Rhombus-shaped tetranuclear [Ln4] complexes [Ln = Dy(III) and Ho(III)]: synthesis, structure, and SMM behavior.

PubMed

Chandrasekhar, Vadapalli; Hossain, Sakiat; Das, Sourav; Biswas, Sourav; Sutter, Jean-Pascal

2013-06-03

The reaction of a new hexadentate Schiff base hydrazide ligand (LH3) with rare earth(III) chloride salts in the presence of triethylamine as the base afforded two planar tetranuclear neutral complexes: [{(LH)2Dy4}(μ2-O)4](H2O)8·2CH3OH·8H2O (1) and [{(LH)2Ho4}(μ2-O)4](H2O)8·6CH3OH·4H2O (2). These neutral complexes possess a structure in which all of the lanthanide ions and the donor atoms of the ligand remain in a perfect plane. Each doubly deprotonated ligand holds two Ln(III) ions in its two distinct chelating coordination pockets to form [LH(Ln)2](4+) units. Two such units are connected by four [μ2-O](2-) ligands to form a planar tetranuclear assembly with an Ln(III)4 core that possesses a rhombus-shaped structure. Detailed static and dynamic magnetic analysis of 1 and 2 revealed single-molecule magnet (SMM) behavior for complex 1. A peculiar feature of the χM" versus temperature curve is that two peaks that are frequency-dependent are revealed, indicating the occurrence of two relaxation processes that lead to two energy barriers (16.8 and 54.2 K) and time constants (τ0 = 1.4 × 10(-6) s, τ0 = 7.2 × 10(-7) s). This was related to the presence of two distinct geometrical sites for Dy(III) in complex 1.

Magnetism and transport properties of layered rare-earth cobaltates Ln{sub 0.3}CoO{sub 2}

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

Knížek, K., E-mail: knizek@fzu.cz; Novák, P.; Jirák, Z.

2015-05-07

The ab-initio (GGA+U) electronic structure calculations of layered cobaltates Ln{sub 0.3}CoO{sub 2} (Ln = La, Pr, Nd) prepared by ionic exchange from Na{sub 0.90}CoO{sub 2} precursors have been performed. The data are used for numerical modeling of Seebeck coefficient within Boltzmann transport theory using BoltzTraP program [G. K. H. Madsen and D. J. Singh, Comput. Phys. Commun. 175, 67 (2006)], as well as for determination of the crystal field split levels of rare-earth ions using a method based on a transformation of Bloch states into the basis of Wannier functions [P. Novák et al., Phys. Rev. B 87, 205139 (2013)]. An overallmore » agreement with observed magnetism and transport properties is obtained. In particular, the high p-type thermopower is well reproduced in a broad temperature range, but instead of theoretical linear decrease down to the lowest temperatures, the real systems exhibit an anomalous change of Seebeck sign, which might be related to the change of bare metallic carriers into the polaronic ones.« less

Relaxor-ferroelectric BaLnZT (Ln = La, Nd, Sm, Eu, and Sc) ceramics for actuator and energy storage application

NASA Astrophysics Data System (ADS)

Ghosh, Sarit K.; Mallick, Kaushik; Tiwari, B.; Sinha, E.; Rout, S. K.

2018-01-01

Lead free ceramics Ba1-x Ln2x/3Zr0.3Ti0.7O3 (Ln = La, Nd, Sm, Eu and Sc), x = 0.02-0.10 are investigated for electrostrictive effect and energy storage properties in the proximity of relaxor-paraelectric phase boundary. Relaxor phase evidence from slim hysteresis loop and low remnant polarization are the key parameters responsible for improve the electrostrictive effect and energy storage properties simultaneously. With increase in rare earth content negative strain disappeared and almost hysteresis free strain is achieved. Strain-hysteresis profile in term of S-E, S-E 2 and S-P 2 is used to analyze the electrostrictive behavior of these ceramics. An average strain (S%) ˜ 0.03%, is accomplished at initial concentrations of x = 0.02-0.04 and electrostrictive coefficients (Q 11, and M 11) as well as the energy storage density is improved by a factor of 1.2 and 2.6 respectively when compare with pure (x = 0.0) ceramic. Above x ≥ 0.06, all compositions show a stable behavior which suggested the possibilities of these relaxor ceramics towards high precision actuators and energy storage application.

Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

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

Wang, Fang; Tang, Chunying; Chen, Ruihong

2013-10-15

Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in themore » neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential

To bend or not to bend: experimental and computational studies of structural preference in Ln(Tp(iPr)2)2 (Ln = Sm, Tm).

PubMed

Momin, Aurélien; Carter, Lee; Yang, Yi; McDonald, Robert; Essafi Labouille, Stéphanie; Nief, François; Del Rosal, Iker; Sella, Andrea; Maron, Laurent; Takats, Josef

2014-11-17

The synthesis and characterization of Ln(Tp(iPr2))2 (Ln = Sm, 3Sm; Tm, 3Tm) are reported. While the simple (1)H NMR spectra of the compounds indicate a symmetrical solution structure, with equivalent pyrazolyl groups, the solid-state structure revealed an unexpected, "bent sandwich-like" geometry. By contrast, the structure of the less sterically congested Tm(Tp(Me2,4Et))2 (4) adopts the expected symmetrical structure with a linear B-Tm-B arrangement. Computational studies to investigate the origin of the unexpected bent structure of the former compounds indicate that steric repulsion between the isopropyl groups forces the Tp ligands apart and permits the development of unusual interligand C-H···N hydrogen-bonding interactions that help stabilize the structure. These results find support in the similar geometry of the Tm(III) analogue [Tm(Tp(iPr2))2]I, 3Tm(+), and confirm that the low symmetry is not the result of a metal-ligand interaction. The relevance of these results to the general question of the coordination geometry of MX2 and M(C5R5)2 (M = heavy alkaline earth and Ln(II), X = halide, and C5R5 = bulky persubstituted cyclopentadienyl) complexes and the importance of secondary H-bonding and nonbonding interactions on the structure are highlighted.

Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors: Morphology-tunable and luminescence properties

NASA Astrophysics Data System (ADS)

Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

2018-02-01

4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu3 + and Tb3 +. Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B2O3·H2O:Ln3 + (Ln = Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu3 +-doped, Tb3 +-doped and Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu3 + shows a red emission (615 nm); the Tb3 + shows a green emission (545 nm); for the Eu3 +/Tb3 + co-doped 4ZnO·B2O3·H2O phosphors, a combination of blue (5d-4f of Eu2 +), green (5D4-7F5 of Tb3 +) and red (5D0-7F2 of Eu3 +) emissions emerges to achieve white emission. In addition, the energy transfer among Eu3 +, Eu2 + and Tb3 + ions was also discussed.

Hydrothermal synthesis of 4ZnO·B2O3·H2O:Ln3+ (Ln=Eu, Tb) phosphors: Morphology-tunable and luminescence properties.

PubMed

Cao, Shiwei; Jiao, Yang; Han, Weifang; Ge, Chunhua; Song, Bo; Wang, Jie; Zhang, Xiangdong

2018-02-05

4ZnO·B 2 O 3 ·H 2 O:Ln 3+ (Ln=Eu, Tb) phosphors with different morphologies have been successfully synthesized via one-step hydrothermal method through regulating the molar amount of Eu 3+ and Tb 3+ . Comprehensive scanning electron microscopy (SEM), X-ray diffraction (XRD) Fourier transform infrared spectrum (FT-IR) and inductively coupled plasma atomic emission spectrometer (ICP-AES) characterizations all confirm that obtained products are 4ZnO·B 2 O 3 ·H 2 O:Ln 3+ (Ln=Eu, Tb). The experimental results displayed that the morphology and photoluminescence of compounds is regularly changed with increased the molar amount of rare earth ions. For the Eu 3+ -doped, Tb 3+ -doped and Eu 3+ /Tb 3+ co-doped 4ZnO·B 2 O 3 ·H 2 O phosphors of morphologies, the rod-like structures gradually changed to flower-like structures, fine wire-like structure and hybrid structure, respectively. To their photoluminescence, the Eu 3+ shows a red emission (615nm); the Tb 3+ shows a green emission (545nm); for the Eu 3+ /Tb 3+ co-doped 4ZnO·B 2 O 3 ·H 2 O phosphors, a combination of blue (5d-4f of Eu 2+ ), green ( 5 D 4 - 7 F 5 of Tb 3+ ) and red ( 5 D 0 - 7 F 2 of Eu 3+ ) emissions emerges to achieve white emission. In addition, the energy transfer among Eu 3+ , Eu 2+ and Tb 3+ ions was also discussed. Copyright © 2017. Published by Elsevier B.V.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Facile hydrothermal crystallization of NaLn(WO4)2 (Ln=La-Lu, and Y), phase/morphology evolution, and photoluminescence

NASA Astrophysics Data System (ADS)

Shi, Xiaofei; Li, Ji-Guang; Wang, Xuejiao; Zhu, Qi; Kim, Byung-Nam; Sun, Xudong

2017-12-01

Hydrothermal reaction of Ln nitrate and Na2WO4 at pH=8 and 200 °C for 24 hours, in the absence of any additive, has directly produced the scheelite-type sodium lanthanide tungstate of NaLn(WO4)2 for the larger Ln3+ of Ln=La-Dy (including Y, Group I) and an unknown compound that can be transformed into NaLn(WO4)2 by calcination at the low temperature of 600 °C for the smaller Ln3+ of Ln=Ho-Lu (Group II). With the successful synthesis of NaLn(WO4)2 for the full spectrum of Ln, the effects of lanthanide contraction on the structural features, crystal morphology, and IR responses of the compounds were clarified. The temperature- and time-course phase/morphology evolutions and the phase conversion upon calcination were thoroughly studied for the Group I and Group II compounds with Ln=La and Lu for example, respectively. Unknown intermediates were characterized by elemental analysis, IR absorption, thermogravimetry, and differential scanning calorimetry to better understand their chemical composition and coordination. The photoluminescence properties of NaEu(WO4)2 and NaTb(WO4)2, including excitation, emission, fluorescence decay, and quantum efficiency of luminescence, were also comparatively studied for the as-synthesized and calcination products.

Bi3+ sensitized Y2WO6:Ln3+ (Ln=Dy, Eu, and Sm) phosphors for solar spectral conversion.

PubMed

Huang, M N; Ma, Y Y; Xiao, F; Zhang, Q Y

2014-01-01

The phosphors of Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) were synthesized by solid-state reaction in this study. The crystal structure, photoluminescence properties and energy transfer mechanism were investigated. By introducing Bi3+ ions, the excitation band of the phosphors was broadened to be 250-380 nm, which could be absorbed by the dye-sensitized solar cells (DSSCs). The overlap between excitation of W-O groups/Bi3+ and the emission of Ln3+ (Dy, Eu, and Sm) indicated that the probability of energy transfer from W-O groups and Bi3+ to Ln3+. The energy transfer efficiency from Bi3+ to Ln3+ (Ln=Dy, Eu and Sm) are calculated to be 16%, 20% and 58%. This work suggested that Y2WO6:Bi3+, Ln3+ (Ln=Dy, Eu and Sm) might be a promising ultraviolet-absorbing luminescent converter to enhance the photoelectrical conversion efficiency of dye-sensitized solar cells (DSSCs). Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of the phase transition in Pb{sub 0.88}Ln{sub 0.08}Ti{sub 0.98}Mn{sub 0.02}O{sub 3} (Ln=La, Sm, Eu) piezoceramics based on the Stefan-Boltzmann law

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

Suaste, Ernesto; Castillo, Victor; Gonzalez, Ruben

2004-07-15

A method for determination of the phase transition in piezoelectric ceramic based on the relationship expressed by the Stefan-Boltzmann law is reported, i.e., by means of the radiation that the piezoelectric ceramic emits when it is subjected to different temperatures. The experiment is performed in piezoelectric ceramic based on PbTiO{sub 3} modified by the partial substitution of rare earths for Pb in the Pb{sub 0.88}(Ln){sub 0.08}Ti{sub 0.98}Mn{sub 0.02}O{sub 3} system (Ln=La, Sm, Eu). From the measured emitted radiation, the value of the emissivity is calculated for each type of piezoelectric ceramic.

One-dimensional coordination polymers of whole row rare earth tris-pivalates

NASA Astrophysics Data System (ADS)

Tsymbarenko, Dmitry; Martynova, Irina; Grebenyuk, Dimitry; Shegolev, Vsevolod; Kuzmina, Natalia

2018-02-01

Fourteen 1D coordination polymers of rare earth pivalates [Ln(Piv)3]∞ (Ln = Y, La, Pr, Nd, Sm-Lu) were synthesized and characterized by powder X-ray diffraction, IR spectroscopy, TGA, and conventional elemental analysis. Crystal structures of [La(Piv)3]∞, [Yb(Piv)3]∞, [Lu(Piv)3]∞ were determined by means of single crystal X-ray analysis at 120 K, those of [Y(Piv)3]∞ and [Ho(Piv)3]∞ - from powder XRD data at 293 K. Transformation of [Ln(Piv)3]∞ structure and Piv- anions coordination mode along the whole row has been derived from powder XRD and IR spectroscopy results, and shown to crucially affect the relative location of 1D chains in the crystal structure, as well as the Ln···Ln distance within the single chain. Negative thermal expansion along 1D [Ln(Piv)3]∞ chain was revealed for Ln = Tm, Yb, Lu. Enforcement of 1D polymeric structure with the decrease of Ln ionic radius has been established from solid-state DFT calculations.

Microwave hydrothermal synthesis and characterization of rare-earth stannate nanoparticles

NASA Astrophysics Data System (ADS)

Huang, Shuang; Xu, Hua-lan; Zhong, Sheng-liang; Wang, Lei

2017-07-01

Rare-earth stannate (Ln2Sn2O7 (Ln = Y, La-Lu)) nanocrystals with an average diameter of 50 nm were prepared through a facile microwave hydrothermal method at 200°C within 60 min. The products were well characterized. The effect of reaction parameters such as temperature, reaction time, pH value, and alkali source on the preparation was investigated. The results revealed that the pH value plays an important role in the formation process of gadolinium stannate (Gd2Sn2O7) nanoparticles. By contrast, the alkali source had no effect on the phase composition or morphology of the final product. Uniform and sphere-like nanoparticles with an average size of approximately 50 nm were obtained at the pH value of 11.5. A possible formation mechanism was briefly proposed. Gd2Sn2O7:Eu3+ nanoparticles displayed strong orange-red emission. Magnetic measurements revealed that Gd2Sn2O7 nanoparticles were paramagnetic. The other rare-earth stannate Ln2Sn2O7 (Ln = Y, La-Lu) nanocrystals were prepared by similar approaches.

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

Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions

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

Boteju, Kasuni Chathurika; Wan, Suchen; Venkatesh, Amrit

Here, a new bulky silazido ligand, –N(SiHMe 2)Dipp (Dipp = C 6H 3-2,6- iPr 2) supports planar, three-coordinate homoleptic rare earth complexes Ln{N(SiHMe 2)Dipp} 3 (Ln = Sc, Y, Lu) that each contain three secondary Ln←HSi interactions and one agostic CH bond. Y{N(SiHMe 2)Dipp} 3 and acetophenone react via hydrosilylation, rather than by insertion into the Y–N bond or enolate formation.

Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions

DOE PAGES

Boteju, Kasuni Chathurika; Wan, Suchen; Venkatesh, Amrit; ...

2018-06-05

Here, a new bulky silazido ligand, –N(SiHMe 2)Dipp (Dipp = C 6H 3-2,6- iPr 2) supports planar, three-coordinate homoleptic rare earth complexes Ln{N(SiHMe 2)Dipp} 3 (Ln = Sc, Y, Lu) that each contain three secondary Ln←HSi interactions and one agostic CH bond. Y{N(SiHMe 2)Dipp} 3 and acetophenone react via hydrosilylation, rather than by insertion into the Y–N bond or enolate formation.

Controllable synthesis of Ln3+ (Ln = Tb, Eu) doped zinc phosphate nano-/micro-structured materials: phase, morphology and luminescence properties

NASA Astrophysics Data System (ADS)

Yue, Dan; Lu, Wei; Li, Chunyang; Zhang, Xinlei; Liu, Chunxia; Wang, Zhenling

2014-01-01

Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These investigations indicate that different phosphate sources MnH(3-n)PO4 (M = NH4+ or Na+, n = 1, 2, 3) can lead to the altering of morphology from nanosheet to microflower, but have no significant effect on the phase structure of the samples. The microlump, nanosheet, and microflower (constructed by the primary microlumps or nanosheets) of orthorhombic ZPT:Ln3+ could be selectively prepared by adjusting the pH value from 3.5 to 7.0. A mixture of orthorhombic ZPT:Ln3+ and monoclinic AZP:Ln3+ with a microflower morphology was obtained when the pH value was adjusted to 8.0. Monoclinic AZP:Ln3+ microplate, microcube and nanoparticle morphologies were obtained at pH values of 8.5, 9.0 and 11.0 respectively. The phase transformation and growth mechanism of the diverse morphologies were proposed, and ZPT:Ln3+ (Ln3+ = Eu or Tb) samples exhibit red or green emission under the excitation of UV light.Ln3+ (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln3+) and ammonium zinc phosphate (AZP:Ln3+) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These

Synthesis, crystal and electronic structure of the quaternary sulfides Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi)

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

Kussainova, Ardak M.; Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716; Akselrud, Lev G.

2016-01-15

The series of quaternary sulfides with general formula Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi) have been synthesized by solid-state reactions. Three representative members have been structurally characterized by single-crystal X-ray diffraction. La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46), Z=4, a=13.401(2) Å, b=7.592(1) Å, c=7.598(1) Å, V=773.1(3) Å{sup 3}). The bismuth analogs of composition La{sub 2}CuBiS{sub 5} and Ce{sub 2}CuBiS{sub 5} crystallize with the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62), Z=4). Lattice parameters for La{sub 2}CuBiS{sub 5}: a=11.9213(5) Å, b=3.9967(2) Å, c=17.0537(8) Å, V=812.56(7) Å{sup 3}; lattice parameters formore » Ce{sub 2}CuBiS{sub 5}: a=11.9179(15) Å, b=3.9596(5) Å, c=16.955(2) Å, V=800.13(17) Å{sup 3}). The similarities and the differences between the two structures are discussed. Electronic structure calculations for La{sub 2}CuSbS{sub 5} and La{sub 2}CuBiS{sub 5} are also presented; they suggest semiconducting behavior with energy gaps exceeding 1.7 eV. - Graphical abstract: La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46). Its bismuth analog La{sub 2}CuBiS{sub 5} crystallizes in the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62)). Z=4, a=11.9213(5) Å, b=3.9967(2) Å, c=17.0536(10) Å, V=813.53(10) Å{sup 3}). The structures are based on rare-earth metal atoms coordinated by S atoms in a trigonal-prismatic and/or square-antiprismatic fashion, Cu-centered tetrahedra, and pnictogen atoms in pyramidal or distorted octahedral coordination. - Highlights: • Ln{sub 2}CuSbS{sub 5} are complex quarternary phases crystallizing in their own structure type. • Ln{sub 2}CuSbS{sub 5} and Ce{sub 2}CuBiS{sub 5} are new compound in the respective ternary phase diagrams. • Ln{sub 2}CuSbS{sub 5} on one side, and Ln{sub 2}CuBiS{sub 5} on the other are not isotypic.« less

Crystal structures and magnetic properties of lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr)

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

Doi, Yoshihiro, E-mail: doi@sci.hokudai.ac.jp; Satou, Tatsuya; Hinatsu, Yukio

2013-10-15

The synthesis, crystal structures and magnetic properties of LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) were investigated. The LnCr(BO{sub 3}){sub 2} compounds crystallize in the dolomite-type structure with space group R3{sup ¯}, in which the Ln and Cr ions occupy two octahedral sites. From the result of structural analysis, it was found that there is an anti-site disorder between these two sites and its chemical formula is more exactly Ln{sub 1−r}Cr{sub r}[Cr{sub 1−r}Ln{sub r}](BO{sub 3}){sub 2}. On the other hand, the LnSc(BO{sub 3}){sub 2} adopt the calcite-type structure with space group R3{sup ¯}c. The Ln and Sc ions randomly occupymore » an octahedral site and the chemical formula is represented as (Ln{sub 0.5}Sc{sub 0.5})BO{sub 3}. From the magnetic susceptibility and specific heat measurements, we found that all the LnCr(BO{sub 3}){sub 2} show an antiferromagnetic transition at 6.1–8.1 K. This transition is mainly due to the ordering of Cr{sup 3+} magnetic moments. Among the compounds with magnetic Ln{sup 3+} ions, only YbCr(BO{sub 3}){sub 2} shows an antiferromagnetic ordering of Ln{sup 3+} ion at 2.1 K. - Graphical abstract: The lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) have the dolomite-type (Ln=Cr) and calcite-type (Ln=Sc) structures. Both structures are similar to each other except for the difference in the partially or fully disordered arrangements of octahedral sites. At low temperatures, the LnCr(BO{sub 3}){sub 2} compounds show an antiferromagnetic transition due to a long-range ordering of Cr{sup 3+} moments. Among them only YbCr(BO{sub 3}){sub 2} shows an antiferromagnetic ordering of Ln{sup 3+} ion at 2.1 K. Display Omitted - Highlights: • Lanthanide containing borates LnM(BO{sub 3}){sub 2} (Ln=Y, Ho–Lu; M=Sc, Cr) have been synthesized. • LnCr(BO{sub 3}){sub 2} has the dolomite-type structure with an anti-site disorder between Ln and Cr sites. • LnSc(BO{sub 3}){sub 2} has the calcite

Effect of A-TIG Welding Process on the Weld Attributes of Type 304LN and 316LN Stainless Steels

NASA Astrophysics Data System (ADS)

Vasudevan, M.

2017-03-01

The specific activated flux has been developed for enhancing the penetration performance of TIG welding process for autogenous welding of type 304LN and 316LN stainless steels through systematic study. Initially single-component fluxes were used to study their effect on depth of penetration and tensile properties. Then multi-component activated flux was developed which was found to produce a significant increase in penetration of 10-12 mm in single-pass TIG welding of type 304LN and 316LN stainless steels. The significant improvement in penetration achieved using the activated flux developed in the present work has been attributed to the constriction of the arc and as well as reversal of Marangoni flow in the molten weld pool. The use of activated flux has been found to overcome the variable weld penetration observed in 316LN stainless steel with <50 ppm of sulfur. There was no degradation in the microstructure and mechanical properties of the A-TIG welds compared to that of the welds produced by conventional TIG welding on the contrary the transverse strength properties of the 304LN and 316LN stainless steel welds produced by A-TIG welding exceeded the minimum specified strength values of the base metals. Improvement in toughness values were observed in 316LN stainless steel produced by A-TIG welding due to refinement in the weld microstructure in the region close to the weld center. Thus, activated flux developed in the present work has greater potential for use during the TIG welding of structural components made of type 304LN and 316LN stainless steels.

Controllable synthesis of Ln3+ (Ln = Tb, Eu) doped zinc phosphate nano-/micro-structured materials: phase, morphology and luminescence properties.

PubMed

Yue, Dan; Lu, Wei; Li, Chunyang; Zhang, Xinlei; Liu, Chunxia; Wang, Zhenling

2014-02-21

Ln(3+) (Ln = Tb, Eu) doped zinc phosphate tetrahydrate (ZPT:Ln(3+)) and ammonium zinc phosphate (AZP:Ln(3+)) nano-/micro-structured materials were synthesized in aqueous solution without the addition of any structure-directing agent. The phase structures, morphologies and luminescence properties of the as-synthesized samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy and lifetime. These investigations indicate that different phosphate sources MnH(3-n)PO4 (M = NH4(+) or Na(+), n = 1, 2, 3) can lead to the altering of morphology from nanosheet to microflower, but have no significant effect on the phase structure of the samples. The microlump, nanosheet, and microflower (constructed by the primary microlumps or nanosheets) of orthorhombic ZPT:Ln(3+) could be selectively prepared by adjusting the pH value from 3.5 to 7.0. A mixture of orthorhombic ZPT:Ln(3+) and monoclinic AZP:Ln(3+) with a microflower morphology was obtained when the pH value was adjusted to 8.0. Monoclinic AZP:Ln(3+) microplate, microcube and nanoparticle morphologies were obtained at pH values of 8.5, 9.0 and 11.0 respectively. The phase transformation and growth mechanism of the diverse morphologies were proposed, and ZPT:Ln(3+) (Ln(3+) = Eu or Tb) samples exhibit red or green emission under the excitation of UV light.

Magnetic Nature of the CrIII-LnIII Interactions in [CrIII2LnIII3] Clusters with Slow Magnetic Relaxation.

PubMed

Zhao, Xiao-Qing; Xiang, Shuo; Wang, Jin; Bao, Dong-Xu; Li, Yun-Chun

2018-02-01

Two 3 d -4 f hetero-metal pentanuclear complexes with the formula {[Cr III 2 Ln III 3 L 10 (OH) 6 (H 2 O) 2 ]Et 3 NH} [Ln=Tb ( 1 ), Dy ( 2 ); HL=pivalic acid, Et 3 N=triethylamine] have been produced. The metal core of each cluster is made up of a trigonal bipyramid with three Ln III ions (plane) and two Cr III ions (above and below) held together by six μ 3 -OH bridges. Also reported with this series is the diamagnetic Cr III -Y III analogue ( 3 ). Fortunately, we successfully prepared Al III -Ln III analogues with the formula {[Al III 2 Ln III 3 L 10 (OH) 6 (H 2 O) 2 ]Et 3 NH⋅H 2 O} [Ln=Tb ( 4 ), Dy ( 5 )], containing diamagnetic Al III ions, which can be used to evaluate the Cr III -Ln III magnetic nature through a diamagnetic substitution method. Subsequently, static (dc) magnetic susceptibility studies reveal dominant ferromagnetic interactions between Cr III and Ln III ions. Dynamic (ac) magnetic susceptibility studies show frequency-dependent out-of-phase ( χ '') signals for [Cr III 2 Tb III 3 ] ( 1 ), [Cr III 2 Dy III 3 ] ( 2 ), and [Al III 2 Dy III 3 ] ( 5 ), which are derived from the single-ion behavior of Ln III ions and/or the Cr III -Ln III ferromagnetic interactions.

General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y).

PubMed

Geng, Fengxia; Matsushita, Yoshitaka; Ma, Renzhi; Xin, Hao; Tanaka, Masahiko; Izumi, Fujio; Iyi, Nobuo; Sasaki, Takayoshi

2008-12-03

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water

Systems Ln-Fe-O ( Ln=Eu, Gd): thermodynamic properties of ternary oxides using solid-state electrochemical cells

NASA Astrophysics Data System (ADS)

Parida, S. C.; Rakshit, S. K.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

2003-05-01

The standard molar Gibbs energies of formation of LnFeO 3(s) and Ln3Fe 5O 12(s) where Ln=Eu and Gd have been determined using solid-state electrochemical technique employing different solid electrolytes. The reversible e.m.f.s of the following solid-state electrochemical cells have been measured in the temperature range from 1050 to 1255 K. Cell (I): (-)Pt / { LnFeO 3(s)+ Ln2O 3(s)+Fe(s)} // YDT/CSZ // {Fe(s)+Fe 0.95O(s)} / Pt(+); Cell (II): (-)Pt/{Fe(s)+Fe 0.95O(s)}//CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+); Cell (III): (-)Pt/{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}//YSZ//{Ni(s)+NiO(s)}/Pt(+); and Cell(IV):(-)Pt/{Fe(s)+Fe 0.95O(s)}//YDT/CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+). The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the e.m.f. data. The standard Gibbs energies of formation of solid EuFeO 3, Eu 3Fe 5O 12, GdFeO 3 and Gd 3Fe 5O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by Δ fG°m(EuFeO 3, s) /kJ mol -1 (± 3.2)=-1265.5+0.2687( T/K) (1050 ⩽ T/K ⩽ 1570), Δ fG°m(Eu 3Fe 5O 12, s)/kJ mol -1 (± 3.5)=-4626.2+1.0474( T/K) (1050 ⩽ T/K ⩽ 1255), Δ fG°m(GdFeO 3, s) /kJ mol -1 (± 3.2)=-1342.5+0.2539( T/K) (1050 ⩽ T/K ⩽ 1570), and Δ fG°m(Gd 3Fe 5O 12, s)/kJ·mol -1 (± 3.5)=-4856.0+1.0021( T/K) (1050 ⩽ T/K ⩽ 1255). The uncertainty estimates for Δ fG°m include the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagrams for the systems Eu-Fe-O and Gd-Fe-O and chemical potential diagrams for the system Gd-Fe-O were computed at 1250 K.

Phase transformation pathways of ultrafast-laser-irradiated Ln2O3 (Ln =Er -Lu )

NASA Astrophysics Data System (ADS)

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung; Solomon, Jonathan M.; Asta, Mark; Mao, Wendy L.; Yalisove, Steven M.; Ewing, Rodney C.

2018-01-01

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln2O3 (Ln =Er -Lu ), and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln =Tm -Lu , consistent with the material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln =Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.

Magnetic Nature of the CrIII–LnIII Interactions in [CrIII 2LnIII 3] Clusters with Slow Magnetic Relaxation

PubMed Central

Xiang, Shuo; Wang, Jin; Bao, Dong‐Xu; Li, Yun‐Chun

2018-01-01

Abstract Two 3d‐4f hetero‐metal pentanuclear complexes with the formula {[CrIII 2LnIII 3L10(OH)6(H2O)2]Et3NH} [Ln=Tb (1), Dy (2); HL=pivalic acid, Et3N=triethylamine] have been produced. The metal core of each cluster is made up of a trigonal bipyramid with three LnIII ions (plane) and two CrIII ions (above and below) held together by six μ 3‐OH bridges. Also reported with this series is the diamagnetic CrIII–YIII analogue (3). Fortunately, we successfully prepared AlIII–LnIII analogues with the formula {[AlIII 2LnIII 3L10(OH)6(H2O)2]Et3NH⋅H2O} [Ln=Tb (4), Dy (5)], containing diamagnetic AlIII ions, which can be used to evaluate the CrIII–LnIII magnetic nature through a diamagnetic substitution method. Subsequently, static (dc) magnetic susceptibility studies reveal dominant ferromagnetic interactions between CrIII and LnIII ions. Dynamic (ac) magnetic susceptibility studies show frequency‐dependent out‐of‐phase (χ′′) signals for [CrIII 2TbIII 3] (1), [CrIII 2DyIII 3] (2), and [AlIII 2DyIII 3] (5), which are derived from the single‐ion behavior of LnIII ions and/or the CrIII–LnIII ferromagnetic interactions. PMID:29435404

Synthesis, crystal structure, optical and thermal properties of lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho).

PubMed

Förg, Katharina; Höppe, Henning A

2015-11-28

Lanthanide hydrogen-polyphosphates Ln[H(PO3)4] (Ln = Tb, Dy, Ho) were synthesised as colourless (Ln = Tb, Dy) and light pink (Ln = Ho) crystalline powders by reaction of Tb4O7/Dy2O3/Ho2O3 with H3PO3 at 380 °C. All compounds crystallise isotypically (P2(1)/c (no. 14), Z = 4, a(Tb) = 1368.24(4) pm, b(Tb) = 710.42(2) pm, c(Tb) = 965.79(3) pm, β(Tb) = 101.200(1)°, 3112 data, 160 parameters, wR2 = 0.062, a(Ho) = 1363.34(5) pm, b(Ho) = 709.24(3) pm, c(Ho) = 959.07(4) pm, β(Ho) = 101.055(1)°, 1607 data, 158 parameters, wR2 = 0.058). The crystal structure comprises two different infinite helical chains of corner-sharing phosphate tetrahedra. In-between these chains the lanthanide ions are located, coordinated by seven oxygen atoms belonging to four different polyphosphate chains. Vibrational, UV/Vis and fluorescence spectra of Ln[H(PO3)4] (Ln = Tb, Dy, Ho) as well as Dy[H(PO3)4]:Ln (Ln = Ce, Eu) and the magnetic and thermal behaviour of Tb[H(PO3)4] are reported.

Syntheses, structures, and magnetic properties of a family of heterometallic heptanuclear [Cu5Ln2] (Ln = Y(III), Lu(III), Dy(III), Ho(III), Er(III), and Yb(III)) complexes: observation of SMM behavior for the Dy(III) and Ho(III) analogues.

PubMed

Chandrasekhar, Vadapalli; Dey, Atanu; Das, Sourav; Rouzières, Mathieu; Clérac, Rodolphe

2013-03-04

Sequential reaction of the multisite coordination ligand (LH3) with Cu(OAc)2·H2O, followed by the addition of a rare-earth(III) nitrate salt in the presence of triethylamine, afforded a series of heterometallic heptanuclear complexes containing a [Cu5Ln2] core {Ln = Y(1), Lu(2), Dy(3), Ho(4), Er(5), and Yb(6)}. Single-crystal X-ray crystallography reveals that all the complexes are dicationic species that crystallize with two nitrate anions to compensate the charge. The heptanuclear aggregates in 1-6 are centrosymmetrical complexes, with a hexagonal-like arrangement of six peripheral metal ions (two rare-earth and four copper) around a central Cu(II) situated on a crystallographic inversion center. An all-oxygen environment is found to be present around the rare-earth metal ions, which adopt a distorted square-antiprismatic geometry. Three different Cu(II) sites are present in the heptanuclear complexes: two possess a distorted octahedral coordination sphere while the remaining one displays a distorted square-pyramidal geometry. Detailed static and dynamic magnetic properties of all the complexes have been studied and revealed the single-molecule magnet behavior of the Dy(III) and Ho(III) derivatives.

Enthalpies of melting of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm)

NASA Astrophysics Data System (ADS)

Andreev, P. O.; Mikhalkina, O. G.; Andreev, O. V.; Elyshev, A. V.

2015-05-01

The melting temperatures and enthalpies of such congruently melting compounds as LaSF ( T m = 1713 ± 7 K, Δ H = 45.7 ± 4.6 kJ/mol), CeSF ( T m = 1683 ± 7 K, Δ H = 40.7 ± 4.1 kJ/mol), PrSF ( T m = 1661 ± 7 K, Δ H = 39.7 ± 4.0 kJ/mol), NdSF ( T m = 1654 ± 7 K, Δ H = 40.2 ± 4.0 kJ/mol), and SmSF ( T m = 1587 ± 7 K, Δ H = 36.1 ± 3.6 kJ/mol) are determined via synchronous thermal analysis. The tetrad effect is evident in the change of the melting temperatures and enthalpies of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm) depending on r(Ln3+).

Magnetic upconverting fluorescent NaGdF4:Ln3+ and iron-oxide@NaGdF4:Ln3+ nanoparticles

NASA Astrophysics Data System (ADS)

Shrivastava, Navadeep; Rocha, Uéslen; Muraca, Diego; Jacinto, Carlos; Moreno, Sergio; Vargas, J. M.; Sharma, S. K.

2018-05-01

Microwave assisted solvothermal method has been employed to synthesize multifunctional upconverting β-NaGdF4:Ln3+ and magnetic-upconverting Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (Ln = Yb and Er) nanoparticles. The powder x-ray diffraction data confirms the hexagonal structure of NaGdF4:Ln3+ and high resolution transmission electron microscopy shows the formation of rod shaped NaGdF4:Ln3+ (˜ 20 nm) and ovoid shaped Fe3O4/γ-Fe2O3@NaGdF4:Ln3+ (˜ 15 nm) nanoparticles. The magnetic hysteresis at 300 K for β-NaGdF4:Ln3+ demonstrates paramagnetic features, whereas iron-oxide@β-NaGdF4:Ln3+ exhibits superparamagnetic behavior along with a linear component at large applied field due to paramagnetic NaGdF4 matrix. Both nanoparticle samples provide an excellent green emitting [(2H11/2, 4S3/2)→4I15/2 (˜ 540 nm)] upconversion luminescence emission under excitation at 980 nm. The energy migration between Yb and Er in NaGdF4 matrix has been explored from 300-800 nm. Intensity variation of blue, green and red lines and the observed luminescence quenching due to the presence of Fe3O4/γ-Fe2O3 in the composite has been proposed. These kinds of materials contain magnetic and luminescence characteristics into single nanoparticle open new possibility for bioimaging applications.

