Pr-SSSS-SSSS-M4DOTMA and Pr-SSSS-SSSS-M8SPy, as well as the TSAP of Yb-SSSS-SSSS-M8SPy are more stable than their corresponding isomers. PMID:26857249

40 CFR 60.296 - Test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., g/kg. cs=concentration of particulate matter, g/dsm. Qsd=volumetric flow rate, dscm/hr. A=zero... (borosilicate) glass, wool fiberglass, and flat glass. P=glass production rate, kg/hr. (2) Method 5 shall be...

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.

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

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.

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

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.

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.

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

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

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.

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.

Advancing the scientific basis of trivalent actinide-lanthanide separations

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

Nash, K.L.

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

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.

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

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.

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

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

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 variable composition of the aqueous medium. This project targets in particular two problematic issues in designing combined process systems: managing the chemistry of challenging aqueous species (like Zr 4+) and optimizing the composition and properties of combined extractant organic phases.« less

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, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

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 in order to ensure its future development. This permitted the design of future generations of taggants and provided brightness- or color-tunable compounds as well as temperature-sensitive and soluble taggants. We hope to demonstrate here that strong fundamental research is a very effective tool to create a technological breakthrough that allows the development of efficient applicative research and competitive products and finally contributes to economic growth.

Inhibiting the oxidation of diamond during preparing the vitrified dental grinding tools by depositing a ZnO coating using direct urea precipitation method.

PubMed

Wang, Yanhui; Yuan, Yungang; Cheng, Xiaozhe; Li, Xiaohu; Zang, Jianbing; Lu, Jing; Yu, Yiqing; Xu, Xipeng

2015-08-01

Oxidation of diamond during the manufacturing of vitrified dental grinding tools would reduce the strength and sharpness of tools. Zinc oxide (ZnO) coating was deposited on diamond particles by urea precipitation method to protect diamond in borosilicate glass. The FESEM results showed that the ZnO coating was formed by plate-shaped particles. According to the TG results, the onset oxidation temperature of the ZnO-coated diamond was about 70 °C higher than the pristine diamond. The EDS results showed that ZnO diffused into the borosilicate glass during sintering. As the result, the bending strength of the composites containing ZnO-coated diamond was increased by 24% compared to that of the composites containing pristine diamond. Copyright © 2015 Elsevier B.V. All rights reserved.

Magnetic Glass Ceramics by Sintering of Borosilicate Glass and Inorganic Waste.

PubMed

Ponsot, Inès M M M; Pontikes, Yiannis; Baldi, Giovanni; Chinnam, Rama K; Detsch, Rainer; Boccaccini, Aldo R; Bernardo, Enrico

2014-07-31

Ceramics and glass ceramics based on industrial waste have been widely recognized as competitive products for building applications; however, there is a great potential for such materials with novel functionalities. In this paper, we discuss the development of magnetic sintered glass ceramics based on two iron-rich slags, coming from non-ferrous metallurgy and recycled borosilicate glass. The substantial viscous flow of the glass led to dense products for rapid treatments at relatively low temperatures (900-1000 °C), whereas glass/slag interactions resulted in the formation of magnetite crystals, providing ferrimagnetism. Such behavior could be exploited for applying the obtained glass ceramics as induction heating plates, according to preliminary tests (showing the rapid heating of selected samples, even above 200 °C). The chemical durability and safety of the obtained glass ceramics were assessed by both leaching tests and cytotoxicity tests.

Evaluations of candidate encapsulation designs and materials for low-cost silicon photovoltaic arrays

NASA Technical Reports Server (NTRS)

Gaines, G. B.; Carmichael, D. C.; Sliemers, F. A.; Brockway, M. C.; Bunk, A. R.; Nance, G. P.

1978-01-01

Three encapsulation designs for silicon photovoltaic arrays based on cells with silk-screened Ag metallization have been evaluated: transparent polymeric coatings over cells laminated between two films or sheets of polymeric materials; cells adhesively bonded to a glass cover with a polymer pottant and a glass or other substrate component. Silicone and acrylic coatings were assessed, together with acrylic sheet, 0.635 mm fiberglass-reinforced polyester sheet, 0.102 mm polycarbonate/acrylic dual-layer film, 0.127 mm fluorocarbon film, soda-lime glass, borosilicate glass, low-iron glass, and several adhesives. The encapsulation materials were characterized by light transmittance measurements, determination of moisture barrier properties and bond strengths, and by the performance of cells before and after encapsulation. Silicon and acrylic coatings provided inadequate protection. Acrylic and fluorocarbon films displayed good weatherability and acceptable optical transmittance. Borosilicate, low-iron and soda-lime-float glasses were found to be acceptable candidate encapsulants for most environments.

Extraction of heavy metal ions from waste colored glass through phase separation.

PubMed

Chen, Danping; Masui, Hirotsugu; Miyoshi, Hiroshi; Akai, Tomoko; Yazawa, Tetsuo

2006-01-01

A new method utilizing phase separation phenomena for the extraction of heavy metal ions used as colorants in colored glass is proposed. Colored soda-lime-silica glass containing Co or Cr as a colorant was remelted with B2O3 to yield soda-lime-borosilicate glass. The soda-lime-borosilicate glass thus obtained was leached in 1M nitric acid at 90 degrees C to dissolve the borate phase. All cations (Na, Ca, Cr and Co) concentrated in the borate phase are successfully leached out with the dissolution of the borate phase, when the amount of the B2O3 added to the glass and heat treatment conditions are properly chosen. Porous silicate glass powders with high SiO2 purity are obtained as the result of the leaching. Porous glass can also be formed as bulk material by controlling the composition of additives during the remelting.

Washing and caustic leaching of Hanford tank sludges: results of FY 1996 studies. Revision

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

Lumetta, G.J.; Rapko, B.M.; Wagner, M.J.

During the past few years, the primary mission at the US Department of Energy`s Hanford Site has changed from producing plutonium to restoring the environment. Large volumes of high-level radioactive wastes (HLW), generated during past Pu production and other operations, are stored in underground tanks on site. The current plan for remediating the Hanford tank farms consists of waste retrieval, pretreatment, treatment (immobilization), and disposal. The HLW will be immobilized in a borosilicate glass matrix and then disposed of in a geologic repository. Because of the expected high cost of HLW vitrification and geologic disposal, pretreatment processes will be implementedmore » to reduce the volume of borosilicate glass produced in disposing of the tank wastes. On this basis, a pretreatment plan is being developed. This report describes the sludge washing and caustic leaching test conducted to create a Hanford tank sludge pretreatment flowsheet.« less

Application of atomic layer deposited microchannel plates to imaging photodetectors with high time resolution

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

Siegmund, O. H. W.; McPhate, J. B.; Tremsin, A. S.

Novel microchannel plates have been constructed using borosilicate glass micro-capillary array substrates with 20 mu m and 10 mu m pores and coated with resistive, and secondary electron emissive, layers by atomic layer deposition. Microchannel plates in 33 mm, 50 mm and 20 cm square formats have been made and tested. Although their amplification, imaging, and timing properties are comparable to standard glass microchannel plates, the background rates and lifetime characteristics are considerably improved. Sealed tube detectors based on the Planacon tube, and a 25 mm cross delay line readout tube with a GaN(Mg) opaque photocathode deposited on borosilicate microchannelmore » plates have been fabricated. Considerable progress has also been made with 20 cm microchannel plates for a 20 cm format sealed tube sensor with strip-line readout that is being developed for Cherenkov light detection.« less

Magnetic Glass Ceramics by Sintering of Borosilicate Glass and Inorganic Waste

PubMed Central

Ponsot, Inès M. M. M.; Pontikes, Yiannis; Baldi, Giovanni; Chinnam, Rama K.; Detsch, Rainer; Boccaccini, Aldo R.; Bernardo, Enrico

2014-01-01

Ceramics and glass ceramics based on industrial waste have been widely recognized as competitive products for building applications; however, there is a great potential for such materials with novel functionalities. In this paper, we discuss the development of magnetic sintered glass ceramics based on two iron-rich slags, coming from non-ferrous metallurgy and recycled borosilicate glass. The substantial viscous flow of the glass led to dense products for rapid treatments at relatively low temperatures (900–1000 °C), whereas glass/slag interactions resulted in the formation of magnetite crystals, providing ferrimagnetism. Such behavior could be exploited for applying the obtained glass ceramics as induction heating plates, according to preliminary tests (showing the rapid heating of selected samples, even above 200 °C). The chemical durability and safety of the obtained glass ceramics were assessed by both leaching tests and cytotoxicity tests. PMID:28788146

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-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. Electronic supplementary information (ESI) available: TEM images of MnWO4 nanoparticles synthesized at pH = 7, 180 °C pH = 9, 180 °C pH = 6, 200 °C with various amino acid molecules as capped agents, survey XPS spectra, FTIR spectrum of glycine capped MnWO4 nanorods, photos of glycine capped MnWO4 nanorods in various solutions including PBS, DMEM cell medium, and FBS, in vivo coronal view CT images of a rat before and after intravenous injection of iobitridol at different timed intervals, in vivo CT imaging of the rat one month after intravenous injection of MnWO4 nanorods, CT values of the heart, liver, spleen and kidney of a rat before and after intravenous administration of MnWO4 nanorods and iobitridol at different time intervals, hematology analysis and blood biochemical assay. See DOI: 10.1039/c3nr05455a

Method of determining lanthanidies in a transition element host

DOEpatents

De Kalb, Edward L.; Fassel, Velmer A.

1976-02-03

A phosphor composition contains a lanthanide activator element within a host matrix having a transition element as a major component. The host matrix is composed of certain rare earth phosphates or vanadates such as YPO.sub.4 with a portion of the rare earth replaced with one or more of the transition elements. On X-ray or other electromagnetic excitation, trace lanthanide impurities or additives within the phosphor are spectrometrically determined from their characteristic luminescence.

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-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.

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.

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.

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

Optimization of Time-Resolved Fluorescence Assay for Detection of Eu-DOTA-labeled Ligand-Receptor Interactions

PubMed Central

De Silva, Channa R.; Vagner, Josef; Lynch, Ronald; Gillies, Robert J.; Hruby, Victor J.

2010-01-01

Lanthanide-based luminescent ligand binding assays are superior to traditional radiolabel assays due to improved sensitivity and affordability in high throughput screening while eliminating the use of radioactivity. Despite significant progress using lanthanide(III)-coordinated chelators such as DTPA derivatives, dissociation-enhanced lanthanide fluoroimmunoassays (DELFIA) have not yet been successfully used with more stable chelators, e.g. DOTA derivatives, due to the incomplete release of lanthanide(III) ions from the complex. Here, a modified and an optimized DELFIA procedure incorporating an acid treatment protocol is introduced for use with Eu(III)-DOTA labeled peptides. Complete release of Eu(III) ions from DOTA labeled ligands was observed using hydrochloric acid (2.0 M) prior to the luminescent enhancement step. NDP-α-MSH labeled with Eu(III)-DOTA was synthesized and the binding affinity to cells overexpressing the human melanocortin-4 receptors (hMC4R) was evaluated using the modified protocol. Binding data indicate that the Eu(III)-DOTA linked peptide bound to these cells with an affinity similar to its DTPA analogue. The modified DELFIA procedure was further used to monitor the binding of an Eu(III)-DOTA labeled heterobivalent peptide to the cells expressing both hMC4R and CCK-2 (Cholecystokinin) receptors. The modified assay provides superior results and is appropriate for high-throughput screening of ligand libraries. PMID:19852924

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.