Phase transformation pathways of ultrafast-laser-irradiated Ln 2 O 3 ( Ln = Er – Lu )

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

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln 2O 3 ( Ln = Er – Lu ) , and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln = Tm – Lu , consistent with themore » material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln = Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.« less

Phase transformation pathways of ultrafast-laser-irradiated Ln 2 O 3 ( Ln = Er – Lu )

DOE PAGES

Rittman, Dylan R.; Tracy, Cameron L.; Chen, Chien-Hung; ...

2018-01-10

Ultrafast laser irradiation causes intense electronic excitations in materials, leading to transient high temperatures and pressures. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln 2O 3 ( Ln = Er – Lu ) , and explore the mechanism by which the phase transformation occurs. A combination of grazing incidence x-ray diffraction and transmission electron microscopy are used to determine the magnitude and depth-dependence of the phase transformation, respectively. Although all compositions undergo the same transformation, their transformation mechanisms differ. The transformation is pressure-driven for Ln = Tm – Lu , consistent with themore » material's phase behavior under equilibrium conditions. However, the transformation is thermally driven for Ln = Er , revealing that the nonequilibrium conditions of ultrafast laser irradiation can lead to novel transformation pathways. Ab initio molecular-dynamics simulations are used to examine the atomic-scale effects of electronic excitation, showing the production of oxygen Frenkel pairs and the migration of interstitial oxygen to tetrahedrally coordinated constitutional vacancy sites, the first step in a defect-driven phase transformation.« less

Theoretical aspects of photonic band gap in 1D nano structure of LN: MgLN periodic layer

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

Sisodia, Namita, E-mail: namitasisodiya@gmail.com

2015-06-24

By using the transfer matrix method, we have analyzed the photonic band gap properties in a periodic layer of LN:MgLN medium. The Width of alternate layers of LN and MgLN is in the range of hundred nanometers. The birefringent and ferroelectric properties of the medium (i.e ordinary, extraordinary refractive indices and electric dipole moment) is given due considerations in the formulation of photonic band gap. Effect of electronic transition dipole moment of the medium on photonic band gap is also taken into account. We find that photonic band gap can be modified by the variation in the ratio of themore » width of two medium. We explain our findings by obtaining numerical values and the effect on the photonic band gap due to variation in the ratio of alternate medium is shown graphically.« less

Lanthanide contraction effect on crystal structures, magnetic, and dielectric properties in ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd)

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

Han, L.; Yao, C. G.; Meng, J. L.

The crystal structures, magnetic, and dielectric properties for the ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd) have been investigated. The crystal structure has been solved by Rietveld refinements of X-ray diffraction data in the monoclinic space group P2{sub 1}/n (No. 14). The Co{sup 2+} and Sb{sup 5+} ions are almost fully ordered over the B-site, and the octahedral framework displays significant tilting distortion according to the Glazer's tilt system a{sup –}a{sup –}c{sup +}. As the result of lanthanide contraction from La{sup 3+} to Nd{sup 3+}, the B-site sublattice distortions become stronger accompanying with the reduction of themore » tolerance factor and coordination number. The magnetization measurements show an antiferromagnetic ordering with large effective magnetic moments (μ{sub eff}) suggesting that the orbital component is significant. The maximum values of isothermal magnetization increase with the decrease in radii of rare earth ions, which is attributed to the weakening of antiferromagnetic interaction via Co{sup 2+}–O–Sb{sup 5+}–O–Co{sup 2+} paths. The dielectric constants present frequency dependence and monotonically decrease with the ionic radii reduction from La{sup 3+} to Nd{sup 3+} due to the suppression of electron transfer. These results indicate that the magnetic and dielectric properties can be tuned by controlling the degree of lattice distortion, which is realized by introducing different Ln{sup 3+} ions at the A-site.« less

Decanuclear Ln10 Wheels and Vertex-Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties.

PubMed

Das, Sourav; Dey, Atanu; Kundu, Subrata; Biswas, Sourav; Narayanan, Ramakirushnan Suriya; Titos-Padilla, Silvia; Lorusso, Giulia; Evangelisti, Marco; Colacio, Enrique; Chandrasekhar, Vadapalli

2015-11-16

The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual-wavelength Nd:CaLnAlO4 lasers at 1.365 and 1.390 μm

NASA Astrophysics Data System (ADS)

Loiko, Pavel; Maria Serres, Josep; Mateos, Xavier; Xu, Xiaodong; Xu, Jun; Griebner, Uwe; Petrov, Valentin; Aguiló, Magdalena; Díaz, Francesc; Major, Arkady

2018-02-01

Tetragonal calcium rare-earth aluminates, CaLnAlO4, are attractive laser host crystals. The emission of Nd3+ ions at 1.3- 1.4 μm due to the 4F3/2 -> 4I13/2 transition is of interest for medicine, fiber optics, and light conversion. We report on compact Nd:CaLnAlO4 lasers using a plane-plane cavity. With an a-cut 0.8 at.% Nd:CaYAlO4 crystal diode-pumped at 802 nm, a maximum continuous-wave output power of 365 mW was achieved at 1.365 & 1.390 μm corresponding to the σ-polarization. The 4F3/2 -> 4I13/2 laser performance of the Nd:CaLnAlO4 crystals was compared to that from a monoclinic Nd:KGd(WO4)2. At the 4F3/2-> 4I11/2 transition (1.08 μm), a Nd:CaYAlO4 micro-laser generated multi-watt output (>4 W) with a slope efficiency of 39%.

Cation deficient layered Ruddlesden-Popper-related oxysulfides La2LnMS2O5 (Ln=La, Y; M=Nb, Ta).

PubMed

Cario, Laurent; Popa, Aurelian Florin; Lafond, Alain; Guillot-Deudon, Catherine; Kabbour, Houria; Meerschaut, A; Clarke, Simon J; Adamson, Paul

2007-11-12

The structures of the new oxysulfide Ruddlesden-Popper phases La2LnMS2O5 (Ln=La, Y; M=Nb, Ta) are reported together with an iodide-containing variant: La3-xNb1+xS2O5I2x (0LnMO5] or [La1-xNb1+xO5I2x]. In the oxide slabs, the trivalent and pentavalent cations are disordered on the long-length scale probed by diffraction methods, but bond length considerations suggest that they must be ordered at least on the length scale of the unit cell. The [LnMO5] block of the iodide-free compounds derive from the ideal [Ti2O5] blocks found in Ln2Ti2S2O5 (Ln=Nd-Er; Y) by the formal substitution of two Ti4+ ions with one Ln3+ and one M5+ion. The unusual partial insertion of iodide in the perovskite voids of the [LaNbO5] block in La3NbS2O5 was found to be coupled to a La/Nb substitution, maintaining the charge balance within the [La1-xNb1+xO5I2x]2- block. The Nb5+ ions were found to be too resistant to reduction to undergo the intercalation of alkali metals observed in the Ln2Ti2S2O5 series.

Trap Depth Engineering of SrSi2O2N2:Ln2+,Ln3+ (Ln2+ = Yb, Eu; Ln3+ = Dy, Ho, Er) Persistent Luminescence Materials for Information Storage Applications.

PubMed

Zhuang, Yixi; Lv, Ying; Wang, Le; Chen, Wenwei; Zhou, Tian-Liang; Takeda, Takashi; Hirosaki, Naoto; Xie, Rong-Jun

2018-01-17

Deep-trap persistent luminescence materials exhibit unique properties of energy storage and controllable photon release under additional stimulation, allowing for both wavelength and intensity multiplexing to realize high-capacity storage in the next-generation information storage system. However, the lack of suitable persistent luminescence materials with deep traps is the bottleneck of such storage technologies. In this study, we successfully developed a series of novel deep-trap persistent luminescence materials in the Ln 2+ /Ln 3+ -doped SrSi 2 O 2 N 2 system (Ln 2+ = Yb, Eu; Ln 3+ = Dy, Ho, Er) by applying the strategy of trap depth engineering. Interestingly, the trap depth can be tailored by selecting different codopants, and it monotonically increases from 0.90 to 1.18 eV in the order of Er, Ho, and Dy. This is well explained by the energy levels indicated in the host-referred binding energy scheme. The orange-red-emitting SrSi 2 O 2 N 2 :Yb,Dy and green-emitting SrSi 2 O 2 N 2 :Eu,Dy phosphors are demonstrated to be good candidates of information storage materials, which are attributed to their deep traps, narrow thermoluminescence glow bands, high emission efficiency, and excellent chemical stability. This work not only validates the suitability of deep-trap persistent luminescence materials in the information storage applications, but also broadens the avenue to explore such kinds of new materials for applications in anticounterfeiting and advanced displays.

Antiferromagnetic coupling between rare earth ions and semiquinones in a series of 1:1 complexes.

PubMed

Caneschi, Andrea; Dei, Andrea; Gatteschi, Dante; Poussereau, Sandrine; Sorace, Lorenzo

2004-04-07

We use the strategy of diamagnetic substitution for obtaining information on the crystal field effects in paramagnetic rare earth ions using the homologous series of compounds with the diamagnetic tropolonato ligand, Ln(Trp)(HBPz(3))(2), and the paramagnetic semiquinone ligand, Ln(DTBSQ)(HBPz(3))(2), (DTBSQ = 3,5-di-tert-butylsemiquinonato, Trp = tropolonate, HBPz(3)= hydrotrispyrazolylborate) for Ln = Sm(iii), Eu(iii), Gd(iii), Tb(iii), Dy(iii), Ho(iii), Er(iii) or Yb(iii). The X-ray crystal structure of a new form of tropolonate derivative is presented, which shows, as expected, a marked similarity with the structure of the semiquinonate derivative. The Ln(Trp)(HBPz(3))(2) derivatives were then used as a reference for the qualitative determination of crystal field effects in the exchange coupled semiquinone derivatives. Through magnetisation and susceptibility measurements this empirical diamagnetic substitution method evidenced for Er(iii), Tb(iii), Dy(iii) and Yb(iii) derivatives a dominating antiferromagnetic coupling. The increased antiferromagnetic contribution compared to other radical-rare earth metal complexes formed by nitronyl nitroxide ligands may be related to the increased donor strength of the semiquinone ligand.

Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds

DOE PAGES

Pindwal, Aradhana; Yan, KaKing; Patnaik, Smita; ...

2017-10-09

Homoleptic tris(alkyl) rare earth complexes Ln{C(SiHMe 2) 3} 3 (Ln = La, 1a; Ce, 1b; Pr, 1c; Nd, 1d) are synthesized in high yield from LnI 3THF n and 3 equiv of KC(SiHMe 2) 3. X-ray diffraction studies reveal 1a–d are isostructural, pseudo-C 3-symmetric molecules that contain two secondary Ln←HSi interactions per alkyl ligand (six total). Spectroscopic assignments are supported by comparison with Ln{C(SiDMe 2) 3} 3 and DFT calculations. Here, the Ln←HSi and terminal SiH exchange rapidly on the NMR time scale at room temperature, but the two motifs are resolved at low temperature. Variable-temperature NMR studies provide activationmore » parameters for the exchange process in 1a (ΔH ‡ = 8.2(4) kcal·mol –1; ΔS ‡ = –1(2) cal·mol –1K –1) and 1a-d 9 (ΔH ‡ = 7.7(3) kcal·mol –1; ΔS ‡ = –4(2) cal·mol –1K –1). Comparisons of lineshapes, rate constants (kH/kD), and slopes of ln(k/T) vs 1/T plots for 1a and 1a-d 9 reveal that an inverse isotope effect dominates at low temperature. DFT calculations identify four low-energy intermediates containing five β-Si–H→Ln and one γ-C–H→Ln. The calculations also suggest the pathway for Ln←HSi/SiH exchange involves rotation of a single C(SiHMe 2) 3 ligand that is coordinated to the Ln center through the Ln–C bond and one secondary interaction. These robust organometallic compounds persist in solution and in the solid state up to 80 °C, providing potential for their use in a range of synthetic applications. For example, reactions of Ln{C(SiHMe 2) 3} 3 and ancillary proligands, such as bis-1,1-(4,4-dimethyl-2-oxazolinyl)ethane (HMeC(Ox Me2) 2) give {MeC(Ox Me2) 2}Ln{C(SiHMe 2) 3} 2, and reactions with disilazanes provide solvent-free lanthanoid tris(disilazides).« less

Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds

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

Pindwal, Aradhana; Yan, KaKing; Patnaik, Smita

Homoleptic tris(alkyl) rare earth complexes Ln{C(SiHMe 2) 3} 3 (Ln = La, 1a; Ce, 1b; Pr, 1c; Nd, 1d) are synthesized in high yield from LnI 3THF n and 3 equiv of KC(SiHMe 2) 3. X-ray diffraction studies reveal 1a–d are isostructural, pseudo-C 3-symmetric molecules that contain two secondary Ln←HSi interactions per alkyl ligand (six total). Spectroscopic assignments are supported by comparison with Ln{C(SiDMe 2) 3} 3 and DFT calculations. Here, the Ln←HSi and terminal SiH exchange rapidly on the NMR time scale at room temperature, but the two motifs are resolved at low temperature. Variable-temperature NMR studies provide activationmore » parameters for the exchange process in 1a (ΔH ‡ = 8.2(4) kcal·mol –1; ΔS ‡ = –1(2) cal·mol –1K –1) and 1a-d 9 (ΔH ‡ = 7.7(3) kcal·mol –1; ΔS ‡ = –4(2) cal·mol –1K –1). Comparisons of lineshapes, rate constants (kH/kD), and slopes of ln(k/T) vs 1/T plots for 1a and 1a-d 9 reveal that an inverse isotope effect dominates at low temperature. DFT calculations identify four low-energy intermediates containing five β-Si–H→Ln and one γ-C–H→Ln. The calculations also suggest the pathway for Ln←HSi/SiH exchange involves rotation of a single C(SiHMe 2) 3 ligand that is coordinated to the Ln center through the Ln–C bond and one secondary interaction. These robust organometallic compounds persist in solution and in the solid state up to 80 °C, providing potential for their use in a range of synthetic applications. For example, reactions of Ln{C(SiHMe 2) 3} 3 and ancillary proligands, such as bis-1,1-(4,4-dimethyl-2-oxazolinyl)ethane (HMeC(Ox Me2) 2) give {MeC(Ox Me2) 2}Ln{C(SiHMe 2) 3} 2, and reactions with disilazanes provide solvent-free lanthanoid tris(disilazides).« less

On the structural and luminescent properties of the M'LnTaO/sub 4/ rare earth tantalates

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

Brixner, L.H.; Chen, H.-Y.

1983-12-01

The structure of M YTaO/sub 4/ has been redetermined and was refined to an R value of 0.034. M'YTaO/sub 4/ crystallizes in P2/a symmetry with a = 5.298(1),b = 5.451(1),c = 5.111(1)A,..beta.. = 96.45 deg. At temperatures > 1450/sup 0/C,M'YTaO/sub 4/ will convert by way of a reconstructive transformation into the I4/sub 1//a symmetry of scheelite, and, upon cooling, a second-order ferroelastic transition (4/mF2/m) to M (fergusonite) YTaO/sub 4/ occurs. There are significant structural differences between M and M'YTaO/sub 4/ which are discussed. M'LnTaO/sub 4/ compounds exist from Ln = Sm to Lu. As a host for luminescent ions, M'YTaO/submore » 4/ is superior to the M modification, as well as all other compounds in the Y/sub 2/O/sub 2/Ta/sub 2/O/sub 5/ phase diagram.« less

Unusual undecanuclear heterobimetallic Zn4Ln7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen.

PubMed

Ke, Hongshan; Lu, Xiaohua; Wei, Wen; Wang, Wenyuan; Xie, Gang; Chen, Sanping

2017-06-27

The synthesis, characterization and properties of two unprecedented undecanuclear heterobimetallic Zn 4 Ln 7 complexes of formula [Zn 4 Ln 7 (L) 8 (O 2 ) 2 (OH) 4 (Cl) 4 (H 2 O) 4 ]·Cl·4H 2 O·4CH 3 CN (Ln = Gd (1), Dy (2)) encapsulating two peroxide anions are presented, representing a very rare example of a 3d-peroxo-Ln system and expanding the realm of metal-peroxo complexes. These eleven metal ions are arranged in a peculiar structural motif, where Zn 4 is located at the peripheral shell wrapping Ln 7 in the inner core. The Zn ions are penta-coordinate in all cases, linked to the NO 2 donor atoms from the L 2- ligand and to a hydroxyl group, and the apical position is occupied by a chloride anion. All Ln III ions in these systems are octa-coordinate with LnO 8 and LnNO 7 coordination spheres. Magnetocaloric effect (MCE) behavior has been found in the Gd analogue due to multiple low lying excited states arising from antiferromagnetic Gd-Gd exchange interactions. The Dy derivative shows frequency dependent out-of-phase signals indicating the presence of slow relaxation of magnetization below 8 K under zero applied direct current (dc) field, but without reaching a maximum, which is due to a faster quantum tunneling relaxation. The effective barrier extracted from the frequency dependent data is U eff = 11.2 K and a τ 0 of 4.18 × 10 -6 s.

A Family of A-Site Cation-Deficient Double-Perovskite-Related Iridates: Ln9Sr2Ir4O24 (Ln = La, Pr, Nd, Sm).

PubMed

Ferreira, Timothy; Smith, Mark D; Zur Loye, Hans-Conrad

2018-06-21

The compositions of the general formula Ln 11- x Sr x Ir 4 O 24 (Ln = La, Pr, Nd, Sm; 1.37 ≥ x ≥ 2) belonging to a family of A-site cation-deficient double-perovskite-related oxide iridates were grown as highly faceted single crystals from a molten strontium chloride flux. Their structures were determined by single-crystal X-ray diffraction. On the basis of the single-crystal results, additional compositions, Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm), were prepared as polycrystalline powders via solid-state reactions and structurally characterized by Rietveld refinement. The compositions Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) contain Ir(V) and Ir(IV) in a 1:3 ratio with an average iridium oxidation state of 4.25. The single-crystal compositions La 9.15 Sr 1.85 Ir 4 O 24 and Pr 9.63 Sr 1.37 Ir 4 O 24 contain relatively less Ir(V), with the average iridium oxidation states being 4.21 and 4.09, respectively. The magnetic properties of Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) were measured, and complex magnetic behavior was observed in all cases at temperatures below 30 K.

Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare-Earth Complexes: Non-Redox Oxygen Atom Transfer.

PubMed

Hong, Jianquan; Tian, Haiwen; Zhang, Lixin; Zhou, Xigeng; Del Rosal, Iker; Weng, Linhong; Maron, Laurent

2018-01-22

The preferential substitution of oxo ligands over alkyl ones of rare-earth complexes is commonly considered as "impossible" due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare-earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln-oxo bond, but also protect the highly reactive Ln-alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non-redox rare-earth-mediated oxygen atom transfer from ketones to CS 2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare-earth oxo complexes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable emission in Ln3+ (Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor synthesized by combustion method

NASA Astrophysics Data System (ADS)

Kolte, M. M.; Pawade, V. B.; Bhattacharya, A. B.; Dhoble, S. J.

2018-05-01

Ln3+ (Ln = Ce3+/Dy3+, Ce3+/Tb3+) doped KNa3Al4Si4O16 phosphor has been synthesized by Combustion method (CS) at 550° C successfully. Ln3+ (Ln = Ce3+, Dy3+, Tb3+) ions when doped in KNa3Al4Si4O16 host lattice, it shows blue and green emission band under the near Ultraviolet (NUV) excitation wavelength. The Photoluminescence excitation (PLE) and emission spectra are observed due to f-f and d-f transition of rare earth ions. Also, an effective energy transfer (ET) study from Ce3+ → Dy3+ and Ce3+ → Tb3+ ions has been studied and confirmed on the basis of Dexter-Foster theory. Further synthesized phosphor is well characterized by XRD, SEM, TEM and decay time measurement. However, the analysis of crystallite size, lattice strain has been studied by using theoretical as well as experimental techniques. Hence, the observed tunable emission in Ln3+ doped KNa3Al4Si4O16 phosphor may be applicable for solid state lighting technology.

New Antimony Lanthanide Disulfide Dibromides LnSbS

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

Gout, D.; Jobic, S.; Evain, M.

2001-05-01

CeSbS{sub 2}Br{sub 2} (I), Ce{sub 1/2}La{sub 1/2}SbS{sub 2}Br{sub 2} (II), and LaSbS{sub 2}Br{sub 2} (III) have been synthesized at 700 C from a mixture of LnBr{sub 3}, Ln{sub 2}S{sub 3}, Sb, and S and characterized by single-crystal X-ray diffraction. The three phases are isostructural (space group P2{sub 1}/c, Z=4) and crystallize in a novel, dense, bidimensional structure with cell parameters a=8.709(3) {angstrom}, b=9.187(2) {angstrom}, c=17.397(5) {angstrom} {beta}=104.26(3) for I, a=8.739(7) {angstrom}, b=9.219(7) {angstrom}, c=17.41(2) {angstrom}, =104.3(1) for II, and a=8.785(1) {angstrom}, b=9.236(2) {angstrom}, c=17.372(3) {angstrom}, {beta}=104.09(2) for III. In these compounds, [Ln S{sub 5}Br{sub 4}] and [Ln S{sub 3}Br{sub 6}]more » (Ln=Ce, La) distorted tricapped trigonal prisms define infinite {sub {infinity}}{sup 2}[LnS{sub 2}Br{sub 2}] layers counterbalanced and capped by antimony cations. In good accordance with the structural features, the charge balance in these materials is to be written Ln{sup III}Sb{sup III}S{sup -II}{sub 2}Br{sup -I}{sub 2}. These compounds exhibit a yellow hue with a measured absorption threshold of 2.42(1), 2.55(1), and 2.72(1) eV for I, II, and III, respectively. In the two cerium containing bromothioantimonates I and II, the origin of the color is assigned to a Ce-4f{yields}Ce-5d electronic transition, which shifts to higher energy from I to II due either to a matrix effect (increase of the mean Ln-S distances under the substitution of Ce for La) or to an atomic ordering between Ce and La cations on the Ln(1) and Ln(2) crystallographic sites. In contrast, the electronic transition at play in III involves a charge transfer from the bromine and sulfur ions to the antimony ions, the latter contributing substantially to the lowermost levels of the conduction band.« less

Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

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

Kazmierczak, Karolina; Hoeppe, Henning A., E-mail: henning@ak-hoeppe.d

2011-05-15

The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrationalmore » and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.« less

In pursuit of the rhabdophane crystal structure: from the hydrated monoclinic LnPO{sub 4}.0.667H{sub 2}O to the hexagonal LnPO{sub 4} (Ln = Nd, Sm, Gd, Eu and Dy)

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

Mesbah, Adel, E-mail: adel.mesbah@cea.fr; Clavier, Nicolas; Elkaim, Erik

The dehydration process of the hydrated rhabdophane LnPO{sub 4}.0.667H{sub 2}O (Ln = La to Dy) was thoroughly studied over the combination of in situ high resolution synchrotron powder diffraction and TGA experiments. In the case of SmPO{sub 4}.0.667H{sub 2}O (monoclinic, C2), a first dehydration step was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2) with Z =12 and a =17.6264(1) Å, b =6.9704(1) Å, c =12.1141(1) Å, β=133.74(1) °, V =1075.33(1) Å{sup 3}. In agreement with the TGA and dilatometry experiments, all the water molecules were evacuated above 220 °C yielding to the anhydrousmore » form, which crystallizes in the hexagonal P3{sub 1}21 space group with a =7.0389(1) Å, c =6.3702(1) Å and V =273.34(1) Å{sup 3}. This study was extended to selected LnPO{sub 4}.0.667H{sub 2}O samples (Ln= Nd, Gd, Eu, Dy) and the obtained results confirmed the existence of two dehydration steps before the stabilization of the anhydrous form, with the transitory formation of LnPO{sub 4}.0.5H{sub 2}O. - Graphical abstract: The dehydration process of the rhabdophane SmPO{sub 4}.0.667H{sub 2}O was studied over combination of in situ high resolution synchrotron powder diffraction and TGA techniques, a first dehydration was identified around 80 °C leading to the formation of SmPO{sub 4}.0.5H{sub 2}O (Monoclinic, C2). Then above 220 °C, the anhydrous form of the rhabdophane SmPO{sub 4} was stabilized and crystallizes in the hexagonal P3{sub 1}21 space group. - Highlights: • In situ synchrotron powder diffraction was carried out during the dehydration of the rhabdopahe LnPO{sub 4}.0.667H{sub 2}O. • The heat of the rhabdophane LnPO{sub 4}.0.667H{sub 2}O leads to LnPO{sub 4}.0.5H{sub 2}O then to anhydrous rhabdophane LnPO{sub 4}. • LnPO{sub 4}.0.5H{sub 2}O (monoclinic, C2) and LnPO{sub 4} (Hexagonal, P3{sub 1}21) were solved over the use of direct methods.« less

In pursuit of the rhabdophane crystal structure: from the hydrated monoclinic LnPO4.0.667H2O to the hexagonal LnPO4 (Ln = Nd, Sm, Gd, Eu and Dy)

NASA Astrophysics Data System (ADS)

Mesbah, Adel; Clavier, Nicolas; Elkaim, Erik; Szenknect, Stéphanie; Dacheux, Nicolas

2017-05-01

The dehydration process of the hydrated rhabdophane LnPO4.0.667H2O (Ln = La to Dy) was thoroughly studied over the combination of in situ high resolution synchrotron powder diffraction and TGA experiments. In the case of SmPO4.0.667H2O (monoclinic, C2), a first dehydration step was identified around 80 °C leading to the formation of SmPO4.0.5H2O (Monoclinic, C2) with Z =12 and a =17.6264(1) Å, b =6.9704(1) Å, c =12.1141(1) Å, β=133.74(1) °, V =1075.33(1) Å3. In agreement with the TGA and dilatometry experiments, all the water molecules were evacuated above 220 °C yielding to the anhydrous form, which crystallizes in the hexagonal P3121 space group with a =7.0389(1) Å, c =6.3702(1) Å and V =273.34(1) Å3. This study was extended to selected LnPO4.0.667H2O samples (Ln= Nd, Gd, Eu, Dy) and the obtained results confirmed the existence of two dehydration steps before the stabilization of the anhydrous form, with the transitory formation of LnPO4.0.5H2O.

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

Microchip Yb:CaLnAlO4 lasers with up to 91% slope efficiency.

PubMed

Loiko, Pavel; Serres, Josep Maria; Mateos, Xavier; Xu, Xiaodong; Xu, Jun; Jambunathan, Venkatesan; Navratil, Petr; Lucianetti, Antonio; Mocek, Tomas; Zhang, Xuzhao; Griebner, Uwe; Petrov, Valentin; Aguiló, Magdalena; Díaz, Francesc; Major, Arkady

2017-07-01

Multi-watt continuous-wave (CW) operation of tetragonal rare-earth calcium aluminate Yb:CaLnAlO 4 (Ln=Gd,Y)) crystals in plano-plano microchip lasers was demonstrated with an almost quantum-defect-limited slope efficiency. Pumped at 978 nm by an InGaAs laser diode, a 3.4 mm long 8 at. % Yb:CaGdAlO 4 laser generated 7.79 W at 1057-1065 nm with a slope efficiency of η=84% (with respect to the absorbed pump power). An even higher η=91% was achieved with a 2.5 mm long 3 at. % Yb:CaYAlO 4 laser, from which 5.06 W were extracted at 1048-1056 nm. Both lasers produced linearly polarized output (σ-polarization) with an almost circular diffraction-limited beam (Mx,y2<1.1). The output performance of the developed lasers was modeled, yielding an internal loss coefficient as low as 0.004-0.007  cm -1 . In addition, their spectroscopic properties were revisited.

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.

Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

PubMed

Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

2008-04-07

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

Covalently-bonded grafting of [Ln3(Benzimidazole)4]-arrayed (Ln = Tb, Nd, Yb or Er) complex monomers into PNBE (poly(norbornene)) with highly luminous color-purity green-light or efficient NIR luminescence

NASA Astrophysics Data System (ADS)

Liu, Lin; Fu, Guorui; Feng, Heini; Guan, Jiaqing; Li, Fengping; Lü, Xingqiang; Wong, Wai-Kwok; Jones, Richard A.

2017-07-01

Within series of Ln3-grafted polymers Poly({[Ln3(L)4(NO3)6]·(NO3)·(H3O)2}-co-NBE) (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3; Ln = Nd, 4; Ln = Yb, 5; Ln = Er, 6 or Ln = Gd, 7) obtained from ring-opening metathesis polymerization (ROMP) of norbornene (NBE) with each of allyl-functionalized complex monomers {[Ln3(L)4(NO3)6]·(NO3)·(H3O)2} (HL = 4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol), PNBE-assisted effective energy transfer renders Poly(3-co-NBE) Tb3+-centered highly luminous color-purity green-light with an attractive quantum yield of 87% and efficient near-infrared (NIR) luminescence (ΦNdL = 0.61%; ΦYbL = 1.47% and ΦErL = 0.03%) for Nd3+-, Yb3+- or Er3+-grafted polymers.

Efficient Rare-Earth-Based Coordination Polymers as Green Photocatalysts for the Synthesis of Imines at Room Temperature.

PubMed

Aguirre-Díaz, Lina M; Snejko, Natalia; Iglesias, Marta; Sánchez, Félix; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

2018-06-18

Five new rare-earth coordination polymers (CPs) were designed in order to offer a remarkable platform that contains light-harvesting antennas and catalytic active centers to achieve solar-energy conversion as green alternatives in the synthesis of imines. These five new spirobifluorene-containing Ln-CPs, named [Er 3 (Hsfdc) 3 (sfdc) 3 (H 2 O)]· xH 2 O (RPF-30-Er), [Ln(Hsfdc)(sfdc)(EtOH)]·S (RPF-31-Ln, where Ln = La, Nd, and Sm and S = H 2 O or EtOH), and [Ho(Hsfdc)(sfdc)(H 2 O)] (RPF-32-Ho) (RPF = rare-earth polymeric framework and H 2 sfdc = 9,9'-spirobi[9 H-fluorene]-2,2'-dicarboxylic acid), have been solvothermally synthesized, and their structural features can be described as follows: (i) RPF-30-Er shows a 3D framework in which the inorganic trimers (secondary building units) are cross-linked by Hsfdc - and sfdc 2- linkers displaying a pcu topology. (ii) The isostructural RPF-31-Ln series of materials, together with RPF-32-Ho, exhibit a 1D network of chains growing along the a axis with a ribbon-of-rings topology type. The photocatalytic activity of the RPF- n materials was tested in the oxidative coupling of amines using molecular oxygen and air as oxidizing agents under warm light. Among the materials investigated, RPF-31-Nd was chosen to further investigate the approach in the selectivity of different amine derivates.

Luminescent LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) hollow porous spheres for encapsulation of biomolecules

NASA Astrophysics Data System (ADS)

Li, Dan; Liu, Chunlei; Jiang, Lianzhou

2015-10-01

In this study, LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) hollow porous spheres, synthesized via self-sacrificing templated route, are developed for enzyme immobilization and protein adsorption. The four LuVO4 hollow spheres with diameter of 180 nm, 280 nm, 370 nm and 480 nm were obtained. The size of LuVO4 hollow sphere is dependent on Lu(OH)CO3 template. Upon excitation by UV light, hollow LuVO4:Ln3+ (Ln = Eu, Sm, Dy, Er) spheres exhibit red (Eu3+), orange (Sm3+), yellow-green (Dy3+), and green (Er3+) emissions. The good biocompatibility of sample is validated by MTT assay. Due to structure feature and size of obtained sample, the rapid encapsulation of biomolecules within samples has been achieved. Furthermore, the hollow spheres show different biomolecules adsorption capacities at different buffer solution pH values. The release behaviors of two kinds of biomolecules (lysozyme and bovine serum albumin) are also investigated. LuVO4 hollow spheres are suitable carriers for biomolecules. The emission intensity of Eu3+ in the LuVO4:Eu3+ varies with the released amount of LYZ. This enables the monitoring of release process by the change in the luminescence intensity.

Structural and dielectric characteristics of Ba3Ln3Ti5Nb5O30 (Ln = La, Nd, Sm) filled tungsten bronze ceramics

NASA Astrophysics Data System (ADS)

Chen, Wang; Gao, Ting Ting; Zhu, Xiao Li; Chen, Xiang Ming

2018-03-01

In the present work, the structural, dielectric and relaxor ferroelectric properties were investigated for Ba3Ln3Ti5Nb5O30 (Ln = La, Nd, Sm) ceramics. The filled tungsten bronze phase with space group P4/mbm was confirmed for all compositions, while a small amount of secondary phase was detected in Ba3Nd3Ti5Nb5O30 and Ba3Sm3Ti5Nb5O30. The typical relaxor ferroelectric behaviors were observed: a broad peak of dielectric constant shifting to higher temperatures and decreasing its magnitude with increasing frequency and the frequency dispersion obeying the Vogel-Fulcher relationship. The P-E (polarization-electric field) hysteresis loops were obtained for Ba3Ln3Ti5Nb5O30 (Ln = La, Nd, Sm) ceramics at low temperatures. The nanoscale ferroelectric 180° domains with strip-like shape were observed in the paraelectric matrix at room temperature, where the commensurate structural modulations were determined in the domains and incommensurate ones were determined in the matrix. The significant differences were determined between the present ceramics and Ba4Ln2Ti4Nb6O30 and Ba5LnTi3Nb7O30 because of the different distribution patterns of A1 and A2 cations.

Highly-efficient multi-watt Yb:CaLnAlO4 microchip lasers

NASA Astrophysics Data System (ADS)

Loiko, Pavel; Serres, Josep Maria; Mateos, Xavier; Xu, Xiaodong; Xu, Jun; Yumashev, Konstantin; Griebner, Uwe; Petrov, Valentin; Aguiló, Magdalena; Díaz, Francesc; Major, Arkady

2017-02-01

Tetragonal rare-earth calcium aluminates, CaLnAlO4 where Ln = Gd or Y (CALGO and CALYO, respectively), are attractive laser crystal hosts due to their locally disordered structure and high thermal conductivity. In the present work, we report on highly-efficient power-scalable microchip lasers based on 8 at.% Yb:CALGO and 3 at.% Yb:CALYO crystals grown by the Czochralski method. Pumped by an InGaAs laser diode at 978 nm, the 6 mm-long Yb:CALGO microchip laser generated 7.79 W at 1057-1065 nm with a slope efficiency of η = 84% (with respect to the absorbed pump power) and an optical-to-optical efficiency of ηopt = 49%. The 3 mm-long Yb:CALYO microchip laser generated 5.06 W at 1048-1056 nm corresponding to η = 91% and ηopt = 32%. Both lasers produced linearly polarized output (σ- polarization) with an almost circular beam profile and beam quality factors M2 x,y <1.1. The output performance of the developed lasers was modeled yielding a loss coefficient as low as 0.004-0.007 cm-1. The results indicate that the Yb3+- doped calcium aluminates are very promising candidates for high-peak-power passively Q-switched microchip lasers.

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

Slow Magnetic Relaxation and Single-Molecule Toroidal Behaviour in a Family of Heptanuclear {CrIII LnIII6 } (Ln=Tb, Ho, Er) Complexes.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Swain, Abinash; Moubaraki, Boujemaa; Damjanović, Marko; Wernsdorfer, Wolfgang; Rajaraman, Gopalan; Murray, Keith S

2018-01-15

The synthesis, magnetic properties, and theoretical studies of three heterometallic {Cr III Ln III 6 } (Ln=Tb, Ho, Er) complexes, each containing a metal topology consisting of two Ln 3 triangles connected via a Cr III linker, are reported. The {CrTb 6 } and {CrEr 6 } analogues display slow relaxation of magnetization in a 3000 Oe static magnetic field. Single-crystal measurements reveal opening up of the hysteresis loop for {CrTb 6 } and {CrHo 6 } molecules at low temperatures. Ab initio calculations predict toroidal magnetic moments in the two Ln 3 triangles, which are found to couple, stabilizing a con-rotating ferrotoroidal ground state in Tb and Ho examples and extend the possibility of observing toroidal behaviour in non Dy III complexes for the first time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

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

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

DOE PAGES

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing; ...

2017-06-30

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Magnetic properties of the doubly ordered perovskite NaLnCoWO6 (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) family

NASA Astrophysics Data System (ADS)

Zuo, Peng; Klein, Holger; Darie, Céline; Colin, Claire V.

2018-07-01

The focus of this study is on the magnetic properties of the very recently synthesized doubly ordered perovskite family NaLnCoWO6 (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb). Magnetic characterizations were performed by magnetic susceptibility vs. temperature, isothermal magnetization and heat capacity measurements. All these compounds have been determined as antiferromagnets with Néel temperatures from 4 K to 13.1 K. When the lanthanide is magnetic, additional transitions were observed below the Néel temperature which are attributed to the polarization of the magnetic Ln3+ sublattice by the ordered Co2+ one. Taking into account the magnetic ordering found in this study and the polar structure in the nine compounds NaLnCoWO6 (Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) reported before, these compounds can be classified as new Type I multiferroics.

Formation and Fragmentation Chemistry of Tripositive Ln(TMGA)33+ Complexes in the Gas Phase.

PubMed

Chen, Xiuting; Li, Qingnuan; Gong, Yu

2017-08-01

Electrospray ionization (ESI) of LnCl 3 (Ln = La-Lu except Pm) and TMGA (tetramethyl glutaramide) mixtures resulted in the formation of gas-phase Ln(TMGA) 3 3+ complexes, where tripositive lanthanide cation was coordinated by three neutral TMGA ligands. Collision induced dissociation (CID) was employed to investigate the fragmentation chemistry of these tripositive complexes. Ln(TMGA) 2 (TMGA- 45) 3+ resulting from C carbonyl -N bond cleavage of TMGA and hydrogen transfer is the major CID product for all Ln(TMGA) 3 3+ except Eu(TMGA) 3 3+ which predominantly forms divalent Eu II (TMGA) 2 2+ complex via loss of TMGA + . Analogous Yb II (TMGA) 2 2+ and Sm II (TMGA) 2 2+ complexes arising from charge reduction were also observed, in competition with the formation of charge conserving Yb III (TMGA)(TMGA-H) 2+ and Sm III (TMGA)(TMGA-H) 2+ products. The yield of these charge reducing products follows their reduction potentials in condensed phase. In addition to Ln(TMGA) 3 3+ , tripositive ions such as Ln(TMGA) 4 3+ and Ln(TMGA) 2 3+ were experimentally identified as well. While the former was observed along with Ln(TMGA) 3 3+ during ESI, the latter was observed upon CID of Ln(TMGA) 3 3+ , suggesting two TMGA molecules can stabilize Ln 3+ in the gas phase. Graphical Abstract ᅟ.

High Specific Power Motors in LN2 and LH2

NASA Technical Reports Server (NTRS)

Brown, Gerald V.; Jansen, Ralph H.; Trudell, Jeffrey J.

2007-01-01

A switched reluctance motor has been operated in liquid nitrogen (LN2) with a power density as high as that reported for any motor or generator. The high performance stems from the low resistivity of Cu at LN2 temperature and from the geometry of the windings, the combination of which permits steady-state rms current density up to 7000 A/cm2, about 10 times that possible in coils cooled by natural convection at room temperature. The Joule heating in the coils is conducted to the end turns for rejection to the LN2 bath. Minimal heat rejection occurs in the motor slots, preserving that region for conductor. In the end turns, the conductor layers are spaced to form a heat-exchanger-like structure that permits nucleate boiling over a large surface area. Although tests were performed in LN2 for convenience, this motor was designed as a prototype for use with liquid hydrogen (LH2) as the coolant. End-cooled coils would perform even better in LH2 because of further increases in copper electrical and thermal conductivities. Thermal analyses comparing LN2 and LH2 cooling are presented verifying that end-cooled coils in LH2 could be either much longer or could operate at higher current density without thermal runaway than in LN2.

High Specific Power Motors in LN2 and LH2

NASA Technical Reports Server (NTRS)

Brown, Gerald V.; Jansen, Ralph H.; Trudell, Jeffrey J.

2007-01-01

A switched reluctance motor has been operated in liquid nitrogen (LN2) with a power density as high as that reported for any motor or generator. The high performance stems from the low resistivity of Cu at LN2 temperature and from the geometry of the windings, the combination of which permits steady-state rms current density up to 7000 A/sq cm, about 10 times that possible in coils cooled by natural convection at room temperature. The Joule heating in the coils is conducted to the end turns for rejection to the LN2 bath. Minimal heat rejection occurs in the motor slots, preserving that region for conductor. In the end turns, the conductor layers are spaced to form a heat-exchanger-like structure that permits nucleate boiling over a large surface area. Although tests were performed in LN2 for convenience, this motor was designed as a prototype for use with liquid hydrogen (LH2) as the coolant. End-cooled coils would perform even better in LH2 because of further increases in copper electrical and thermal conductivities. Thermal analyses comparing LN2 and LH2 cooling are presented verifying that end-cooled coils in LH2 could be either much longer or could operate at higher current density without thermal runaway than in LN2.

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

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

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Interplay of structural chemistry and magnetism in perovskites; A study of CaLn2Ni2WO9; Ln=La, Pr, Nd

NASA Astrophysics Data System (ADS)

Chin, Chun-Mann; Paria Sena, Robert; Hunter, Emily C.; Hadermann, Joke; Battle, Peter D.

2017-07-01

Polycrystalline samples of CaLn2Ni2WO9 (Ln=La, Pr, Nd) have been synthesized and characterised by a combination of X-ray and neutron diffraction, electron microscopy and magnetometry. Each composition adopts a perovskite-like structure with a 5.50, b 5.56, c 7.78 Å, β 90.1° in space group P21/n. Of the two crystallographically distinct six-coordinate sites, one is occupied entirely (Ln=Pr) or predominantly (Ln=La, Nd) by Ni2+ and the other by Ni2+ and W6+ in a ratio of approximately 1:2. None of the compounds shows long-range magnetic order at 5 K. The magnetometry data show that the magnetic moments of the Ni2+ cations form a spin glass below 30 K in each case. The Pr3+ moments in CaPr2Ni2WO9 also freeze but the Nd3+ moments in CaNd2Ni2WO9 do not. This behaviour is contrasted with that observed in other (A,A')B2B'O9 perovskites.

Synthesis, structures, and luminescent and magnetic properties of Ln-Ag heterometal-organic frameworks.

PubMed

Zhao, Xiao-Qing; Zhao, Bin; Wei, Shi; Cheng, Peng

2009-12-07

A series of Ln-Ag heterometal-organic frameworks based on 4-hydroxylpyridine-2,6-dicarboxylic acid (H(3)CAM) with formulas {LaAg(2)(CAM)(HCAM)(H(2)O)(2)}(n) (1), {LnAg(HCAM)(2)(H(2)O)(3)}(n) (Ln = Pr, 2; Nd, 3; Sm, 4; Eu, 5), and {LnAg(3)(CAM)(2)(H(2)O)}(n) (Ln = Gd, 6; Tb, 7; Dy, 8; Tm, 9; Yb, 10), have been synthesized with the hydrothermal reaction of Ln(OH)(3), Ag(2)O, and H(3)CAM at 160 degrees C. The single-crystal X-ray diffraction analyses reveal that three kinds of structures are exclusively governed by the size of lanthanide ions and the progression of structures is mainly ascribed to the lanthanide contraction effect. Compound 1 consists of a 3D network with an alpha-polonium-like Ag(+)-homometallic net and helical La(3+) chain. Compounds 2-5 display a 2D honeycomb-like structure with 18-membered Ln(3)Ag(3)O(12) motifs, and compounds 6-10 can be described as a sandwich-like 3D framework built of a 3D Ag(+)-homometallic net and 2D Ln(3+)-4(4) layer. In 4 (Sm), 5 (Eu), 7 (Tb), and 8 (Dy) samples, the efficient energy transfer from CAM to Ln(III) ions was observed, which results in the typical intense emissions of corresponding Ln(III) ions in the visible region, and the strongest emissions are (4)G(5/2) --> (6)H(7/2) (602 nm), (5)D(0) --> (7)F(2) (614 nm), (5)D(4) --> (7)F(5) (548 nm), and (4)F(9/2) --> (6)H(13/2) (576 nm) transitions. Variable-temperature magnetic susceptibility measurements of 6-10 show that the ferromagnetic interaction between gadolinium(III) ions appears in 6, whereas the mu(eff) values of 7-10 smoothly decrease on cooling. For the orbital contribution of Ln(III) ions, it is very difficult to determine the intrinsic magnetic interactions between Ln(III) ions.

Crystal and electronic structure of the new quaternary sulfides TlLnAg2S3 (Ln = Nd, Sm and Gd)

NASA Astrophysics Data System (ADS)

Assoud, Abdeljalil; Shi, Yixuan; Guo, Quansheng; Kleinke, Holger

2017-12-01

The quaternary sulfides TlLnAg2S3 (Ln: Nd, Sm and Gd) were prepared via solid state reactions by heating the elements in the stoichiometric ratio under exclusion of air up to 750 °C. They are isostructural, adopting a new structure type in the space group Pnma with a = 13.8141(3) Å, b = 4.1649(1) Å, c = 11.4008(2) Å, V = 655.94(2) Å3, Z = 4 for TlNdAg2S3. The crystal structure contains AgS4 tetrahedra and LnS6 octahedra, which are interconnected to form linear chains running along the b axis. The melting point of TlNdAg2S3 was determined to be 540 °C. Electronic structure calculations show that these materials are semiconductors in agreement with their orange/yellow colors.

Vibrational and elastic properties of Ln2Sn2O7 (Ln = La, Sm, Gd, Dy, Ho, Er, Yb, or Lu)

NASA Astrophysics Data System (ADS)

Akbudak, S.; Kushwaha, A. K.

2018-04-01

In this study, an eight-parameter bond-bending force constant model was used to calculate the zone center phonon frequencies, elastic constants, and related properties of the stannate compounds Ln2Sn2O7 (Ln = La, Sm, Gd, Dy, Ho, Er, Yb, or Lu) with a pyrochlore structure. We found that the Snsbnd O bond strengths dominate the Ln-O and Osbnd O bonds. We also found that all of the materials are ductile and anisotropic in nature. The anisotropic nature of the compounds increases in the order of: La2Sn2O7 < Sm2Sn2O7 < Gd2Sn2O7 < Dy2Sn2O7 < Ho2Sn2O7 < Er2Sn2O7 < Yb2Sn2O7 < Lu2Sn2O7.

Surprising luminescent properties of the polyphosphates Ln(PO3)3:Eu (Ln = Y, Gd, Lu).

PubMed

Höppe, Henning A; Kazmierczak, Karolina; Kacprzak, Sylwia; Schellenberg, Inga; Pöttgen, Rainer

2011-10-21

The optical emission properties of the lanthanoid catena-polyphosphates Ln(PO(3))(3) (Ln = Y, Gd, Lu) doped with europium were investigated. Incommensurately modulated β-Y(PO(3))(3):Eu (super space group Cc (0|0.364|0)0) and Gd(PO(3))(3):Eu (space group I2/a) show the usual emission characteristics of Eu(3+), while in Lu(PO(3))(3):Eu (space group Cc) the europium is unprecedentedly partially reduced to the divalent state, as proven by both a broad emission band at 406 nm excited at 279 nm and an EPR spectroscopic investigation. (151)Eu-Mössbauer spectroscopy showed that only a very small part of the europium is reduced in Lu(PO(3))(3):Eu. An explanation for this unusual behaviour is given. This journal is © The Royal Society of Chemistry 2011

Enhancement of the red emission in CaTiO 3:Pr 3+ by addition of rare earth oxides

NASA Astrophysics Data System (ADS)

Zhang, Xianmin; Zhang, Jiahua; Zhang, Xia; Chen, Li; Luo, Yongshi; Wang, Xiao-jun

2007-02-01

Enhancement of the 1D 2- 3H 4 red emission of CaTiO 3:Pr 3+ with addition of rare earth oxides Ln 2O 3 (Ln = Lu, La, Gd) is reported. Ca 2+ and Ti 4+ in CaTiO 3 can be substituted by Ln 3+ ions as donors and acceptors, respectively. Ca 2+ and Ti 4+ vacancies, as quenching centers in the host, are effectively suppressed by the self-compensation, leading to the increase of lifetimes and then the emission efficiency of 1D 2. The red fluorescence intensity for CaTiO 3:Pr 3+ phosphor co-doped with 5 mol% Lu 2O 3 is nearly 3 times greater than that of the Lu-free samples.

Polymeric nanocomposites loaded with fluoridated hydroxyapatite Ln3+ (Ln = Eu or Tb)/iron oxide for magnetic targeted cellular imaging

PubMed Central

Pan, Jie; Liu, Wei-Jiao; Hua, Chao; Wang, Li-Li; Wan, Dong; Gong, Jun-Bo

2015-01-01

Objective To fabricate polymeric nanocomposites with excellent photoluminescence, magnetic properties, and stability in aqueous solutions, in order to improve specificity and sensitivity of cellular imaging under a magnetic field. Methods Fluoridated Ln3+-doped HAP (Ln3+-HAP) NPs and iron oxides (IOs) can be encapsulated with biocompatible polymers via a modified solvent exaction/evaporation technique to prepare polymeric nanocomposites with fluoridated Ln3+-HAP/iron oxide. The nanocomposites were characterized for surface morphology, fluorescence spectra, magnetic properties and in vitro cytotoxicity. Magnetic targeted cellular imaging of such nanocomposites was also evaluated with confocal laser scanning microscope using A549 cells with or without magnetic field. Results The fabricated nanocomposites showed good stability and excellent luminescent properties, as well as low in vitro cytotoxicity, indicating that the nanocomposites are suitable for biological applications. Nanocomposites under magnetic field achieved much higher cellular uptake via an energy-dependent pathway than those without magnetic field. Conclusion The nanocomposites fabricated in this study will be a promising tool for magnetic targeted cellular imaging with improved specificity and enhanced selection. PMID:26487962

Facile in-situ reduction: Crystal growth and magnetic studies of reduced vanadium (III/IV) silicates CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y)

NASA Astrophysics Data System (ADS)

Abeysinghe, Dileka; Smith, Mark D.; Morrison, Gregory; Yeon, Jeongho; zur Loye, Hans-Conrad

2018-04-01

A series of lanthanide containing mixed-valent vanadium (III/IV) silicates of the type CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm-Lu, Y) was synthesized as high quality single crystals from a molten chloride eutectic flux, BaCl2/NaCl. Utilizing Ca metal as the reducing agent, an in-situ reduction of V5+ to V3+/4+ as well as of Ce4+ to Ce3+ was achieved. The structures of 14 reported isostructural compounds were determined by single crystal X-ray diffraction. They crystallize in the tilasite (CaMgAsO4F) structure type in the monoclinic space group C2/c. The extended structure contains 1D chains of VO6 octahedra that are connected to each other via SiO4 groups and (Ca/Ln)O7 polyhedra. The magnetic susceptibility and the field dependent magnetization data were measured for CaxLn1-xVSiO5 (Ln = Ce-Nd, Sm, Gd-Lu, Y), and support the existence of antiferromagnetic behavior at low temperatures.

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.

The Hydrofacies Approach and Why ln K σ 2 <5-10 is Unlikely

NASA Astrophysics Data System (ADS)

Fogg, G. E.

2004-12-01

When heterogeneity of geologic systems is characterized in terms of hydrofacies rather than solely based on K measurements, the resulting flow and transport models typically contain not only aquifer materials but also significant volumes (10-70%) of aquitard materials. This leads to clear, heuristic rationale for the ln K σ 2 commonly exceeding 5 to 10, contradicting published data on ln K σ 2. I will explain the inconsistencies between commonly held assumptions of low (<1-2) ln K σ 2 and abundant geologic and hydrologic field data that indicate substantially larger values. The K data commonly cited in support of the low ln K σ 2 assumption have been misinterpreted because of unintentional, biased sampling. Geologic fundamentals and field data indicate that ln K σ 2 is commonly >10 and can easily exceed 20 in typical sedimentary deposits (not surficial soils) at spatial scales on the order of 101 to 102 m. Presence of large ln K σ 2 can be paramount in transport models and is often requisite for modeling observed transport phenomena such as preferential flow, extreme tailing, difficult remediation including frequent pump-and-treat failure, and significant, unanticipated mixing of groundwater ages.

Family of defect-dicubane Ni4Ln2 (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 complexes: rare Tb(III) and Ho(III) examples showing SMM behavior.

PubMed

Zhao, Lang; Wu, Jianfeng; Ke, Hongshan; Tang, Jinkui

2014-04-07

Reactions of Ln(III) perchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2 complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d-4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2 (5) complex containing diamagnetic Y(III) atoms was also isolated to assist the magnetic studies. Interestingly, complexes 2 and 3 exhibit SMM characteristics and 4 shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni-Y species suggests that the Ln ions' contribution to the slow relaxation must be effectual as previously observed in other Ni-Dy samples. However, the observation of χ″ signals with zero dc field for the Ni-Tb and Ni-Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni-Tb and Ni-Ho complexes.

Magnetism of cyano-bridged hetero-one-dimensional Ln3+-M3+ complexes (Ln3+ = Sm, Gd, Yb; M3+ = FeLS, Co).

PubMed

Figuerola, Albert; Diaz, Carmen; Ribas, Joan; Tangoulis, Vassilis; Sangregorio, Claudio; Gatteschi, Dante; Maestro, Miguel; Mahía, José

2003-08-25

The reaction of Ln(NO(3))(3).aq with K(3)[Fe(CN)(6)] or K(3)[Co(CN)(6)] and 2,2'-bipyridine in water led to five one-dimensional complexes: trans-[M(CN)(4)(mu-CN)(2)Ln(H(2)O)(4) (bpy)](n)().XnH(2)O.1.5nbpy (M = Fe(3+) or Co(3+); Ln = Sm(3+), Gd(3+), or Yb(3+); X = 4 or 5). The structures for [Fe(3)(+)-Sm(3+)] (1), [Fe(3)(+)-Gd(3+)] (2), [Fe(3)(+)-Yb(3+)] (3), [Co(3)(+)-Gd(3+)] (4), and [Co(3)(+)-Yb(3+)] (5) have been solved; they crystallize in the triclinic space P1 and are isomorphous. The [Fe(3+)-Sm(3+)] complex is a ferrimagnet, its magnetic studies suggesting the onset of weak ferromagnetic 3-D ordering at 3.5 K. The [Fe(3+)-Gd(3+)] interaction is weakly antiferromagnetic. The isotropic nature of Gd(3+) allowed us to evaluate the exchange interaction (J = 0.77 cm(-)(1)).

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

Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment† †Electronic supplementary information (ESI) available: Additional computational details, spectroscopic information, crystallographic data collection, structure solution, and refinement (PDF), X-ray diffraction details of compounds 1-Ln (Ln = Nd, Gd, Dy, and Er), 2-Nd, 2-Ln/3-Ln (Ln = Gd, Dy, Er), 2-Dy/4-Dy, and 5-Dy/6-Dy. CCDC (CIF, 1538987–1538995 and 1566075 for 2-Dy/3-Dy), and DFT-optimized structural coordinates for 2-Nd and 2-Gd. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02337e Click here for additional data file. Click here for additional data file. Click here for additional data file.

PubMed Central

Fieser, Megan E.; Palumbo, Chad T.; La Pierre, Henry S.; Halter, Dominik P.; Voora, Vamsee K.; Ziller, Joseph W.

2017-01-01

A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3–, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures. PMID:29163894

Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

2012-02-27

A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion-irradiation resistance of the orthorhombic Ln2TiO5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) series

NASA Astrophysics Data System (ADS)

Aughterson, Robert D.; Lumpkin, Gregory R.; Ionescu, Mihail; Reyes, Massey de los; Gault, Baptiste; Whittle, Karl R.; Smith, Katherine L.; Cairney, Julie M.

2015-12-01

The response of Ln2TiO5 (where Ln is a lanthanide) compounds exposed to high-energy ions was used to test their suitability for nuclear-based applications, under two different but complementary conditions. Eight samples with nominal stoichiometry Ln2TiO5 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy), of orthorhombic (Pnma) structure were irradiated, at various temperatures, with 1 MeV Kr2+ ions in-situ within a transmission electron microscope. In each case, the fluence was increased until a phase transition from crystalline to amorphous was observed, termed critical dose Dc. At certain elevated temperatures, the crystallinity was maintained irrespective of fluence. The critical temperature for maintaining crystallinity, Tc, varied non-uniformly across the series. The Tc was consistently high for La, Pr, Nd and Sm2TiO5 before sequential improvement from Eu to Dy2TiO5 with Tc's dropping from 974 K to 712 K. In addition, bulk Dy2TiO5 was irradiated with 12 MeV Au+ ions at 300 K, 723 K and 823 K and monitored via grazing-incidence X-ray diffraction (GIXRD). At 300 K, only amorphisation is observed, with no transition to other structures, whilst at higher temperatures, specimens retained their original structure. The improved radiation tolerance of compounds containing smaller lanthanides has previously been attributed to their ability to form radiation-induced phase transitions. No such transitions were observed here.

Experimental and theoretical studies of the products of reaction between Ln(hfa) 3 and Cu(acac) 2 (Ln = La, Y; acac = acetylacetonate, hfa = hexafluoroacetylacetonate)

NASA Astrophysics Data System (ADS)

Rogachev, Andrey Yu.; Mironov, Andrey V.; Nemukhin, Alexander V.

2007-04-01

The new unusual heterobimetallic complex [La(hfa) 3Cu(acac) 2(H 2O)] ( I) was obtained in the reaction La(hfa) 3·2H 2O with Cu(acac) 2 in CHCl 3. This is the first example of such type of heterobimetallic complexes based on the Cu(acac) 2 species. According to the X-ray single crystal analysis, complex I crystallizes in the monoclinic space group P2 1/c, with a = 12.516(3) Å, b = 17.757(4) Å, c = 17.446(4) Å, β = 93.90(3)° and Z = 4. The structure consists of isolated heterobinuclear molecules with the coordination number of La being 9. The molecules are further assembled into dimers via hydrogen bonds. The theoretical modeling of the structure and the properties of parent monometallic complexes Ln(hfa) 3 (Ln = La, Y) and Cu(acac) 2 is described. The comparative theoretical study of lanthanide complexes indicates relations in formation of a heterobimetallic complex to the Lewis acidity of original monometallic complexes. In particular, the Lewis acidity and charge of the central metal ion in Ln(hfa) 3 are the key parameters accounting for the formation of [Ln(hfa) 3Cu(acac) 2].

Why Was Kelvin's Estimate of the Earth's Age Wrong?

ERIC Educational Resources Information Center

Lovatt, Ian; Syed, M. Qasim

2014-01-01

This is a companion to our previous paper in which we give a published example, based primarily on Perry's work, of a graph of ln "y" versus "t" when "y" is an exponential function of "t". This work led us to the idea that Lord Kelvin's (William Thomson's) estimate of the Earth's age was…

Modifying the size and uniformity of upconversion Yb/Er:NaGdF4 nanocrystals through alkaline-earth doping.

PubMed

Lei, Lei; Chen, Daqin; Huang, Ping; Xu, Ju; Zhang, Rui; Wang, Yuansheng

2013-11-21

NaGdF4 is regarded as an ideal upconversion (UC) host material for lanthanide (Ln(3+)) activators because of its unique crystal structure, high Ln(3+) solubility, low phonon energy and high photochemical stability, and Ln(3+)-doped NaGdF4 UC nanocrystals (NCs) have been widely investigated as bio-imaging and magnetic resonance imaging agents recently. To realize their practical applications, controlling the size and uniformity of the monodisperse Ln(3+)-doped NaGdF4 UC NCs is highly desired. Unlike the routine routes by finely adjusting the multiple experimental parameters, herein we provide a facile and straightforward strategy to modify the size and uniformity of NaGdF4 NCs via alkaline-earth doping for the first time. With the increase of alkaline-earth doping content, the size of NaGdF4 NCs increases gradually, while the size-uniformity is still retained. We attribute this "focusing" of size distribution to the diffusion controlled growth of NaGdF4 NCs induced by alkaline-earth doping. Importantly, adopting the Ca(2+)-doped Yb/Er:NaGdF4 NCs as cores, the complete Ca/Yb/Er:NaGdF4@NaYF4 core-shell particles with excellent size-uniformity can be easily achieved. However, when taking the Yb/Er:NaGdF4 NCs without Ca(2+) doping as cores, they could not be perfectly covered by NaYF4 shells, and the obtained products are non-uniform in size. As a result, the UC emission intensity of the complete core-shell NCs increases by about 30 times in comparison with that of the cores, owing to the effective surface passivation of the Ca(2+)-doped cores and therefore protection of Er(3+) in the cores from the non-radiative decay caused by surface defects, whereas the UC intensity of the incomplete core-shell NCs is enhanced by only 3 times.

Predictable self-assembled [2×2] Ln(III)4 square grids (Ln = Dy,Tb)-SMM behaviour in a new lanthanide cluster motif.

PubMed

Anwar, Muhammad Usman; Thompson, Laurence Kenneth; Dawe, Louise Nicole; Habib, Fatemah; Murugesu, Muralee

2012-05-14

The ditopic carbohydrazone ligand (L1) produces the square, self-assembled [2×2] grids [Dy(4)(L1)(4)(OH)(4)]Cl(2) (1) and [Ln(4)(L1)(4)(μ(4)-O)(μ(2)-1,1-N(3))(4)] (Ln = Dy (2), Tb (3)), with 2 exhibiting SMM behaviour. Two relaxation processes occur with U(eff) = 51 K, 91 K in the absence of an external field, and one with U(eff) = 270 K in the presence of a 1600 Oe optimum field. This journal is © The Royal Society of Chemistry 2012

Anomalies of the electronic structure and physical properties of rare-earth cobaltites near spin crossover

NASA Astrophysics Data System (ADS)

Dudnikov, V. A.; Orlov, Yu. S.; Kazak, N. V.; Platunov, M. S.; Ovchinnikov, S. G.

2016-10-01

The features of the characteristics of LnCoO3 cobaltites, where Ln is a rare-earth element, are discussed. Both experiment and theory demonstrate that their essentials are related to the low-spin ground state of cobalt ions. The thermally induced occupation of the excited high-spin state gives rise to peaks in the magnetic susceptibility, specific heat, and thermal expansion, as well as to a smooth insulator-metal transition. The analysis is based both on the data from the current literature concerning LaCoO3 and in many aspects on our own studies of GdCoO3 and La1- x Gd x CoO3 solid solutions.

Recent Advanced in Rare Earth Chemistry: IREC (International Rare Earth Conference) 85 Held at Zurich (Switzerland) on 4-8 Mar 85.

DTIC Science & Technology

1985-06-04

compounds were employed since 1979. The polyfunc- studied using time-resolved spectro- tlonal ligands (L) included crown ethers scopy, and the...structure of rare earth * Aqueous complexes with cyclic poly - compounds (for example Cs3Ln2X9), was ethers crown ethers , Alstad, Univer- presented by A...Approved for public release; distribution unlimited U.S. Office of Naval Research, London ag - ’ 3 k) I 5.’ - ~1 I 9 ’<I. A -i I. 4. -A kA IS7 ASS

Octanuclear Heterobimetallic {Ni4Ln4} Assemblies Possessing Ln4 Square Grid [2 × 2] Motifs: Synthesis, Structure, and Magnetism.

PubMed

Biswas, Sourav; Goura, Joydeb; Das, Sourav; Topping, Craig V; Brambleby, Jamie; Goddard, Paul A; Chandrasekhar, Vadapalli

2016-09-06

Octanuclear heterobimetallic complexes, [Ln4Ni4(H3L)4(μ3-OH)4(μ2-OH)4]4Cl·xH2O·yCHCl3 (Dy(3+), x = 30.6, y = 2 (1); Tb(3+), x = 28, y = 0 (2) ; Gd(3+), x = 25.3, y = 0 (3); Ho(3+), x = 30.6, y = 3 (4)) (H5L = N1,N3-bis(6-formyl-2-(hydroxymethyl)-4-methylphenol)diethylenetriamine) are reported. These are assembled by the cumulative coordination action of four doubly deprotonated compartmental ligands, [H3L](2-), along with eight exogenous -OH ligands. Within the core of these complexes, four Ln(3+)'s are distributed to the four corners of a perfect square grid while four Ni(2+)'s are projected away from the plane of the Ln4 unit. Each of the four Ni(2+)'s possesses distorted octahedral geometry while all of the Ln(3+)'s are crystallographically equivalent and are present in an elongated square antiprism geometry. The magnetic properties of compound 3 are dominated by an easy-plane single-ion anisotropy of the Ni(2+) ions [DNi = 6.7(7) K] and dipolar interactions between Gd(3+) centers. Detailed ac magnetometry reveals the presence of distinct temperature-dependent out-of-phase signals for compounds 1 and 2, indicative of slow magnetic relaxation. Magnetochemical analysis of complex 1 implies the 3d and the 4f metal ions are engaged in ferromagnetic interactions with SMM behavior, while dc magnetometry of compound 2 is suggestive of an antiferromagnetic Ni-Tb spin-exchange with slow magnetic relaxation due to a field-induced level crossing. Compound 4 exhibits an easy-plane single-ion anisotropy for the Ho(3+) ions and weak interactions between spin centers.

Sonochemical synthesis of highly luminescent Ln 2O 3:Eu 3+ (Y, La, Gd) nanocrystals

DOE PAGES

Alammar, Tarek; Cybinska, Joanna; Campbell, Paul S.; ...

2015-05-12

In this study, sonication of Ln(CH 3COO) 3·H 2O, Eu(CH 3COO) 3·H 2O and NaOH dissolved in the ionic liquid-butyl-3-methylimidazolium bis(trifluoromethane)sulfonylamide lead to Ln(OH) 3:Eu (Ln: Gd, La, Y) nanoparticles. Subsequent calcination at 800 °C for 3 h allowed to obtain Ln 2O 3:Eu nanopowders. Gd 2O 3 and Y 2O 3 were obtained in the C-type lanthanide sequioxide structure, whereas La 2O 3 crystallized in the A-type. Structure, morphology, and luminescent properties of the nano-oxides were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dispersive X-ray (EDX), and photoluminescence (PL). SEM studies revealed that the synthesized Gdmore » 2O 3:Eu, La 2O 3:Eu, and Y 2O 3:Eu formed nano-spindle, -sheets, and -rods in shape, respectively. The nanoscale materials show very efficient red emission due to the intraconfigurational f–f transitions of Eu 3+. The quantum yields for Ln 2O 3:Eu (5%) were determined to be 4.2% for Ln=Gd, 13.8% for Ln=Y and 5.2% for Ln=La. The asymmetric ratio I 02/I 01 of Eu 3+ varies from 5.3 for Gd 2O 3, to 5.6 for Y 2O 3 to 6.5 for La 2O 3, which increased the color chromaticity.« less

Anion dependent self-assembly of 56-metal Cd-Ln nanoclusters with enhanced near-infrared luminescence properties

NASA Astrophysics Data System (ADS)

Yang, Xiaoping; Schipper, Desmond; Zhang, Lijie; Yang, Keqin; Huang, Shaoming; Jiang, Jijun; Su, Chengyong; Jones, Richard A.

2014-08-01

Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined.Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined. Electronic supplementary information (ESI) available: Full experimental and characterization details for 1-4. CCDC 972369-972372. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr03075c

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.

Self-assembled 3D sphere-like SrMoO4 and SrMoO4:Ln3+ (Ln=Eu, Sm, Tb, Dy) microarchitectures: facile sonochemical synthesis and optical properties.

PubMed

Zhang, Junjun; Li, Ruiqing; Liu, Lu; Li, Linlin; Zou, Lianchun; Gan, Shucai; Ji, Guijuan

2014-09-01

Three-dimensional (3D) well-defined SrMoO4 and SrMoO4:Ln(3+) (Ln=Eu, Sm, Tb, Dy) hierarchical structures of obvious sphere-like shape have been successfully synthesized using a large-scale and facile sonochemical route without using any catalysts or templates. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), and photoluminescence (PL) spectra were used to characterize the samples. The intrinsic structural feature of SrMoO4 and external factor, namely the ultrasonic time and the pH value, are responsible for the ultimate shape evolutions of the product. The possible formation mechanism for the product is presented. Additionally, the PL properties of SrMoO4 and SrMoO4:Ln(3+) (Ln=Eu, Sm, Tb, Dy) hierarchical structures were investigated in detail. The Ln(3+) ions doped SrMoO4 samples exhibit respective bright red-orange, yellow, green and white light of Eu(3+), Sm(3+), Tb(3+) and Dy(3+) under ultraviolet excitation, and have potential application in the field of color display. Simultaneously, this novel and efficient pathway could open new opportunities for further investigating about the properties of molybdate materials. Copyright © 2014 Elsevier B.V. All rights reserved.

Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

NASA Astrophysics Data System (ADS)

Johannesson, Kevin H.; Zhou, Xiaoping

1999-01-01

-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

PubMed

Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

2013-11-04

Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

Enhancement of superconductivity near the pressure-induced semiconductor-metal transition in the BiS₂-based superconductors LnO₀.₅F₀.₅BiS₂ (Ln = La, Ce, Pr, Nd).

PubMed

Wolowiec, C T; White, B D; Jeon, I; Yazici, D; Huang, K; Maple, M B

2013-10-23

Measurements of electrical resistivity were performed between 3 and 300 K at various pressures up to 2.8 GPa on the BiS2-based superconductors LnO0.5F0.5BiS2 (Ln=Pr, Nd). At lower pressures, PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2 exhibit superconductivity with critical temperatures Tc of 3.5 and 3.9 K, respectively. As pressure is increased, both compounds undergo a transition at a pressure Pt from a low Tc superconducting phase to a high Tc superconducting phase in which Tc reaches maximum values of 7.6 and 6.4 K for PrO0.5F0.5BiS2 and NdO0.5F0.5BiS2, respectively. The pressure-induced transition is characterized by a rapid increase in Tc within a small range in pressure of ∼0.3 GPa for both compounds. In the normal state of PrO0.5F0.5BiS2, the transition pressure Pt correlates with the pressure where the suppression of semiconducting behaviour saturates. In the normal state of NdO0.5F0.5BiS2, Pt is coincident with a semiconductor-metal transition. This behaviour is similar to the results recently reported for the LnO0.5F0.5BiS2 (Ln=La, Ce) compounds. We observe that Pt and the size of the jump in Tc between the two superconducting phases both scale with the lanthanide element in LnO0.5F0.5BiS2 (Ln=La, Ce, Pr, Nd).

Single-ion 4f element magnetism: an ab-initio look at Ln(COT)2(-).

PubMed

Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène; Autschbach, Jochen

2015-12-14

The electron densities associated with the Ln 4f shell, and spin and orbital magnetizations ('magnetic moment densities'), are investigated for the Ln(COT)2(-) series. The densities are obtained from ab-initio calculations including spin-orbit coupling. For Ln = Ce, Pr the magnetizations are also derived from crystal field models and shown to agree with the ab-initio results. Analysis of magnetizations from ab-initio calculations may be useful in assisting research on single molecule magnets.

Theoretical Study on the Photoelectron Spectra of Ln(COT)2-: Lanthanide Dependence of the Metal-Ligand Interaction.

PubMed

Nakajo, Erika; Masuda, Tomohide; Yabushita, Satoshi

2016-12-08

We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT) 2 - (Ln = La-Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e 1g < e 1u < e 2g < e 2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e 2u symmetry. Because the magnitude of this 4f-ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

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

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

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

2009-05-15

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

Insight into substrate binding in Shibasaki's Li3(THF)n(BINOLate)3Ln complexes and implications in catalysis.