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-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.

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

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.

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.

Water Triple-Point Comparisons: Plateau Averaging or Peak Value?

NASA Astrophysics Data System (ADS)

Steur, P. P. M.; Dematteis, R.

2014-04-01

With a certain regularity, national metrology institutes conduct comparisons of water triple-point (WTP) cells. The WTP is the most important fixed point for the International Temperature Scale of 1990 (ITS-90). In such comparisons, it is common practice to simply average all the single measured temperature points obtained on a single ice mantle. This practice is quite reasonable whenever the measurements show no time dependence in the results. Ever since the first Supplementary Information for the International Temperature Scale of 1990, published by the Bureau International des Poids et Mesures in Sèvres, it was strongly suggested to wait at least 1 day before taking measurements (now up to 10 days), in order for a newly created ice mantle to stabilize. This stabilization is accompanied by a change in temperature with time. A recent improvement in the sensitivity of resistance measurement enabled the Istituto Nazionale di Ricerca Metrologica to detect more clearly the (possible) change in temperature with time of the WTP on a single ice mantle, as for old borosilicate cells. A limited investigation was performed where the temperature of two cells was monitored day-by-day, from the moment of mantle creation, where it was found that with (old) borosilicate cells it may be counterproductive to wait the usual week before starting measurements. The results are presented and discussed, and it is suggested to adapt the standard procedure for comparisons of WTP cells allowing for a different data treatment with (old) borosilicate cells, because taking the temperature dependence into account will surely reduce the reported differences between cells.

Corrosion of inconel in high-temperature borosilicate glass melts containing simulant nuclear waste

NASA Astrophysics Data System (ADS)

Mao, Xianhe; Yuan, Xiaoning; Brigden, Clive T.; Tao, Jun; Hyatt, Neil C.; Miekina, Michal

2017-10-01

The corrosion behaviors of Inconel 601 in the borosilicate glass (MW glass) containing 25 wt.% of simulant Magnox waste, and in ZnO, Mn2O3 and Fe2O3 modified Mg/Ca borosilicate glasses (MZMF and CZMF glasses) containing 15 wt.% of simulant POCO waste, were evaluated by dimensional changes, the formation of internal defects and changes in alloy composition near corrosion surfaces. In all three kinds of glass melts, Cr at the inconel surface forms a protective Cr2O3 scale between the metal surface and the glass, and alumina precipitates penetrate from the metal surface or formed in-situ. The corrosion depths of inconel 601 in MW waste glass melt are greater than those in the other two glass melts. In MW glass, the Cr2O3 layer between inconel and glass is fragmented because of the reaction between MgO and Cr2O3, which forms the crystal phase MgCr2O4. In MZMF and CZMF waste glasses the layers are continuous and a thin (Zn, Fe, Ni, B)-containing layer forms on the surface of the chromium oxide layer and prevents Cr2O3 from reacting with MgO or other constituents. MgCr2O4 was observed in the XRD analysis of the bulk MW waste glass after the corrosion test, and ZrSiO4 in the MZMF waste glass, and ZrSiO4 and CaMoO4 in the CZMF waste glass.

Light, Strong Insulating Tiles

NASA Technical Reports Server (NTRS)

Cordia, E.; Schirle, J.

1987-01-01

Improved lightweight insulating silica/aluminum borosilicate/silicon carbide tiles combine increased tensile strength with low thermal conductivity. Changes in composition substantially improve heat-insulating properties of silica-based refractory tile. Silicon carbide particles act as high-emissivity radiation scatterers in tile material.

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

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.

Novel carbon-ion fuel cells. Final report, October 1, 1993--September 30, 1996

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

Cocks, F.H.

1997-01-01

Mixed lanthanide dicarbides having the fluorite crystal structure have been synthesized using the elemental lanthanide metals and elemental carbon that was 99.9% pure carbon-13 isotope. A two step process of first, arc furnace melting of the components, followed by an annealing step in a high vacuum furnace, was adopted as the standard method of fabricating small cast ingots of the dicarbides. The crystal structure of the various lanthanide dicarbides produced were confirmed by x-ray diffraction under protective atmospheres at both room temperature at Duke University and at high temperature at Oak Ridge National Laboratory. After more than 15 combinations ofmore » cerium or lanthanum with dopants were tried, low temperature x-ray diffraction showed that Ce{sub .5}Er{sub .5}C{sub 2} had been successfully stabilized and had the desired fluorite crystal structure at room temperature. The fluorite crystal structure lanthanide dicarbide cast ingots were further prepared by having flat and clean surfaces ground onto their surfaces by high-speed milling machines inside argon gas atmosphere gloveboxes. The surfaces thus created were then coated with carbon-12 by the arc evaporation method under low pressure argon gas. The coated ingots were then allowed to have carbon diffusion occur from the surface coating of carbon-12 into the ingot of dicarbide that had been synthesized from carbon-13. After the diffusion run, the cast ingots were slit down the axis perpendicular to the carbon coating. The fracture surface created was then squared and polished by high,speed milling in a glove box with a argon atmosphere. The high diffusion co-efficient of carbon in lanthanide dicarbides having the fluorite crystal structure would make possible the manufacture of a carbon-ion electrolyte for use in a battery or a fuel cell that could consume solid carbon as it`s feedstock.« less

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

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.

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.

Apparatus and method for automated monitoring of airborne bacterial spores

NASA Technical Reports Server (NTRS)

Ponce, Adrian (Inventor)

2009-01-01

An apparatus and method for automated monitoring of airborne bacterial spores. The apparatus is provided with an air sampler, a surface for capturing airborne spores, a thermal lysis unit to release DPA from bacterial spores, a source of lanthanide ions, and a spectrometer for excitation and detection of the characteristic fluorescence of the aromatic molecules in bacterial spores complexed with lanthanide ions. In accordance with the method: computer-programmed steps allow for automation of the apparatus for the monitoring of airborne bacterial spores.

Activated phosphors having matrices of yttrium-transition metal compound

DOEpatents

De Kalb, E.L.; Fassel, V.A.

1975-07-01

A method is described for preparing a phosphor composition containing a lanthanide activator element with a host matrix having a transition element as a major component. The host matrix is composed of certain rare earth phosphates or vanadates such as YPO$sub 4$ with a portion of the rare earth replaced with one or more of the transition elements. On x-ray or other electromagnetic excitation, trace lanthanide impurities or additives within the phosphor are spectrometrically determined from their characteristic luminescence. (auth)

TmDOTA -: A Sensitive Probe for MR Thermometry in Vivo

NASA Astrophysics Data System (ADS)

Zuo, Chun S.; Mahmood, Ashfaq; Sherry, A. Dean

2001-07-01

The lanthanide complex, thulium 1,4,7,10-tetraazacyclodo- decane-1,4,7,10-tetraacetic acid (TmDOTA-), has been investigated as an agent for MR thermometry in vivo. The chemical shifts of the TmDOTA- protons were highly sensitive to temperature at a clinically relevant field strength, yet insensitive to pH and the presence of Ca2+. Given the excellent stability of lanthanide-DOTA complexes and high thermal sensitivity, TmDOTA- is expected to be a good candidate for MR thermometry in vivo.

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.

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.

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 a 1D two-unit repeating (zweier) chain via corner-sharing. These 1D copper(I) chloride chains are inserted into the tunnels of the neodymium(III) tellurite via Nd-Cl-Cu bridges. Luminescent studies show that ErCuTe(2)O(6)Cl and Nd(4)Cu(TeO(3))(5)Cl(3) exhibit strong luminescence in the near-IR region. Magnetic measurements indicate the antiferromagnetic interactions between magnetic centers in these compounds.

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 having a strong charge-transfer character. A second primary result comes from an an x-ray excited optical luminescence (XEOL) study that demonstrates, for the first time, that the high flux of modern synchrotron light sources can induce high fractional populations of excited states in trivalent lanthanide phosphors. In this work we have identified the leading-order nonlinear-response mechanism by drawing on strong similarities between XEOL and cathodoluminescence. These results establish the groundwork for studies that would allow deeper inquiry into energy-transfer mechanisms through time-resolved x-ray pump/optical-probe spectroscopies, through time-resolved x-ray emission spectroscopy, or through quantifying of higher-order nonlinear effects at further-enhanced fractional excitation levels. The above scientific results are augmented by a supporting effort in instrumental methodology. This includes the development of high-efficiency x-ray emission spectrometers and their use in collaborations to study pressure-induced changes in f-electron physics and to characterize the intermediate states that occur after photoexcitation of the photosystem-II protein.

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.

Structure and bulk modulus of Ln-doped UO2 (Ln = La, Nd) at high pressure

NASA Astrophysics Data System (ADS)

Rittman, Dylan R.; Park, Sulgiye; Tracy, Cameron L.; Zhang, Lei; Palomares, Raul I.; Lang, Maik; Navrotsky, Alexandra; Mao, Wendy L.; Ewing, Rodney C.

2017-07-01

The structure of lanthanide-doped uranium dioxide, LnxU1-xO2-0.5x+y (Ln = La, Nd), was investigated at pressures up to ∼50-55 GPa. Samples were synthesized with different lanthanides at different concentrations (x ∼ 0.2 and 0.5), and all were slightly hyperstoichiometric (y ∼ 0.25-0.4). In situ high-pressure synchrotron X-ray diffraction was used to investigate their high-pressure phase behavior and determine their bulk moduli. All samples underwent a fluorite-to-cotunnite phase transformation with increasing pressure. The pressure of the phase transformation increased with increasing hyperstoichiometry, which is consistent with results from previous computational simulations. Bulk moduli are inversely proportional to both the ionic radius of the lanthanide and its concentration, as quantified using a weighted cationic radius ratio. This trend was found to be consistent with the behavior of other elastic properties measured for Ln-doped UO2, such as Young's modulus.

Air electrode composition for solid oxide fuel cell

DOEpatents

Kuo, Lewis; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

An air electrode composition for a solid oxide fuel cell is disclosed. The air electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO.sub.3. The A-site of the air electrode composition comprises a mixed lanthanide in combination with rare earth and alkaline earth dopants. The B-site of the composition comprises Mn in combination with dopants such as Mg, Al, Cr and Ni. The mixed lanthanide comprises La, Ce, Pr and, optionally, Nd. The rare earth A-site dopants preferably comprise La, Nd or a combination thereof, while the alkaline earth A-site dopant preferably comprises Ca. The use of a mixed lanthanide substantially reduces raw material costs in comparison with compositions made from high purity lanthanum starting materials. The amount of the A-site and B-site dopants is controlled in order to provide an air electrode composition having a coefficient of thermal expansion which closely matches that of the other components of the solid oxide fuel cell.