PubMed

Wooten, Alfred J; Carroll, Patrick J; Walsh, Patrick J

2008-06-11

Heterobimetallic Lewis acids M 3(THF) n (BINOLate) 3Ln [M = Li, Na, K; Ln = lanthanide(III)] are exceptionally useful asymmetric catalysts that exhibit high levels of enantioselectivity across a wide range of reactions. Despite their prominence, important questions remain regarding the nature of the catalyst-substrate interactions and, therefore, the mechanism of catalyst operation. Reported herein are the isolation and structural characterization of 7- and 8-coordinate heterobimetallic complexes Li 3(THF) 4(BINOLate) 3Ln(THF) [Ln = La, Pr, and Eu], Li 3(py) 5(BINOLate) 3Ln(py) [Ln = Eu and Yb], and Li 3(py) 5(BINOLate) 3La(py) 2 [py = pyridine]. Solution binding studies of cyclohexenone, DMF, and pyridine with Li 3(THF) n (BINOLate) 3Ln [Ln = Eu, Pr, and Yb] and Li 3(DMEDA) 3(BINOLate) 3Ln [Ln = La and Eu; DMEDA = N, N'-dimethylethylene diamine] demonstrate binding of these Lewis basic substrate analogues to the lanthanide center. The paramagnetic europium, ytterbium, and praseodymium complexes Li 3(THF) n (BINOLate) 3Ln induce relatively large lanthanide-induced shifts on substrate analogues that ranged from 0.5 to 4.3 ppm in the (1)H NMR spectrum. X-ray structure analysis and NMR studies of Li 3(DMEDA) 3(BINOLate) 3Ln [Ln = Lu, Eu, La, and the transition metal analogue Y] reveal selective binding of DMEDA to the lithium centers. Upon coordination of DMEDA, six new stereogenic nitrogen centers are formed with perfect diastereoselectivity in the solid state, and only a single diastereomer is observed in solution. The lithium-bound DMEDA ligands are not displaced by cyclohexenone, DMF, or THF on the NMR time scale. Use of the DMEDA adduct Li 3(DMEDA) 3(BINOLate) 3La in three catalytic asymmetric reactions led to enantioselectivities similar to those obtained with Shibasaki's Li 3(THF) n (BINOLate) 3La complex. Also reported is a unique dimeric [Li 6(en) 7(BINOLate) 6Eu 2][mu-eta (1),eta (1)-en] structure [en = ethylenediamine]. On the basis of these studies, it is

Validation of the CQU-DTU-LN1 series of airfoils

NASA Astrophysics Data System (ADS)

Shen, W. Z.; Zhu, W. J.; Fischer, A.; Garcia, N. R.; Cheng, J. T.; Chen, J.; Madsen, J.

2014-12-01

The CQU-DTU-LN1 series of airfoils were designed with an objective of high lift and low noise emission. In the design process, the aerodynamic performance is obtained using XFOIL while noise emission is obtained with the BPM model. In this paper we present some validations of the designed CQU-DTU-LN118 airfoil by using wind tunnel measurements in the acoustic wind tunnel located at Virginia Tech and numerical computations with the inhouse Q3uic and EllipSys 2D/3D codes. To show the superiority of the new airfoils, comparisons with a NACA64618 airfoil are made. For the aerodynamic features, the designed Cl and Cl/Cd agrees well with the experiment and are in general higher than those of the NACA airfoil. For the acoustic features, the noise emission of the LN118 airfoil is compared with the acoustic measurements and that of the NACA airfoil. Comparisons show that the BPM model can predict correctly the noise changes.

Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

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

Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.

2010-09-23

In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development ofmore » a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both

Intergranular Corrosion Behavior of 304LN Stainless Steel Heat Treated at 623 K (350 °C)

NASA Astrophysics Data System (ADS)

Singh, Raghuvir; Kumar, Mukesh; Ghosh, Mainak; Das, Gautam; Singh, P. K.; Chattoraj, I.

2013-01-01

Low temperature sensitization of 304LN stainless steel from the two pipes, differing slightly in chemical composition, has been investigated; specimens were aged at 623 K (350 °C) for 20,000 hours and evaluated for intergranular corrosion and degree of sensitization. The base and heat-affected zone (HAZ) of the 304LN-1 appear resistant to sensitization, while 304LN-2 revealed a "dual" type microstructure at the transverse section and HAZ. The microstructure at 5.0-mm distance from the fusion line indicates qualitatively less sensitization as compared to that at 2.0 mm. The 304LN-2 base alloy shows overall lower degree of sensitization values as compared to the 304LN-1. A similar trend of degree of sensitization was observed in the HAZ where it was higher in the 304LN-1 as compared to the 304LN-2. The weld zone of both the stainless steels suffered from cracking during ASTM A262 practice E, while the parent metals and HAZs did not show such fissures. A mottled image within the ferrite lamella showed spinodal decomposition. The practice E test and transmission electron microscopy results indicate that the interdendritic regions may suffer from failure due to carbide precipitation and due to the evolution of brittle phase from spinodal decomposition.

Rare-earth organic frameworks involving three types of architecture tuned by the lanthanide contraction effect: hydrothermal syntheses, structures and luminescence.

PubMed

Deng, Zhao-Peng; Kang, Wei; Huo, Li-Hua; Zhao, Hui; Gao, Shan

2010-07-21

The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) () for type I, {[Ln(apca)(ox)(H(2)O)(2)].H(2)O}(n) (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D "snowflake" chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex exhibits strong blue emission and complex exhibits characteristic luminescence of Eu(3+).

LN-1-255, a penicillanic acid sulfone able to inhibit the class D carbapenemase OXA-48.

PubMed

Vallejo, Juan A; Martínez-Guitián, Marta; Vázquez-Ucha, Juan C; González-Bello, Concepción; Poza, Margarita; Buynak, John D; Bethel, Christopher R; Bonomo, Robert A; Bou, German; Beceiro, Alejandro

2016-08-01

Carbapenemases are the most important mechanism responsible for carbapenem resistance in Enterobacteriaceae. Among carbapenemases, OXA-48 presents unique challenges as it is resistant to β-lactam inhibitors. Here, we test the capacity of the compound LN-1-255, a 6-alkylidene-2'-substituted penicillanic acid sulfone, to inhibit the activity of the carbapenemase OXA-48. The OXA-48 gene was cloned and expressed in Klebsiella pneumoniae and Escherichia coli in order to obtain MICs in the presence of inhibitors (clavulanic acid, tazobactam and sulbactam) and LN-1-255. OXA-48 was purified and steady-state kinetics was performed with LN-1-255 and tazobactam. The covalent binding mode of LN-1-255 with OXA-48 was studied by docking assays. Both OXA-48-producing clinical and transformant strains displayed increased susceptibility to carbapenem antibiotics in the presence of 4 mg/L LN-1-255 (2-32-fold increased susceptibility) and 16 mg/L LN-1-255 (4-64-fold increased susceptibility). Kinetic assays demonstrated that LN-1-255 is able to inhibit OXA-48 with an acylation efficiency (k2/K) of 10 ± 1 × 10(4) M(-1) s(-1) and a slow deacylation rate (koff) of 7 ± 1 × 10(-4) s(-1). IC50 was 3 nM for LN-1-255 and 1.5 μM for tazobactam. Lastly, kcat/kinact was 500-fold lower for LN-1-255 than for tazobactam. In these studies, carbapenem antibiotics used in combination with LN-1-255 are effective against the carbapenemase OXA-48, an important emerging mechanism of antibiotic resistance. This provides an incentive for further investigations to maximize the efficacy of penicillin sulfone inhibition of class D plasmid-carried Enterobacteriaceae carbapenemases. © The Author 2016. Published by Oxford University Press on behalf of the British Society for Antimicrobial Chemotherapy. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Evolution of magnetism in LnCuGa3 (Ln = La-Nd, Sm-Gd) studied via μSR and specific heat

NASA Astrophysics Data System (ADS)

Graf, M. J.; Hettinger, J. D.; Nemeth, K.; Dally, R.; Baines, C.; Subbarao, U.; Peter, S. C.

2017-12-01

Muon spin rotation/relaxation (μSR) and specific heat measurements are presented for polycrystalline LnCuGa3, with Ln = La-Nd, and Sm-Gd. All materials undergo magnetic ordering transitions, apart from non-magnetic LaCuGa3, and PrCuGa3, which shows the onset of short range correlations below 3 K but no long-range magnetic order down to T = 25 mK. While magnetic order in the Ce and Nd compounds is incommensurate with the lattice, the order is commensurate for the Sm and Eu compounds. The strong damping in GdCuGa3 prevents us from determining the nature of magnetism in that system. SmCuGa3 exhibits two precessional frequencies, which appear at different temperatures, suggesting inhomogeneous magnetic ordering or a second magnetic/structural phase transition.

Chemical Substitution and High Pressure Effects on Superconductors in the LnOBiS$$_2$$ (Ln = La-Nd) System

DOE PAGES

Fang, Yuankan; Wolowiec, Christian T.; Yazici, Duygu; ...

2015-12-14

A large number of compounds which contain BiSmore » $$_2$$ layers exhibit enhanced superconductivity upon electron doping. Much interest and research effort has been focused on BiS$$_2$$-based compounds which provide new opportunities for exploring the nature of superconductivity. Important to the study of BiS2-based superconductors is the relation between structure and superconductivity. By modifying either the superconducting BiS$$_2$$ layers or the blocking layers in these layered compounds, one can effectively tune the lattice parameters, local atomic environment, electronic structure, and other physical properties of these materials. In this article, we will review some of the recent progress on research of the effects of chemical substitution in BiS$$_2$$-based compounds, with special attention given to the compounds in the LnOBiSS$$_2$$ (Ln = La-Nd) system. Strategies which are reported to be essential in optimizing superconductivity of these materials will also be discussed.« less

Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

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

Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.

2015-03-15

Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}

Current advances in lanthanide ion (Ln(3+))-based upconversion nanomaterials for drug delivery.

PubMed

Yang, Dongmei; Ma, Ping'an; Hou, Zhiyou; Cheng, Ziyong; Li, Chunxia; Lin, Jun

2015-03-21

Lanthanide ion (Ln(3+))-based upconversion nano/micromaterials that emit higher-energy visible light when excited by low-energy NIR light have aroused considerable attention in the forefront of materials science and biomedical fields, which stems from their unique optical and chemical properties including minimum photodamage to living organisms, low autofluorescence, high signal-to-noise ratio and detection sensitivity, and high penetration depth in biological or environmental samples. Thus, Ln(3+)-based upconversion materials are rising new stars and are quickly emerging as potential candidates to revolutionize novel biomedical applications. In this review article, we mainly focus on the recent progress in various chemical syntheses of Ln(3+)-based upconversion nanomaterials, with special emphasis on their application in stimuli-response controlled drug release and subsequent therapy. Functional groups that are introduced into the stimuli-responsive system can respond to external triggers, such as pH, temperature, light, and even magnetic fields, which can regulate the movement of the pharmaceutical cargo and release the drug at a desired time and in a desired area. This is crucial to boost drug efficacy in cancer treatment while minimizing the side effects of cytotoxic drugs. Many multifunctional (magnetic/upconversion luminescence and porous) composite materials based on Ln(3+) have been designed for controlled drug delivery and multimodal bioimaging. Finally, the challenges and future opportunities for Ln(3+)-based upconversion materials are discussed.

Fabrication of Ln-MOFs with color-tunable photoluminescence and sensing for small molecules

NASA Astrophysics Data System (ADS)

Wang, Shengyan; Shan, Liang; Fan, Yong; Jia, Jia; Xu, Jianing; Wang, Li

2017-01-01

Three isomorphic lanthanide metal-organic frameworks (Ln-MOFs) [LnL(H2O)2]·2H2O (Ln=Tb for 1, Eu for 2, Gd for 3) have been constructed from flexible organic ligand 4-(2-carboxyphenoxy)benzene-1,3-dioic acid (H3L). They exhibit two-dimensional (2D) layered structure with the rhombus windows along the b axis. This network can be described as a shubnikov plane net with Schäfli symbol of (43)2(46.66.83). Solid state luminescent studies indicate that 1 and 2 show the characteristic red, and green emissions of the corresponding Ln3+ ions, respectively, while 3 exhibits blue emission arising from the organic ligand. Then by adjusting the relative amounts of different luminescent components into the well-defined host framework, a series of new co-doped Ln-MOF, Tb1-xEuxL (4) (x refers to the molar ratios of Eu3+ and Tb3+), with tunable luminescence have been fabricated. The luminescent color of 4 can be tuned from green to red due to the energy transfer from the Tb3+ to Eu3+ ions by changing the doping concentration of the Eu3+ ions. In addition, 2 exhibits good stability in different solvents and excellent fluorescence sensing for small molecules, especially for CH3CN and nitrobenzene.

3d-4f {Co(II)3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts.

PubMed

Evangelisti, Fabio; Moré, René; Hodel, Florian; Luber, Sandra; Patzke, Greta Ricarda

2015-09-02

Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [Co(II)3Ln(hmp)4(OAc)5H2O] ({Co(II)3Ln(OR)4}; Ln = Ho-Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {Co(II)3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln(3+) centers as redox-inactive Ca(2+) analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s(-1)). Furthermore, they open up the important family of 3d-4f complexes for photocatalytic applications. The stability of the {Co(II)3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln(3+) centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born-Oppenheimer molecular dynamics studies.

Oxygen ionic conductivity of NTE materials of cubic Zr 1- xLn xW 2- yMo yO 8- x/2 (Ln = Er, Yb)

NASA Astrophysics Data System (ADS)

Li, Hai-Hua; Xia, Hai-Ting; Jing, Xi-Ping; Zhao, Xin-Hua

2008-08-01

Cubic Zr 1- xLn xW 2- yMo yO 8- x/2 (Ln = Er: x = 0.01, 0.02, 0.03; y = 0; Ln = Yb: x = 0.02, 0.03; y = 0.4) solid solutions, well-known negative thermal expansion (NTE) materials were prepared by using conventional solid state reactions. The morphology and the composition of the fracture surfaces of the ceramic pellets were determined by SEM and EDX technology. The conductance properties of the pellets, such as conductivity and conductance activation energy, were studied by AC impedance spectroscopy and the materials perform clearly oxygen ionic conduction with the conductivity of about 10 -4 S cm -1 at 673 K, a comparable value to that of ceria based solid electrolytes. The substitution of Mo for W enhanced the thermal stability of ZrW 2O 8, so that the conductivity of Zr 0.98Yb 0.02W 1.6Mo 0.4O 7.99 ceramic can be measured up to 873 K, which is about 5.9 × 10 -4 S cm -1.

A Study of Submicron Grain Boundary Precipitates in Ultralow Carbon 316LN Steels

NASA Astrophysics Data System (ADS)

Downey, S.; Han, K.; Kalu, P. N.; Yang, K.; Du, Z. M.

2010-04-01

This article reports our efforts in characterization of an ultralow carbon 316LN-type stainless steel. The carbon content in the material is one-third that in a conventional 316LN, which further inhibits the formation of grain boundary carbides and therefore sensitizations. Our primary effort is focused on characterization of submicron size precipitates in the materials with the electron backscatter diffraction (EBSD) technique complemented by Auger electron spectroscopy (AES). Thermodynamic calculations suggested that several precipitates, such as M23C6, Chi, Sigma, and Cr2N, can form in a low carbon 316LN. In the steels heat treated at 973 K (700 °C) for 100 hours, a combination of EBSD and AES conclusively identified the grain boundary precipitates (≥100 nm) as Cr2N, which has a hexagonal closed-packed crystallographic structure. Increases of the nitrogen content promote formation of large size Cr2N precipitates. Therefore, prolonged heat treatment at relatively high temperatures of ultralow carbon 316LN steels may result in a sensitization.

High pressure luminescence spectra of CaMoO4:Ln3+ (Ln = Pr, Tb)

NASA Astrophysics Data System (ADS)

Mahlik, S.; Behrendt, M.; Grinberg, M.; Cavalli, E.; Bettinelli, M.

2013-03-01

Photoluminescence spectra and luminescence kinetics of pure CaMoO4 and CaMoO4 doped with Ln3+ (Ln = Pr or Tb) are presented. The spectra were obtained at high hydrostatic pressure up to 240 kbar applied in a diamond anvil cell. At ambient pressure undoped and doped samples exhibit a broad band emission extending between 380 and 700 nm with a maximum at 520 nm attributed to the {{MoO}}_{4}^{2-} luminescence. CaMoO4 doped with Pr3+ or Tb3+ additionally yields narrow emission lines related to f-f transitions. The undoped CaMoO4 crystal was characterized by a strong MoO{}_{4}^{2-} emission up to 240 kbar. In the cases of CaMoO4:Pr3+ and CaMoO4:Tb3+, high hydrostatic pressure caused quenching of Pr3+ and Tb3+ emission, and this effect was accompanied by a strong shortening of the luminescence lifetime. In doped samples, CaMoO4:Pr3+ and CaMoO4:Tb3+, quenching of the emission band attributed to {{MoO}}_{4}^{2-} was also observed, and at pressure above 130 kbar this luminescence was totally quenched. The effects mentioned above were related to the influence of the praseodymium (terbium) trapped exciton PTE (ITE—impurity trapped exciton) on the efficiency of the Pr3+ (Tb3+) and {{MoO}}_{4}^{2-} emissions.

Three series of heterometallic NiII-LnIII Schiff base complexes: synthesis, crystal structures and magnetic characterization.

PubMed

Jiang, Lin; Liu, Yue; Liu, Xin; Tian, Jinlei; Yan, Shiping

2017-09-26

Three series of Ni II -Ln III complexes were synthesized with the general formulae [(μ 3 -CO 3 ) 2 {Ni(HL)(CH 3 -CH 2 OH)Ln(CH 3 COO)} 2 ]·2CH 3 CH 2 OH (1-6) (Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6); H 3 L = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2-prop-anol), [Ni(HL)Ln(dbm) 3 ]·CH 3 OH 2 ·2CH 2 Cl 2 (7-10) (Ln = Tb (7), Eu (8), Gd (9), Ho (10); Hdbm = 1,3-diphenyl-1,3-propanedione) and [Ni(HL)(H 2 O)(tfa)Ln(hfac) 2 ] (11-15) (Ln = Tb (11), Dy (12), Eu (13), Gd (14), Ho (15); Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, tfa - = trifluoroacetate) using compartmental Schiff base ligands in conjunction with auxiliary ligands. For the NiLn series, the tetranuclear structure could be considered as two Ni II -Ln III dinuclear subunits bridged by two carbonates derived from atmospheric carbon dioxide. The Ln III ions of complexes 1-6 were octa-coordinated with distorted triangular dodecahedral geometry, while the Ln III ions of the dinuclear complexes 7-15 were nona-coordinated with distorted muffin geometry. The magnetic properties of the three series complexes were studied using dc and ac magnetic measurements. For the Ni II -Gd III complexes, the dc magnetic susceptibility measurements suggested the existence of the anticipated ferromagnetic interaction between Ni II and Gd III ions. The fitting of the χ M T vs. T data processed by PHI software provided the parameters g = 2.08 (J = +0.87 cm -1 ) for 9 and g = 2.02 (J = +1.83 cm -1 ) for 14. The interaction exchange was magneto-structurally correlated to the Ni-O-Gd angle (α) and Ni(μ-O)Gd dihedral angle (β). With an applied dc field, complexes 1 (Tb), 2 (Dy), 7 (Tb) and 12 (Dy) exhibited single magnetic relaxation with SMM parameters of U eff /k = 13.60 K, 11.52 K, 7.69 K and 5.14 K, respectively. Analysis of the Cole-Cole plots for complexes 2 and 7 suggested that a single relaxation process was mainly involved in the relaxation process, with α values in the range of 0.37-0.17 and 0

Multi-site evaluation of the LN34 pan-lyssavirus real-time RT-PCR assay for post-mortem rabies diagnostics

PubMed Central

Dettinger, Lisa; Powell, James W.; Seiders, Melanie; Condori, Rene Edgar Condori; Griesser, Richard; Okogi, Kenneth; Carlos, Maria; Pesko, Kendra; Breckenridge, Mike; Simon, Edson Michael M.; Chu, Maria Yna Joyce V.; Davis, April D.; Brunt, Scott J.; Orciari, Lillian; Yager, Pamela; Carson, William C.; Hartloge, Claire; Saliki, Jeremiah T.; Deldari, Mojgan; Hsieh, Kristina; Wadhwa, Ashutosh; Wilkins, Kimberly; Rabideau, Patricia; Gruhn, Nina; Cadet, Rolain; Isloor, Shrikrishna; Nath, Sujith S.; Joseph, Tomy; Gao, Jinxin; Wallace, Ryan; Reynolds, Mary; Olson, Victoria A.

2018-01-01

Rabies is a fatal zoonotic disease that requires fast, accurate diagnosis to prevent disease in an exposed individual. The current gold standard for post-mortem diagnosis of human and animal rabies is the direct fluorescent antibody (DFA) test. While the DFA test has proven sensitive and reliable, it requires high quality antibody conjugates, a skilled technician, a fluorescence microscope and diagnostic specimen of sufficient quality. The LN34 pan-lyssavirus real-time RT-PCR assay represents a strong candidate for rabies post-mortem diagnostics due to its ability to detect RNA across the diverse Lyssavirus genus, its high sensitivity, its potential for use with deteriorated tissues, and its simple, easy to implement design. Here, we present data from a multi-site evaluation of the LN34 assay in 14 laboratories. A total of 2,978 samples (1,049 DFA positive) from Africa, the Americas, Asia, Europe, and the Middle East were tested. The LN34 assay exhibited low variability in repeatability and reproducibility studies and was capable of detecting viral RNA in fresh, frozen, archived, deteriorated and formalin-fixed brain tissue. The LN34 assay displayed high diagnostic specificity (99.68%) and sensitivity (99.90%) when compared to the DFA test, and no DFA positive samples were negative by the LN34 assay. The LN34 assay produced definitive findings for 80 samples that were inconclusive or untestable by DFA; 29 were positive. Five samples were inconclusive by the LN34 assay, and only one sample was inconclusive by both tests. Furthermore, use of the LN34 assay led to the identification of one false negative and 11 false positive DFA results. Together, these results demonstrate the reliability and robustness of the LN34 assay and support a role for the LN34 assay in improving rabies diagnostics and surveillance. PMID:29768505

Photoinduced dynamics to photoluminescence in Ln3+ (Ln = Ce, Pr) doped β-NaYF4 nanocrystals computed in basis of non-collinear spin DFT with spin-orbit coupling

NASA Astrophysics Data System (ADS)

Han, Yulun; Vogel, Dayton J.; Inerbaev, Talgat M.; May, P. Stanley; Berry, Mary T.; Kilin, Dmitri S.

2018-03-01

In this work, non-collinear spin DFT + U approaches with spin-orbit coupling (SOC) are applied to Ln3+ doped β-NaYF4 (Ln = Ce, Pr) nanocrystals in Vienna ab initio Simulation Package taking into account unpaired spin configurations using the Perdew-Burke-Ernzerhof functional in a plane wave basis set. The calculated absorption spectra from non-collinear spin DFT + U approaches are compared with that from spin-polarised DFT + U approaches. The spectral difference indicates the importance of spin-flip transitions of Ln3+ ions. Suite of codes for nonadiabatic dynamics has been developed for 2-component spinor orbitals. On-the-fly nonadiabatic coupling calculations provide transition probabilities facilitated by nuclear motion. Relaxation rates of electrons and holes are calculated using Redfield theory in the reduced density matrix formalism cast in the basis of non-collinear spin DFT + U with SOC. The emission spectra are calculated using the time-integrated method along the excited state trajectories based on nonadiabatic couplings.

Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

PubMed

Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

2013-06-17

Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius

Room temperature synthesis of hydrophilic Ln(3+)-doped KGdF4 (Ln = Ce, Eu, Tb, Dy) nanoparticles with controllable size: energy transfer, size-dependent and color-tunable luminescence properties.

PubMed

Yang, Dongmei; Li, Guogang; Kang, Xiaojiao; Cheng, Ziyong; Ma, Ping'an; Peng, Chong; Lian, Hongzhou; Li, Chunxia; Lin, Jun

2012-06-07

In this paper, we demonstrate a simple, template-free, reproducible and one-step synthesis of hydrophilic KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) nanoparticles (NPs) via a solution-based route at room temperature. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) and cathodoluminescence (CL) spectra are used to characterize the samples. The results indicate that the use of water-diethyleneglycol (DEG) solvent mixture as the reaction medium not only allows facile particle size control but also endows the as-prepared samples with good water-solubility. In particular, the mean size of NPs is monotonously reduced with the increase of DEG content, from 215 to 40 nm. The luminescence intensity and absolute quantum yields for KGdF(4): Ce(3+), Tb(3+) NPs increase remarkably with particle sizes ranging from 40 to 215 nm. Additionally, we systematically investigate the magnetic and luminescence properties of KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) NPs. They display paramagnetic and superparamagnetic properties with mass magnetic susceptibility values of 1.03 × 10(-4) emu g(-1)·Oe and 3.09 × 10(-3) emu g(-1)·Oe at 300 K and 2 K, respectively, and multicolor emissions due to the energy transfer (ET) process Ce(3+)→ Gd(3+)→ (Gd(3+))(n)→ Ln(3+), in which Gd(3+) ions play an intermediate role in this process. Representatively, it is shown that the energy transfer from Ce(3+) to Tb(3+) occurs mainly via the dipole-quadrupole interaction by comparison of the theoretical calculation and experimental results. This kind of magnetic/luminescent dual-function materials may have promising applications in multiple biolabels and MR imaging.

Heterometallic [Mn5-Ln4] single-molecule magnets with high anisotropy barriers.

PubMed

Mereacre, Valeriu; Ako, Ayuk M; Clérac, Rodolphe; Wernsdorfer, Wolfgang; Hewitt, Ian J; Anson, Christopher E; Powell, Annie K

2008-01-01

The reaction of [Mn6O2(Piv)(10)(4-Me-py)(2.5)(PivH)(1.5)] (1) (py: pyridine, Piv: pivilate) with N-methyldiethanolamine (mdeaH2) and Ln(NO3)3 x 6 H2O in MeCN leads to a series of nonanuclear compounds [Mn5Ln4(O)6(mdea)2(mdeaH)2(Piv)6(NO3)4(H2O)2]2 MeCN (Ln=Tb(III) (2), Dy(III) (3), Ho(III) (4), Y(III) (5)). Single-crystal X-ray diffraction shows that compounds 2-5 are isostructural, with the central core composed of two distorted {Mn(IV)Mn(III)Ln2O4} cubanes sharing a Mn(IV) vertex, representing a new heterometallic 3d-4f motif for this class of ligand. The four new compounds display single-molecule magnet (SMM) behaviour, which is modulated by the lanthanide ion used. Moreover, the values found for Delta(eff) and tau(o) for 3 of 38.6 K and 3.0 x 10(-9) s respectively reveal that the complex 3 exhibits the highest energy barrier recorded so far for 3d-4f SMMs. The slow relaxation of the magnetisation for 3 was confirmed by mu-SQUID measurements on an oriented single crystal and the observation of M versus H hysteresis loops below 1.9 K.

Synthesis, structure, and polymorphism of A{sub 3}LnSi{sub 2}O{sub 7} (A=Na, K; Ln=Sm, Ho, Yb)

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

Latshaw, Allison M.; Yeon, Jeongho; Smith, Mark D.

2016-03-15

Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family, K{sub 3}SmSi{sub 2}O{sub 7}, Na{sub 3}HoSi{sub 2}O{sub 7}, and two polymorphs of Na{sub 3}YbSi{sub 2}O{sub 7}, are reported. K{sub 3}SmSi{sub 2}O{sub 7} crystallizes in the hexagonal space group P6{sub 3}/mcm, Na{sub 3}HoSi{sub 2}O{sub 7} and Na{sub 3}YbSi{sub 2}O{sub 7} crystallize in the hexagonal space group P6{sub 3}/m, and Na{sub 3}YbSi{sub 2}O{sub 7} crystallizes in the trigonal space group P31c. The Na{sub 3}YbSi{sub 2}O{sub 7} composition that crystallizes in P31c is a new structure type. The magnetic properties for the Ho and Yb analogs are reported. - Graphical abstract: The differentmore » structure types and polymorphs of the A{sub 3}LnSi{sub 2}O{sub 7} family reported. - Highlights: • Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family are presented. • Na{sub 3}YbSi{sub 2}O{sub 7} is reported as two polymorphs, one is a new structure type. • Crystals synthesized out of molten fluoride fluxes.« less

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

PubMed

Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

2016-08-15

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Rare earth elements geochemistry in springs from Taftan geothermal area SE Iran

NASA Astrophysics Data System (ADS)

Shakeri, Ata; Ghoreyshinia, Sayedkazem; Mehrabi, Behzad; Delavari, Morteza

2015-10-01

Concentrations of rare earth elements (REEs) were determined in springs and andesitic-dacitic rocks of Taftan geothermal field. Hydrochemical results of major ions indicate that thermal springs are Na-SO4-Cl and Ca-SO4-Cl types. Concentrations of REEs are in ranges of 10- 4 to 1.2 and 49 to 62 times of chondrite for springwater and rock samples, respectively. The thermal (STS and TTS) and the cold (APS) springs with low pH values exhibit a very high REE contents (0.64 to 3.15 mg/l). Saturation index indicates that Fe and Al phases can control dissolved REE concentration in FTS and PF cold springs. The speciation of REE complexes indicates dominant presence of LnSO4+ and free ion in the Taftan thermal springs. In APS cold spring with pH 4, fluoride complexes are dominate over the free ion and sulfate species, while in PF and FTS cold springs with pH 6.4 and 7, respectively, carbonate complexes (LnCO3+) are predominant species. Chondrite-normalized pattern for the low-pH waters show very distinctive gull-wing patterns, characteristic feature of acid-sulfate geothermal systems, and are similar to those of the host rocks. Chemical characteristics of rare earth elements in spring and volcanic rock samples indicate that REEs are originated from the andesitic-dacitic host rocks. Whole-rock-normalized REE patterns and petrographic evidences show that rare earth elements leached mainly from marginal alteration of minerals and matrix decomposition in volcanic rocks. In chondrite-normalized REE patterns, significant negative Eu anomaly in the cold springs compare to the thermal and acidic springs indicates that alteration of plagioclase is more intense in the later, corresponding to increasing in temperature and acidic state of reactant water.

Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters.

PubMed

Akhtar, Muhammad Nadeem; Lan, Yanhua; AlDamen, Murad A; Zheng, Yan-Zhen; Anson, Christopher E; Powell, Annie K

2018-03-06

Three isostructural lanthanide series with a core of MnMnLn 2 are reported. These three families have the formulae of [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (piv) 6 (NO 3 ) 2 ] {no crystallization solvent, Ln = La, Ce, Pr, Nd, Eu (1-4, 6); solv = 3MeCN, Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y (5, 7-13)}, where H 2 edte = N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and piv = pivalate; [MnMnLn 2 (μ 4 -O) 2 (H 2 edte) 2 (benz) 6 (NO 3 ) 2 ], where benz = benzoate, or [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (benz) 6 (NO 3 ) 2 ]·2MeCN {Ln = Gd, Tb, Dy (14-16); and [MnMnLn 2 (μ 4 -O) 2 (edteH 2 ) 2 (piv) 8 ].solv {solv = 4MeCN, Ln = La (17); solv = 2MeCN·tol·H 2 O, Ln = Pr, Nd, Sm, Tb (18-20, 22); solv = 2MeCN·H 2 O, Ln = Gd (21). These compounds crystallize in two different systems, namely, monoclinic in the space groups P2 1 /n for 1-4, 6, and 14-16 and C2/c for 5, 7-13, 18-20, and 22 and triclinic in the space group P1[combining macron] for 17 and 21. The crystal structures of these compounds display a face-fused dicubane structure connected by different types of bridged oxygen atoms. Solid-state dc magnetic susceptibility characterization was carried out for 1-22, and fitting showed that Mn III Mn III is antiferromagnetically (AF) coupled and Mn II Mn III , Mn II Ln and Mn III Ln are weakly ferromagnetically coupled. In addition, ac measurements were carried out and showed that only 7, 15, and 22 for Tb, 8 and 16 for Dy, and 20 for Sm exhibited slow magnetization relaxation. In the case of 15, it was possible to determine the energy barrier of the slow-relaxation behavior by fitting peak temperatures to the Arrhenius law, which gave a value of U eff = 21.2 K and a pre-exponential factor of τ 0 = 4.0 × 10 -9 s.

Preparation and cathodoluminescence characteristics of rare earth activated BaAl2O4 phosphors.

PubMed

Benourdja, S; Kaynar, Ümit H; Ayvacikli, M; Karabulut, Y; Guinea, J Garcia; Canimoglu, A; Chahed, L; Can, N

2018-04-18

Undoped and Pr, Sm and Tb activated BaAl 2 O 4 phosphors have been synthesized by solid state reaction method and combustion method. The structure and morphological observation of the phosphor samples were monitored by X-ray powder diffraction (XRD) and environmental scanning electron microscope (ESEM) coupled to an energy dispersive X-ray spectrometer (EDS). The all diffraction peaks are well assigned to standard data card (PDF♯17-306). Emission properties of the samples were explored using light emission induced by an electron beam (i.e cathodoluminescence, CL) at room temperature (RT). Undoped BaAl 2 O 4 sample exhibits a broad defect emission from 300 to 500 nm from the aluminate defect centres. CL spectra recorded at room temperature display that the as-prepared BaAl 2 O 4 :Ln (Ln=Pr, Sm and Tb) phosphors exhibit different luminescence colors coming from different rare earth activator ions. The transition 4 G 5/2 → 6 H 7/2 located at 606 and 610 nm for Sm 3+ can occur as hypersensitive transition having the selection rule ΔJ = ± 1. For the Tb 3+ doped samples, they exhibit D45 green line emissions. The proposed luminescent mechanisms of all doped rare earth ions are also discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Exploring the Influence of Diamagnetic Ions on the Mechanism of Magnetization Relaxation in {CoIII2LnIII2} (Ln = Dy, Tb, Ho) "Butterfly" Complexes.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Murray, Keith S; Rajaraman, Gopalan

2017-03-06

The synthesis and magnetic and theoretical studies of three isostructural heterometallic [Co III 2 Ln III 2 (μ 3 -OH) 2 (o-tol) 4 (mdea) 2 (NO 3 ) 2 ] (Ln = Dy (1), Tb (2), Ho (3)) "butterfly" complexes are reported (o-tol = o-toluate, (mdea) 2- = doubly deprotonated N-methyldiethanolamine). The Co III ions are diamagnetic in these complexes. Analysis of the dc magnetic susceptibility measurements reveal antiferromagnetic exchange coupling between the two Ln III ions for all three complexes. ac magnetic susceptibility measurements reveal single-molecule magnet (SMM) behavior for complex 1, in the absence of an external magnetic field, with an anisotropy barrier U eff of 81.2 cm -1 , while complexes 2 and 3 exhibit field induced SMM behavior, with a U eff value of 34.2 cm -1 for 2. The barrier height for 3 could not be quantified. To understand the experimental observations, we performed DFT and ab initio CASSCF+RASSI-SO calculations to probe the single-ion properties and the nature and magnitude of the Ln III -Ln III magnetic coupling and to develop an understanding of the role the diamagnetic Co III ion plays in the magnetization relaxation. The calculations were able to rationalize the experimental relaxation data for all complexes and strongly suggest that the Co III ion is integral to the observation of SMM behavior in these systems. Thus, we explored further the effect that the diamagnetic Co III ions have on the magnetization blocking of 1. We did this by modeling a dinuclear {Dy III 2 } complex (1a), with the removal of the diamagnetic ions, and three complexes of the types {K I 2 Dy III 2 } (1b), {Zn II 2 Dy III 2 } (1c), and {Ti IV 2 Dy III 2 } (1d), each containing a different diamagnetic ion. We found that the presence of the diamagnetic ions results in larger negative charges on the bridging hydroxides (1b > 1c > 1 > 1d), in comparison to 1a (no diamagnetic ion), which reduces quantum tunneling of magnetization effects, allowing for more desirable SMM

Synthesis and anisotropic properties of single crystalline Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb)

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

Morrison, Gregory; Prestigiacomo, Joseph; Haldolaarachchige, Neel

2016-04-15

Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb) have been grown using the self-flux method under Ru-poor conditions. The structure of the Gd analog is found to be highly dependent on the synthesis method. Gd{sub 2}Ru{sub 3}Al{sub 15.08} orders antiferromagnetically at 17.5 K. Tb{sub 2}Ru{sub 3}Al{sub 15.05} enters an antiferromagnetic state at 16.6 K followed by a likely incommensurate-to-commensurate transition at 14.9 K for crystals oriented with H//ab. For crystals oriented with H//c, a broad maximum is observed in the temperature dependent M/H, indicative of a highly anisotropic magnetic system with the hard axis in the c-direction. The magnetizationmore » as a function of field and magnetoresistance along the ab-direction of Tb{sub 2}Ru{sub 3}Al{sub 15.05} display a stepwise behavior and indicate strong crystalline electric field effects. - Graphical abstract: Single crystal, structure, and highly anisotropic magnetoresistance due to strong crystalline electric field effects of Tb{sub 2}Ru{sub 3}Al{sub 15.05}. - Highlights: • Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} were grown for the first time via flux growth. • The structure of Gd{sub 2}Ru{sub 3}Al{sub 15.09} differs from that of arc melted Gd{sub 2}Ru{sub 3.08}Al{sub 15}. • Tb{sub 2}Ru{sub 3}Al{sub 15.05} exhibits highly anisotropic magnetic and transport properties. • The properties of Tb{sub 2}Ru{sub 3}Al{sub 15.05} arise due to crystalline electric field effects.« less

PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (LN) OVEN BUILDING, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

PERSPECTIVE VIEW LOOKING SOUTHWEST AT THE CYANAMIDE (L-N) OVEN BUILDING, AMMONIA SPHERES IN FOREGROUND. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

PubMed

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

High temperature transport properties of co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu; 0.02 ≤ x ≤ 0.08)

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

Nag, Abanti, E-mail: abanti@nal.res.in; Bose, Rapaka S.C.

Highlights: • The thermoelectric Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu) perovskite are prepared by solid state reaction. • The high temperature transport properties are explored. • The co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} shows non-metal-like temperature dependence of resistivity. • The Seebeck coefficient of Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} exhibits metallic nature. • The puzzling transport phenomenon is originated from oxygen vacancy related defect centres. - Abstract: The co-substituted Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} (Ln = Yb, Lu; 0.02 ≤ x ≤ 0.08) are synthesized by solid-state reaction and the electronic transport propertiesmore » are investigated. Rietveld refinement confirms the formation of single phase orthorhombic structure with gradual increase of cell parameters with doping level. The electronic transport properties such as Seebeck coefficient and electrical resistivity decrease with increasing the dopant concentration for both the co-substituted compositions. All the compositions of Ca{sub 1−x}Ln{sub x}Mn{sub 1−x}Nb{sub x}O{sub 3} show nonmetal-like temperature dependence of resistivity; whereas metal-like temperature dependence of thermopower. This inconsistency is explained by the formation of oxygen vacancy associated defect centres that originates from partial reduction of Mn{sup 4+} to Mn{sup 3+} due to co-substitution. The defect centres act as extrinsic carriers and cause additional contribution to the entropy of the system, leading to increase of Seebeck coefficient as a function of temperature. The transport mechanism of charge carriers is explained in the framework of Mott’s small polaron hopping mechanism.« less

Theoretical study on the anion photoelectron spectra of Ln(COT)2- including the spin-orbit effects

NASA Astrophysics Data System (ADS)

Nakajo, Erika; Yabushita, Satoshi

2017-06-01

The multiplet level splittings for both anion and neutral sandwich complexes Ln(COT)2 (Ln = Ce-Yb, COT = 1,3,5,7-cyclooctatetraene) were calculated with spin-orbit interactions to analyze their anion photoelectron spectra. The theoretically simulated spectra obtained with these energies and the pole strengths are generally consistent with the experimental spectra for the X peak. The magnitudes of the energy splittings, relative peak intensities, and their Ln dependence are reproduced. In comparison to our previous calculations, the inclusion of spin-orbit interactions with the SO-MCQDPT2 method makes the simulated spectra more consistent with the results of the experiment.

Infrared detector Dewars - Increased LN2 hold time and vacuum jacket life spans

NASA Technical Reports Server (NTRS)

Jennings, D. E.; Boyd, W. J.; Blass, W. E.

1976-01-01

IR detector Dewars commonly suffer from shorter than desired LN2 hold times and insulation jacket vacuum corruption over relatively short time periods. In an attempt to solve this problem for a 9144 detector Dewar, small 1 liter/s appendage ion pumps were selected for continuous pumping of the vacuum jackets. This procedure extended LN2 hold times from 20 to 60 h and virtually eliminated vacuum jacket corruption. Thus the detector systems are usable continuously over periods of 6 months or more.

Re-dispersion and film formation of GdVO4 :  Ln3+ (Ln3+ = Dy3+, Eu3+, Sm3+, Tm3+) nanoparticles: particle size and luminescence studies.

PubMed

Shanta Singh, N; Ningthoujam, R S; Phaomei, Ganngam; Singh, S Dorendrajit; Vinu, A; Vatsa, R K

2012-04-21

GdVO(4) : Ln(3+) (Ln(3+) = Dy(3+), Eu(3+), Sm(3+), Tm(3+)) nanoparticles are prepared by a simple chemical route at 140 °C. The crystallite size can be tuned by varying the pH of the reaction medium. Interestingly, the crystallite size is found to increase significantly when pH increases from 6 to 12. This is related to slower nucleation of the GdVO(4) formation with increase of VO(4)(3-) present in solution. The luminescence study shows an efficient energy transfer from vanadate absorption of GdVO(4) to Ln(3+) and thereby enhanced emissions are obtained. A possible reaction mechanism at different pH values is suggested in this study. As-prepared samples are well dispersed in ethanol, methanol and water, and can be incorporated into polymer films. Luminescence and its decay lifetime studies confirm the decrease in non-radiative transition probability with the increase of heat treatment temperature. Re-dispersed particles will be useful in potential applications of life science and the film will be useful in display devices.

AlN/Pt/LN structure for SAW sensors capable of operating at high temperature

NASA Astrophysics Data System (ADS)

Naumenko, Natalya; Nicolay, Pascal

2017-08-01

There is a need for wireless sensors able to operate in the intermediate temperature range (ITR) between 300 °C and 600 °C. Surface acoustic wave (SAW) sensors are promising candidates to solve this issue. However, existing SAW sensors most often fail in the ITR, due to the quick degradation of the sensor housing in extreme conditions. A promising way to circumvent the issue is to use "package-less" devices, where the acoustic waves are guided in a multilayered structure where they are intrinsically protected from adverse environmental effects. We present here an innovative multilayered structure that fulfills all the basic requirements, to achieve a wireless and "package-less" SAW Sensor for the ITR. The structure is made of a thin AlN layer deposited on top of a Y + 128°LN substrate and equipped with buried Pt electrodes. Numerical simulations of the acoustic waves propagating in SAW resonators built on this structure reveal the existence of a useful Rayleigh-type SAW that propagates at the AlN/LN interface with a velocity up to 4500 m/s and a high electromechanical coupling k2=5.6%, without leakage into the substrate. The existence of this mode is due to specific properties of the Y + 128°LN cut, which are analyzed in detail in this paper. The performances of an optimized AlN/Pt/LN structure are also compared to the ones of previously suggested "package-less" structures, including AlN/ZnO/Sapphire. It is shown that better device characteristics can be expected from the AlN/Pt/LN structure in the ITR.

Quaternary Chalcogenide-Based Misfit Nanotubes LnS(Se)-TaS(Se)2 (Ln = La, Ce, Nd, and Ho): Synthesis and Atomic Structural Studies.

PubMed

Lajaunie, Luc; Radovsky, Gal; Tenne, Reshef; Arenal, Raul

2018-01-16

We have synthesized quaternary chalcogenide-based misfit nanotubes LnS(Se)-TaS 2 (Se) (Ln = La, Ce, Nd, and Ho). None of the compounds described here were reported in the literature as a bulk compound. The characterization of these nanotubes, at the atomic level, has been developed via different transmission electron microscopy techniques, including high-resolution scanning transmission electron microscopy, electron diffraction, and electron energy-loss spectroscopy. In particular, quantification at sub-nanometer scale was achieved by acquiring high-quality electron energy-loss spectra at high energy (∼between 1000 and 2500 eV). Remarkably, the sulfur was found to reside primarily in the distorted rocksalt LnS lattice, while the Se is associated with the hexagonal TaSe 2 site. Consequently, these quaternary misfit layered compounds in the form of nanostructures possess a double superstructure of La/Ta and S/Se with the same periodicity. In addition, the interlayer spacing between the layers and the interatomic distances within the layer vary systematically in the nanotubes, showing clear reduction when going from the lightest (La atom) to the heaviest (Ho) atom. Amorphous layers, of different nature, were observed at the surface of the nanotubes. For La-based NTs, the thin external amorphous layer (inferior to 10 nm) can be ascribed to a Se deficiency. Contrarily, for Ho-based NTs, the thick amorphous layer (between 10 and 20 nm) is clearly ascribed to oxidation. All of these findings helped us to understand the atomic structure of these new compounds and nanotubes thereof.

PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (LN) COOLING SHED, MILL ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

PERSPECTIVE VIEW LOOKING NORTHWEST AT CYANAMIDE (L-N) COOLING SHED, MILL BUILDING AND CONVEYOR BRIDGE. NOTE CORNERSTONE ON THE MILL BUILDING. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

Large Hexadecametallic {Mn(III) -Ln(III) } Wheels: Synthesis, Structural, Magnetic, and Theoretical Characterization.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Moubaraki, Boujemaa; Murray, Keith S; Rajaraman, Gopalan

2015-11-09

The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {Mn(III) 8 Ln(III) 8 } (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2 , in the presence of ortho-toluic or benzoic acid are reported. From the seven wheels studied the {Mn8 Dy8 } and {Mn8 Y8 } analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8 Y8 } complex due to weak ferromagnetic Mn(III) -Mn(III) interactions. Ab initio CASSCF+RASSI-SO calculations on the {Mn8 Dy8 } wheel estimated the Mn(III) -Dy(III) exchange interaction as -0.1 cm(-1) . This weak exchange along with unfavorable single-ion anisotropy of Dy(III) /Mn(III) ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g-anisotropy of the Dy(III) ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8 Ln8 } clusters reported here are the largest heterometallic Mn(III) Ln(III) wheels and the largest {3d-4f} wheels to exhibit SMM behavior reported to date. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING SOUTHEAST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHWEST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING WEST AT INGERSOLL-RAND COMPRESSORS #BE565 & 564. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

DETAIL INTERIOR VIEW OF THE CYANAMIDE (LN) OVEN BUILDING LOOKING ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

DETAIL INTERIOR VIEW OF THE CYANAMIDE (L-N) OVEN BUILDING LOOKING NORTHEAST AT A C. 1932 CHICAGO PNEUMATIC COMPRESSOR. (NOT ORIGINAL LOCATION). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

Observations on the T lnR term in the quark-antiquark free energy

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

Kiskis, J.

1986-06-15

Consider the response of a pure gauge theory at temperature T to an external quark-antiquark pair separated by R. In the confining phase, the leading term in the free energy at large R is sigmaR. A string-model calculation has given T lnR for the next-to-leading term. In this paper, the origin of the T lnR term is considered in a more general context that includes the analog spin model and the lattice gauge theory at strong coupling. The connection with transverse fluctuations is emphasized.

Hetero-metallic {3d-4f-5d} complexes: preparation and magnetic behavior of trinuclear [(L(Me2)Ni-Ln){W(CN)(8)}] compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L(Me2) = Schiff base) and variable SMM characteristics for the Tb derivative.

PubMed

Sutter, Jean-Pascal; Dhers, Sébastien; Rajamani, Raghunathan; Ramasesha, S; Costes, Jean-Pierre; Duhayon, Carine; Vendier, Laure

2009-07-06

Assembling bimetallic {Ni-Ln}(3+) units and {W(CN)(8)}(3-) is shown to be an efficient route toward heteronuclear {3d-4f-5d} compounds. The reaction of either the binuclear [{L(Me2)Ni(H(2)O)(2)}{Ln(NO(3))(3)}] complexes or their mononuclear components [L(Me2)Ni] and Ln(NO(3))(3) with (HNBu(3))(3){W(CN)(8)} in dmf followed by diffusion of tetrahydrofuran yielded the trinuclear [{L(Me2)NiLn}{W(CN)(8)}] compounds 1 (Ln = Y), 2a,b (Gd), 3a,b (Tb), 4 (Dy), 5 (Ho), and 6 (Er) as crystalline materials. All of the derivatives possess the trinuclear core resulting from the linkage of the {W(CN)(8)} to the Ni center of the {Ni-Ln} unit. Differences are found in the solvent molecules acting as ligands and/or in the lattice depending on the crystallization conditions. For all the compounds ferromagnetic {Ni-W} and {Ni-Ln} (Ln = Gd, Tb, Dy, and Er} interactions are operative resulting in high spin ground states. Parameterization of the magnetic behaviors for the Y and Gd derivatives confirmed the strong cyano-mediated {Ni-W} interaction (J(NiW) = 27.1 and 28.5 cm(-1)) compared to the {Ni-Gd} interaction (J(NiGd) = 2.17 cm(-1)). The characteristic features for slow relaxation of the magnetization are observed for two Tb derivatives, but these are modulated by the crystal phase. Analysis of the frequency dependence of the alternating current susceptibility data yielded U(eff)/k(B) = 15.3 K and tau(0) = 4.5 x 10(-7) s for one derivative whereas no maxima of chi(M)'' appear above 2 K for the second one.

Synthesis, structure, and luminescence property of a series of Ag–Ln coordination polymers with the N-heterocyclic carboxylato ligand

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

Jin, Jing, E-mail: jinjing_crystal@126.com; Chen, Chong; Gao, Yan

Six Ln–Ag coordination polymers {[LnAg_2(IN)_4(H_2O)_5]·NO_3·2H_2O}{sub n} (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg_2(IN)_4(H_2O)_2]·NO_3·H_2O}{sub n} (3), [LnAg(pdc){sub 2}]{sub n} (Ln=Eu(4) and Pr (5), H{sub 2}pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc){sub 2}(H{sub 2}O){sub 4}]{sub n} (6) (H{sub 2}bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)–(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or inmore » the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln–Ag coordination polymers. This can be attributed to the tune of inner levels in Ln–Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV–vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework. - Graphical abstract: Six Ag–Ln coordination polymers have been hydrothermally synthesized and characterized. The photoluminescence properties were studied. The distortion of coordination geometry of Ag(I) ion affect structure framework. Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions. - Highlights: • Six Ln–Ag polymers have been synthesized and characterized. • The distortion of coordination geometry of Ag(I) ion affect structure framework. • Introduction of Ag(I) cause wonderful changes to

Near-infrared photoluminescence in La0.98AlO3: 0.02Ln3+(Ln = Nd/Yb) for sensitization of c-Si solar cells

NASA Astrophysics Data System (ADS)

Sawala, N. S.; Koparkar, K. A.; Bajaj, N. S.; Omanwar, S. K.

2016-05-01

The host matrix LaAlO3 was synthesized by conventional solid state reaction method in which the Nd3+ ions and Yb3+ ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd3+ ion doped LaAlO3 converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb3+ ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La0.98AlO3: 0.02Ln3+(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.

Influence of lanthanides on spin-relaxation and spin-structure in a family of Fe 7Ln 4 single molecule magnets

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

Prodius, Denis; Mereacre, Valeriu; Singh, Prashant

A family of isostructural undecanuclear 3d–4f coordination clusters of formula [Fe III 7Ln III 4O 4(OH) 3(tea) 2(Htea) 3(Piv) 7(H 2O) 2(NO 3) 3], where Ln = Y (1), Gd (2), Tb (3), Dy (4); PivH ≡ pivalic acid and H 3tea ≡ triethanolamine, was synthesised in this paper. The central Fe7 core of the coordination cluster can be described in terms of two {Fe 4O 2} butterfly motifs sharing a common body Fe atom. The two Fe 4 mean-planes subtend a dihedral angle of ca. 72°. The Tb (3) and Dy (4) compounds show Single Molecule Magnet (SMM) behaviourmore » as confirmed by ac-susceptibility and μ-SQUID measurements. Furthermore, 57Fe Mössbauer spectra of 1–4 confirm the presence of high-spin Fe III sites. The spectra of all complexes in the high temperature range (30–300 K) show broad overlapping doublets which were assigned to the body and wing-tip pairs of metal ions within the Fe 7 core. The low temperature Mössbauer spectra show dependence on the nature of the rare-earth metal as a result of its interaction with the iron sites. Finally, we observed a transition from fast (2), to intermediate (1) and very slow (frozen) (3, 4) spin fluctuation phenomena in these compounds.« less

Influence of lanthanides on spin-relaxation and spin-structure in a family of Fe 7Ln 4 single molecule magnets

DOE PAGES

Prodius, Denis; Mereacre, Valeriu; Singh, Prashant; ...

2018-03-01

A family of isostructural undecanuclear 3d–4f coordination clusters of formula [Fe III 7Ln III 4O 4(OH) 3(tea) 2(Htea) 3(Piv) 7(H 2O) 2(NO 3) 3], where Ln = Y (1), Gd (2), Tb (3), Dy (4); PivH ≡ pivalic acid and H 3tea ≡ triethanolamine, was synthesised in this paper. The central Fe7 core of the coordination cluster can be described in terms of two {Fe 4O 2} butterfly motifs sharing a common body Fe atom. The two Fe 4 mean-planes subtend a dihedral angle of ca. 72°. The Tb (3) and Dy (4) compounds show Single Molecule Magnet (SMM) behaviourmore » as confirmed by ac-susceptibility and μ-SQUID measurements. Furthermore, 57Fe Mössbauer spectra of 1–4 confirm the presence of high-spin Fe III sites. The spectra of all complexes in the high temperature range (30–300 K) show broad overlapping doublets which were assigned to the body and wing-tip pairs of metal ions within the Fe 7 core. The low temperature Mössbauer spectra show dependence on the nature of the rare-earth metal as a result of its interaction with the iron sites. Finally, we observed a transition from fast (2), to intermediate (1) and very slow (frozen) (3, 4) spin fluctuation phenomena in these compounds.« less

Targeted replacement: systematic studies of dodecanuclear {MLn} coordination clusters (M = Cr, Co; Ln = Dy, Y).

PubMed

Chen, Sihuai; Mereacre, Valeriu; Zhao, Zhiying; Zhang, Wanwan; Zhang, Mengsi; He, Zhangzhen

2018-06-05

Three dodecanuclear 3d-4f coordination clusters, [CrIII6LnIII6(μ3-OH)8(tbdea)6(C6H5COO)16]·2H2O (Ln = Dy (1), Y (2)) and [CoIII6DyIII6(μ3-OH)8(nbdea)6(m-CH3C6H4COO)16]·2H2O·2CH3CN (3), have been synthesized under solvothermal conditions and characterized. Single-crystal X-ray diffraction analysis revealed that all three compounds possess an analogous {MIII6LnIII6} core (M = Cr, Co; Ln = Dy, Y) and dc magnetic susceptibility studies indicated that the magnetic exchange couplings between DyIII ions are dominant antiferromagnetic, while the CrIII-DyIII interactions are weakly ferromagnetic. Furthermore, the ac magnetic susceptibility measurements showed that both CrIII6DyIII6 compound 1 and CoIIi6DyIII6 compound 3 containing highly anisotropic DyIII ions displayed single-molecule magnetic (SMM) behavior with the energy barrier Ueff increasing from 12.8 K (for 1) to 20.8 K (for 3), indicating that weak 3d-4f exchange couplings enhance the QTM and reduce the energy barrier.

Design of Round-trip Trajectories to Near-Earth Asteroids Utilizing a Lunar Flyby

NASA Technical Reports Server (NTRS)

Hernandez, Sonia; Barbee, Brent W.

2011-01-01

There are currently over 7,700 known Near-Earth Asteroids (NEAs), and more are being discovered on a continual basis. Current models predict that the actual order of magnitude of the NEA population may range from 10' to 10 6 . The close proximity of NEA orbits to Earth's orbit makes it possible to design short duration round-trip trajectories to NEAs under the proper conditions. In previous work, 59 potentially accessible NEAs were identified for missions that depart Earth between the years 2016 and 2050 and have round-trip flight times of a year or less. We now present a new method for designing round-trip trajectories to NEAs in which the Moon's gravity aids the outbound trajectory via a lunar flyby. In some cases this gravity assist can reduce the overall spacecraft propellant required for the mission, which in turn can allow NEAs to be reached which would otherwise be inaccessible to a given mission architecture. Results are presented for a specific case study on NEA 2003 LN6.

Fatigue Properties of Modified 316LN Stainless Steel at 4 K for High Field Cable-In Applications

NASA Astrophysics Data System (ADS)

Toplosky, V. J.; Walsh, R. P.; Han, K.

2010-04-01

Cable-In-Conduit-Conductor (CICC) alloys, exposed to Nb3Sn reaction heat-treatments, such as modified 316LN require a design specific database. A lack of fatigue life data (S-n curves) that could be applied in the design of the ITER CS and the NHMFL Series Connected Hybrid magnets is the impetus for the research presented here. The modified 316LN is distinguished by a lower carbon content and higher nitrogen content when compared to conventional 316LN. Because the interstitial alloying elements affect the mechanical properties significantly, it is necessary to characterize this alloy in a systematic way. In conjunction, to ensure magnet reliability and performance, several criteria and expectations must be met, including: high fatigue life at the operating stresses, optimal stress management at cryogenic temperatures and thin walled conduit to reduce coil mass. Tension-tension load control axial fatigue tests have good applicability to CICC solenoid magnet design, thus a series of 4 K strength versus fatigue life curves have been generated. In-situ samples of 316LN base metal, seam welded, butt welded and seam plus butt welded are removed directly from the conduit in order to address base and weld material fatigue life variability. The more than 30 fatigue tests show good grouping on the fatigue life curve and allow discretionary 4 K fatigue life predictions for conduit made with modified 316LN.

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

Yasukawa, Akemi, E-mail: yasukawa@cc.hirosaki-u.ac.jp; Kandori, Kazuhiko; Tanaka, Hidekazu

Highlights: Black-Right-Pointing-Pointer LnCaHap solid solution particles were prepared using five types of heavy rare earth ions by a precipitation method. Black-Right-Pointing-Pointer The length and the crystallinity of the LnCaHap particles first increased and then decreased with increasing Ln{sup 3+} contents. Black-Right-Pointing-Pointer A series of YCaHap solid solution particles formed with Y/(Y + Ca) = 0-0.10 were investigated using various methods in detail. -- Abstract: Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Er{sup 3+} and Yb{sup 3+}) were synthesized using a precipitation method and characterized using various means. Thesemore » Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X{sub Ln}]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X{sub Y}] {<=} 0.10 for substituting Y system and at [X{sub Ln}] {<=} 0.01-0.03 for substituting the other Ln systems. LnPO{sub 4} was mixed with LnCaHap at higher [X{sub Ln}] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X{sub Y}] = 0-0.10 were investigated using XRD, TEM, ICP-AES, IR and TG-DTA in detail.« less

Hydrothermal synthesis and photoluminescent properties of hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower-like clusters

NASA Astrophysics Data System (ADS)

Amurisana, Bao.; Zhiqiang, Song.; Haschaolu, O.; Yi, Chen; Tegus, O.

2018-02-01

3D hierarchical GdPO4·H2O:Ln3+ (Ln3+ = Eu3+, Ce3+, Tb3+) flower clusters were successfully prepared on glass slide substrate by a simple, economical hydrothermal process with the assistance of disodium ethylenediaminetetraacetic acid (Na2H2L, where L4- = (CH2COO)2N(CH2)2N(CH2COO)24-). In this process, Na2H2L was used as both a chelating agent and a structure-director. The hierarchical flower clusters have an average diameter of 7-12 μm and are composed of well-aligned microrods. The influence of the molar ratio of Na2H2L/Gd3+ and reaction time on the morphology was systematically studied. A possible crystal growth and formation mechanism of hierarchical flower clusters is proposed based on the evolution of morphology as a function of reaction time. The self-assembled GdPO4·H2O:Ln3+ superstructures exhibit strong orange-red (Eu3+, 5D0 → 7F1), green (Tb3+, 5D4 → 7F5) and near ultraviolet emissions (Ce3+, 5d → 7F5/2) under ultraviolet excitation, respectively. This study may provide a new channel for building hierarchically superstructued oxide micro/nanomaterials with optical and new properties.

Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

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

Pashchenko, A. V., E-mail: alpash@mail.ru; Pashchenko, V. P.; Prokopenko, V. K.

2017-01-15

The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La{sub 0.3}Ln{sub 0.3}Sr{sub 0.3}Mn{sub 1.1}O{sub 3–δ} manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, {sup 55}Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3̅c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, or Eu{sup 3+} when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure,more » which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T{sub ms}) and ferromagnet–paramagnet (T{sub C}) phase transitions and the increase in electrical resistivity ρ and activation energy E{sub a} with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d{sup 4}(Mn{sup 3+})–2p{sup 6}(O{sup 2–})–3d{sup 3}(Mn{sup 4+})–V{sup (a)}–3d{sup 4}(Mn{sup 3+}). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric {sup 55}Mn NMR spectra support the high-frequency electronic double exchange Mn{sup 3+}(3d{sup 4}) ↔ O{sup 2–}(2p{sup 6}) ↔ Mn{sup 4+}(3d{sup 3}) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the

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

Structure-property relations in lanthanide borate glasses

NASA Technical Reports Server (NTRS)

Chakraborty, I. N.; Day, D. E.; Lapp, J. C.; Shelby, J. E.

1985-01-01

Glass formation in the system Ln2O3-B2O3 (Ln = Nd, Sm) was studied. Glasses could be formed in the range from 0 to 28 mol pct rare-earth oxide (Ln2O3), but liquid immiscibility in these systems limits the range of homogeneous glasses to 0 to 1.5 and 25 to 28 mol pct Ln2O3. The infrared spectra indicate that the rare-earth-rich glasses are structurally similar to rare-earth metaborates (LnB3O6) which contain (B3O6)-infinity chains. The variation in density, transformation temperature, thermal expansion coefficient, and transformation-range viscosity of these glasses with the size of the rare-earth ion is discussed. Glasses near the metaborate composition have a transformation temperature of about 700 C, which is high for binary borate glasses. Glasses could not be formed in the systems Eu2O3-, Gd2O3-, Ho2O3-, and Er2O3-B2O3, even by quenching at 1300 C/s. The sudden lack of glass formation in the system Ln2O3-B2O3 with Ln(3+) ions smaller than Sm(3+) is explained on the basis of the size effect of the Ln(3+) ion on the stability of (B3O6)-infinity chains in these metaborates.

Mutual separation of Am/Cm/Ln by the use of Novel-Triamide, NTAamide and water-soluble diglycolamide

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

Sasaki, Yuji; Tsubata, Yasuhiro; Kitatsuji, Yoshihiro

2013-07-01

The new extractant, NTAamide (C8) (N,N,N',N',N'',N''-hexa-octyl-nitriro-tri-acetamide) is a triamide having nitrogen and oxygen atoms in the central frame, then NTAamide (C8) has hybrid performance of complexation to metals by soft and hard donors. It is clear that NTAamide(C8) can extract trivalent An from diluted nitric acid showing small D(Ln), then the separation of An from Ln can be carried out. The separation factor (SF) of Am/Cm by NTAamide(C8) is approximate 1.78-2.08, which is not so high to separate each other. The combination of NTAamide(C8) of extractant and TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a masking agent shows relatively high SF(Am/Cm) of maximal 6.5.more » It is obvious that NTAamide(C8) is a promising extractant to achieve the mutual separation among Am/Cm/Ln. The concept of flow-sheet for Am/Cm/Ln separation is designed using NTAamide(C8) and TEDGA. (authors)« less

New Composites LnBDC@AC and CB[6]@AC: From Design toward Selective Adsorption of Methylene Blue or Methyl Orange

PubMed Central

Santos, Guilherme de C.; Barros, Amanda L.; de Oliveira, Carlos A. F.; da Luz, Leonis L.; da Silva, Fausthon F.; Demets, Grégoire J.-F.; Alves Júnior, Severino

2017-01-01

New porous composites LnBDC@AC (AC = Activated carbon, Ln = Eu and Gd and BDC = 1,4-benzenedicaboxylate) and CB[6]@AC (CB[6] = Cucurbit[6]uril) were obtained using hydrothermal route. The LnBDC and CB[B] are located inside the pore of the carbon materials as was observed in SEM-EDS, XRPD and FT-IR analysis. Porosimetry analysis showed values typically between AC and LnBDC material, with pore size and surface area, respectively, 29,56 Å and 353.98 m2g-1 for LnBDC@AC and 35,53 Å and 353.98 m2g-1 for CB[6]@AC. Both materials showed good absorptive capacity of metil orange (MO) and methylene blue (MB) with selectivity as a function of pH. For acid pH, both materials present selectivity by MB and alkaline pH for MO, with notable performance for CB[6]@AC. Additionally, europium luminescence was used as structural probe to investigate the coordination environment of Eu3+ ions in the EuBDC@AC composite after adsorption experiment. PMID:28107440

Impact of Na- and K-C pi-interactions on the structure and binding of M3(sol)n(BINOLate)3Ln catalysts.

PubMed

Wooten, Alfred J; Carroll, Patrick J; Walsh, Patrick J

2007-08-16

Shibasaki's heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K; Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-pi interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes.

Kramers non-magnetic superconductivity in LnNiAsO superconductors.

PubMed

Li, Yuke; Luo, Yongkang; Li, Lin; Chen, Bin; Xu, Xiaofeng; Dai, Jianhui; Yang, Xiaojun; Zhang, Li; Cao, Guanghan; Xu, Zhu-an

2014-10-22

We investigated a series of nickel-based oxyarsenides LnNiAsO (Ln=La, Ce, Pr, Nd, Sm) compounds. CeNiAsO undergoes two successive anti-ferromagnetic transitions at TN1=9.3 K and TN2=7.3 K; SmNiAsO becomes an anti-ferromagnet below TN≃3.5 K; NdNiAsO keeps paramagnetic down to 2 K but orders anti-ferromagnetically below TN≃1.3 K. Superconductivity was observed only in Kramers non-magnetic LaNiAsO and PrNiAsO with Tc=2.7 K and 0.93 K, respectively. The superconductivity of PrNiAsO is further studied by upper critical field and specific heat measurements, which reveal that PrNiAsO is a weakly coupled Kramers non-magnetic superconductor. Our work confirms that the nickel-based oxyarsenide superconductors are substantially different in mechanism to iron-based ones, and are likely to be described by the conventional superconductivity theory.

Describing complex cells in primary visual cortex: a comparison of context and multi-filter LN models.

PubMed

Westö, Johan; May, Patrick J C

2018-05-02

Receptive field (RF) models are an important tool for deciphering neural responses to sensory stimuli. The two currently popular RF models are multi-filter linear-nonlinear (LN) models and context models. Models are, however, never correct and they rely on assumptions to keep them simple enough to be interpretable. As a consequence, different models describe different stimulus-response mappings, which may or may not be good approximations of real neural behavior. In the current study, we take up two tasks: First, we introduce new ways to estimate context models with realistic nonlinearities, that is, with logistic and exponential functions. Second, we evaluate context models and multi-filter LN models in terms of how well they describe recorded data from complex cells in cat primary visual cortex. Our results, based on single-spike information and correlation coefficients, indicate that context models outperform corresponding multi-filter LN models of equal complexity (measured in terms of number of parameters), with the best increase in performance being achieved by the novel context models. Consequently, our results suggest that the multi-filter LN-model framework is suboptimal for describing the behavior of complex cells: the context-model framework is clearly superior while still providing interpretable quantizations of neural behavior.

Impact of Na- and K-C π-Interactions on the Structure and Binding of M3(sol)n(BINOLate)3Ln Catalysts

PubMed Central

Wooten, Alfred J.; Carroll, Patrick J.; Walsh, Patrick J.

2008-01-01

Shibasaki’s heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K, Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-π interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes. PMID:17658838

Nickel(0)-Catalyzed Inert C-O Bond Functionalization: Organo Rare-Earth Metal Complex as the Coupling Partner.

PubMed

Yan, Xiangqian; Yang, Fanzhi; Cai, Guilong; Meng, Qingwei; Li, Xiaofang

2018-02-02

An organo rare-earth metal complex has been employed as a highly efficient nucleophile in Ni(0)-catalyzed C-O bond functionalization. The optimized catalytic system which consists of Ni(cod) 2 , PCy 3 , and t-BuONa could smoothly convert 1 equiv of naphthyl ethers to alkylated naphthalene analogues with 0.4 equiv of Ln(CH 2 SiMe 3 ) 3 (THF) 2 , delivering good to excellent yields. The reaction system could also activate the ArCH 2 -O bond with mild base.

Preliminary evaluation of cavitation resistance of type 316LN stainless steel in mercury using a vibratory horn

NASA Astrophysics Data System (ADS)

Pawel, S. J.; Manneschmidt, E. T.

2003-05-01

Type 316LN stainless steel in a variety of conditions (annealed, cold-worked, surface-modified) was exposed to cavitation conditions in stagnant mercury using a vibratory horn. The test conditions included peak-to-peak displacement of the specimen surface of 25 μm at a frequency of 20 kHz and a mercury temperature in the range -5 to 80 °C. Following a brief incubation period in which little or no damage was observed, specimens of annealed 316LN exhibited increasing weight loss and surface roughening with increasing exposure times. Examination of test surfaces with the scanning electron microscope revealed primarily general/uniform wastage in all cases but, for long exposure times, a few randomly oriented 'pits' were also observed. Type 316LN that was 50% cold-worked was considerably more resistant to cavitation erosion damage than annealed material, but the surface modifications (CrN coating, metallic glass coating, laser treatment to form a diamond-like surface) provided little or no protection for the substrate. In addition, the cavitation erosion resistance of other materials - Inconel 718, Nitronic 60, and Stellite 3 - was also compared with that of 316LN for identical screening test conditions.

Heterometallic Zn3 Ln3 Ensembles Containing (μ6 -CO3 ) Ligand and Triangular Disposition of Ln3+ ions: Analysis of Single-Molecule Toroic (SMT) and Single-Molecule Magnet (SMM) Behavior.

PubMed

Goura, Joydeb; Colacio, Enrique; Herrera, Juan Manuel; Suturina, Elizaveta A; Kuprov, Ilya; Lan, Yanhua; Wernsdorfer, Wolfgang; Chandrasekhar, Vadapalli

2017-11-21

Two new heterometallic Zn 3 Ln 3 (Ln 3+ =Dy, Tb) complexes, with a double triangular topology of the metal ions, have been assembled from the polytopic Mannich base ligand 6,6'-{[2-(dimethylamino)ethylazanediyl]bis(methylene)}bis(2-methoxy-4-methylphenol) (H 2 L) with the aid of an in situ generated carbonate ligand from atmospheric CO 2 fixation. Theoretical calculations indicate axial ground states for the Ln 3+ ions in these complexes, with their local magnetic moments being almost coplanar and tangential to the Ln 3+ atoms that define the equilateral triangle. Therefore, they can be considered as single-molecule toroics (SMTs) with almost zero total magnetic moment. Micro-SQUID measurements on the Dy 3+ counterpart show hysteresis loops below 3 K that have an S-shape, with large coercive fields opening upon cooling. This behavior is typical of a single molecule magnet (SMM) with very slow zero-field relaxation. At around ±0.35 T, the loops have a broad step, which is due to a direct relaxation process and corresponds to an acceleration of the relaxation of the magnetization, also observed at this magnetic field from ac susceptibility measurements. Simulations suggest that the broad step corresponds to two level avoidance of crossing points where the spin chiral Kramers doublet meets excited states of the coupled manifold, whose position is defined by exchange and dipole interactions. The Tb 3+ counterpart does not exhibit SMM behavior, which is due to the fact that the degeneracy of the ground state of the exchange coupled system is lifted at zero field, thus favoring quantum tunneling of magnetization (QTM). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

PubMed

Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

2016-06-21

Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

Fatigue induced cracking in aluminum LN-2 shroud of 39 foot vacuum chamber

NASA Technical Reports Server (NTRS)

Edwards, A. A.

1984-01-01

Fourteen years after completion of Ford's 39-foot space simulation chamber, leaks began to appear in its LN2 shroud. Although the shroud had been tight since its acceptance, cracks appeared in 1983 in some of the field welds of the one inch tubes which interconnect the LN2 panels. The resulting leaks were large enough to prevent pump down to high vacuum and could be heard easily when the chamber was at ambient conditions. New cracks appeared during each thermal cycle making it impossible to utilize the chamber for thermal vacuum testing. The analysis presented here implies that many, if not all, of the aluminum LN2 shrouds now in use may be in various stages of fatigue failure. The probability is high that fatigue cracks are working through the aluminum tubing in heat-affected zones of some field welds. The cracks may not be apparent yet, but after the shroud has experienced a certain number of thermal cycles these cracks will work through the material and become serious leaks. Fortunately, appropriate planning, analysis, and checking can, with a relatively small expenditure of money, help to avoid large and unexpected shroud failures and keep the chamber operational as long as it is needed.