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

Che, Guang-Bo, E-mail: guangboche@jlnu.edu.cn; Liu, Shu-Yu; Zhang, Qing

Four new lanthanide complexes [Ln(O–NCP){sub 2}(NO{sub 3})]{sub n} based on multifunctional N,O-donor ligand 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (O–HNCP) and Ln(NO{sub 3}){sub 3}·6H{sub 2}O (Ln=Nd(1), La(2), Sm(3), Eu(4)) have been achieved under hydrothermal conditions and characterized by elemental analyses, infrared spectra and single crystal X-ray diffraction. Structural analyses revealed that all of these four complexes possess similar two-dimensional layer structures. In addition, thermal stability and luminescent properties of these complexes were also investigated. - Graphical abstract: A series of lanthanide(III) coordination polymers with intriguing structures based on 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline ligand have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have beenmore » investigated. - Highlights: • Four lanthanide(III) complexes have been hydrothermally synthesized. • The N,O-donor O–HNCP was used as the ligand. • TGA and PL properties of complexes 1–4 have been investigated.« less

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

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

Lines, Amanda M.; Wang, Zheming; Clark, Sue B.

Fast, cost effective, and robust means of detecting and quantifying lanthanides are needed for supporting more efficient tracking within the nuclear, medicinal, and industrial fields. Spectroelectrochemistry (SEC) is a powerful technique combining electrochemistry and spectroscopy that can meet those needs. The primary limitation of SEC as a detection method for lanthanides is their low molar absorptivity in absorbance based measurements and low emission intensities in fluorescence based measurements; both lead to high limits of detection. These limitations can be circumvented by complexing the lanthanides with sensitizing ligands that enhance fluorescence, thereby dropping the limits of detection. Complexation may also stabilizemore » the metal ions in solution and improve the electrochemical reversibility, or Nernstian behavior, of the redox couples. To demonstrate this concept, studies were completed using europium in complexes with four different sensitizing ligands. Initial work indicates Eu in the four complexes studied does display the necessary characteristics for SEC analysis, which was successfully and reproducibly applied to all Eu complexes.« less

Air electrode composition for solid oxide fuel cell

DOEpatents

Kuo, L.; Ruka, R.J.; Singhal, S.C.

1999-08-03

An air electrode composition for a solid oxide fuel cell is disclosed. The air electrode material is based on lanthanum manganite having a perovskite-like crystal structure ABO{sub 3}. The A-site of the air electrode composition comprises a mixed lanthanide in combination with rare earth and alkaline earth dopants. The B-site of the composition comprises Mn in combination with dopants such as Mg, Al, Cr and Ni. The mixed lanthanide comprises La, Ce, Pr and, optionally, Nd. The rare earth A-site dopants preferably comprise La, Nd or a combination thereof, while the alkaline earth A-site dopant preferably comprises Ca. The use of a mixed lanthanide substantially reduces raw material costs in comparison with compositions made from high purity lanthanum starting materials. The amount of the A-site and B-site dopants is controlled in order to provide an air electrode composition having a coefficient of thermal expansion which closely matches that of the other components of the solid oxide fuel cell. 3 figs.

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.

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.

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.

Eu(III) and Tb(III) complexes with the nonsteroidal anti-inflammatory drug carprofen: synthesis, crystal structure, and photophysical properties.

PubMed

Zhou, Xianju; Zhao, Xiaoqi; Wang, Yongjie; Wu, Bing; Shen, Jun; Li, Li; Li, Qingxu

2014-12-01

Two new lanthanide complexes with general formula [Ln2(carprofen)6(DMF)2] (Ln = Eu (1), Tb (2), DMF = N,N-dimethylformamide, carprofen = 6-chloro-α-methylcarbazole-2-acetic acid) have been synthesized by a hydrothermal method. Complex 1 was characterized by single-crystal X-ray diffraction (XRD), and it was found to crystallize in the monoclinic space group C2/c. The coordination of the ligand to the lanthanide ion has been investigated by Fourier-transform infrared (FTIR) spectra and ultraviolet-visible (UV-vis) absorption spectra. Complex 1 emits red light, but the antenna effect of the ligand is not effective, whereas complex 2 presents intense green emission with effective energy transfer from the ligand. The different performance of the two complexes is related to the energy matching between the excited states of the lanthanide ion and the triplet state of the ligand. The intramolecular energy transfer mechanisms are also discussed.

CaO-MgO-Al 2O 3-SiO 2 (CMAS) corrosion of Gd 2Zr 2O 7 and Sm 2Zr 2O 7

DOE PAGES

Wang, Honglong; Bakal, Ahmet; Zhang, Xingxing; ...

2016-08-08

Ceramic thermal barrier coatings are applied to superalloys used in gas turbine engineering to increase the operating temperature and the energy conversion efficiency. However, dust consisting of CaO-MgO-Al 2O 3-SiO 2 (CMAS) from the air can be injected into the engines and corrode the thermal barrier coatings. Lanthanide zirconates are promising materials in thermal barrier coatings due to their low thermal conductivities, good phase stability and good corrosion resistance. However, the corrosion resistance mechanism of CMAS on lanthanide zirconates is still not clearly understood. In this work, the corrosion mechanism of Gd 2Zr 2O 7 and Sm 2Zr 2O 7more » in CMAS is studied. Here, the results show that the CMAS can easily react with lanthanide zirconate thermal barrier coatings to form a dense layer, which can resist further corrosion« less

Structure and bulk modulus of Ln-doped UO 2 (Ln = La, Nd) at high pressure

DOE PAGES

Rittman, Dylan R.; Park, Sulgiye; Tracy, Cameron L.; ...

2017-04-10

The structure of lanthanide-doped uranium dioxide, Ln xU 1-xO 2-0.5x+y (Ln = La, Nd), was investigated at pressures up to ~50–55 GPa. Samples were synthesized with different lanthanides at different concentrations (x ~ 0.2 and 0.5), and all were slightly hyperstoichiometric (y ~ 0.25–0.4). In situ high-pressure synchrotron X-ray diffraction was used to investigate their high-pressure phase behavior and determine their bulk moduli. All samples underwent a fluorite-to-cotunnite phase transformation with increasing pressure. The pressure of the phase transformation increased with increasing hyperstoichiometry, which is consistent with results from previous computational simulations. Bulk moduli are inversely proportional to both themore » ionic radius of the lanthanide and its concentration, as quantified using a weighted cationic radius ratio. As a result, this trend was found to be consistent with the behavior of other elastic properties measured for Ln-doped UO 2, such as Young's modulus.« 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.

The Electromagnetic Counterpart of the Binary Neutron Star Merger LIGO/Virgo GW170817. IV. Detection of Near-infrared Signatures of r-process Nucleosynthesis with Gemini-South

NASA Astrophysics Data System (ADS)

Chornock, R.; Berger, E.; Kasen, D.; Cowperthwaite, P. S.; Nicholl, M.; Villar, V. A.; Alexander, K. D.; Blanchard, P. K.; Eftekhari, T.; Fong, W.; Margutti, R.; Williams, P. K. G.; Annis, J.; Brout, D.; Brown, D. A.; Chen, H.-Y.; Drout, M. R.; Farr, B.; Foley, R. J.; Frieman, J. A.; Fryer, C. L.; Herner, K.; Holz, D. E.; Kessler, R.; Matheson, T.; Metzger, B. D.; Quataert, E.; Rest, A.; Sako, M.; Scolnic, D. M.; Smith, N.; Soares-Santos, M.

2017-10-01

We present a near-infrared spectral sequence of the electromagnetic counterpart to the binary neutron star merger GW170817 detected by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo. Our data set comprises seven epochs of J+H spectra taken with FLAMINGOS-2 on Gemini-South between 1.5 and 10.5 days after the merger. In the initial epoch, the spectrum is dominated by a smooth blue continuum due to a high-velocity, lanthanide-poor blue kilonova component. Starting the following night, all of the subsequent spectra instead show features that are similar to those predicted in model spectra of material with a high concentration of lanthanides, including spectral peaks near 1.07 and 1.55 μm. Our fiducial model with 0.04 M ⊙ of ejecta, an ejection velocity of v = 0.1c, and a lanthanide concentration of X lan = 10-2 provides a good match to the spectra taken in the first five days, although it over-predicts the late-time fluxes. We also explore models with multiple fitting components, in each case finding that a significant abundance of lanthanide elements is necessary to match the broad spectral peaks that we observe starting at 2.5 days after the merger. These data provide direct evidence that binary neutron star mergers are significant production sites of even the heaviest r-process elements.

The Electromagnetic Counterpart of the Binary Neutron Star Merger LIGO/Virgo GW170817. IV. Detection of Near-infrared Signatures of r-process Nucleosynthesis with Gemini-South

DOE PAGES

Chornock, R.; Berger, E.; Kasen, D.; ...

2017-10-16

Here, we present a near-infrared spectral sequence of the electromagnetic counterpart to the binary neutron star merger GW170817 detected by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo. Our data set comprises seven epochs of J+H spectra taken with FLAMINGOS-2 on Gemini-South between 1.5 and 10.5 days after the merger. In the initial epoch, the spectrum is dominated by a smooth blue continuum due to a high-velocity, lanthanide-poor blue kilonova component. Starting the following night, all of the subsequent spectra instead show features that are similar to those predicted in model spectra of material with a high concentration of lanthanides, including spectralmore » peaks near 1.07 and 1.55 μm. Our fiducial model with 0.04 M ⊙ of ejecta, an ejection velocity of v = 0.1c, and a lanthanide concentration of X lan = 10 –2 provides a good match to the spectra taken in the first five days, although it over-predicts the late-time fluxes. We also explore models with multiple fitting components, in each case finding that a significant abundance of lanthanide elements is necessary to match the broad spectral peaks that we observe starting at 2.5 days after the merger. These data provide direct evidence that binary neutron star mergers are significant production sites of even the heaviest r-process elements.« less

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

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

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

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.

The Electromagnetic Counterpart of the Binary Neutron Star Merger LIGO/Virgo GW170817. IV. Detection of Near-infrared Signatures of r -process Nucleosynthesis with Gemini-South

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

Chornock, R.; Berger, E.; Cowperthwaite, P. S.