Syntheses, structures and properties of three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers based on 2,2'-dipyridyl-5,5'-dicarboxylate ligands.

PubMed

Zhao, Junwei; Cheng, Yamin; Shang, Sensen; Zhang, Fang; Chen, Li; Chen, Lijuan

2013-12-01

Three new two-dimensional Cu(I)-Ln(III) heterometallic coordination polymers [Ln(III)Cu2(I)(Hbpdc)4] · Cl · xH2O [Ln(III) = La(III), x = 8 (1); Ln(III) = Pr(III), x=9 (2); Ln(III) = Eu(III), x = 8 (3)] (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1-3 display the two-dimensional sheet structure constructed from [Cu(I)(Hbpdc)2](-) fragments through Ln(3+) connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the Eu(III) ions, Hbpdc(-) ligands and Cu(I) cations make contributions to its luminescent properties simultaneously. Copyright © 2013 Elsevier B.V. All rights reserved.

Observation of Slow Relaxation and Single-Molecule Toroidal Behavior in a Family of Butterfly-Shaped Ln4 Complexes.

PubMed

Biswas, Sourav; Das, Sourav; Gupta, Tulika; Singh, Saurabh Kumar; Pissas, Michael; Rajaraman, Gopalan; Chandrasekhar, Vadapalli

2016-12-19

A family of five isostructural butterfly complexes with a tetranuclear [Ln 4 ] core of the general formula [Ln 4 (LH) 2 (μ 2 -η 1 η 1 Piv)(η 2 -Piv)(μ 3 -OH) 2 ]⋅x H 2 O⋅y MeOH⋅z CHCl 3 (1: Ln=Dy III , x=2, y=2, z=0; 2: Ln=Tb III , x=0, y=0, z=6; 3: Ln=Er III , x=2, y=2, z=0; 4: Ln=Ho III , x=2, y=2, z=0; 5: Ln=Yb III , x=2, y=2, z=0; LH 4 =6-{[bis(2-hydroxyethyl)amino]methyl}-N'-(2-hydroxy-3-methoxybenzylidene)picolinohydrazide; PivH=pivalic acid) was isolated and characterized both structurally and magnetically. Complexes 1-5 were probed by direct and alternating current (dc and ac) magnetic susceptibility measurements and, except for 1, they did not display single-molecule magnetism (SMM) behavior. The ac magnetic susceptibility measurements show frequency-dependent out-of-phase signals with one relaxation process for complex 1 and the estimated effective energy barrier for the relaxation process was found to be 49 K. We have carried out extensive ab initio (CASSCF+RASSI-SO+SINGLE_ANISO+POLY_ANISO) calculations on all the five complexes to gain deeper insights into the nature of magnetic anisotropy and the presence and absence of slow relaxation in these complexes. Our calculations yield three different exchange coupling for these Ln 4 complexes and all the extracted J values are found to be weakly ferro/antiferromagentic in nature (J 1 =+2.35, J 2 =-0.58, and J 3 =-0.29 cm -1 for 1; J 1 =+0.45, J 2 =-0.68, and J 3 =-0.29 cm -1 for 2; J 1 =+0.03, J 2 =-0.98, and J 3 =-0.19 cm -1 for 3; J 1 =+4.15, J 2 =-0.23, and J 3 =-0.54 cm -1 for 4 and J 1 =+0.15, J 2 =-0.28, and J 3 =-1.18 cm -1 for 5). Our calculations reveal the presence of very large mixed toroidal moment in complex 1 and this is essentially due to the specific exchange topology present in this cluster. Our calculations also suggest presence of single-molecule toroics (SMTs) in complex 2. For complexes 3-5 on the other hand, the transverse anisotropy was computed to be large

Analyses of Small Punch Creep Deformation Behavior of 316LN Stainless Steel Having Different Nitrogen Contents

NASA Astrophysics Data System (ADS)

Ganesh Kumar, J.; Laha, K.; Ganesan, V.; Prasad Reddy, G. V.

2018-05-01

The small punch creep (SPC) behavior of 316LN stainless steel (SS) containing 0.07, 0.11 and 0.14 wt.% nitrogen has been investigated at 923 K. The transient and tertiary SPC deformation of 316LN SS with various nitrogen contents have been analyzed according to the equation proposed for SPC deflection, δ = δ0 + δT (1 - e^{ - κ t} ) + \\dot{δ }s t + δ3 e^{[ φ( {t - tr } )} ]. The relationships among the rate of exhaustion of transient creep ( κ), steady-state deflection rate (\\dot{δ }s) and the rate of acceleration of tertiary creep ( φ) revealed the interrelationships among the three stages of SPC curve. The first-order reaction rate theory was found to be applicable to SPC deformation throughout the transient as well as tertiary region, in all the investigated steels. The initial and final creep deflection rates were decreased, whereas time to attain steady-state deflection rate increased with the increase in nitrogen content. By increasing the nitrogen content in 316LN SS from 0.07 to 0.14 wt.%, each stage of SPC was prolonged, and consequently, the values of κ, \\dot{δ }s and φ were lowered. Using the above parameters, the master curves for both transient and tertiary SPC deflections were constructed for 316LN SS containing different nitrogen contents.

Analyses of Small Punch Creep Deformation Behavior of 316LN Stainless Steel Having Different Nitrogen Contents

NASA Astrophysics Data System (ADS)

Ganesh Kumar, J.; Laha, K.; Ganesan, V.; Prasad Reddy, G. V.

2018-04-01

The small punch creep (SPC) behavior of 316LN stainless steel (SS) containing 0.07, 0.11 and 0.14 wt.% nitrogen has been investigated at 923 K. The transient and tertiary SPC deformation of 316LN SS with various nitrogen contents have been analyzed according to the equation proposed for SPC deflection, δ = δ0 + δT (1 - e^{ - κ t} ) + \\dot{δ }s t + δ3 e^[ φ( t - tr ) ]. The relationships among the rate of exhaustion of transient creep (κ), steady-state deflection rate (\\dot{δ }s ) and the rate of acceleration of tertiary creep (φ) revealed the interrelationships among the three stages of SPC curve. The first-order reaction rate theory was found to be applicable to SPC deformation throughout the transient as well as tertiary region, in all the investigated steels. The initial and final creep deflection rates were decreased, whereas time to attain steady-state deflection rate increased with the increase in nitrogen content. By increasing the nitrogen content in 316LN SS from 0.07 to 0.14 wt.%, each stage of SPC was prolonged, and consequently, the values of κ, \\dot{δ }s and φ were lowered. Using the above parameters, the master curves for both transient and tertiary SPC deflections were constructed for 316LN SS containing different nitrogen contents.

Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

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

Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping

2015-05-15

By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D)more » 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.« less

β-SiH-containing tris(silazido) rare-earth complexes as homogeneous and grafted single-site catalyst precursors for hydroamination

DOE PAGES

Eedugurala, Naresh; Wang, Zhuoran; Yan, KaKing; ...

2017-01-25

A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds Ln{N(SiHMe 2) tBu} 3 (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1–3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln←H–Si interactions. These features are retained in solvent-coordinated 2·Et 2O, 2·THF, and 3·THF. The change in spectroscopic features characterizing the secondary interactions (ν SiH, 1 J SiH) from the unactivated SiH in the silazane HN(SiHMe 2) tBumore » follows the trend 3 > 2 > 1 ≈ 2·Et 2O > 2·THF ≈ 3·THF. Ligand lability follows the same pattern, with Et 2O readily dissociating from 2·Et 2O while THF is displaced only during surface grafting reactions. 1 and 2·THF graft onto mesoporous silica nanoparticles (MSN) to give Ln{N(SiHMe 2) tBu} n@MSN (Ln = Sc (1@MSN), Y (2@MSN)) along with THF and protonated silazido as HN(SiHMe 2) tBu and H 2N tBu. The surface species are characterized by multinuclear and multidimensional solid-state (SS) NMR spectroscopic techniques, as well as diffuse reflectance FTIR, elemental analysis, and reaction stoichiometry. A key 1 J SiH SSNMR measurement reveals that the grafted sites most closely resemble Ln·THF adducts, suggesting that siloxane coordination occurs in grafted compounds. These species catalyze the hydroamination/bicyclization of aminodialkenes, and both solution-phase and interfacial conditions provide the bicyclized product with equivalent cis:trans ratios. As a result, similar diastereoselectivities mediated by catalytic sites under the two conditions suggest similar effective environments.« less

Synthesis, crystal structures and luminescent properties of two 4 d-4 f Ln-Ag heterometallic coordination polymers based on anion template

NASA Astrophysics Data System (ADS)

Fan, Le-Qing; Chen, Yuan; Wu, Ji-Huai; Huang, Yun-Fang

2011-04-01

Two new 4 d-4 f Ln-Ag heterometallic coordination polymers, {[ Ln3Ag 5(IN) 10(H 2O) 7]·4(ClO 4)·4(H 2O)} n ( Ln=Eu ( 1) and Sm ( 2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions by reactions of Ln2O 3, AgNO 3, HIN and HClO 4, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. It is proved that HClO 4 not only adjusts the pH value of the reaction mixture, but also acts as anion template. The structure determination reveals that 1 and 2 are isostructural and feature a novel two-dimensional (2D) layered hetrometallic structure constructed from one-dimensional Ln-carboxylate chains and pillared Ag(IN) 2 units. The 2D layers are further interlinked through Ag⋯Ag and Ag⋯O(ClO 4-) multiple weak interactions, which form a rare Ag-ClO 4 ribbon in lanthanide-transition metal coordination polymers, to give rise to a three-dimensional supramolecular architecture. Moreover, the luminescent properties of these two compounds have also been investigated at room temperature.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

PubMed

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800 °C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Evaluation of the photocatalytic activity of Ln3+-TiO2 nanomaterial using fluorescence technique for real wastewater treatment.

PubMed

Saif, M; Aboul-Fotouh, S M K; El-Molla, S A; Ibrahim, M M; Ismail, L F M

2014-07-15

Evaluation the photocatalytic activity of different Ln(3+) modified TiO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, xmol Ln(3+) modified TiO2 nanomaterials (Ln = Nd(3+), Sm(3+), Eu(3+), Gd(3+), Dy(3+) and Er(3+) ions; x = 0.005, 0.008, 0.01, 0.02 and 0.03) were synthesized by sol-gel method and characterized using different advanced techniques. The photocatalytic efficiency of the modified TiO2 expressed in the charge carrier separation and OH radicals formation were assigned using TiO2 fluorescence quenching and fluorescence probe methods, respectively. The obtained fluorescence measurements confirm that doping treatment significantly decreases the electron-hole recombination probability in the obtained Ln(3+)/TiO2. Moreover, the rate of OH radicals formation is increased by doping. The highly active nanoparticles (0.02Gd(3+)/TiO2 and 0.01Eu(3+)/TiO2) were applied for industrial wastewater treatment using solar radiation as a renewable energy source. Copyright © 2014 Elsevier B.V. All rights reserved.

Mimicking the magnetic properties of rare earth elements using superatoms.

PubMed

Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A W

2015-04-21

Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel "magic boron" counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters.

[The characteristics of type I, III collagen and LN in pulmonary fibrosis induced by uranium ore dust in rats].

PubMed

Hu, Ying-chun; Luo, Zhen-hua; Yuan, Xing-jiang; Yang, Li-ping; Wang, Shou-feng; Li, Guang-yue; He, Xing-peng

2011-02-01

To explore the characteristics of LN and type I, III collagen in pulmonary fibrosis induced by uranium ore dust in rats. 60 adult Wistar rats were divided randomly into two groups, control group (30 rats) and uranium ore dust group (30 rats). Non-exposed intratracheal instillation method was used. Uranium ore dust group was exposed 20 mg/ml uranium ore dust suspension 1ml per rat, meanwhile control group was exposed normal saline 1ml per rat. Post-exposed the 7, 14, 21, 30 and 60 d, 6 rats in each group were killed randomly, lung tissue were collected. The pathological changes in lung tissue were observed by microscope using HE staining, the collagen I and III in lungs were observed by polarizing microscope using Biebrich scarlet staining. The expression of LN protein in lung tissue was observed by immunohistochemistry-SP. During lung fibrosis, a large amount of the proliferated I and III collagen in lungs were observed. Post-exposure to uranium ore dust, the characteristics in proliferated collagen in lungs were type I collagen deposited in lung interstitium mainly in the early stage. The area percentage of collagen I and III was increased significantly at 7, 14, 21, 30 and 60d in the experimental group as compared with that in the control group (P < 0.05 or P < 0.01). The over expression of LN in the lung tissue were observed. The expression of LN was distributed in the lung tissue as thickening of the linear or cluster. The integral optical density of LN was increased significantly at 21, 30 and 60 d in the experimental group as compared with that in the control group (P < 0.05 or P < 0.01). After exposure to uranium ore dust, the characteristics in proliferated collagen in lungs are the type of I collagen deposited in lung interstitium mainly in the early stage, while the type of III collagen increase significantly at the later period. The overexpression of LN exists in the process of pulmonary fibrosis. It suggests that LN has a role effect in the process of

Observation of Vacancies, Faults, and Superstructures in Ln5Mo2O12 (Ln = La, Y, and Lu) Compounds with Direct Mo-Mo Bonding.

PubMed

Colabello, Diane M; Sobalvarro, Elizabeth M; Sheckelton, John P; Neuefeind, Joerg C; McQueen, Tyrel M; Khalifah, Peter G

2017-11-06

Among oxide compounds with direct metal-metal bonding, the Y 5 Mo 2 O 12 (A 5 B 2 O 12 ) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2 O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal-metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal-metal bonding have integer oxidation states resulting from the lifting of orbital degeneracy typically induced by the metal-metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5 Mo 2 O 12 (Ln = La-Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2 O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1-2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5 Mo 2 O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. This represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one

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.

Syntheses, crystal structures and properties of series of 4d-4f ln(III)-Ag(I) heterometallic coordination polymers

NASA Astrophysics Data System (ADS)

Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian; Long, Yi; Yue, Shan-Tang; Liu, Ying-Liang

2015-05-01

By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d-4f Ln(III)-Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, {[LnIIIAgI(na)(ina)(ox)]·2(H2O)}n [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail.

Creep rupture strength of activated-TIG welded 316L(N) stainless steel

NASA Astrophysics Data System (ADS)

Sakthivel, T.; Vasudevan, M.; Laha, K.; Parameswaran, P.; Chandravathi, K. S.; Mathew, M. D.; Bhaduri, A. K.

2011-06-01

316L(N) stainless steel plates were joined using activated-tungsten inert gas (A-TIG) welding and conventional TIG welding process. Creep rupture behavior of 316L(N) base metal, and weld joints made by A-TIG and conventional TIG welding process were investigated at 923 K over a stress range of 160-280 MPa. Creep test results showed that the enhancement in creep rupture strength of weld joint fabricated by A-TIG welding process over conventional TIG welding process. Both the weld joints fractured in the weld metal. Microstructural observation showed lower δ-ferrite content, alignment of columnar grain with δ-ferrite along applied stress direction and less strength disparity between columnar and equiaxed grains of weld metal in A-TIG joint than in MP-TIG joint. These had been attributed to initiate less creep cavitation in weld metal of A-TIG joint leading to improvement in creep rupture strength.

Snynthesis and magnetization of BaLn2O4 (Ln = lanthanide)

NASA Astrophysics Data System (ADS)

Lundberg, Matthew

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

Near-infrared photoluminescence in La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{sup 3+}(Ln = Nd/Yb) for sensitization of c-Si solar cells

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

Sawala, N. S., E-mail: nssawala@gmail.com; Koparkar, K. A.; Omanwar, S. K.

2016-05-06

The host matrix LaAlO{sub 3} was synthesized by conventional solid state reaction method in which the Nd{sup 3+} ions and Yb{sup 3+} ions successfully doped at 2mol% concentrations. The phase purity was confirmed by X ray powder diffraction (XRD) method. The photoluminescence (PL) properties were studied by spectrophotometer in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Nd{sup 3+} ion doped LaAlO{sub 3} converts a visible (VIS) green photon (587 nm) into near infrared (NIR) photon (1070 nm) while Yb{sup 3+} ion doped converts ultra violet (UV) photon (221 nm) into NIR photon (980 nm). The La{sub 0.98}AlO{sub 3}: {sub 0.02}Ln{supmore » 3+}(Ln = Nd / Yb) can be potentiality used for betterment of photovoltaic (PV) technology. This result further indicates its potential application as a luminescence converter layer for enhancing solar cells performance.« less

Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

PubMed

Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

2014-06-16

Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

Building 1D lanthanide chains and non-symmetrical [Ln2] "triple-decker" clusters using salen-type ligands: magnetic cooling and relaxation phenomena.

PubMed

Canaj, Angelos B; Siczek, Milosz; Otręba, Marta; Lis, Tadeusz; Lorusso, Giulia; Evangelisti, Marco; Milios, Constantinos J

2016-11-22

A solvothermal reaction between Ln(NO 3 ) 3 ·6H 2 O (Ln: Gd, Tb and Dy), 2-hydroxy-1-naphthaldehyde, 2-OH-naphth, and ethylenediamine, en, in MeOH in the presence of a base, NEt 3 , led to the formation of the 1D coordination polymers [Ln(L)(MeO)(MeOH) 0.5 ] n ·MeOH (Ln = Gd (1·MeOH), Tb(2), Dy (3·MeOH); H 2 L = 1,1'-((1E,1'E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(naphthalen-2-ol), the Schiff-base ligand derived from the condensation of 2-OH-naphth and en), while a similar reaction in an excess of NaN 3 yielded 1D coordination polymers [Ln(L)(N 3 ) 0.75 (MeO) 0.25 (MeOH)] n (Ln = Gd (4), Tb (5), Dy (6)). Finally, upon replacing ethylenediamine with o-phenylenediamine, o-phen, we managed to isolate the discrete dimers [Dy 2 (L') 3 (MeOH)]·2MeOH (7·2MeOH) and [Gd 2 (L') 3 (MeOH)]·2MeOH (8·2MeOH) (H 2 L' = 1,1'-((1E,1'E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene))bis (naphthalen-2-ol), the Schiff-base ligand from the condensation of 2-OH-naphth and o-phen). Polymers 1-3 describe one-dimensional chains, containing alternating seven- and eight-coordinate Ln III metal centers, polymers 4-6 contain eight-coordinate lanthanide ions, while in both 7 and 8 the two Ln III centers are eight- and seven-coordinate, adopting square antiprismatic and "piano-stool" geometry, respectively. The magnetocaloric properties of the three Gd III analogues were determined from magnetic measurements, yielding the magnetic entropy change -ΔS m = 21.8, 23.0 and 16.0 J kg -1 K -1 at T = 3.0 K on demagnetization of 7 T to 0, for 1, 4 and 8, respectively. The study of the magnetic properties also revealed that all three Dy III analogues (3, 6 and 7) display out-of-phase signals, therefore suggesting slow magnetic relaxation, while such behaviour was not established in the Tb III analogues.

Understanding the Mechanism of Magnetic Relaxation in Pentanuclear {MnIVMnIII2LnIII2} Single-Molecule Magnets.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Moubaraki, Boujemaa; Murray, Keith S; Rajaraman, Gopalan

2018-02-05

A new family of heterometallic pentanuclear complexes of formulas [Mn IV Mn III 2 Ln III 2 O 2 (benz) 4 (mdea) 3 (NO 3 ) 2 (MeOH)] (Ln = Dy (1-Dy), Tb (2-Tb), Gd (3-Gd), Eu (4-Eu), Sm (5-Sm), Nd (6-Nd), Pr (7-Pr); benz(H) = benzoic acid; mdeaH 2 = N-methyldiethanolamine) and [Mn IV Mn III 2 Ln III 2 O 2 (o-tol) 4 (mdea) 3 (NO 3 ) 2 (MeOH)] (Ln = Gd (8-Gd), Eu (9-Eu); o-tol(H) = o-toluic acid) have been isolated and structurally, magnetically, and theoretically characterized. dc magnetic susceptibility measurements reveal dominant antiferromagnetic magnetic interactions for each complex, except for 2-Tb and 3-Gd, which reveal an upturn in the χ M T product at low temperatures. The magnetic interactions between the spin centers in the Gd derivatives, 3-Gd and 8-Gd, which display markedly different χ M T vs T profiles, were found to be due to the interactions of the Gd III -Gd III ions which change from ferromagnetic (3-Gd) to antiferromagnetic (8-Gd) due to structural differences. ac magnetic susceptibility measurements reveal a nonzero out-of-phase component for 1-Dy and 7-Pr, but no maxima were observed above 2 K (H dc = 0 Oe), which suggests single-molecule magnet (SMM) behavior. Out-of-phase signals were observed for complexes 2-Tb, 4-Eu, 8-Gd, and 9-Eu, in the presence of a static dc field (H dc = 2000, 3000 Oe). The anisotropic nature of the lanthanide ions in the benzoate series (1-Dy, 2-Tb, 5-Sm, 6-Nd, and 7-Pr) were thoroughly investigated using ab initio methods. CASSCF calculations predict that the origin of SMM behavior in 1-Dy and 7-Pr and the applied field SMM behavior in 2-Tb does not solely originate from the single-ion anisotropy of the lanthanide ions. To fully understand the relaxation mechanism, we have employed the Lines model to fit the susceptibility data using the POLY_ANISO program, which suggests that the zero-field SMM behavior observed in complexes 1-Dy and 7-Pr is due to weak Mn III/IV -Ln III and Ln III -Ln III couplings and an

Remote refilling of LN2 cryostats for high sensitivity astronomical applications

NASA Astrophysics Data System (ADS)

l'Allemand, J. L. Lizon a.

2017-12-01

The most sensitive observation mode of the ESO VLT (European Southern Observatory Very Large Telescope) is the interferometric mode, where the 4 Units Telescopes are directed to the same stellar object in order to operate as a gigantic interferometer. The beam is then re-combined in the main interferometry laboratory and fed into the analyzing instruments. In order not to disturb the performance of the Interferometer, this room is considered as a sanctuary where one enters only in case of extreme need. A simple opening of the door would create air turbulences affecting the stability for hours. Any cold spot in the room could also cause convection which might change the optical path by fraction of a micron. Most of the instruments are operating at cryogenic temperatures using passive cooling based on LN2 bath cryostat. For this reason, dedicated strategy has been developed for the transfer of LN2 to the various instruments. The present document describes the various aspects and care taken in order to guarantee the very high thermal and mechanical environmental stability.

Phase transformation pathways of Ln2O3 irradiated by ultrafast laser

NASA Astrophysics Data System (ADS)

Rittman, Dylan; Solomon, Jonathan; Chen, Curtis; Tracy, Cameron; Yalisove, Steven; Asta, Mark; Mao, Wendy; Ewing, Rodney

Ultrafast laser irradiation induces highly non-equilibrium conditions in materials through intense electronic excitation over very short timescales. Here, we show that ultrafast laser irradiation drives an irreversible cubic-to-monoclinic phase transformation in Ln2O3 (Ln = Er-Lu). A combination of grazing incidence X-ray diffraction and transmission electron microscopy is used to characterize the amount and depth-dependence of the phase transformation. Results indicate that-although all materials experience the same transformation-it is achieved through different damage mechanisms (pressure vs. thermal), and the short timescales associated with damage provides non-equilibrium routes of material modification. Ab initio molecular dynamics are used to isolate the effects of electronic excitations, and results are shown to be consistent with the trend in radiation resistance observed experimentally. Overall, this study provides a path to gain insight into the relationship between a material's equilibrium phase diagram and its behavior under highly non-equilibrium conditions. DOE/BES.

Co-Expression of α9β1 Integrin and VEGF-D Confers Lymphatic Metastatic Ability to a Human Breast Cancer Cell Line MDA-MB-468LN

PubMed Central

Majumder, Mousumi; Rodriguez-Torres, Mauricio; Torres-Garcia, Jose; Wiebe, Ryan; Timoshenko, Alexander V.; Bhattacharjee, Rabindra N.; Chambers, Ann F.; Lala, Peeyush K.

2012-01-01

Introduction and Objectives Lymphatic metastasis is a common occurrence in human breast cancer, mechanisms remaining poorly understood. MDA-MB-468LN (468LN), a variant of the MDA-MB-468GFP (468GFP) human breast cancer cell line, produces extensive lymphatic metastasis in nude mice. 468LN cells differentially express α9β1 integrin, a receptor for lymphangiogenic factors VEGF-C/-D. We explored whether (1) differential production of VEGF-C/-D by 468LN cells provides an autocrine stimulus for cellular motility by interacting with α9β1 and a paracrine stimulus for lymphangiogenesis in vitro as measured with capillary-like tube formation by human lymphatic endothelial cells (HMVEC-dLy); (2) differential expression of α9 also promotes cellular motility/invasiveness by interacting with macrophage derived factors; (3) stable knock-down of VEGF-D or α9 in 468LN cells abrogates lymphangiogenesis and lymphatic metastasis in vivo in nude mice. Results A comparison of expression of cyclo-oxygenase (COX)-2 (a VEGF-C/-D inducer), VEGF-C/-D and their receptors revealed little COX-2 expression by either cells. However, 468LN cells showed differential VEGF-D and α9β1 expression, VEGF-D secretion, proliferative, migratory/invasive capacities, latter functions being stimulated further with VEGF-D. The requirement of α9β1 for native and VEGF-D-stimulated proliferation, migration and Erk activation was demonstrated by treating with α9β1 blocking antibody or knock-down of α9. An autocrine role of VEGF-D in migration was shown by its impairment by silencing VEGF-D and restoration with VEGF-D. 468LN cells and their soluble products stimulated tube formation, migration/invasiveness of HMVEC-dLy cell in a VEGF-D dependent manner as indicated by the loss of stimulation by silencing VEGF-D in 468LN cells. Furthermore, 468LN cells showed α9-dependent stimulation of migration/invasiveness by macrophage products. Finally, capacity for intra-tumoral lymphangiogenesis and lymphatic

Model-free nuclear magnetic resonance study of intermolecular free energy landscapes in liquids with paramagnetic Ln3+ spotlights: theory and application to Arg-Gly-Asp.

PubMed

Fries, Pascal H

2012-01-28

We propose an easily applicable method for investigating the pair distribution function of a lanthanide Ln(3+) complex LnL (L = ligand) with respect to any solvent or solute molecule A carrying observable nuclear spins. Let r be the distance of Ln(3+) to the observed nuclear spin I. We derive a simple expression of the experimental value of the configurational average of 1/r(6) in terms of longitudinal paramagnetic relaxation (rate) enhancements (PREs) of the spin I measured on a standard high-resolution NMR spectrometer and due to well-chosen concentrations of LnL complexes in which Ln(3+) is a fast-relaxing paramagnetic lanthanide or the slowly-relaxing gadolinium Gd(3+). The derivation is justified in the general case of a molecule A which is by turns in a bound state where it follows the complex and a free state where it moves independently. It rests on the expression of the underlying PRE theory in terms of the angle-dependent pair distribution function of LnL and A. The simplifications of this theory in the high-field regime and under the condition of fast exchange between bound and free states are carefully discussed. We also show that original information on the angle dependence of the molecular pair distribution function can be gained from the measured paramagnetic dipolar shifts induced by complexed fast-relaxing Ln(3+) ions. The method is illustrated by the case study of the anionic Lnttha(3-) = [Ln(3+)(ttha)](3-) (ttha(6-) = triethylene tetraamine hexacetate) complex interacting with the biologically important tripeptide Arg-Gly-Asp (RGD) which carries peripheral ionic groups. The usefulness of an auxiliary reference outer sphere probe solute is emphasized. © 2012 American Institute of Physics

High-quality draft genome sequence of Effusibacillus lacus strain skLN1T, facultative anaerobic spore-former isolated from freshwater lake sediment.

PubMed

Watanabe, Miho; Tokizawa, Riho; Kojima, Hisaya; Fukui, Manabu

2017-01-01

10.1601/nm.25721 strain skLN1 T is the type strain of the type species in the genus 10.1601/nm.25720 which is the one of the genera in the family 10.1601/nm.5070 within the phylum 10.1601/nm.3874. 10.1601/nm.25721 strain skLN1 T is a Gram-positive, spore-forming thermophilic neutrophile isolated from freshwater lake sediment. Here, we present the draft genome sequence of strain skLN1 T , which consists of 3,902,380 bp with a G + C content of 50.38%.

Replication of Beta- and Gammaretroviruses Is Restricted in I/LnJ Mice via the Same Genetic Mechanism▿

PubMed Central

Case, Laure K.; Petell, Lydia; Yurkovetskiy, Leonid; Purdy, Alexandra; Savage, Katherine J.; Golovkina, Tatyana V.

2008-01-01

Mice of the I/LnJ inbred strain are unique in their ability to mount a robust and sustained humoral immune response capable of neutralizing infection with a betaretrovirus, mouse mammary tumor virus (MMTV). Virus-neutralizing antibodies (Abs) coat MMTV virions secreted by infected cells, preventing virus spread and hence the formation of mammary tumors. To investigate whether I/LnJ mice resist infection with other retroviruses besides MMTV, the animals were infected with murine leukemia virus (MuLV), a gammaretrovirus. MuLV-infected I/LnJ mice produced virus-neutralizing Abs that block virus transmission and virally induced disease. Generation of virus-neutralizing Abs required gamma interferon but was independent of interleukin-12. This unique mechanism of retrovirus resistance is governed by a single recessive gene, virus infectivity controller 1 (vic1), mapped to chromosome 17. In addition to controlling the antivirus humoral immune response, vic1 is also required for an antiviral cytotoxic response. Both types of responses were maintained in mice of the susceptible genetic background but congenic for the I/LnJ vic1 locus. Although the vic1-mediated resistance to MuLV resembles the mechanism of retroviral recovery controlled by the resistance to Friend virus 3 (rfv3) gene, the rfv3 gene has been mapped to chromosome 15 and confers resistance to MuLV but not to MMTV. Thus, we have identified a unique virus resistance mechanism that controls immunity against two distinct retroviruses. PMID:18057254

Series of edge-sharing bi-triangle Ln4 clusters with a μ4-NO3- bridge: syntheses, structures, luminescence, and the SMM behavior of the Dy4 analogue.

PubMed

Zou, Hua-Hong; Wang, Rong; Chen, Zi-Lu; Liu, Dong-Cheng; Liang, Fu-Pei

2014-02-14

A series of Ln4 clusters, [Ln4L2(μ3-OH)2(μ4-NO3)(NO3)4(OCH3)(H2O)]·xMeCN·yMeOH (Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), L = 2-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-6-methoxyphenol), have been synthesized by the reaction of Ln(NO)3 and a Schiff-base ligand formed in situ. The six complexes display similar structures, with an overall metal core comprising two edge-sharing triangular Ln3 units linked by a μ4-NO3(-) bridge. The luminescence spectrum of complex 2 shows the characteristic emission of the Tb(III) ions. The magnetic susceptibility studies reveal that the Ln(III) ions are very weakly interacting in all six compounds. Frequency dependence of the ac-susceptibility was found for 3, suggesting a typical single-molecule magnet (SMM) behavior with an anisotropic barrier of 28 K.

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

PubMed

Adam, Christian; Beele, Björn B; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J

2015-02-01

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15 N labeling and characterized by NMR and LIFDI-MS methods. 15 N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15 N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP) 3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP) 3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

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

Observation of Vacancies, Faults, and Superstructures in Ln 5Mo 2O 12 (Ln = La, Y, and Lu) Compounds with Direct Mo–Mo Bonding

DOE PAGES

Colabello, Diane M.; Sobalvarro, Elizabeth M.; Sheckelton, John P.; ...

2017-10-26

Among oxide compounds with direct metal–metal bonding, the Y 5Mo 2O 12 (A 5B 2O 12) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal–metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal–metal bonding have integer oxidation states resulting from the lifting of orbital degeneracymore » typically induced by the metal–metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5Mo 2O 12 (Ln = La–Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown in this paper that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1–2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5Mo 2O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. Finally, this represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic

Observation of Vacancies, Faults, and Superstructures in Ln 5Mo 2O 12 (Ln = La, Y, and Lu) Compounds with Direct Mo–Mo Bonding

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

Colabello, Diane M.; Sobalvarro, Elizabeth M.; Sheckelton, John P.

Among oxide compounds with direct metal–metal bonding, the Y 5Mo 2O 12 (A 5B 2O 12) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal–metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal–metal bonding have integer oxidation states resulting from the lifting of orbital degeneracymore » typically induced by the metal–metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5Mo 2O 12 (Ln = La–Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown in this paper that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1–2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5Mo 2O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. Finally, this represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic

Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

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

Karthik, Chinnathambi, E-mail: Karthikchinnathambi@boisestate.edu; Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415; Anderson, Thomas J.

2012-10-15

A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which becamemore » weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.« less

Color tunable emission in Ce3+ and Tb3+ co-doped Ba2Ln(BO3)2Cl (Ln=Gd and Y) phosphors for white light-emitting diodes.

PubMed

Zhang, Niumiao; Guo, Chongfeng; Jing, Heng; Jeong, Jung Hyun

2013-12-01

Ce(3+) and Tb(3+) co-doped Ba2Ln(BO3)2Cl (Ln=Y and Gd) green emitting phosphors were prepared by solid state reaction in reductive atmosphere. The emission and excitation spectra as well as luminescence decays were investigated, showing the occurrence of efficient energy transfer from Ce(3+) to Tb(3+) in this system. The phosphors exhibit both a blue emission from Ce(3+) and a green emission from Tb(3+) under near ultraviolet light excitation with 325-375 nm wavelength. Emission colors of phosphors could be tuned from deep blue through cyan to green by adjusting the Tb(3+) concentrations. The energy transfer efficiency and emission intensity of Ba2Y(BO3)2Cl:Ce(3+), Tb(3+) precede those of Ba2Gd(BO3)2Cl:Ce(3+), Tb(3+), and the sample Ba2Y(BO3)2Cl:0.03Ce(3+), 0.10Tb(3+) is the best candidate for n-UV LEDs. Copyright © 2013 Elsevier B.V. All rights reserved.

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

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

Li, Yan; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen; Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de

2014-12-15

We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computedmore » for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.« less

A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior

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

Carter, Korey P.; Pope, Simon J. A.; Cahill, Christopher L.

Fifteen new lanthanide p-chlorobenzoic acid complexes, [PrL3(terpy)(H2O)]2 (1), [LnL3(terpy)(H2O)]2 (Ln = Nd (2), Sm (3), and Eu (4)), and [LnL3(terpy)(H2O)] (Ln = Sm (3'), Eu (4'), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11), Lu (12), and Y (13); HL: p-chlorobenzoic acid; terpy: 2,2':6',2''-terpyridine), have been synthesized hydrothermally at varying temperatures and structurally characterized by single crystal and powder X-ray diffraction. The series is comprised of binuclear molecular units (Pr–Eu) that give way to mononuclear molecular complexes (Sm–Y) as the lanthanide contraction takes effect. All fifteen complexes feature a tridentate terpyridine ligand, p-chlorobenzoic acidmore » ligands exhibiting multiple binding modes, bidentate, bridging bidentate, and monodentate, and a bound water molecule. Binuclear complexes 1–4 are stitched together via intermolecular interactions: aromatic–aromatic interactions for 1, halogen•••halogen interactions for 2–4, to form 1D chains. Mononuclear complexes 3', 4', and 5–13 utilize supramolecular hydrogen and halogen bonding to form 2D sheets. Visible and near-IR solid state luminescence studies were performed on complexes 2, 3, 3', 4, 4', 6, 7 and 11 and the characteristic visible luminescence of Sm(III), Eu(III), Tb(III), and Dy(III) was exhibited. The near-IR spectra of the Nd(III) and Yb(III) complexes exhibit weak characteristic luminescence, showing that terpy can act as a sensitizing chromophore in these systems.« less

Orthopositronium Lifetime: Analytic Results in O({alpha}) and O({alpha}{sup 3}ln{alpha})

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

Kniehl, Bernd A.; Kotikov, Anatoly V.; Veretin, Oleg L.

2008-11-07

We present the O({alpha}) and O({alpha}{sup 3}ln{alpha}) corrections to the total decay width of orthopositronium in closed analytic form, in terms of basic irrational numbers, which can be evaluated numerically to arbitrary precision.

Recovering Rare Earth Elements from Aqueous Solution with Porous Amine–Epoxy Networks

DOE PAGES

Wilfong, Walter Christopher; Kail, Brian W.; Bank, Tracy L.; ...

2017-05-12

Recovering aqueous rare earth elements (REEs) from domestic water sources is one key strategy to diminish the U.S.’s foreign reliance of these precious commodities. Herein, we synthesized an array of porous, amine–epoxy monolith and particle REE recovery sorbents from different polyamine, namely tetraethylenepentamine, and diepoxide (E2), triepoxide (E3), and tetra-epoxide (E4) monomer combinations via a polymer-induced phase separation (PIPS) method. The polyamines provided -NH 2 (primary amine) plus -NH (secondary amine) REE adsorption sites, which were partially reacted with C–O–C (epoxide) groups at different amine/epoxide ratios to precipitate porous materials that exhibited a wide range of apparent porosities and REEmore » recoveries/affinities. Specifically, polymer particles (ground monoliths) were tested for their recovery of La 3+, Nd 3+, Eu 3+, Dy 3+, and Yb 3+ (Ln 3+) species from ppm-level, model REE solutions (pH ≈ 2.4, 5.5, and 6.4) and a ppb-level, simulated acid mine drainage (AMD) solution (pH ≈ 2.6). Screening the sorbents revealed that E3/TEPA-88 (88% theoretical reaction of -NH 2 plus -NH) recovered, overall, the highest percentage of Ln 3+ species of all particles from model 100 ppm- and 500 ppm-concentrated REE solutions. Water swelling (monoliths) and ex situ, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (ground monoliths/particles) data revealed the high REE uptake by the optimized particles was facilitated by effective distribution of amine and hydroxyl groups within a porous, phase-separated polymer network. In situ DRIFTS results clarified that phase separation, in part, resulted from polymerization of the TEPA-E3 (N-N-diglycidyl-4-glycidyloxyaniline) species in the porogen via C–N bond formation, especially at higher temperatures. Most importantly, the E3/TEPA-88 material cyclically recovered >93% of ppb-level Ln 3+ species from AMD solution in a recovery–strip–recovery scheme, highlighting

Synchrotron X-ray diffraction and Raman spectroscopy of Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis

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

Siqueira, K.P.F.; Soares, J.C.; Granado, E.

2014-01-15

Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten-salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized into the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited a different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility formore » the non-centrosymmetric C 222{sub 1} space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3{sup ¯}m space group). Nonetheless, broad scattering at forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics. - Graphical abstract: Raman spectrum for Sm{sub 3}NbO{sub 7} ceramics showing their 27 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. Display Omitted - Highlights: • Ln{sub 3}NbO{sub 7} ceramics were obtained by molten-salt synthesis. • SXRD, SHG and Raman scattering confirmed orthorhombic and cubic structures. • Ccmm instead of C222{sub 1} is the correct structure for Sm–Gd ceramics. • Pmcn space group was confirmed for La-, Pr- and Nd-based ceramics. • For Tb–Lu ceramics, ordered domains of a pyrochlore structure were observed.« less

The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

2015-03-01

Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

PubMed

Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

2014-02-03

There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)3]·2CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

Influence of Secondary Cyclic Hardening on the Low Cycle Fatigue Behavior of Nitrogen Alloyed 316LN Stainless Steel

NASA Astrophysics Data System (ADS)

Prasad Reddy, G. V.; Sandhya, R.; Mathew, M. D.; Sankaran, S.

2013-12-01

In this article, the occurrence of secondary cyclic hardening (SCH) and its effect on high-temperature cyclic deformation and fatigue life of 316LN Stainless steel are presented. SCH is found to result from planar slip mode of deformation and enhance the degree of hardening over and above that resulted from dynamic strain aging. The occurrence of SCH is strongly governed by the applied strain amplitude, test temperature, and the nitrogen content in the 316LN SS. Under certain test conditions, SCH is noticed to decrease the low cycle fatigue life with the increasing nitrogen content.

Phase transformations in Ln2O3 materials irradiated with swift heavy ions

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Lang, Maik; Zhang, Fuxiang; Trautmann, Christina; Ewing, Rodney C.

2015-11-01

Phase transformations induced in the cubic C-type lanthanide sesquioxides, Ln2O3 (Ln = Sm, Gd, Ho, Tm, and Lu), by dense electronic excitation are investigated. The structural modifications resulting from exposure to beams of 185 MeV Xe and 2246 MeV Au ions are characterized using synchrotron x-ray diffraction and Raman spectroscopy. The formation of a B-type polymorph, an X-type nonequilibrium phase, and an amorphous phase are observed. The specific phase formed and the transformation rate show dependence on the material composition, as well as the ion beam mass and energy. Atomistic mechanisms for these transformations are determined, indicating that formation of the B-type phase results from the production of anti-Frenkel defects and the aggregation of anion vacancies into planar clusters, whereas formation of the X-type and amorphous phases requires extensive displacement of both anions and cations. The observed variations in phase behavior with changing lanthanide ionic radius and deposited electronic energy density are related to the energetics of these transformation mechanisms.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

PubMed

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

“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

Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

PubMed

Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

2008-02-04

New heterospin complexes have been obtained by combining the binuclear complexes [{Cu(H(2)O)L(1)}Ln(O(2)NO)(3)] or [{CuL(2)}Ln(O(2)NO)(3)] (L(1) = N,N'-propylene-di(3-methoxysalicylideneiminato); L(2) = N,N'-ethylene-di(3-methoxysalicylideneiminato); Ln = Gd(3+), Sm(3+), Tb(3+)), with the mononuclear [CuL(1)(2)] and the nickel dithiolene complexes [Ni(mnt)(2)](q)- (q = 1, 2; mnt = maleonitriledithiolate), as follows: (1)infinity[{CuL(1)}(2)Ln(O(2)NO){Ni(mnt)(2)}].Solv.CH(3)CN (Ln = Gd(3+), Solv = CH(3)OH (1), Ln = Sm(3+), Solv = CH(3)CN (2)) and [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)][Ni(mnt)(2)] (3) with [Ni(mnt)2]2-, [{(CH(3)CN)CuL(1)}(2)Ln(H(2)O)][Ni(mnt)(2)]3.2CH(3)CN (Ln = Gd(3+) (4), Sm(3+) (5), Tb(3+) (6)), and [{(CH(3)OH)CuL(2)}{CuL(2)}Gd(O(2)NO){Ni(mnt)(2)}][Ni(mnt)(2)].CH(2)Cl(2) (7) with [Ni(mnt))(2]*-. Trinuclear, almost linear, [CuLnCu] motifs are found in all the compounds. In the isostructural 1 and 2, two trans cyano groups from a [Ni(mnt)2]2- unit bridge two trimetallic nodes through axial coordination to the Cu centers, thus leading to the establishment of infinite chains. 3 is an ionic compound, containing discrete [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)](2+) cations and [Ni(mnt)(2)](2-) anions. Within the series 4-6, layers of discrete [CuLnCu](3+) motifs alternate with stacks of interacting [Ni(mnt)(2)](*-) radical anions, for which two overlap modes, providing two different types of stacks, can be disclosed. The strength of the intermolecular interactions between the open-shell species is estimated through extended Hückel calculations. In compound 7, [Ni(mnt)(2)](*-) radical anions coordinate group one of the Cu centers of a trinuclear [Cu(2)Gd] motif through a CN, while discrete [Ni(mnt)(2)](*-) units are also present, overlapping in between, but also with the coordinated ones. Furthermore, the [Cu(2)Gd] moieties dimerize each other upon linkage by two nitrato groups, both acting as chelate toward the gadolinium ion from one unit and monodentate toward a

Synthesis, characterization and antitumor activity of Ln(III) complexes with hydrazone Schiff base derived from 2-acetylpyridine and isonicotinohydrazone

PubMed Central

Xie, Jing; Shen, Shanshan; Chen, Ruhua; Xu, Jun; Dong, Kun; Huang, Jiancui; Lu, Qin; Zhu, Wenjiao; Ma, Tieliang; Jia, Lei; Cai, Hongxin; Zhu, Taofeng

2017-01-01

In the present study, two isostructural lanthanide (Ln)(III) complexes, namely Ln(HL)2(NO3)(CH3OH)2)·CH3OH, where Ln = La in complex 1 and Ce in complex 2, and hydrogen ligand (HL) = (E)-N'-[1-(2-pyridinyl)ethylidene]isonicotinohydrazone, have been isolated and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction analysis. The results revealed that the acylhydrazone ligand HL in each complex was deprotonated as an anionic ligand and coordinated to the central La(III) ion via enolization of oxygen and nitrogen atoms. Furthermore, the antitumor effects and potential mechanisms of the two complexes were explored in the human lung cancer cell line A549 and in the human gastric cancer cell lines BGC823 and SGC7901. In the present study, the roles the two complexes on the proliferation and apoptosis of the above tumor cell lines were determined by MTT assay and Annexin V/propidium iodide flow cytometry, respectively. Furthermore, various apoptosis-associated key genes, including caspase 3, B cell lymphoma (Bcl)-2-associated X protein (Bax) and Bcl-2, were detected by western blotting to explore the possible antitumor mechanisms of the two complexes. The results revealed that the two complexes had comparable antitumor activities in terms of inhibiting proliferation and inducing apoptosis in tumor cell lines. The changes in the protein expression levels of caspase 3, Bax and Bcl-2 further verified the apoptosis-promoting mechanisms of the two complexes in tumor cell lines. These findings have a great potential in biomedical applications of novel Ln(III) complexes. PMID:28599443

Chiroptical methods in a wide wavelength range for obtaining Ln3+ complexes with circularly polarized luminescence of practical interest.

PubMed

Górecki, Marcin; Carpita, Luca; Arrico, Lorenzo; Zinna, Francesco; Di Bari, Lorenzo

2018-05-29

We studied enantiopure chiral trivalent lanthanide (Ln3+ = La3+, Sm3+, Eu3+, Gd3+, Tm3+, and Yb3+) complexes with two fluorinated achiral tris(β-diketonate) ligands (HFA = hexafluoroacetylacetonate and TTA = 2-thenoyltrifluoroacetonate), incorporating a chiral bis(oxazolinyl)pyridine (PyBox) unit as a neutral ancillary ligand, by the combined use of optical and chiroptical methods, ranging from UV to IR both in absorption and circular dichroism (CD), and including circularly polarized luminescence (CPL). Ultimately, all the spectroscopic information is integrated into a total and a chiroptical super-spectrum, which allows one to characterize a multidimensional chemical space, spanned by the different Ln3+ ions, the acidity and steric demand of the diketone and the chirality of the PyBox ligand. In all cases, the Ln3+ ions endow the systems with peculiar chiroptical properties, either allied to f-f transitions or induced by the metal onto the ligand. In more detail, we found that Sm3+ complexes display interesting CPL features, which partly superimpose and partly integrate the more common Eu3+ properties. Especially, in the context of security tags, the pair Sm/Eu may be a winning choice for chiroptical barcoding.

Host composition dependent tunable multicolor emission in the single-phase Ba2(Ln(1-z)Tb(z))(BO3)2Cl:Eu phosphors.

PubMed

Xia, Zhiguo; Zhuang, Jiaqing; Meijerink, Andries; Jing, Xiping

2013-05-14

A new strategy based on the host composition design has been adopted to obtain efficient color-tunable emission from Ba2Ln(0.97-z)Tb(z)(BO3)2Cl:0.03Eu (Ln = Y, Gd and Lu, z = 0-0.97) phosphors. This study reveals that the single-phase Ba2Ln(1-z)Tb(z)(BO3)2Cl compounds can be applied to use allowed Eu(2+) absorption transitions to sensitize Eu(3+) emission via the energy transfer Eu(2+) → (Tb(3+))n → Eu(3+). The powder X-ray diffraction (XRD) and Rietveld refinement analysis shows single-phase Ba2Ln(1-z)Tb(z)(BO3)2Cl. As-prepared Ba2Ln(0.97-z)Tb(z)(BO3)2Cl:0.03Eu phosphors show intense green, yellow, orange and red emission under 377 nm near ultraviolet (n-UV) excitation due to a variation in the relative intensities of the Eu(2+), Tb(3+) and Eu(3+) emission depending on the Tb content (z) in the host composition, allowing color tuning. The variation in emission color is explained by energy transfer and has been investigated by photoluminescence and lifetime measurements and is further characterized by the Commission Internationale de l'éclairage (CIE) chromaticity indexes. The quantum efficiencies of the phosphors are high, up to 74%, and show good thermal stabilities up to 150 °C. This investigation demonstrates the possibility to sensitize Eu(3+) line emission by Eu(2+)via energy migration over Tb(3+) resulting in efficient color tunable phosphors which are promising for use in solid-state white light-emitting diodes (w-LEDs).

Reduced expression of α-L-Fucosidase-1 (FUCA-1) predicts recurrence and shorter cancer specific survival in luminal B LN+ breast cancer patients.

PubMed

Bonin, Serena; Parascandolo, Alessia; Aversa, Cinzia; Barbazza, Renzo; Tsuchida, Nobuo; Castellone, Maria Domenica; Stanta, Giorgio; Vecchio, Giancarlo

2018-03-16

The lysosomal enzyme α-L-Fucosidase-1 (FUCA-1) catalyzes the hydrolytic cleavage of terminal fucose residues. FUCA-1 gene is down-regulated in highly aggressive and metastatic human tumors as its inactivation perturbs the fucosylation of proteins involved in cell adhesion, migration and metastases. Negativity to FUCA-1 was significantly related to the development of later recurrences in breast cancer patients with lymph node involvement at diagnosis. Cancer specific survival of luminal B LN+ patients was influenced by FUCA-1 expression as luminal B LN+ patients with positive expression had a longer cancer specific survival. FUCA-1 mRNA expression was inversely related to cancer stage and lymph node involvement. WB and qPCR analysis of FUCA-1 expression in breast cancer-derived cell lines confirmed an inverse relationship with tumor aggressiveness. This study shows that, within LN+ breast cancer patients, FUCA-1 is able to identify a sub-set of non recurrent patients characterized by the positive expression of FUCA-1 and that, within luminal B LN+ patients, the expression of FUCA-1 predicts longer cancer specific survival. We have analyzed FUCA-1 in 305 breast cancer patients by Immunohistochemistry (IHC), and by qPCR in breast cancer patients and in breast cancer cell lines.

Synthesis, characterization and thermal decomposition of tetramethylammonium rare earth double selenates

NASA Astrophysics Data System (ADS)

Divekar, Sandesh K.; Achary, S. Nagabhusan; Ajgaonkar, Vishnu R.

2018-06-01

A series of double selenates, as (CH3)4NLn(SeO4)2rad 4H2O (Ln = Rare earth ion like La, Pr, Nd, Sm, Gd, Tb, Dy) was crystallized from mixed solution and characterized in detail for their structure, vibrational and optical properties as well as thermal stabilities. The crystal structure of the praseodymium compound was obtained by single crystal X-ray diffraction (XRD) and revealed a monoclinic (C2/c) lattice with chains formed by PrO8 and SeO4 units. The chains with compositions [Pr(SeO4)4(H2O)4]- are stacked in three dimensions and the (CH3)4N+ ions located in between them provide charge neutrality to the structure. The characterization of other compounds were carried out from powder XRD data and revealed that they all are isostructural to Pr-compound. All the functional groups were identified by Raman and IR spectroscopic studies. Solid state 77Se NMR revealed noticeable changes in selenium environment in these compounds. The optical absorption studies on the compounds show strong band edge absorptions in UV region. Thermal stabilities of the compounds, as investigated by simultaneous TG-DTA techniques indicate their sequential decompositions due to loss of H2O, (CH3)4N+ group, SeO2 and finally leaving their corresponding rare earth oxides.

A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

DOE PAGES

Schneemeyer, L. F.; Siegrist, T.; Besara, T.; ...

2015-04-06

The family of rare earth molybdenum bronzes, reduced ternary molybdates of composition LnMo 16O 44, was synthesized and a detailed structural study carried out. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with themore » unique isolated ReO 3-type Mo 8O 36 structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μ B moments on each Mo. We suggest that the Mo 8O 36 units behave like pseudoatoms with spin ½ derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. As a result, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal.« less

Femtomolar Ln(III) affinity in peptide-based ligands containing unnatural chelating amino acids.

PubMed

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

2012-05-07

The incorporation of unnatural chelating amino acids in short peptide sequences leads to lanthanide-binding peptides with a higher stability than sequences built exclusively from natural residues. In particular, the hexadentate peptide P(22), which incorporates two unnatural amino acids Ada(2) with aminodiacetate chelating arms, showed picomolar affinity for Tb(3+). To design peptides with higher denticity, expected to show higher affinity for Ln(3+), we synthesized the novel unnatural amino acid Ed3a(2) which carries an ethylenediamine triacetate side-chain and affords a pentadentate coordination site. The synthesis of the derivative Fmoc-Ed3a(2)(tBu)(3)-OH, with appropriate protecting groups for direct use in the solid phase peptide synthesis (Fmoc strategy), is described. The two high denticity peptides P(HD2) (Ac-Trp-Ed3a(2)-Pro-Gly-Ada(2)-Gly-NH(2)) and P(HD5) (Ac-Trp-Ada(2)-Pro-Gly-Ed3a(2)-Gly-NH(2)) led to octadentate Tb(3+) complexes with femtomolar stability in water. The position of the high denticity amino acid Ed3a(2) in the hexapeptide sequence appears to be critical for the control of the metal complex speciation. Whereas P(HD5) promotes the formation of polymetallic species in excess of Ln(3+), P(HD2) forms exclusively the mononuclear complex. The octadentate coordination of Tb(3+) by both P(HD) leads to total dehydration of the metal ion in the mononuclear complexes with long luminescence lifetimes (>2 ms). Hence, we demonstrated that unnatural amino acids carrying polyaminocarboxylate side-chains are interesting building blocks to design high affinity Ln-binding peptides. In particular the novel peptide P(HD2) forms a unique octadentate Tb(3+) complex with femtomolar stability in water and an improvement of the luminescence properties with respect to the trisaquo TbP(22) complex by a factor of 4.

Oxycarbonitride phosphors and light emitting devices using the same

DOEpatents

Li, Yuanqiang; Romanelli, Michael Dennis; Tian, Yongchi

2013-10-08

Disclosed herein is a novel family of oxycarbidonitride phosphor compositions and light emitting devices incorporating the same. Within the sextant system of M--Al--Si--O--N--C--Ln and quintuplet system of M--Si--O--N--C--Ln (M=alkaline earth element, Ln=rare earth element), the phosphors are composed of either one single crystalline phase or two crystalline phases with high chemical and thermal stability. In certain embodiments, the disclosed phosphor of silicon oxycarbidonitrides emits green light at wavelength between 530-550 nm. In further embodiments, the disclosed phosphor compositions emit blue-green to yellow light in a wavelength range of 450-650 nm under near-UV and blue light excitation.

Oxycarbonitride phosphors and light emitting devices using the same

DOEpatents

Li, Yuanqiang; Romanelli, Michael Dennis; Tian, Yongchi

2014-07-08

Disclosed herein is a novel family of oxycarbonitride phosphor compositions and light emitting devices incorporating the same. Within the sextant system of M--Al--Si--O--N--C--Ln and quintuplet system of M--Si--O--N--C--Ln (M=alkaline earth element, Ln=rare earth element), the phosphors are composed of either one single crystalline phase or two crystalline phases with high chemical and thermal stability. In certain embodiments, the disclosed phosphor of silicon oxycarbonitrides emits green light at wavelength between 530-550 nm. In further embodiments, the disclosed phosphor compositions emit blue-green to yellow light in a wavelength range of 450-650 nm under near-UV and blue light excitation.

Radioluminescence studies of colloidal oleate-capped β-Na(Gd,Lu)F4:Ln3+ nanoparticles (Ln = Ce, Eu, Tb).

PubMed

Cooper, Daniel R; Capobianco, John A; Seuntjens, Jan

2018-04-26

We report on the synthesis, characterization, and radioluminescence quantification of several new varieties of nanoparticles with the general composition β-NaLnF4, incorporating known luminescent activator/sensitizer pairs. Using Monte Carlo modeling to complement luminescence measurements, we have calculated the radioluminescence yields and intrinsic conversion efficiencies of colloidally-dispersed nanoparticles by comparison to an organic liquid scintillator. While five of the compositions had low to modest radioluminescence yields relative to bulk materials, colloidal β-Na(Lu0.65Gd0.2Tb0.15)F4 displayed a strong output of 39 460 photons per MeV absorbed, comparable to some of the best non-hygroscopic bulk crystal scintillators and X-ray phosphors such as Gd2O2S:Tb. Measurements of β-Na(Lu0.65Gd0.2Tb0.15)F4 powder samples revealed persistent luminescence as well as stable charge trapping, warranting further investigation.

Pseudoreticulocytosis in a patient with hemoglobin Köln due to autofluorescent erythrocytes enumerated as reticulocytes by the Cell-Dyn 4000.

PubMed

Sato, Shoko; Hirayama, Koichi; Koyama, Akio; Harano, Teruo; Nagasawa, Toshiro; Ninomiya, Haruhiko

2004-01-01

Pseudoreticulocytosis in a 25-year-old female patient with hemoglobin Köln is reported. The abnormal hemoglobin, hemoglobin Köln (beta chain, Val98-->Met), had previously been confirmed in the patient at the age of 21 years, as well as in her mother, by polymerase chain reaction-based direct sequence analysis of the beta globin gene. The patient underwent splenectomy at the age of 22 years. On her admission to our hospital for treatment of an immunoglobulin A nephropathy, an analysis by an automated hematology analyzer, the Abbott Cell-Dyn 4000 (CD4000), reported a marked reticulocytosis. Staining by the Brecher method with new methylene blue indicated a moderate reticulocytosis (5.7%) of a lesser extent than that indicated by the CD4000 (51.1%). The frequencies of red blood cells (RBC) with Pappenheimer bodies (13.8%), Heinz bodies (32.7%), and Howell-Jolly bodies (0.3%) were increased. The CD4000 detects RBC with RNA fluorescently stained with CD4K530 as reticulocytes. Autofluorescence of RBC with hemoglobin Köln, as we demonstrated by flow cytometry and fluorescent microscopy, was considered to have caused the pseudoreticulocytosis on the fully automated reticulocyte enumeration by the CD4000.

Design and synthesis of heterobimetallic Ru(II)-Ln(III) complexes as chemodosimetric ensembles for the detection of biogenic amine odorants.

PubMed

Chow, Cheuk-Fai; Lam, Michael H W; Wong, Wai-Yeung

2013-09-03

The detection of neutral biogenic amines plays a crucial role in food safety. Three new heterobimetallic Ru(II)-Ln(III) donor-acceptor complexes, KPrRu, KNdRu, and KSmRu, K{[Ru((II))((t)Bubpy)(CN)4]2-Ln((III))(H2O)4} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine), have been synthesized and characterized. Their photophysical and X-ray crystallographic data were reported in this study. These complexes were found to be selective for biogenic amine vapors, such as histamine, putrescine, and spermidine, with a detection limit down to the ppb level. The sensitivities of these complexes to the amines were recorded as ~log K = 3.6-5.0. Submicron rods of the complexes, with a nanoscale diameter and microscale length, were obtained through a simple precipitation process. Free-standing polymeric films with different degrees of porosity were fabricated by blending the submicron rods with polystyrene polymer. The polymer with the highest level of porosity exhibited the strongest luminescence enhancement after amine exposure. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Ln(III) blended polymer film.

A new series of lanthanide coordination polymers with 2,2‧-bipyridine and glutaric acid: Synthesis, crystal structures and properties of [Ln(bipy)(glut)(NO3)

NASA Astrophysics Data System (ADS)

Wang, Chunguang; Xing, Yongheng; Li, Zhangpeng; Li, Jing; Zeng, Xiaoqing; Ge, Maofa; Niu, Shuyun

2009-08-01

A series of new lanthanide coordination polymers, with the formula [Ln(bipy)(glut)(NO 3)] (Ln = Eu ( 1), Tb ( 2), Sm ( 3), Pr ( 4); bipy = 2,2'-bipyridine; H 2glut = glutaric acid), have been synthesized under the hydrothermal condition and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analyses reveal that all four complexes are isostructural and crystallized in monoclinic system, P2 1/ c space group. For these complexes, the Ln 3+ are all linked through glutaric acid ligands to form 1D chain-like polymeric structures, and bipy and NO3- are coordinated on two sides of the chains. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 are discussed in detail.

Physicochemical and photocatalytic studies of Ln3+- ZnO for water disinfection and wastewater treatment applications

NASA Astrophysics Data System (ADS)

Ibrahim, Marwa M.; Asal, Saad

2017-12-01

In the present work, x mol Ln3+ modified ZnO Nano-particles (Ln = Sm3+, Eu3+ and Gd3+ ions; x = 0.008, 0.015, 0.025, 0.03 and 0.05) were synthesized by precipitation method. These Nano-particles are characterized by different advanced techniques; such as X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive spectroscopic (EDX), UV-Visible diffuse reflectance, and fluorescence (FL) spectroscopy. Doping by lanthanides improves the crystal, surface area, porosity, morphology, as well as the optical adsorption and emission of UV light properties of the prepared photo-catalysts. Photo-catalytic activity for the prepared Nano-materials was determined using both, fluorescent probe and dye methods. Results showed that the highly active Nano-particle is 0.025 Gd3+-ZnO. The highly active sample (0.025 mol Gd3+- ZnO) successfully mineralized textile dye and real refractory wastewater samples under sunlight illumination using CPC photo-reactor. Prepared photo-catalysts were also applied for water disinfection.

Coordinating properties of uridine 5'-monophosphate with selected Ln(3+) ions in ionic micellar media.

PubMed

Sudhiranjan Singh, M; Homendra, Naorem; Lonibala, R K

2012-12-01

Coordinating properties of uridine 5'-monophosphate (UMP) towards trivalent La, Pr, Nd, Sm, Eu and Gd ions in presence of cationic and anionic micelles have been investigated by potentiometric pH-titration and spectroscopic methods. Stability constants of the 2:1 complexes have been determined and the change in free energy, enthalpy and entropy associated with the complexation are also calculated. Nd(III) complexes isolated from aqueous and aqueous-micellar media do not show any significant structural difference. Formation of Ln(III) complexes in all cases completes below pH 7.5 showing that UMP best interacts with Ln(3+) ions at the physiological pH range 7.3-7.5. The nucleobase is not involved in the complexation and the metal ion coordination of UMP is through the phosphate moiety only. Coordinating tendency of UMP with lanthanides, Nd(III) ion in particular, at different pH is also discussed. Luminescent properties of Eu(III) complex and its decay lifetime are also presented. This information may prove helpful regarding the use of lanthanides as biological probes for calcium/magnesium ions.

On the Constitutive Model of Nitrogen-Containing Austenitic Stainless Steel 316LN at Elevated Temperature

PubMed Central

Zhang, Lei; Feng, Xiao; Wang, Xin; Liu, Changyong

2014-01-01

The nitrogen-containing austenitic stainless steel 316LN has been chosen as the material for nuclear main-pipe, which is one of the key parts in 3rd generation nuclear power plants. In this research, a constitutive model of nitrogen-containing austenitic stainless steel is developed. The true stress-true strain curves obtained from isothermal hot compression tests over a wide range of temperatures (900–1250°C) and strain rates (10−3–10 s−1), were employed to study the dynamic deformational behavior of and recrystallization in 316LN steels. The constitutive model is developed through multiple linear regressions performed on the experimental data and based on an Arrhenius-type equation and Zener-Hollomon theory. The influence of strain was incorporated in the developed constitutive equation by considering the effect of strain on the various material constants. The reliability and accuracy of the model is verified through the comparison of predicted flow stress curves and experimental curves. Possible reasons for deviation are also discussed based on the characteristics of modeling process. PMID:25375345

Towards hybrid biocompatible magnetic rHuman serum albumin-based nanoparticles: use of ultra-small (CeLn)3/4+ cation-doped maghemite nanoparticles as functional shell

NASA Astrophysics Data System (ADS)

Israel, Liron L.; Kovalenko, Elena I.; Boyko, Anna A.; Sapozhnikov, Alexander M.; Rosenberger, Ina; Kreuter, Jörg; Passoni, Lorena; Lellouche, Jean-Paul

2015-01-01

Human serum albumin (HSA) is a protein found in human blood. Over the last decade, HSA has been evaluated as a promising drug carrier. However, not being magnetic, HSA cannot be used for biomedical applications such as magnetic resonance imaging (MRI) and magnetic drug targeting. Therefore, subsequent composites building on iron oxide nanoparticles that are already used clinically as MRI contrast agents are extensively studied. Recently and in this context, innovative fully hydrophilic ultra-small CAN-stabilized maghemite ((CeLn)3/4+-γ-Fe2O3) nanoparticles have been readily fabricated. The present study discusses the design, fabrication, and characterization of a dual phase hybrid core (rHSA)-shell ((CeLn)3/4+-γ-Fe2O3 NPs) nanosystem. Quite importantly and in contrast to widely used encapsulation strategies, rHSA NP surface-attached (CeLn)3/4+-γ-Fe2O3 NPs enabled to exploit both rHSA (protein functionalities) and (CeLn)3/4+-γ-Fe2O3 NP surface functionalities (COOH and ligand L coordinative exchange) in addition to very effective MRI contrast capability due to optimal accessibility of H2O molecules with the outer magnetic phase. Resulting hybrid nanoparticles might be used as a platform modular system for therapeutic (drug delivery system) and MR diagnostic purposes.

[Synthesis and study on the interaction of rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane with DNA].

PubMed

Lu, Xiao-Hong; Lin, Qiu-Yue; Hu, Rui-Ding; Liu, Wei-Dong; Feng, Jie

2007-06-01

Four rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane were synthesized and characterized by elemental analysis, conductivity measurement, thermal studies, IR and electronic spectra. The composition of the four complexes is [Ln(H2L)(NO3)2](NO3) x 3H2O (Ln=Sm, Eu, Gd, Tb). Results of spectral measurements indicate that the oxygen of carbonyl and the nitrogen of pyridyl coordinate with Ln(III) respectively, and the NO3- shows bidentate coordination. So the four complexes are 1 : 1 chelated complexes. The interaction between [Sm(H2L) (NO3)2](NO3) x 3H2O and DNA was studied by employing UV-Visible (UV-Vis) spectra, fluorescence spectra and SERS spectra. Experimental results show that with the incremental addition of DNA, the bands at 265 nm show hypochromism accompanied by a small red shift and the binding constant Kb Obtained is 1.24 x 10(5). Meanwhile fluorescence spectra show that the addition of [Sm(H2L) (NO3)2] (NO3) x 3H2O to DNA pretreated with EB causes an appreciable reduction in fluorescence intensity, indicating that the complex competes with ethidium bromide in binding to DNA, and free ethidium bromide increases. The addition of DNA causes the SERS signals of the complex to weaken and the band at 1 282 cm(-1) to disappear, which suggests that the planar pyridine molecule of the ligand may partly be inserted into the double-stranded helix plane in DNA, making pi electronic density of aromatic rings in complex change. The above phenomena indicate that [Sm(H2L) (NO3)] (NO3) x 3H2O interacts intensively with DNA.

Ln(3+)-doped nanoparticles for upconversion and magnetic resonance imaging: some critical notes on recent progress and some aspects to be considered.

PubMed

van Veggel, Frank C J M; Dong, Cunhai; Johnson, Noah J J; Pichaandi, Jothirmayanantham

2012-12-07

In this feature article we will critically discuss the synthesis and characterisation aspects of Ln(3+)-doped nanoparticles (NPs) that show upconversion, upon 980 nm excitation. Upconversion is a non-linear process that converts two or more low-energy photons, often near-infrared photons, into one of higher energy, e.g. blue and 800 nm from Tm(3+) and green and red from Er(3+) or Ho(3+). Nearly all researchers use the absorption of 980 nm light by Yb(3+) as the sensitiser for the co-doped emissive Ln(3+) ions. The focus will be on LnF(3) and MLnF(4) (M = alkali metal) as the host matrix, because most progress has been made with these. In particular we will argue that a detailed understanding of how the dopant ions and the host Ln(3+) ions are distributed (in the core) and how (doped) shell growth occurs is not well understood. Moreover, their use as optical and magnetic resonance imaging contrast agents will be discussed. We will argue that deep-tissue imaging beyond 600 μm with retention of optical resolution, i.e. to see fine structure such as blood capillaries in brain tissues, has not yet been achieved. Three key parameters have been identified as impediments: (i) the low absorption efficiency of the Yb(3+) sensitiser, (ii) the low quantum yield of upconversion, and (iii) the long-lived excited states. On the other hand, there are very encouraging results that suggest that these nanoparticles could be developed into very potent magnetic resonance imaging (MRI) contrast agents.

Ln3+-doped nanoparticles for upconversion and magnetic resonance imaging: some critical notes on recent progress and some aspects to be considered

NASA Astrophysics Data System (ADS)

van Veggel, Frank C. J. M.; Dong, Cunhai; Johnson, Noah J. J.; Pichaandi, Jothirmayanantham

2012-11-01

In this feature article we will critically discuss the synthesis and characterisation aspects of Ln3+-doped nanoparticles (NPs) that show upconversion, upon 980 nm excitation. Upconversion is a non-linear process that converts two or more low-energy photons, often near-infrared photons, into one of higher energy, e.g. blue and 800 nm from Tm3+ and green and red from Er3+ or Ho3+. Nearly all researchers use the absorption of 980 nm light by Yb3+ as the sensitiser for the co-doped emissive Ln3+ ions. The focus will be on LnF3 and MLnF4 (M = alkali metal) as the host matrix, because most progress has been made with these. In particular we will argue that a detailed understanding of how the dopant ions and the host Ln3+ ions are distributed (in the core) and how (doped) shell growth occurs is not well understood. Moreover, their use as optical and magnetic resonance imaging contrast agents will be discussed. We will argue that deep-tissue imaging beyond 600 μm with retention of optical resolution, i.e. to see fine structure such as blood capillaries in brain tissues, has not yet been achieved. Three key parameters have been identified as impediments: (i) the low absorption efficiency of the Yb3+ sensitiser, (ii) the low quantum yield of upconversion, and (iii) the long-lived excited states. On the other hand, there are very encouraging results that suggest that these nanoparticles could be developed into very potent magnetic resonance imaging (MRI) contrast agents.

Three novel lanthanide metal-organic frameworks (Ln-MOFs) constructed by unsymmetrical aromatic dicarboxylatic tectonics: synthesis, crystal structures and luminescent properties.

PubMed

Wu, Ya-Pan; Li, Dong-Sheng; Xia, Wei; Guo, Sha-Sha; Dong, Wen-Wen

2014-09-11

Three novel Ln(III)-based coordination polymers, {[Ln2 (2,4-bpda)3 (H2O)x]·yH2O}n (Ln = La (III) (1), x = 2, y = 0, Ce (III) (2), Pr (III) (3), x = 4, y = 1) (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid) have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7)-connected (42·5) (44·51·66·8) topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8)-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3), b = 14.500 (3), c = 18.800 (4) Å, β = 91.00 (3), V = 4033.9 (14) Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4), b = 12.9981 (4), c = 25.7567 (11) Å, β = 104.028 (4), V = 1374.16 (7) Å3 and Z = 4.

Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

NASA Astrophysics Data System (ADS)

Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

2015-01-01

For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

ONR (Office of Naval Research) Far East Scientific Bulletin. Volume 9, Number 1, January to March 1984.

DTIC Science & Technology

1984-03-01

science are Professor Toyomi Ohta, who holds the chair in Electronic Computation, and Professor Yoshiaki Koga, who holds the chair in Communication...and N. Imanaka, G. Adachi, and J. Shiokawa . reported on sodium sulfate doped with NaVO3 and/or Ln2 (SO4 )3 (Ln = rare earths). In aninteresting

TES/Aura L2 Ammonia (NH3) Lite Nadir V6 (TL2NH3LN)

Atmospheric Science Data Center

2017-07-20

TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Ammonia Order Data:  Earthdata Search:   Order Data ...

Method for synthesizing fine-grained phosphor powders of the type (RE.sub.1- Ln.sub.x)(P.sub.1-y V.sub.y)O.sub.4

DOEpatents

Phillips, Mark L. F.