We present a near-infrared spectral sequence of the electromagnetic counterpart to the binary neutron star merger GW170817 detected by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo. Our data set comprises seven epochs of J + H spectra taken with FLAMINGOS-2 on Gemini-South between 1.5 and 10.5 days after the merger. In the initial epoch, the spectrum is dominated by a smooth blue continuum due to a high-velocity, lanthanide-poor blue kilonova component. Starting the following night, all of the subsequent spectra instead show features that are similar to those predicted in model spectra of material with a high concentration of lanthanides, includingmore » spectral peaks near 1.07 and 1.55 μ m. Our fiducial model with 0.04 M {sub ⊙} of ejecta, an ejection velocity of v = 0.1 c , and a lanthanide concentration of X {sub lan} = 10{sup −2} provides a good match to the spectra taken in the first five days, although it over-predicts the late-time fluxes. We also explore models with multiple fitting components, in each case finding that a significant abundance of lanthanide elements is necessary to match the broad spectral peaks that we observe starting at 2.5 days after the merger. These data provide direct evidence that binary neutron star mergers are significant production sites of even the heaviest r -process elements.« less

The Electromagnetic Counterpart of the Binary Neutron Star Merger LIGO/Virgo GW170817. IV. Detection of Near-infrared Signatures of r-process Nucleosynthesis with Gemini-South

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

Chornock, R.; Berger, E.; Kasen, D.

Here, we present a near-infrared spectral sequence of the electromagnetic counterpart to the binary neutron star merger GW170817 detected by Advanced Laser Interferometer Gravitational-wave Observatory (LIGO)/Virgo. Our data set comprises seven epochs of J+H spectra taken with FLAMINGOS-2 on Gemini-South between 1.5 and 10.5 days after the merger. In the initial epoch, the spectrum is dominated by a smooth blue continuum due to a high-velocity, lanthanide-poor blue kilonova component. Starting the following night, all of the subsequent spectra instead show features that are similar to those predicted in model spectra of material with a high concentration of lanthanides, including spectralmore » peaks near 1.07 and 1.55 μm. Our fiducial model with 0.04 M ⊙ of ejecta, an ejection velocity of v = 0.1c, and a lanthanide concentration of X lan = 10 –2 provides a good match to the spectra taken in the first five days, although it over-predicts the late-time fluxes. We also explore models with multiple fitting components, in each case finding that a significant abundance of lanthanide elements is necessary to match the broad spectral peaks that we observe starting at 2.5 days after the merger. These data provide direct evidence that binary neutron star mergers are significant production sites of even the heaviest r-process elements.« less

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.

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

DOE PAGES

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa; ...

2017-01-24

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

BISON Investigation of the Effect of the Fuel- Cladding Contact Irregularities on the Peak Cladding Temperature and FCCI Observed in AFC-3A Rodlet 4

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

Medvedev, Pavel G.

2016-09-01

The primary objective of this report is to document results of BISON analyses supporting Fuel Cycle Research and Development (FCRD) activities. Specifically, the present report seeks to provide explanation for the microstructural features observed during post irradiation examination of the helium-bonded annular U-10Zr fuel irradiated during the AFC-3A experiment. Post irradiation examination of the AFC-3A rodlet revealed microstructural features indicative of the fuel-cladding chemical interaction (FCCI) at the fuel-cladding interface. Presence of large voids was also observed in the same locations. BISON analyses were performed to examine stress and temperature profiles and to investigate possible correlation between the voids andmore » FCCI. It was found that presence of the large voids lead to a formation of circumferential temperature gradients in the fuel that may have redirected migrating lanthanides to the locations where fuel and cladding are in contact. Resulting localized increase of lanthanide concentration is expected to accelerate FCCI. The results of this work provide important guidance to the post irradiation examination studies. Specifically, the hypothesis of lanthanides being redirected from the voids to the locations where the fuel and the cladding are in contact should be verified by conducting quantitative electron microscopy or Electron Probe Micro-Analyzer (EPMA). The results also highlight the need for computer models capable of simulating lanthanide diffusion in metallic fuel and establish a basis for validation of such models.« less

Alleviating Luminescence Concentration Quenching in Upconversion Nanoparticles through Organic Dye Sensitization.

PubMed

Wei, Wei; Chen, Guanying; Baev, Alexander; He, Guang S; Shao, Wei; Damasco, Jossana; Prasad, Paras N

2016-11-23

The phenomenon of luminescence concentration quenching exists widely in lanthanide-based luminescent materials, setting a limit on the content of lanthanide emitter that can be used to hold the brightness. Here, we introduce a concept involving energy harvesting by a strong absorber and subsequent energy transfer to a lanthanide that largely alleviates concentration quenching. We apply this concept to Nd 3+ emitters, and we show both experimentally and theoretically that the optimal doping concentration of Nd 3+ in colloidal NaYF 4 :Nd upconverting nanoparticles is increased from 2 to 20 mol% when an energy harvestor organic dye (indocyanine green, ICG) is anchored onto the nanoparticle surface, resulting in ∼10 times upconversion brightness. Theoretical analysis indicated that a combination of efficient photon harvesting due to the large absorption cross section of ICG (∼30 000 times higher than that of Nd 3+ ), non-radiative energy transfer (efficiency ∼57%) from ICG to the surface bound Nd 3+ ions, and energy migration among the Nd 3+ ions was able to activate Nd 3+ ions inside the nanoparticle at a rate comparable with that of the pronounced short-range quenching interaction at elevated Nd 3+ concentrations. This resulted in the optimal concentration increase to produce significantly enhanced brightness. Theoretical modeling shows a good agreement with the experimental observation. This strategy can be utilized for a wide range of other lanthanide-doped nanomaterials being utilized for bioimaging and solar cell applications.

Large Binocular Telescope project

NASA Astrophysics Data System (ADS)

Hill, John M.; Salinari, Piero

2000-08-01

The Large Binocular Telescope (LBT) Project is a collaboration between institutions in Arizona, Germany, Italy, and Ohio. The telescope will have two 8.4 meter diameter primary mirrors phased on a common mounting with a 22.8 meter baseline. The second of two borosilicate honeycomb primary mirrors for LBT is being case at the Steward Observatory Mirror Lab this year. The baseline optical configuration of LBT includes adaptive infrared secondaries of a Gregorian design. The F/15 secondaries are undersized to provide a low thermal background focal plane which is unvignetted over a 4 arcminute diameter field-of- view. The interferometric focus combining the light from the two 8.4 meter primaries will reimage the two folded Gregorian focal planes to three central locations. The telescope elevation structure accommodates swing arm spiders which allow rapid interchange of the various secondary and tertiary mirrors as well as prime focus cameras. Maximum stiffness and minimal thermal disturbance were important drivers for the design of the telescope in order to provide the best possible images for interferometric observations. The telescope structure accommodates installation of a vacuum bell jar for aluminizing the primary mirrors in-situ on the telescope. The telescope structure is being fabricated in Italy by Ansaldo Energia S.p.A. in Milan. After pre-erection in the factory, the telescope will be shipped to Arizona in early 2001. The enclosure is being built on Mt. Graham under the auspices of Hart Construction Management Services of Safford, Arizona. The enclosure will be completed by late 2001 and ready for telescope installation.

Silicate, borosilicate, and borate bioactive glass scaffolds with controllable degradation rate for bone tissue engineering applications. II. In vitro and in vivo biological evaluation.

PubMed

Fu, Qiang; Rahaman, Mohamed N; Bal, B Sonny; Bonewald, Lynda F; Kuroki, Keiichi; Brown, Roger F

2010-10-01

In Part I, the in vitro degradation of bioactivAR52115e glass scaffolds with a microstructure similar to that of human trabecular bone, but with three different compositions, was investigated as a function of immersion time in a simulated body fluid. The glasses consisted of a silicate (13-93) composition, a borosilicate composition (designated 13-93B1), and a borate composition (13-93B3), in which one-third or all of the SiO2 content of 13-93 was replaced by B2O3, respectively. This work is an extension of Part I, to investigate the effect of the glass composition on the in vitro response of osteogenic MLO-A5 cells to these scaffolds, and on the ability of the scaffolds to support tissue infiltration in a rat subcutaneous implantation model. The results of assays for cell viability and alkaline phosphatase activity showed that the slower degrading silicate 13-93 and borosilicate 13-93B1 scaffolds were far better than the borate 13-93B3 scaffolds in supporting cell proliferation and function. However, all three groups of scaffolds showed the ability to support tissue infiltration in vivo after implantation for 6 weeks. The results indicate that the required bioactivity and degradation rate may be achieved by substituting an appropriate amount of SiO2 in 13-93 glass with B2O3, and that these trabecular glass scaffolds could serve as substrates for the repair and regeneration of contained bone defects. Copyright 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010.

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.

Method and apparatus for detecting and quantifying bacterial spores on a surface

NASA Technical Reports Server (NTRS)

Ponce, Adrian (Inventor)

2009-01-01

A method and an apparatus for detecting and quantifying bacterial spores on a surface. In accordance with the method: bacterial spores are transferred from a place of origin to a test surface, the test surface comprises lanthanide ions. Aromatic molecules are released from the bacterial spores; a complex of the lanthanide ions and aromatic molecules is formed on the test surface, the complex is excited to generate a characteristic luminescence on the test surface; the luminescence on the test surface is detected and quantified.

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.

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.

Method and Apparatus for Detecting and Quantifying Bacterial Spores on a Surface

NASA Technical Reports Server (NTRS)

Ponce, Adrian (Inventor)

2016-01-01

A method and an apparatus for detecting and quantifying bacterial spores on a surface. In accordance with the method: bacterial spores are transferred from a place of origin to a test surface, the test surface comprises lanthanide ions. Aromatic molecules are released from the bacterial spores; a complex of the lanthanide ions and aromatic molecules is formed on the test surface, the complex is excited to generate a characteristic luminescence on the test surface; the luminescence on the test surface is detected and quantified.

Second-order non-linear optical studies on CdS microcrystallite-doped alkali borosilicate glasses

NASA Astrophysics Data System (ADS)

Liu, Hao; Liu, Qiming; Wang, Mingliang; Zhao, Xiujian

2007-05-01

CdS microcrystal-doped alkali borosilicate glasses were prepared by conventional fusion and heat-treatment method. Utilizing Maker fringe method, second-harmonic generation (SHG) was both observed from CdS-doped glasses before and after certain thermal/electrical poling. While because the direction of polarization axes of CdS crystals formed in the samples is random or insufficient interferences of generated SH waves occur, the fringe patterns obtained in samples without poling treatments showed no fine structures. For the poled samples, larger SH intensity has been obtained than that of the samples without any poling treatments. It was considered that the increase of an amount of hexagonal CdS in the anode surface layer caused by the applied dc field increased the SH intensity. The second-order non-linearity χ(2) was estimated to be 1.23 pm/V for the sample poled with 2.5 kV at 360 °C for 30 min.

Release of Gd-ions from peralkaline borosilicate glass in pure water for neutrino detection in Water-Cherenkov Detectors

NASA Astrophysics Data System (ADS)

Dongol, R.; Sundaram, S. K.

2017-09-01

The addition of Gadolinium (Gd)-based salt, specially GdCl3, in the Water Cherenkov Detectors (WCDs) enhances the sensitivity to neutrino detection. However, the unwanted Cl-based byproducts, significantly reduces the transparency of water and sensitivity of WCDs. An alternative method, to introduce Gd-ions in the WCDs, is through Gd-release from a custom designed Gd-doped glass, when in contact with water. This can potentially eliminate the use of Gd-based salts and byproducts. In this work, we report the Gd-ions release for a Gd-doped peralkaline (Na/Al > 1) borosilicate glass, which closely represents photomultiplier tube (PMT) glass composition used in WCDs. The purpose of the paper is to show that the Gd-ion release from a custom designed glass in the form of beads or powders is feasible and could be used as a controlled Gd-source in future WCDs to enhance neutrino detection. In addition, we present our results of Gd-solubility in the base glass composition.

Failure kinetics in borosilicate glass during rod impact

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

Orphal, Dennis L.; Anderson, Charles E. Jr.; Behner, Thilo

2007-12-12

Failure front (FF) and penetration velocity have been measured for long gold rods impacting and penetrating borosilicate (BS) glass. Data are obtained by visualizing simultaneously FF propagation with a high speed camera and rod penetration with flash X-rays. Results for BS glass are qualitatively similar to those of DEDF (PbO) glass. FF velocity rapidly decreases from an initial value to a lower, approximately constant value. FF velocity increases with impact velocity, v{sub p}. The FF velocity remains significantly lower than the shear velocity, even at the highest impact velocity tested, about 2.5 km/s. The ratio of the FF velocity tomore » the rod penetration velocity, v{sub F}/u, decreases with increasing v{sub p} and appears to be approaching v{sub F}/u = 1 asymptotically, as observed previously for DEDF glass. The separation of the FF and the tip of the rod decreases with increasing impact velocity. Importantly, since v{sub F}/u{>=}1, the gold rod is always penetrating glass behind the FF.« less

Failure and penetration response of borosilicate glass during short-rod impact

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

Anderson, C. E. Jr.; Orphal, D. L.; Behner, Th.

2007-12-12

The failure characterization of brittle materials like glass is of fundamental importance in describing the penetration resistance against projectiles. A critical question is whether this failure front remains 'steady' after the driving stress is removed. A test series with short gold rods (D = 1 mm, L/D{approx_equal}5-11) impacting borosilicate glass at {approx}1 to 2 km/s was carried out to investigate this question. The reverse ballistic method was used for the experiments, and the impact and penetration process was observed simultaneously with five flash X-rays and a 16-frame high-speed optical camera. Very high measurement accuracy was established to ensure reliable results.more » Results show that the failure front induced by rod impact and penetration does arrest (ceases to propagate) after the rod is totally eroded inside the glass. The impact of a second rod after a short time delay reinitiates the failure front at about the same speed.« less

Experimental and computed results investigating time-dependent failure in a borosilicate glass

NASA Astrophysics Data System (ADS)

Chocron, Sidney; Barnette, Darrel; Holmquist, Timothy; Anderson, Charles E.; Bigger, Rory; Moore, Thomas

2017-01-01

Symmetric plate-impact tests of borosilicate glass were performed from low (116 m/s) to higher (351 m/s) velocities. The tests were recorded with an ultra-high-speed camera to see the shock and failure propagation. The velocity of the back of the target was also recorded with a PDV (Photon Doppler Velocimeter). The images show failure nucleation sites that trail the shock wave. Interestingly, even though the failure wave is clearly seen, the PDV never detected the expected recompression wave. The reason might be that at these low impact velocities the recompression wave is too small to be seen and is lost in the noise. This work also presents a new way to interpret the signals from the PDV. By letting part of the signal travel through the target and reflect on the impact side, it is possible to see the PDV decrease in intensity with time, probably due to the damage growth behind the shock wave.

Process parameter effects on material removal in magnetorheological finishing of borosilicate glass.

PubMed

Miao, Chunlin; Lambropoulos, John C; Jacobs, Stephen D

2010-04-01

We investigate the effects of processing parameters on material removal for borosilicate glass. Data are collected on a magnetorheological finishing (MRF) spot taking machine (STM) with a standard aqueous magnetorheological (MR) fluid. Normal and shear forces are measured simultaneously, in situ, with a dynamic dual load cell. Shear stress is found to be independent of nanodiamond concentration, penetration depth, magnetic field strength, and the relative velocity between the part and the rotating MR fluid ribbon. Shear stress, determined primarily by the material mechanical properties, dominates removal in MRF. The addition of nanodiamond abrasives greatly enhances the material removal efficiency, with the removal rate saturating at a high abrasive concentration. The volumetric removal rate (VRR) increases with penetration depth but is insensitive to magnetic field strength. The VRR is strongly correlated with the relative velocity between the ribbon and the part, as expected by the Preston equation. A modified removal rate model for MRF offers a better estimation of MRF removal capability by including nanodiamond concentration and penetration depth.

Application of a novel new multispectral nanoparticle tracking technique

NASA Astrophysics Data System (ADS)

McElfresh, Cameron; Harrington, Tyler; Vecchio, Kenneth S.

2018-06-01

Fast, reliable, and accurate particle size analysis techniques must meet the demands of evolving industrial and academic research in areas of functionalized nanoparticle synthesis, advanced materials development, and other nanoscale enabled technologies. In this study a new multispectral particle tracking analysis (m-PTA) technique enabled by the ViewSizer™ 3000 (MANTA Instruments, USA) was evaluated using solutions of monomodal and multimodal gold and polystyrene latex nanoparticles, as well as a spark eroded polydisperse 316L stainless steel nanopowder, and large (non-Brownian) borosilicate particles. It was found that m-PTA performed comparably to the DLS in evaluation of monomodal particle size distributions. When measuring bimodal, trimodal and polydisperse solutions, the m-PTA technique overwhelmingly outperformed traditional dynamic light scattering (DLS) in both peak detection and relative particle concentration analysis. It was also observed that the m-PTA technique is less susceptible to large particle overexpression errors. The ViewSizer™ 3000 was also found to be successful in accurately evaluating sizes and concentrations of monomodal and bimodal sinking borosilicate particles.

The role of troublesome components in plutonium vitrification

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

Li, Hong; Vienna, J.D.; Peeler, D.K.

1996-05-01

One option for immobilizing surplus plutonium is vitrification in a borosilicate glass. Two advantages of the glass form are (1) high tolerance to feed variability and, (2) high solubility of some impurity components. The types of plutonium-containing materials in the United States inventory include: pits, metals, oxides, residues, scrap, compounds, and fuel. Many of them also contain high concentrations of carbon, chloride, fluoride, phosphate, sulfate, and chromium oxide. To vitrify plutonium-containing scrap and residues, it is critical to understand the impact of each component on glass processing and chemical durability of the final product. This paper addresses glass processing issuesmore » associated with these troublesome components. It covers solubility limits of chlorine, fluorine, phosphate, sulfate, and chromium oxide in several borosilicate based glasses, and the effect of each component on vitrification (volatility, phase segregation, crystallization, and melt viscosity). Techniques (formulation, pretreatment, removal, and/or dilution) to mitigate the effect of these troublesome components are suggested.« less

Size determination of gold nanoparticles in silicate glasses by UV-Vis spectroscopy

NASA Astrophysics Data System (ADS)

Ali, Shahid; Khan, Younas; Iqbal, Yaseen; Hayat, Khizar; Ali, Muhammad

2017-01-01

A relatively easier and more accurate method for the determination of average size of metal nanoparticles/aggregates in silicate glasses based on ultraviolet visible (UV-Vis) spectra fitted with the Mie and Mie-Gans models was reported. Gold ions were diffused into sodalime silicate and borosilicate glasses by field-assisted solid-state ion-exchange technique using the same experimental parameters for both glasses. Transmission electron microscopy was performed to directly investigate the morphology and distribution of the dopant nanoparticles. UV-Vis spectra of the doped glasses showed broad surface plasmon resonance peaks in their fingerprint regions, i.e., at 525 and 500 nm for sodalime silicate and borosilicate glass matrices, respectively. These spectra were fitted with the Mie model for spherical nanoparticles and the Mie-Gans model for spheroidal nanoparticles. Although both the models were developed for colloidal nanoparticles, the size of the nanoparticles/aggregates calculated was accurate to within ˜10% in both the glass matrices in comparison to the size measured directly from the transmission electron microscope images.

Luminescence properties of Dy3+ doped lithium zinc borosilicate glasses for photonic applications.

PubMed

Jaidass, N; Krishna Moorthi, C; Mohan Babu, A; Reddi Babu, M

2018-03-01

Different concentrations of Dy 3+ ions doped lithium zinc borosilicate glasses of chemical composition (30-x) B 2 O 3 - 25 SiO 2 -10 Al 2 O 3 -30 LiF - 5 ZnO - x Dy 2 O 3 (x = 0, 0.1, 0.5, 1.0 and 2.0 mol%) were prepared by the melt quenching technique. The prepared glasses were investigated through X-ray diffraction, optical absorption, photoluminescence and decay measurements. Intensities of absorption bands expressed in terms of oscillator strengths (f) were used to determine the Judd-Ofelt (J-O) intensity parameters Ω λ (λ = 2, 4 and 6). The evaluated J-O parameters were used to determine the radiative parameters such as transition probabilities (A R ), total transition probability rate (A T ), radiative lifetime (τ R ) and branching ratios (β R ) for the excited 4 F 9/2 level of Dy 3+ ions. The chromaticity coordinates determined from the emission spectra were found to be located in the white light region of CIE chromaticity diagram.

Cerium doped glasses: search for a new scintillator

NASA Astrophysics Data System (ADS)

Kielty, Matthew William

Single crystals have been the standard material when it comes to scintillators, but with the ability to easily be produced at a considerably lower cost and fabricated into tailored sizes and shapes there is increasing interest in the development of glass scintillators as an alternative. Ce-doped borosilicate and phosphate glasses were investigated focusing on the effect of different modifiers on their optical properties and luminescence. The borosilicate glasses were prepared aiming at the detection of thermal neutrons, utilizing B-10, while the phosphate glasses were targeting the detection of gamma-rays taking advantage of high Z elements such as, Ba, Bi, Ta, Pb and W. Structural characteristics determined by Raman spectroscopy were coupled with results from photoluminescence and UV-visible transmission measurements, while the index of refraction was estimated using the Gladstone-Dale relation using experimentally obtained density values. This work revealed barium, with its superior optical transmission and luminescent properties, to be the best high Z element for inclusion in the phosphate glasses studied.

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 of phosphoric acid.

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 calculations, while being hundreds of times faster.

A case study of energy transfer mechanism from uranium to europium in ZnAl2O4 spinel host by photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Kumar, Mithlesh; Mohapatra, M.

2016-04-01

Zinc aluminate (ZAO), a member of spinel class of inorganic compounds has been of much interest of late due to its wide range of use in catalysis, optical, electronic and ceramic industries. When doped with several lanthanides, this material has proved to be a potential host matrix for phosphors. As lanthanides suffer from poor (direct) excitation and emission cross sections, the use of a co-dopant ion can help to circumvent this and extract better emission from a lanthanide doped ZAO system. In this connection, energy transfer mechanism from uranium to europium in the ZAO host was investigated by photoluminescence spectroscopic technique. It was seen that uranium gets stabilized in the hexavalent state as UO66 - (octahedral uranate) where as the lanthanide ion, Eu is stabilized in its trivalent state in the ZAO host. In the co-doped system, an efficient energy transfer pathway from the uranate to europium ion was observed. Based upon emission and life time data a suitable mechanism was proposed for the energy transfer (quenching) process. It was proposed that after excitation by photons, the uranate ions transfer their energy to nearby 5D1 level of Eu3 + ions which non-radiatively de-excites to the corresponding lower levels of 5D0. Further this 5D0 level decays in a radiative mode to the 7F manifold giving the characteristic emission profile of trivalent Eu. It was proposed that both static and dynamic types of energy transfer mechanism were responsible for this process.

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.

Development of a High Ionization Efficiency Molten Glass Ion Emitter for TIMS

NASA Astrophysics Data System (ADS)

Cheversia, M. B.; Farmer, G.; Koval, C.; David, D.

2006-12-01

Thermal ionization mass spectrometry (TIMS) remains the method of choice for many high precision isotope ratio determinations but is handicapped by the use of low efficiency ion emitters. For example, ionization efficiencies from molten glass emitters (Si-gel) used for such elements as Pb, Cr, Ru, and Ag are in the range of 0.05-2%, which limits the sample size and the precision to which isotope ratio determinations for these elements can be made. Our aim is to improve the ionization efficiency of the molten glass ion emitter using electrochemical methods. This work builds on recent observations indicating that many metals doped in borosilicate glasses (eg. Bi, Ag), are emitted from the liquid glass (in vacuo) primarily as the neutral metal atom. Our goal is to increase the proportion of singly charged metal atoms in metal-doped molten glasses via oxidation induced by electrochemical methods and to assess whether such in situ oxidation of metal atoms leads to an increase in emitted metal ions. Our experiments are performed in a vacuum chamber that mimics conditions in the sample chamber of the TIMS. A borosilicate glass sample is placed in a miniature ceramic crucible. The crucible contains working and reference Pt electrodes, and a Pt thermocouple. The entire apparatus is wrapped with a resistively heated Ta wire until temperatures in the glass reach approximately 1400°C, to ensure that the glass is molten. By this method, we have produced simple cyclic voltammograms that suggest that over a 100°C temperature range, the borosilicate glass undergoes a transition from resistive behavior as a solid, to a conductive electrolyte, as a molten liquid glass, as expected. The change is evident as an order of magnitude decrease in resistivity of the glass, as interpreted from the voltammograms. The voltammograms produced for the pure borosilicate glasses represent the baseline against which we will compare the electrochemical characteristics of Pb doped glasses. These experiments are currently underway and are designed to determine the speciation of lead in the glass, and to determine the voltages required to induce cathodic currents in the glass corresponding to ionization to Pb+ and Pb2+. By generating a cathodic current and an increased concentration of the oxidized species, we hope to ultimately generate a higher intensity ion beam, higher ionization efficiency for low efficiency elements, and higher precision analyses on small sample sizes for the TIMS.

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.

Fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1999-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

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.

Experimental insights on the electron transfer and energy transfer processes between Ce{sup 3+}-Yb{sup 3+} and Ce{sup 3+}-Tb{sup 3+} in borate glass

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

Sontakke, Atul D., E-mail: sontakke.atul.55a@st.kyoto-u.ac.jp; Katayama, Yumiko; Tanabe, Setsuhisa

2015-03-30

A facile method to describe the electron transfer and energy transfer processes among lanthanide ions is presented based on the temperature dependent donor luminescence decay kinetics. The electron transfer process in Ce{sup 3+}-Yb{sup 3+} exhibits a steady rise with temperature, whereas the Ce{sup 3+}-Tb{sup 3+} energy transfer remains nearly unaffected. This feature has been investigated using the rate equation modeling and a methodology for the quantitative estimation of interaction parameters is presented. Moreover, the overall consequences of electron transfer and energy transfer process on donor-acceptor luminescence behavior, quantum efficiency, and donor luminescence decay kinetics are discussed in borate glass host.more » The results in this study propose a straight forward approach to distinguish the electron transfer and energy transfer processes between lanthanide ions in dielectric hosts, which is highly advantageous in view of the recent developments on lanthanide doped materials for spectral conversion, persistent luminescence, and related applications.« less

Microstructural characterization of annealed U-12Zr-4Pd and U-12Zr-4Pd-5Ln: Investigating Pd as a metallic fuel additive

NASA Astrophysics Data System (ADS)

Benson, Michael T.; He, Lingfeng; King, James A.; Mariani, Robert D.

2018-04-01

Palladium is being investigated as a potential additive to metallic fuel to control fuel-cladding chemical interaction (FCCI). A primary cause of FCCI is the lanthanide fission products moving to the fuel periphery and interacting with the cladding. This interaction will lead to wastage of the cladding and, given enough time or burn-up, eventually to a cladding breach. The current study is a scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization of annealed U-12Zr-4Pd and U-12Zr-4Pd-5Ln, where Ln = 53Nd-25Ce-16Pr-6La. The present study shows that Pd preferentially binds the lanthanides over other fuel constituents, which may prevent lanthanide migration and interaction with the cladding during irradiation. The SEM analysis indicates the 1:1 Pd-Ln compound is being formed, while the TEM analysis, due to higher resolution, found the 1:1 compound, as well as Pd-rich compounds Pd2Ln and Pd3Ln2.

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

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.

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).

How to polymerize ethylene in a highly controlled fashion?

PubMed

Kempe, Rhett

2007-01-01

Very fast, reversible, polyethylene (PE) chain transfer or complex-catalysed "Aufbaureaktion" describes a "living" chain-growing process on a main-group metal or zinc atom; this process is catalysed by an organo-transition-metal or lanthanide complex. PE chains are transferred very fast between the two metal sites and chain growth takes place through ethylene insertion into the transition-metal- or lanthanide-carbon bond-coordinative chain-transfer polymerisation (CCTP). The transferred chains "rest" at the main-group or zinc centre, at which chain-termination processes like beta-H transfer/elimination are of low significance. Such protocols can be used to synthesise very narrowly distributed PE materials (M(w)/M(n)<1.1 up to a molecular weight of about 4000 g mol(-1)) with differently functionalised end groups. Higher molecular-weight polymers can be obtained with a slightly increased M(w)/M(n), since diffusion control and precipitation of the polymers influences the chain-transfer process. Recently, a few transition-metal- or lanthanide-based catalyst systems that catalyse such a highly reversible chain-growing process have been described. They are summarised and compared within this contribution.

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

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

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.

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.

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 .

Separation of actinides from lanthanides

DOEpatents

Smith, B.F.; Jarvinen, G.D.; Ryan, R.R.

1988-03-31

An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form is described. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4- dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

Separation of actinides from lanthanides

DOEpatents

Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

1989-01-01

An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

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.

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)

Electrodeposition of biaxially textured layers on a substrate

DOEpatents

Bhattacharya, Raghu N; Phok, Sovannary; Spagnol, Priscila; Chaudhuri, Tapas

2013-11-19

Methods of producing one or more biaxially textured layer on a substrate, and articles produced by the methods, are disclosed. An exemplary method may comprise electrodepositing on the substrate a precursor material selected from the group consisting of rare earths, transition metals, actinide, lanthanides, and oxides thereof. An exemplary article (150) may comprise a biaxially textured base material (130), and at least one biaxially textured layer (110) selected from the group consisting of rare earths, transition metals, actinides, lanthanides, and oxides thereof. The at least one biaxially textured layer (110) is formed by electrodeposition on the biaxially textured base material (130).

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.

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).

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.

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 luminescence. Nanocompounds formed with CdTe quantum dots and LaF3:Ce nanoparticles optimize both stopping power and scintillation efficiency based on energy transfer from LaF3:Ce to CdTe. Hybrid matrix materials such as ORMOSIL have superior mechanical properties and a better processability than pure molecular material which could be used as carrier of radiation material. Moreover, embedding a lanthanide complex in a hybrid matrix enhances its thermal stability and luminescence output. LaF3:Ce doped ORMOSIL was synthesized by using two different LaF3:Ce, the nanoparticle doping concentration can reach up to 15.66% while its transparency and luminescent properties were maintained. These materials are very promising for radiation detection.

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 morphotypes of anoxygenic phototrophic bacteria Chloroflexus and Chromatium and few bundles of Microcoleus chthonoplastes whereas the lows (at 22 mm depth) were associated with low abundances of cells and morphotype richnesses of these groups of prokaryotes, where M. chthonoplastes, Chloroflexus and Chromatium persisted. Europium showed independent trends from both groups, being closer to the "group B". As an additional fact, the trace element uranium, commonly associated to organic-matter-rich-sediments and in some cases a representative of reducing conditions, seems to be enriched similarly to the light lanthanide "group A". It is hard to withstand at this point, but the preliminary results might suggest a preferential adsorption of light versus heavy lanthanides to the cell walls of some specific types of bacteria. This might be a pure physicochemical effect or a biological mechanism.

Improved Blackbody Simulator

DTIC Science & Technology

1974-06-01

28 - ABS Resins ................... 012 0.02 Carbon & Free-Cutting Steels%,. . . . . 27 - Acrylics ......................... 0.12 0.10 Alloy...Borosilicate Glasses................. 0.7 - Zinc At Its Alloys ................. 65.3 60.5 Alkyds .... .... .............. 010 0.20 Tungsten Carbide Cermet...cast).............47.6 25 ABS Resins ............ .. IS 3 FlowbnFie ........... 7 - Cellulose Acetate ............ &. 1.9 Pajadafi CW

Initial Examination of Low Velocity Sphere Impact of Glass Ceramics

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

Morrissey, Timothy G; Fox, Ethan E; Wereszczak, Andrew A

This report summarizes US Army TARDEC sponsored work at Oak Ridge National Laboratory (ORNL) involving low velocity (< 30 m/s or < 65 mph) sphere impact testing of two materials from the lithium aluminosilicate family reinforced with different amounts of ceramic particulate, i.e., glass-ceramic materials, SCHOTT Resistan{trademark}-G1 and SCHOTT Resistan{trademark}-L. Both materials are provided by SCHOTT Glass (Duryea, PA). This work is a follow-up to similar sphere impact studies completed by the authors on PPG's Starphire{reg_sign} soda-lime silicate glass and SCHOTT BOROFLOAT{reg_sign} borosilicate glass. A gas gun or a sphere-drop test setup was used to produce controlled velocity delivery ofmore » silicon nitride (Si{sub 3}N{sub 4}) spheres against the glass ceramic tile targets. Minimum impact velocities to initiate fracture in the glass-ceramics were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between sphere and target material. Quasistatic spherical indentation was also performed on both glass ceramics and their contact damage responses were compared to those of soda-lime silicate and borosilicate glasses. Lastly, variability of contact damage response was assessed by performing spherical indentation testing across the area of an entire glass ceramic tile. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) Resistan{trademark}-L glass ceramic required the highest velocity of sphere impact for damage to initiate. Starphire{reg_sign} soda-lime silicate glass was second best, then Resistan{trademark}-G1 glass ceramic, and then BOROFLOAT{reg_sign} borosilicate glass. (2) Glass-ceramic Resistan{trademark}-L also required the largest force to initiate ring crack from quasi-static indentation. That ranking was followed, in descending order, by Starphire{reg_sign} soda-lime silicate glass, Resistan{trademark}-G1 glass ceramic, and BOROFLOAT{reg_sign} borosilicate glass. (3) Spheres with a lower elastic modulus require less force to initiate fracture in Resistan{trademark}-G1 from quasi-static spherical indentation. This indicates that friction is affecting ring crack initiation in Resistan{trademark}-G1. Friction also affected ring crack initiation in Starphire{reg_sign} soda-lime silicate and BOROFLOAT{reg_sign} borosilicate glasses. Among these three materials, friction was the most pronounced (largest slope in the RCIF-elastic modulus graph) in the Starphire{reg_sign} and least pronounced in the BOROFLOAT{reg_sign}. The reason for this is not understood, but differences in deformation behavior under high contact stresses could be a cause or contributor to this. (4) The force necessary to initiate contact-induced fracture is higher under dynamic conditions than it is under quasi-static conditions in Resistan{trademark}-L and Resistan{trademark}-G1 glass ceramics. This is a trend observed too in Starphire{reg_sign} and BOROFLOAT{reg_sign}. (5) There is a subtle indication there was intra-tile differences in spherical indentation-induced ring crack initiation forces. This is not a material property nor is it exclusive to glass-ceramic Resistan{trademark}-G1 glass ceramic, rather, it is a statistical mechanical response to an accumulated history of processing and handling of that specific tile.« less

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 emission profiles of upconversion nanoparticles will be further enriched by using a combination of different excitation wavelengths. Finally, the orthorhombic-phase K2YF5 nanobelts doped with upconverting lanthanide ions (Er3+ and Tm3+) were synthesized by using a coprecipitation method. The growth kinetics of the nanobelts can be regulated by either control of the volume ratio of oleic acid in the synthetic system or period of reaction time. It was found that desirable lanthanide-doped K2YF5 nanobelts were yielded through the use of long time high-temperature annealing treatment (270 °C, 6 h) in the presence of low content of oleic acid. The assynthesized lanthanide-doped K2YF5 nanobelts show intense upconversion emissions upon excitation at 980 nm. For example, bright yellow emission was observed from K2YF5:Yb/Er(18/2 mol%), resulting from weak optical transitions of 2H11/2 → 4I15/2 (520 nm) and 4S3/2 → 4I15/2 (540 nm) and a dominant transition of 4F9/2 → 4I15/2 (centered at 650 nm) of the doped Er3+. In the case of K2YF5:Yb/Tm(30/0.5 mol%) nanobelts, three main emission bands centered at 479 (blue), 650 (red) and 800 nm (NIR) corresponding to 1D2 → 3H6, 1D2 → 3H4, and 3H4 ¨ 3H6 transition of Tm3+ were observed.

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.

Exciton generation/dissociation/charge-transfer enhancement in inorganic/organic hybrid solar cells by robust single nanocrystalline LnPxOy (Ln = Eu, Y) doping.

PubMed

Jin, Xiao; Sun, Weifu; Chen, Zihan; Wei, Taihuei; Chen, Chuyang; He, Xingdao; Yuan, Yongbiao; Li, Yue; Li, Qinghua

2014-06-11

Low-temperature solution-processed photovoltaics suffer from low efficiencies because of poor exciton or electron-hole transfer. Inorganic/organic hybrid solar cell, although still in its infancy, has attracted great interest thus far. One of the promising ways to enhance exciton dissociation or electron-hole transport is the doping of lanthanide phosphate ions. However, the underlying photophysical mechanism remains poorly understood. Herein, by applying femtosecond transient absorption spectroscopy, we successfully distinguished hot electron, less energetic electron, hole transport from electron-hole recombination. Concrete evidence has been provided that lanthanide phosphate doping improves the efficiency of both hot electron and "less energetic" electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 12.7 ps, that is, more than 60% faster than pure TiO2 acceptor. Such improvement was ascribed to the facts that the conduction band (CB) edge energy level of TiO2 has been elevated by 0.2 eV, while the valence band level almost remains unchanged, thus not only narrowing the energy offset between CB levels of TiO2 and P3HT, but also meanwhile enlarging the band gap of TiO2 itself that permits one to inhibit electron-hole recombination within TiO2. Consequently, lanthanide phosphate doped TiO2/P3HT bulk-heterojunction solar cell has been demonstrated to be a promising hybrid solar cell, and a notable power conversion efficiency of 2.91% is therefore attained. This work indicates that lanthanide compound ions can efficiently facilitate exciton generation, dissociation, and charge transport, thus enhancing photovoltaic performance.

Surface Functionalization Methods to Enhance Bioconjugation in Metal-Labeled Polystyrene Particles

PubMed Central

Abdelrahman, Ahmed I.; Thickett, Stuart C.; Liang, Yi; Ornatsky, Olga; Baranov, Vladimir; Winnik, Mitchell A.

2011-01-01

Lanthanide-encoded polystyrene particles synthesized by dispersion polymerization are excellent candidates for mass cytometry based immunoassays, however they have previously lacked the ability to conjugate biomolecules to the particle surface. We present here three approaches to post-functionalize these particles, enabling the covalent attachment of proteins. Our first approach used partially hydrolyzed poly(N-vinylpyrrolidone) as a dispersion polymerization stabilizer to synthesize particles with high concentration of -COOH groups on the particle surface. In an alternative strategy to provide -COOH functionality to the lanthanide-encoded particles, we employed seeded emulsion polymerization to graft poly(methacrylic acid) (PMAA) chains onto the surface of these particles. However, these two approaches gave little to no improvement in the extent of bioconjugation. In our third approach, seeded emulsion polymerization was subsequently used as a method to grow a functional polymer shell (in this case, poly(glycidyl methacrylate) (PGMA)) onto the surface of these particles, which proved highly successful. The epoxide-rich PGMA shell permitted extensive surface bioconjugation of NeutrAvidin, as probed by an Lu-labeled biotin reporter (ca. 7 × 105 binding events per particle with a very low amount of non-specific binding) and analyzed by mass cytometry. It was shown that coupling agents such as EDC were not needed, such was the reactivity of the particle surface. These particles were stable and the addition of a polymeric shell was shown did not affect the narrow lanthanide ion distribution within the particle interior as analyzed by mass cytometry. These particles represent the most promising candidates for the development of a highly multiplexed bioassay based on lanthanide-labeled particles to date. PMID:21799543

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

DNA migration mechanism analyses for applications in capillary and microchip electrophoresis

PubMed Central

Forster, Ryan E.; Hert, Daniel G.; Chiesl, Thomas N.; Fredlake, Christopher P.; Barron, Annelise E.

2009-01-01

In 2009, electrophoretically driven DNA separations in slab gels and capillaries have the sepia tones of an old-fashioned technology in the eyes of many, even while they remain ubiquitously used, fill a unique niche, and arguably have yet to reach their full potential. For comic relief, what is old becomes new again: agarose slab gel separations are used to prepare DNA samples for “next-gen” sequencing platforms (e.g., the Illumina and 454 machines)—dsDNA molecules within a certain size range are “cut out” of a gel and recovered for subsequent “massively parallel” pyrosequencing. In this review, we give a Barron lab perspective on how our comprehension of DNA migration mechanisms in electrophoresis has evolved, since the first reports of DNA separations by CE (∼1989) until now, 20 years later. Fused silica capillaries, and borosilicate glass and plastic microchips, quietly offer increasing capacities for fast (and even “ultra-fast”), efficient DNA separations. While the channel-by-channel scaling of both old and new electrophoresis platforms provides key flexibility, it requires each unique DNA sample to be prepared in its own micro- or nanovolume. This Achille's heel of electrophoresis technologies left an opening through which pooled-sample, next-gen DNA sequencing technologies rushed. We shall see, over time, whether sharpening understanding of transitions in DNA migration modes in crosslinked gels, nanogel solutions, and uncrosslinked polymer solutions will allow electrophoretic DNA analysis technologies to flower again. Microchannel electrophoresis, after a quiet period of metamorphosis, may emerge sleeker and more powerful, to claim its own important niche applications. PMID:19582705

75 FR 41850 - Amended Notice of Intent to Modify the Scope of the Surplus Plutonium Disposition Supplemental...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-19

... immobilization). Also, DOE had identified a glass can-in-canister immobilization approach as its preferred... allow immobilization of some or all of the surplus plutonium in glass or ceramic material for disposal... in canisters to be filled with borosilicate glass containing intensely radioactive high-level waste...

Production Process for Strong, Light Ceramic Tiles

NASA Technical Reports Server (NTRS)

Holmquist, G. R.; Cordia, E. R.; Tomer, R. S.

1985-01-01

Proportions of ingredients and sintering time/temperature schedule changed. Production process for lightweight, high-strength ceramic insulating tiles for Space Shuttle more than just scaled-up version of laboratory process for making small tiles. Boron in aluminum borosilicate fibers allows fusion at points where fibers contact each other during sintering, thereby greatly strengthening tiles structure.

Nanoparticle Solutions for Printed Electronics

DTIC Science & Technology

2013-09-19

the printed semiconductor materials and their nanoparticle and colloidal precursors. Without this basic knowledge, further development and the...titania, silica ) were investigated in the production of complementary inks for complex devices. These were either obtained commercially in...layers were also deposited on borosilicate glass and silicon wafers. In the photovoltaic program, hybrid inorganic-organic semiconductor combinations

Electrodeless discharge lamp is easily started, has high stability

NASA Technical Reports Server (NTRS)

Bell, W. E.; Bloom, A. L.

1966-01-01

Electrodeless discharge borosilicate glass lamp is used in various high-resolution optical systems. It is partially charged with krypton, contains small amounts of rubidium, and is enclosed in a hermetically sealed envelope that maintains the lamp at an optimum temperature during discharge. The lamp is quickly started by its excitation coil.

Iodine Solubility in Low-Activity Waste Borosilicate Glass at 1000 °C

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

Riley, Brian J.; Schweiger, Michael J.; Kim, Dong-Sang

2014-04-30

The purpose of this study was to determine the solubility of iodine in a low-activity waste borosilicate glass when heated inside an evacuated and sealed fused quartz ampoule. The iodine was added to glass frit as KI in quantities of 100–24000 ppm iodine (by mass), each mixture was added to an ampoule, the ampoule was heated at 1000 °C for 2 h and then air quenched. In samples with ≥12000 ppm iodine, low viscosity salt phases were observed on the surface of the melts during cooling that solidified into a white coating upon cooling. These salts were identified as mixturesmore » of KI, NaI, and Na2SO4 with X-ray diffraction (XRD). The iodine concentrations in glass specimens were analyzed with inductively-coupled plasma mass spectrometry and the overall iodine solubility was determined to be 10000 ppm by mass. Several crystalline inclusions of iodine sodalite, Na8(AlSiO4)6I2, were observed in the 24000 ppm specimen and were verified with micro-XRD and wavelength dispersive spectroscopy.« less

Mesoscale Phase Field Modeling of Glass Strengthening Under Triaxial Compression

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

Li, Yulan; Sun, Xin

2015-09-28

Recent hydraulic bomb and confined sleeve tests on transparent armor glass materials such as borosilicate glass and soda-lime glass showed that the glass strength was a function of confinement pressure. The measured stress-strain relation is not a straight line as most brittle materials behave under little or no confinement. Moreover, borosilicate glass exhibited a stronger compressive strength when compared to soda-lime glass, even though soda-lime has higher bulk and shear moduli as well as apparent yield strength. To better understand these experimental findings, a mesoscale phase field model is developed to simulate the nonlinear stress versus strain behaviors under confinementmore » by considering heterogeneity formation under triaxial compression and the energy barrier of a micro shear banding event (referred to as pseudo-slip hereafter) in the amorphous glass. With calibrated modeling parameters, the simulation results demonstrate that the developed phase field model can quantitatively predict the pressure-dependent strength, and it can also explain the difference between the two types of glasses from the perspective of energy barrier associated with a pseudo-slip event.« less

Physical and optical properties of lithium borosilicate glasses doped with Dy3+ ions

NASA Astrophysics Data System (ADS)

Ramteke, D. D.; Gedam, R. S.; Swart, H. C.

2018-04-01

The borosilicate glasses with Dy3+ ions were prepared by the melt quench technique with varying concentration of Dy2O3. The glasses were characterized by the density calculation, absorbance and photoluminescence (PL) spectroscopy measurements. Density and molar volume of the glasses increases with increase in Dy3+ ions in the glass matrix. This behavior is correlated with the higher molecular weight and larger ionic radius of Dy3+ ion compared to the other constituents of glass matrix. Emission of Dy3+ doped glasses showed three bands at 482, 573 and at 665 nm which correspond to 6H15/2 (blue), 6H13/2 (yellow) and 6H11/2 (red) transitions. The emission spectra of glasses with different concentration of Dy3+ ions shows that, glasses with 0.5 mol% of Dy2O3 shows highest emission and decreases with further doping. CIE 1931 chromaticity diagram showed that the emission of these glasses was in the white region. Photographs of these glasses under 349 nm Light emitting diode excitation also confirmed the white light emission from these glasses.

Effect of Gd2O3 doping on structure and boron volatility of borosilicate glass sealants in solid oxide fuel cells-A study on the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode

NASA Astrophysics Data System (ADS)

Zhang, Qi; Tan, Shengwei; Ren, Mengyuan; Yang, Hsiwen; Tang, Dian; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Boron volatility is one of the most important properties of borosilicate-based glass sealants in solid oxide fuel cells (SOFCs), as boron contaminants react with lanthanum-containing cathodes, forming LaBO3 and degrading the activity of SOFCs. Here, we report that the reaction between the volatile boron and a La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode during polarization can be significantly reduced by doping aluminoborosilicate glass with Gd2O3. Specifically, the Gd cations in glass with 2 mol.% Gd2O3 dissolve preferentially in the borate-rich environment to form more Gd-metaborate structures and promote the formation of calcium metaborate (CaB2O4); they also condense the B-O network after heat treatment, which suppresses poisoning by boron contaminants on the LSCF cathode. The results provide insights into design and development of a reliable sealing glass for SOFC applications.

Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

NASA Astrophysics Data System (ADS)

Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

2005-10-01

Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

Antagonist effects of calcium on borosilicate glass alteration

NASA Astrophysics Data System (ADS)

Mercado-Depierre, S.; Angeli, F.; Frizon, F.; Gin, S.

2013-10-01

Numerous studies have been conducted on glass and cement durability in contact with water, but very little work to date has focused directly on interactions between the two materials. These interactions are mostly controlled by silicon-calcium reactivity. However, the physical and chemical processes involved remain insufficiently understood to predict the evolution of coupled glass-cement systems used in several industrial applications. Results are reported from borosilicate glass alteration in calcium-rich solutions. Our data show that four distinct behaviors can be expected according to the relative importance of three key parameters: the pH, the reaction progress (short- or long-term alteration) and the calcium concentration. Glass alteration is thus controlled by specific mechanisms depending on the solution chemistry: calcium complexation at the glass surface, precipitation of calcium silicate hydrates (C-S-H) or calcium incorporation in the altered layer. These findings highlight the impact of silicon-calcium interactions on glass durability and open the way for a better understanding of glass-cement mixing in civil engineering applications as well as in nuclear waste storage.

Process Parameter Effects on Material Removal in Magnetorheological Finishing of Borosilicate Glass

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

Miao, C.; Lambroopulos, J.C.; Jacobs, S.D.

2010-04-14

We investigate the effects of processing parameters on material removal for borosilicate glass. Data are collected on a magnetorheological finishing (MRF) spot taking machine (STM) with a standard aqueous magnetorheological (MR) fluid. Normal and shear forces are measured simultaneously, in situ, with a dynamic dual load cell. Shear stress is found to be independent of nanodiamond concentration, penetration depth, magnetic field strength, and the relative velocity between the part and the rotating MR fluid ribbon. Shear stress, determined primarily by the material mechanical properties, dominates removal in MRF. The addition of nanodiamond abrasives greatly enhances the material removal efficiency, withmore » the removal rate saturating at a high abrasive concentration. The volumetric removal rate (VRR) increases with penetration depth but is insensitive to magnetic field strength. The VRR is strongly correlated with the relative velocity between the ribbon and the part, as expected by the Preston equation. A modified removal rate model for MRF offers a better estimation of MRF removal capability by including nanodiamond concentration and penetration depth.« less

Influence of zeolite precipitation on borosilicate glass alteration under hyperalkaline conditions

NASA Astrophysics Data System (ADS)

Mercado-Depierre, S.; Fournier, M.; Gin, S.; Angeli, F.

2017-08-01

This study enables a better understanding of how nucleation-growth of zeolites affects glass dissolution kinetics in hyperalkaline solutions characteristic of cement waters. A 20-oxide borosilicate glass, an inactive surrogate of a typical intermediate level waste glass, was altered in static mode at 50 °C in a hyperalkaline solution rich in Na+, K+ and Ca2+ and at an initial pH50°C of 12.6. Experiments were performed at four glass-surface-area-to-solution-volume (S/V) ratios to investigate various reaction progresses. Two types of glass alteration kinetics were obtained: (i) at low S/V, a sharp alteration resumption occurred after a rate drop regime, (ii) at high S/V, a high dissolution rate was maintained throughout the test duration with a slight progressive slow-down. In all the experiments, zeolites precipitated but the time taken to form stable zeolite nuclei varied dramatically depending on the S/V. Resulting changes in pH affected zeolite composition, morphology, solubility and growth rate. A change in a critical parameter such as S/V affected all the processes controlling glass dissolution.

Iodine solubility in a low-activity waste borosilicate glass at 1000°C

DOE PAGES

Riley, Brian J.; Schweiger, Michael J.; Kim, Dong-Sang; ...

2014-04-30

The purpose of this study was to determine the solubility of iodine in a low-activity waste borosilicate glass when heated inside an evacuated and sealed fused quartz ampoule. The iodine was added to glass frit as KI in quantities of 100–24000 ppm iodine (by mass), each mixture was added to an ampoule, the ampoules were heated at 1000 °C for 2h, and then air quenched. In samples with ≥12000 ppm iodine, low viscosity salt phases were observed on the surface of the melts during cooling that solidified into a white coating upon cooling. These salts were identified as mixtures ofmore » KI, NaI, and Na 2SO 4 with X-ray diffraction (XRD). The iodine concentrations in glass specimens were analyzed with inductively-coupled plasma mass spectrometry and the overall iodine solubility was determined to be 10000 ppm by mass. Several crystalline inclusions of iodine sodalite, Na 8(AlSiO 4) 6I 2, were observed in the 24000 ppm specimen as determined by micro-XRD and wavelength dispersive spectroscopy.« less

High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 2

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

Cunnane, J.C.; Bates, J.K.; Bradley, C.R.

The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion.This document is organized into three volumes. Volumes I and II represent a tiered set of information intended for somewhat different audiences. Volume I is intended to provide an overview of waste glass corrosion,more » and Volume 11 is intended to provide additional experimental details on experimental factors that influence waste glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II. Volume I is intended for managers, decision makers, and modelers, the combined set of Volumes I, II, and III is intended for scientists and engineers working in the field of high-level waste.« less

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

Mitrofanov, Andrey A., E-mail: mitrofanov-a@icloud.com; Silyavka, Elena S.; Shilovskikh, Vladimir V.

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

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.

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

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.

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.

Parameters for the RM1 Quantum Chemical Calculation of Complexes of the Trications of Thulium, Ytterbium and Lutetium

PubMed Central

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

2016-01-01

The RM1 quantum chemical model for the calculation of complexes of Tm(III), Yb(III) and Lu(III) is advanced. Subsequently, we tested the models by fully optimizing the geometries of 126 complexes. We then compared the optimized structures with known crystallographic ones from the Cambridge Structural Database. Results indicate that, for thulium complexes, the accuracy in terms of the distances between the lanthanide ion and its directly coordinated atoms is about 2%. Corresponding results for ytterbium and lutetium are both 3%, levels of accuracy useful for the design of lanthanide complexes, targeting their countless applications. PMID:27223475

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.

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.

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.

Determination of the Stoichiometry between α- and γ1 Subunits of the BK Channel Using LRET.

PubMed

Carrasquel-Ursulaez, Willy; Alvarez, Osvaldo; Bezanilla, Francisco; Latorre, Ramon

2018-06-05

Two families of accessory proteins, β and γ, modulate BK channel gating and pharmacology. Notably, in the absence of internal Ca 2+ , the γ1 subunit promotes a large shift of the BK conductance-voltage curve to more negative potentials. However, very little is known about how α- and γ1 subunits interact. In particular, the association stoichiometry between both subunits is unknown. Here, we propose a method to answer this question using lanthanide resonance energy transfer. The method assumes that the kinetics of lanthanide resonance energy transfer-sensitized emission of the donor double-labeled α/γ1 complex is the linear combination of the kinetics of the sensitized emission in single-labeled complexes. We used a lanthanide binding tag engineered either into the α- or the γ1 subunits to bind Tb +3 as the donor. The acceptor (BODIPY) was attached to the BK pore-blocker iberiotoxin. We determined that γ1 associates with the α-subunit with a maximal 1:1 stoichiometry. This method could be applied to determine the stoichiometry of association between proteins within heteromultimeric complexes. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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.

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.

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

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.

Extraction of metals using supercritical fluid and chelate forming legand

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1998-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Extraction of metals using supercritical fluid and chelate forming ligand

DOEpatents

Wai, C.M.; Laintz, K.E.

1998-03-24

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.