1998-01-01

A method for generating well-crystallized photo- and cathodoluminescent oxide phosphor powders. The method of this invention uses hydrothermal synthesis and annealing to produce nearly monosized (RE.sub.1-x Ln.sub.x)(P.sub.1-y V.sub.y)O.sub.4 (Ln.dbd.Ce.fwdarw.Lu) phosphor grains with crystallite sizes from 0.04 to 5 .mu.m. Such phosphors find application in cathode-ray tube, flat-panel, and projection displays.

Origin of diastereoselectivity in the organolanthanide-mediated intramolecular hydroamination/cyclisation of aminodienes: a computational exploration of constrained geometry CGC-Ln catalysts.

PubMed

Tobisch, Sven

2007-01-01

The regulation of ring-substituent diastereoselectivity in the intramolecular hydroamination/cyclisation (IHC) of alpha-substituted aminodienes by constrained geometry CGC-lanthanide catalysts (CGC=[Me(2)Si(eta(5)-Me(4)C(5))(tBuN)](2-)) has been elucidated by means of a reliable DFT method. The first survey of relevant elementary steps for the 1-methyl-(4E,6)-heptadienylamine substrate (1) and the [{Me(2)Si(eta(5)-Me(4)C(5))(tBuN)}Sm{N(TMS)(2)}] starting material (2) identified the following general mechanistic aspects of Ln-catalysed aminodiene IHC. The substrate-adduct 3-S of the active CGC-Ln-amidodiene compound represents the catalyst's resting state, but the substrate-free form 3' with a chelating amidodiene functionality is the direct precursor for cyclisation. This step proceeds with almost complete regioselectivity through exocyclic ring closure by means of a frontal trajectory, giving rise to the CGC-Ln-azacycle intermediate 4. Subsequent protonolysis of 4 is turnover limiting, whilst the ring-substituent diastereoselectivity is dictated by exocyclic ring closure. Unfavourable close interatomic contacts between the substrate's alpha-substituent and the catalyst backbone have been shown to largely govern the trans/cis selectivity. Substituents of sufficient bulk in the alpha-position of the substrate have been identified as being vital for stereochemical induction. The present study has indicated that the diastereoselectivity of ring closure can be considerably modulated. The variation of the lanthanide's ionic radius and introduction of extra steric pressure at the substrate's alpha-position and/or the CGC N centre have been identified as effective handles for tuning the selectivity. The quantification of these factors reported herein represents the first step toward the rational design of improved CGC-Ln catalyst architectures and will thus aid this process.

Wheel-like Ln18 Cluster Organic Frameworks for Magnetic Refrigeration and Conversion of CO2.

PubMed

Song, Tian-Qun; Dong, Jie; Yang, An-Fei; Che, Xue-Jing; Gao, Hong-Ling; Cui, Jian-Zhong; Zhao, Bin

2018-03-19

Two isostructural 2D MOFs ([Ln 7 (CDA) 6 (HCOO) 3 (μ 3 -OH) 6 (H 2 O) 8 ] n , abbreviated as 1-Gd and 2-Dy) were successfully synthesized under solvothermal conditions. The self-assembly of lanthanide(III) nitrate and 1,1'-cyclopropane-dicarboxylic acid (H 2 CDA) resulted in wheel-like Ln 18 cluster second building units (SBU), which are further linked to six neighboring wheels to generate a 2D ordered honeycomb array. Both 1-Gd and 2-Dy exhibit high thermal stability and decompose above 330 °C. Moreover, they have good solvent stability in ten common solvents and pH stability with pH values from 1 to 13. Magnetic studies reveal that 1-Gd exhibits weak antiferromagnetic coupling between adjacent Gd 3+ ions and has a large magnetocaloric effect of 47.30 J kg -1 K -1 (Δ H = 7.0 T at 2 K), while 2-Dy shows ferromagnetic interaction between adjacent Dy 3+ ions. Interestingly, 1-Gd and 2-Dy can catalyze the cycloaddition of CO 2 to epoxides under mild conditions and can be reused at least five rounds with negligible loss of catalytic performance.

Synthesis and novel luminescence properties of one-dimension BaMoO{sub 4}:Ln{sup 3+} nanostructures

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

Wang, Yuping; Li, Mingxia; Pan, Kai

2015-12-15

Highlights: • String BaMoO{sub 4}:Ln{sup 3+} nanobeans were prepared by a hydrothermal method. • The Decay dynamics were performed to study the photoluminescence of the BaMoO{sub 4}:Eu{sup 3+} nanobeans. • For BaMoO{sub 4}:Er{sup 3+}/Eu{sup 3+}, the {sup 2}P{sub 3/2} → {sup 4}I{sub 11/2} and {sup 2}H{sub 11/2}/{sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} transitions were observed. - Abstract: String BaMoO{sub 4}:Ln{sup 3+} (Ln = Eu, Tb, Er, and Gd) nanobeans were prepared by a hydrothermal method. The samples were characterized by transmission electron microscope, scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscope, and Raman spectrometer. Under direct excitation in themore » charge transfer absorption band, concentration quenching phenomenon occurs and decay dynamics were performed to study the photoluminescence of the string BaMoO{sub 4}:Eu{sup 3+} nanobeans. In the emission spectra of BaMoO{sub 4}:Er{sup 3+}/Eu{sup 3+} under 274 nm excitation, the {sup 2}P{sub 3/2} → {sup 4}I{sub 11/2}, {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2}, and {sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} transitions from Er{sup 3+} ions were observed for the first time. In addition, the photoluminescence properties of BaMoO{sub 4}:Tb{sup 3+}/Eu{sup 3+} and BaMoO{sub 4}:Gd{sup 3+}/Eu{sup 3+} were also investigated.« less

LN2-free Operation of the MEG Liquid Xenon Calorimeter by using a High-power Pulse Tube Cryocooler

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

Haruyama, T.; Kasami, K.; Nishiguchi, H.

2006-04-27

A high-power coaxial pulse tube cryocooler, originally developed in KEK and technology-transferred to Iwatani Industrial Gases Corp (IIGC), has been installed in a large liquid xenon calorimeter to evaluate liquid nitrogen-free (LN2-free) operation of the rare {mu}-particle decay experiment (MEG). Features of this pulse tube cryocooler include the cold-end heat exchanger, designed with sufficient surface area to ensure high-power cooling, and a cylindrical regenerator placed inside the pulse tube giving compact design and ease of fabrication. This production-level cryocooler provides a cooling power of {approx}200 W at 165 K, using a 6 kW Gifford-McMahon (GM)-type compressor. The paper describes themore » detailed configuration of the cryocooler, and the results of the continuous LN2-free operation of the large prototype liquid xenon calorimeter, which ran for more than 40 days without problems.« less

Host-sensitized luminescence properties in CaNb2O6:Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) phosphors with abundant colors.

PubMed

Li, Kai; Liu, Xiaoming; Zhang, Yang; Li, Xuejiao; Lian, Hongzhou; Lin, Jun

2015-01-05

A series of Ln(3+) (Ln(3+) = Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+)) ion doped CaNb2O6 (CNO) phosphors have been prepared via the conventional high-temperature solid-state reaction route. The X-ray diffraction (XRD) and structure refinement, diffuse reflection, photoluminescence (PL), and fluorescent decay curves were used to characterize the as-prepared samples. Under UV radiation, the CNO host present a broad emission band from about 355 to 605 nm centered around 460 nm originating from the NbO6 octahedral groups, which has spectral overlaps with the excitation of f-f transitions of Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) samples. They show both host emission and respective emission lines derived from the characteristic f-f transitions of activators, which present different emission colors owing to the energy transfer from the NbO6 group in the host to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) with increasing activator concentrations. The decreases of decay lifetimes of host emissions in CNO:Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+) demonstrate the energy transfer from the hosts to Eu(3+)/Tb(3+)/Dy(3+)/Sm(3+). The energy transfer mechanisms in CNO:Eu(3+)/Tb(3+)/Dy(3+) phosphors have been determined to be a resonant type via dipole-dipole mechanisms. For CNO:Sm(3+), the metal-metal charge transfer transition (MMCT) might contribute to the different variations of decay lifetimes and emission intensity from CNO:Eu(3+)/Tb(3+)/Dy(3+) samples. The best quantum efficiency is 71.2% for CNO:0.01/0.02Dy(3+). The PL properties of as-prepared materials indicate the promising application in UV-pumped white-emitting lighting diodes field.

Low Cycle Fatigue Behavior of 316LN Stainless Steel Alloyed with Varying Nitrogen Content. Part II: Fatigue Life and Fracture Behavior

NASA Astrophysics Data System (ADS)

Prasad Reddy, G. V.; Sandhya, R.; Sankaran, S.; Mathew, M. D.

2014-10-01

Influence of nitrogen content on low cycle fatigue life and fracture behavior of 316LN stainless steel (SS) alloyed with 0.07 to 0.22 wt pct nitrogen is presented in this paper over a range of total strain amplitudes ( ±0.25 to 1.0 pct) in the temperature range from 773 K to 873 K (500 °C to 600 °C). The combined effect of nitrogen and strain amplitude on fatigue life is observed to be complex i.e., fatigue life either decreases/increases with increase in nitrogen content or saturates/peaks at 0.14 wt pct N depending on strain amplitude and temperature. Coffin-Manson plots (CMPs) revealed both single-slope and dual-slope strain-life curves depending on the test temperature and nitrogen content. 316LN SS containing 0.07 and 0.22 wt pct N showed nearly single-slope CMP at all test temperatures, while 316LN SS with 0.11 and 0.14 wt pct N exhibited marked dual-slope behavior at 773 K (500 °C) that changes to single-slope behavior at 873 K (600 °C). The changes in slope of CMP are found to be in good correlation with deformation substructural changes.

A Highly Efficient UV-Vis-NIR Active Ln(3+)-Doped BiPO4/BiVO4 Nanocomposite for Photocatalysis Application.

PubMed

Ganguli, Sagar; Hazra, Chanchal; Chatti, Manjunath; Samanta, Tuhin; Mahalingam, Venkataramanan

2016-01-12

In this Article, we report the synthesis of Ln(3+) (Yb(3+), Tm(3+))-doped BiPO4/BiVO4 nanocomposite photocatalyst that shows efficient photocatalytic activity under UV-visible-near-infrared (UV-vis-NIR) illumination. Incorporation of upconverting Ln(3+) ion pairs in BiPO4 nanocrystals resulted in strong emission in the visible region upon excitation with a NIR laser (980 nm). A composite of BiPO4 nanocrystals and vanadate was prepared by the addition of vanadate source to BiPO4 nanocrystals. In the nanocomposite, the strong blue emission from Tm(3+) ions via upconversion is nonradiatively transferred to BiVO4, resulting in the production of excitons. This in turn generates reactive oxygen species and efficiently degrades methylene blue dye in aqueous medium. The nanocomposite also shows high photocatalytic activity both under the visible region (0.010 min(-1)) and under the full solar spectrum (0.047 min(-1)). The results suggest that the photocatalytic activity of the nanocomposite under both NIR as well as full solar irradiation is better compared to other reported nanocomposite photocatalysts. The choice of BiPO4 as the matrix for Ln(3+) ions has been discussed in detail, as it plays an important role in the superior NIR photocatalytic activity of the nanocomposite photocatalyst.

Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

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

Jeong, Jihoon; Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712; Azad, Abul K.

2015-03-15

The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttriamore » stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti

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

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites ofmore » the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major

Strategy for earth explorers in global earth sciences

NASA Technical Reports Server (NTRS)

1988-01-01

The goal of the current NASA Earth System Science initiative is to obtain a comprehensive scientific understanding of the Earth as an integrated, dynamic system. The centerpiece of the Earth System Science initiative will be a set of instruments carried on polar orbiting platforms under the Earth Observing System program. An Earth Explorer program can open new vistas in the earth sciences, encourage innovation, and solve critical scientific problems. Specific missions must be rigorously shaped by the demands and opportunities of high quality science and must complement the Earth Observing System and the Mission to Planet Earth. The committee believes that the proposed Earth Explorer program provides a substantial opportunity for progress in the earth sciences, both through independent missions and through missions designed to complement the large scale platforms and international research programs that represent important national commitments. The strategy presented is intended to help ensure the success of the Earth Explorer program as a vital stimulant to the study of the planet.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

PubMed

Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

2016-12-05

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni II -Ln III -W V trimetallics, [(CN) 7 W(CN)Ni(H 2 O)(valpn)Ln(H 2 O) 4 ]·H 2 O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic Dy III and Tb III metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [W V Ni II Ln III ] core structure, [(CN) 7 W(CN)Ni(dmf)(valdmpn)Ln(dmf) 4 ]·H 2 O (Ln = Gd III 7, Tb III 8a, Dy III 9, Ho III 10), [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Tb(dmf) 2.5 (H 2 O) 1.5 ]·H 2 O·0.5dmf 8b, and [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Er(dmf) 3 (H 2 O) 1 ]·H 2 O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel

Modeling correlated motion in thermoelectric skutterudite materials

NASA Astrophysics Data System (ADS)

Keiber, Trevor; Bridges, Frank; Bridges Lab Team

2014-03-01

Filled skutterudite compounds, LnT4X12 (Ln=rare earth; T=Fe,Ru,Os; X=P,As,Sb), have previously been modeled using a rigid cage approximation for the ``rattling'' rare earth atom. The large thermal broadening with temperature of the rattler can be fit using an Einstein model. Recent measurements of the second neighbor Ln-T peaks show an unusually large thermal broadening suggesting motion of the cage of atoms. To incorporate these results we developed three and four mass spring models to give the acoustic and optical phonon mode spectra. For the simplest three mass model we identify the low energy optical mode as the rattling mode. This rattling mode is likely coupled to the acoustic mode, and responsible for the low thermal conductivity of the skutterudite compound. We extend this model to four atoms to describe the CuO4 rings in oxy-skutterudites and the X4 rings in LnT4X12. This talk provides a model for the experimental results of the previous presentation. Support: NSF DMR1005568.

Thermal properties of rare earth cobalt oxides and of La1- x Gd x CoO3 solid solutions

NASA Astrophysics Data System (ADS)

Orlov, Yu. S.; Dudnikov, V. A.; Gorev, M. V.; Vereshchagin, S. N.; Solov'ev, L. A.; Ovchinnikov, S. G.

2016-05-01

Powder X-ray diffraction data for the crystal structure, phase composition, and molar specific heat for La1‒ x Gd x CoO3 cobaltites in the temperature range of 300-1000 K have been analyzed. The behavior of the volume thermal expansion coefficient in cobaltites with isovalent doping in the temperature range of 100-1000 K is studied. It is found that the β( T) curve exhibits two peaks at some doping levels. The rate of the change in the occupation number for the high-spin state of cobalt ions is calculated for the compounds under study taking into account the spin-orbit interaction. With the Birch-Murnaghan equation of state, it is demonstrated that the low-temperature peak in the thermal expansion shifts with the growth of the pressure toward higher temperatures and at pressure P ˜ 7 GPa coincides with the second peak. The similarity in the behavior of the thermal expansion coefficient in the La1- x Gd x CoO3 compounds with the isovalent substitution and the undoped LnCoO3 compound (Ln is a lanthanide) is considered. For the whole series of rare earth cobalt oxides, the nature of two specific features in the temperature dependence of the specific heat and thermal expansion is revealed and their relation to the occupation number for the high-spin state of cobalt ions and to the insulator-metal transition is established.

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.

Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu)

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

Gurusinghe, Nicola N.M.; Figuera, Juand de la; Marco, José F.

2013-09-01

Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A{sub 2}B{sub 2}O{sub 7} of composition Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu) have been prepared. La{sub 2}SrFe{sub 2}O{sub 7} and La{sub 2}BaFe{sub 2}O{sub 7} crystallise in the tetragonal space group I4/mmm. The structures of Eu{sub 2}SrFe{sub 2}O{sub 7} and Nd{sub 2}SrFe{sub 2}O{sub 7} are best described in space group P4{sub 2}/mnm. Substitution on the A site with smaller lanthanide- andmore » larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La{sub 2}BaFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of {sup 57}Fe Mössbauer spectra recorded from La{sub 2}SrFe{sub 2}O{sub 7} between 290 and 600 K indicate a magnetic ordering temperature of T{sub N} ≥ 535 K.« less

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-.

Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Zeynalova, Shadana Sh; Ananyev, Ivan V; Churakov, Andrei V

2017-10-01

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (1), and of the lutetium, [Lu(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (2), and yttrium, [Y(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl 3 (H 2 O) 6 (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands all display a κ 1 O-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 2 Cl(CH 3 OH) 4 ] molecular unit exhibits two intramolecular O-H...O hydrogen bonds, forming six-membered rings, and two intramolecular O-H...Cl interactions, forming four-membered rings. Intermolecular O-H...O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]tetrakis(methanol-κO)(nitrato-κ 2 O,O')neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)(NO 3 )(CH 4 O) 4 ]·2CH 3 OH, (4), have been obtained in an analogous manner from NdCl 3 (H 2 O) 6 . Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)-(3). The κ 2 O,O'-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN Nd = 8). Unlike (1)-(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the

Elasticity of ferropericlase and seismic heterogeneity in the Earth's lower mantle: Ferropericlase High Pressure-Temperature Elasticity

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

Yang, Jing; Lin, Jung-Fu; Jacobsen, Steven D.

2016-12-16

Deciphering the origin of seismic heterogeneity has been one of the major challenges in understanding the geochemistry and geodynamics of the deep mantle. Fully anisotropic elastic properties of constituent minerals at relevant pressure-temperature conditions of the lower mantle can be used to calculate seismic heterogeneity parameters in order to better understand chemically and thermally induced seismic heterogeneities. In this study, the single-crystal elastic properties of ferropericlase (Mg0.94Fe0.06)O were measured using Brillouin spectroscopy and X-ray diffraction at conditions up to 50 GPa and 900 K. The velocity-density results were modeled using third-order finite-strain theory and thermoelastic equations along a representative geothermmore » to investigate high pressure-temperature and compositional effects on the seismic heterogeneity parameters. Our results demonstrate that from 660 to 2000 km, compressional wave anisotropy of ferropericlase increased from 4% to 9.7%, while shear wave anisotropy increased from 9% to as high as 22.5%. The thermally induced lateral heterogeneity ratio (RS/P = ∂lnVS/∂lnVP) of ferropericlase was calculated to be 1.48 at ambient pressure but decreased to 1.43 at 40 GPa along a representative geotherm. The RS/P of a simplified pyrolite model consisting of 80% bridgmanite and 20% ferropericlase was approximately 1.5, consistent with seismic models at depths from 670 to 1500 km, but showed an increased mismatch at lower mantle depths below ~1500 km. This discrepancy below mid-lower mantle could be due to either a contribution from chemically induced heterogeneity or the effects of the Fe spin transition in the deeper parts of the Earth's lower mantle.« less

Earth: Earth Science and Health

NASA Technical Reports Server (NTRS)

Maynard, Nancy G.

2001-01-01

A major new NASA initiative on environmental change and health has been established to promote the application of Earth science remote sensing data, information, observations, and technologies to issues of human health. NASA's Earth Sciences suite of Earth observing instruments are now providing improved observations science, data, and advanced technologies about the Earth's land, atmosphere, and oceans. These new space-based resources are being combined with other agency and university resources, data integration and fusion technologies, geographic information systems (GIS), and the spectrum of tools available from the public health community, making it possible to better understand how the environment and climate are linked to specific diseases, to improve outbreak prediction, and to minimize disease risk. This presentation is an overview of NASA's tools, capabilities, and research advances in this initiative.

Fatigue properties of type 316LN stainless steel in air and mercury

NASA Astrophysics Data System (ADS)

Strizak, J. P.; Tian, H.; Liaw, P. K.; Mansur, L. K.

2005-08-01

An extensive fatigue testing program on 316LN stainless steel was recently carried out to support the design of the mercury target container for the spallation neutron source (SNS) that is currently under construction at the Oak Ridge National Laboratory in the United States. The major objective was to determine the effects of mercury on fatigue behavior. The S- N fatigue behavior of 316LN stainless steel is characterized by a family of bilinear fatigue curves which are dependent on frequency, environment, mean stress and cold work. Generally, fatigue life increases with decreasing stress and levels off in the high cycle region to an endurance limit below which the material will not fail. For fully reversed loading as well as tensile mean stress loading conditions mercury had no effect on endurance limit. However, at higher stresses a synergistic relationship between mercury and cyclic loading frequency was observed at low frequencies. As expected, fatigue life decreased with decreasing frequency, but the response was more pronounced in mercury compared with air. As a result of liquid metal embrittlement (LME), fracture surfaces of specimens tested in mercury showed widespread brittle intergranular cracking as opposed to typical transgranular cracking for specimens tested in air. For fully reversed loading (zero mean stress) the effect of mercury disappeared as frequency increased to 10 Hz. For mean stress conditions with R-ratios of 0.1 and 0.3, LME was still evident at 10 Hz, but at 700 Hz the effect of mercury had disappeared ( R = 0.1). Further, for higher R-ratios (0.5 and 0.75) fatigue curves for 10 Hz showed no environmental effect. Finally, cold working (20%) increased tensile strength and hardness, and improved fatigue resistance. Fatigue behavior at 10 and 700 Hz was similar and no environmental effect was observed.

Study on the dynamic recrystallization model and mechanism of nuclear grade 316LN austenitic stainless steel

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

Wang, Shenglong; Zhang, Mingxian; Wu, Huanchun

In this study, the dynamic recrystallization behaviors of a nuclear grade 316LN austenitic stainless steel were researched through hot compression experiment performed on a Gleeble-1500 simulator at temperatures of 900–1250 °C and strain rates of 0.01–1 s{sup −1}. By multiple linear regressions of the flow stress-strain data, the dynamic recrystallization mathematical models of this steel as functions of strain rate, strain and temperature were developed. Then these models were verified in a real experiment. Furthermore, the dynamic recrystallization mechanism of the steel was determined. The results indicated that the subgrains in this steel are formed through dislocations polygonization and thenmore » grow up through subgrain boundaries migration towards high density dislocation areas and subgrain coalescence mechanism. Dynamic recrystallization nucleation performs in grain boundary bulging mechanism and subgrain growth mechanism. The nuclei grow up through high angle grain boundaries migration. - Highlights: •Establish the DRX mathematical models of nuclear grade 316LN stainless steel •Determine the DRX mechanism of this steel •Subgrains are formed through dislocations polygonization. •Subgrains grow up through subgrain boundaries migration and coalescence mechanism. •DRX nucleation performs in grain boundary bulging mechanism and subgrain growth mechanism.« less

An Earth-sized planet with an Earth-like density.

PubMed

Pepe, Francesco; Cameron, Andrew Collier; Latham, David W; Molinari, Emilio; Udry, Stéphane; Bonomo, Aldo S; Buchhave, Lars A; Charbonneau, David; Cosentino, Rosario; Dressing, Courtney D; Dumusque, Xavier; Figueira, Pedro; Fiorenzano, Aldo F M; Gettel, Sara; Harutyunyan, Avet; Haywood, Raphaëlle D; Horne, Keith; Lopez-Morales, Mercedes; Lovis, Christophe; Malavolta, Luca; Mayor, Michel; Micela, Giusi; Motalebi, Fatemeh; Nascimbeni, Valerio; Phillips, David; Piotto, Giampaolo; Pollacco, Don; Queloz, Didier; Rice, Ken; Sasselov, Dimitar; Ségransan, Damien; Sozzetti, Alessandro; Szentgyorgyi, Andrew; Watson, Christopher A

2013-11-21

Recent analyses of data from the NASA Kepler spacecraft have established that planets with radii within 25 per cent of the Earth's (R Earth symbol) are commonplace throughout the Galaxy, orbiting at least 16.5 per cent of Sun-like stars. Because these studies were sensitive to the sizes of the planets but not their masses, the question remains whether these Earth-sized planets are indeed similar to the Earth in bulk composition. The smallest planets for which masses have been accurately determined are Kepler-10b (1.42 R Earth symbol) and Kepler-36b (1.49 R Earth symbol), which are both significantly larger than the Earth. Recently, the planet Kepler-78b was discovered and found to have a radius of only 1.16 R Earth symbol. Here we report that the mass of this planet is 1.86 Earth masses. The resulting mean density of the planet is 5.57 g cm(-3), which is similar to that of the Earth and implies a composition of iron and rock.

Synthesis of the new quaternary sulfides K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11] and BaLnAgS[sub 3] (Ln = Er, Y, Gd) and the structures of K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11] and BaErAgS[sub 3

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

Wu, Ping; Ibers, J.A.

1994-05-01

Several new quarternary sulfides, K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11] and BaLnAgS[sub 3] (Ln = Er, Y, Gd), have been synthesized by the reaction of the constituent binary chalcogenides and elements at 1000[degrees]C. The crystal structures of K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11] and BaErAgS[sub 3] have been determined by single-crystal X-ray diffraction techniques. Crystal data: K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11]-space group D[sup 8][sub 4h] - P4/ncc, M = 1023.88, Z = 4, a = 8.587(1), c = 27.892(4) [angstrom] (T = 115 K), V = 2056.7(4) [angstrom][sup 3], R[sub W](F[sup 2]) = 0.093 for 1965 observations having F[sup 2][sub 0] >more » 2[sigma](F[sup 2][sub 0]); BaEr AgS[sub 3]-space group C[sup 3][sub 2H] - C2/m, M = 508.65, Z = 4, a = 17.340(4), b = 4.014(1), x = 8.509(2) [angstrom], [beta] = 103.23(3)[degrees], (T = 115 K), V = 576.5(2) [angstrom][sup 3], R[sub W](F[sup 2]) = 0.049 for 1404 observations and 48 variables, R(F) = 0.018 for 1299 observations having F[sup 2][sub 0] > 2[sigma](F[sup 2][sub 0]). In both structures, the rare-earth atoms have octahedral coordination and the octahedra form slabs through edge- and corner-sharing. These slabs are separated by K[sup +] Ba[sup 2+] cations, and are crosslinked into three-dimensional frameworks by Sn[sub 2]S[sub 6] units as edge-sharing SnS[sub 4] tetrahedral pairs in K[sub 2]Y[sub 4]Sn[sub 2]S[sub 11], and by Ag[sub 2]S[sub 9] units as corner-sharing trigonal-bipyramidal AgS[sub 5] pairs in BaEr AgS[sub 3]. From their powder diffraction patterns, BaYAgS[sub 3] and Ba GdAgS[sub 3] appear to be isostructural with BaErAgS[sub 3].« less

In situ hydrothermal syntheses, structures and photoluminescent properties of four novel metal-organic frameworks constructed by lanthanide (Ln=Ce(III), Pr(III), Eu(III)) and Cu(I) metals with flexible dicarboxylate acids and piperazine-based ligands

NASA Astrophysics Data System (ADS)

Ay, Burak; Karaca, Serkan; Yildiz, Emel; Lopez, Valerie; Nanao, Max H.; Zubieta, Jon

2016-01-01

Four novel metal-organic frameworks,[Cu2Cl2(pyrz)]n (1) and (H2pip)n[Ln2(pydc)4(H2O)2]n (Ln=Ce (2), Pr (3) and Eu (4), H2pzdc=2,3-pyrazinedicarboxylic acid, pyrz=pyrazine, H2pydc=2,6-pyridinedicarboxylic acid, H2pip=piperazine) have been synthesized under hydrothermal conditions and characterized by the elemental analysis, ICP, Far IR (FIR), FT-IR spectra, TGA, single crystal X-ray diffraction analysis and powder X-ray diffraction (PXRD). Compound 1 is two-dimensional containing Cl-Cu-Cl sites, while the lanthanide complexes contain one-dimensional infinite Ln-O-Ln chains. All the complexes show high thermal stability. The complexes 1-3 exhibit luminescence emission bands at 584, 598 and 614 nm at room temperature when excited at 300 nm. Complex 4 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.

Crystal Field in Rare-Earth Complexes: From Electrostatics to Bonding.

PubMed

Alessandri, Riccardo; Zulfikri, Habiburrahman; Autschbach, Jochen; Bolvin, Hélène

2018-04-11

The flexibility of first-principles (ab initio) calculations with the SO-CASSCF (complete active space self-consistent field theory with a treatment of the spin-orbit (SO) coupling by state interaction) method is used to quantify the electrostatic and covalent contributions to crystal field parameters. Two types of systems are chosen for illustration: 1) The ionic and experimentally well-characterized PrCl 3 crystal; this study permits a revisitation of the partition of contributions proposed in the early days of crystal field theory; and 2) a series of sandwich molecules [Ln(η n -C n H n ) 2 ] q , with Ln=Dy, Ho, Er, and Tm and n=5, 6, and 8, in which the interaction between Ln III and the aromatic ligands is more difficult to describe within an electrostatic approach. It is shown that a model with three layers of charges reproduces the electrostatic field generated by the ligands and that the covalency plays a qualitative role. The one-electron character of crystal field theory is discussed and shown to be valuable, although it is not completely quantitative. This permits a reduction of the many-electron problem to a discussion of the energy of the seven 4f orbitals. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for synthesizing fine-grained phosphor powders of the type (RE{sub 1{minus}x}Ln{sub x})(P{sub 1{minus}y}V{sub y})O{sub 4}

DOEpatents

Phillips, M.L.F.

1998-04-28

A method for generating well-crystallized photo- and cathodoluminescent oxide phosphor powders is disclosed. The method of this invention uses hydrothermal synthesis and annealing to produce nearly monosized (RE{sub 1{minus}x}Ln{sub x})(P{sub 1{minus}y}V{sub y}O{sub 4}) (Ln{double_bond}Ce{yields}Lu) phosphor grains with crystallite sizes from 0.04 to 5 {micro}m. Such phosphors find application in cathode-ray tube, flat-panel, and projection displays. 4 figs.

Pentanuclear heterometallic {Mn(III)(2)Ln(3)} (Ln = Gd, Dy, Tb, Ho) assemblies in an open-book type structural topology: appearance of slow relaxation of magnetization in the Dy(III) and Ho(III) analogues.

PubMed

Bag, Prasenjit; Chakraborty, Amit; Rogez, Guillaume; Chandrasekhar, Vadapalli

2014-07-07

The reaction of Ln(III) nitrate and Mn(ClO4)2·6H2O salts in the presence of a multidentate sterically unencumbered ligand, (E)-2,2'-(2-hydroxy-3-((2-hydroxyphenylimino)methyl)-5-methylbenzylazanediyl)diethanol (LH4) leads to the isolation of four isostructural pentanuclear hetereometallic complexes [Mn(III)2Gd3(LH)4(NO3)(HOCH3)]ClO4·NO3 (1), [Mn(III)2Dy3(LH)4(NO3)(HOCH3)]ClO4·NO3 (2), [Mn(III)2Tb3(LH)4(NO3)(HOCH3)]ClO4·NO3 (3), and [Mn(III)2Ho3(LH)4(NO3)(HOCH3)]ClO4·NO3 (4) with an open-book type structural topology. 1-4 are dicationic and crystallize in the achiral space group, P21/n. A total of four triply deprotonated ligands, [LH](3-), are involved in holding the pentameric metal framework, {Mn(III)2Ln3}. In these complexes both the lanthanide and the manganese(III) ions are doubly bridged, involving phenolate or ethoxide oxygen atoms. The magnetochemical analysis reveals the presence of global antiferromagnetic interactions among the spin centers at low temperatures in all the four compounds. AC susceptibility measurements show the presence of temperature dependent out-of-phase ac signal for compounds 2 and 4 indicating an SMM behavior.

Scaling of Ln(Permeability) in Sediments and Velocity Distributions in Turbulence: The Possibility of an Analogy.

NASA Astrophysics Data System (ADS)

Molz, F. J.; Kozubowski, T. J.; Miller, R. S.; Podgorski, K.

2005-12-01

The theory of non-stationary stochastic processes with stationary increments gives rise to stochastic fractals. When such fractals are used to represent measurements of (assumed stationary) physical properties, such as ln(k) increments in sediments or velocity increments "delta(v)" in turbulent flows, the resulting measurements exhibit scaling, either spatial, temporal or both. (In the present context, such scaling refers to systematic changes in the statistical properties of the increment distributions, such as variance, with the lag size over which the increments are determined.) Depending on the class of probability density functions (PDFs) that describe the increment distributions, the resulting stochastic fractals will display different properties. Until recently, the stationary increment process was represented using mainly Gaussian, Gamma or Levy PDFs. However, measurements in both sediments and fluid turbulence indicate that these PDFs are not commonly observed. Based on recent data and previous studies referenced and discussed in Meerschaert et al. (2004) and Molz et al. (2005), the measured increment PDFs display an approximate double exponential (Laplace) shape at smaller lags, and this shape evolves towards Gaussian at larger lags. A model for this behavior based on the Generalized Laplace PDF family called fractional Laplace motion, in analogy with its Gaussian counterpart - fractional Brownian motion, has been suggested (Meerschaert et al., 2004) and the necessary mathematics elaborated (Kozubowski et al., 2005). The resulting stochastic fractal is not a typical self-affine monofractal, but it does exhibit monofractal-like scaling in certain lag size ranges. To date, it has been shown that the Generalized Laplace family fits ln(k) increment distributions and reproduces the original 1941 theory of Kolmogorov when applied to Eulerian turbulent velocity increments. However, to make a physically self-consistent application to turbulence, one must adopt a

Evaluation of DC electric field distribution of PPLP specimen based on the measurement of electrical conductivity in LN2

NASA Astrophysics Data System (ADS)

Hwang, Jae-Sang; Seong, Jae-Kyu; Shin, Woo-Ju; Lee, Jong-Geon; Cho, Jeon-Wook; Ryoo, Hee-Suk; Lee, Bang-Wook

2013-11-01

High temperature superconducting (HTS) cable has been paid much attention due to its high efficiency and high current transportation capability, and it is also regarded as eco-friendly power cable for the next generation. Especially for DC HTS cable, it has more sustainable and stable properties compared to AC HTS cable due to the absence of AC loss in DC HTS cable. Recently, DC HTS cable has been investigated competitively all over the world, and one of the key components of DC HTS cable to be developed is a cable joint box considering HVDC environment. In order to achieve the optimum insulation design of the joint box, analysis of DC electric field distribution of the joint box is a fundamental process to develop DC HTS cable. Generally, AC electric field distribution depends on relative permittivity of dielectric materials but in case of DC, electrical conductivity of dielectric material is a dominant factor which determines electric field distribution. In this study, in order to evaluate DC electric field characteristics of the joint box for DC HTS cable, polypropylene laminated paper (PPLP) specimen has been prepared and its DC electric field distribution was analyzed based on the measurement of electrical conductivity of PPLP in liquid nitrogen (LN2). Electrical conductivity of PPLP in LN2 has not been reported yet but it should be measured for DC electric field analysis. The experimental works for measuring electrical conductivity of PPLP in LN2 were presented in this paper. Based on the experimental works, DC electric field distribution of PPLP specimen was fully analyzed considering the steady state and the transient state of DC. Consequently, it was possible to determine the electric field distribution characteristics considering different DC applying stages including DC switching on, DC switching off and polarity reversal conditions.

Discover Earth

NASA Technical Reports Server (NTRS)

Steele, Colleen

1998-01-01

Discover Earth is a NASA-sponsored project for teachers of grades 5-12, designed to: (1) enhance understanding of the Earth as an integrated system; (2) enhance the interdisciplinary approach to science instruction; and (3) provide classroom materials that focus on those goals. Discover Earth is conducted by the Institute for Global Environmental Strategies in collaboration with Dr. Eric Barron, Director, Earth System Science Center, The Pennsylvania State University; and Dr. Robert Hudson, Chair, the Department of Meteorology, University of Maryland at College Park. The enclosed materials: (1) represent only part of the Discover Earth materials; (2) were developed by classroom teachers who are participating in the Discover Earth project; (3) utilize an investigative approach and on-line data; and (4) can be effectively adjusted to classrooms with greater/without technology access. The Discover Earth classroom materials focus on the Earth system and key issues of global climate change including topics such as the greenhouse effect, clouds and Earth's radiation balance, surface hydrology and land cover, and volcanoes and climate change. All the materials developed to date are available on line at (http://www.strategies.org) You are encouraged to submit comments and recommendations about these materials to the Discover Earth project manager, contact information is listed below. You are welcome to duplicate all these materials.

The measurement of Earth rotation on a deformable Earth

NASA Technical Reports Server (NTRS)

Cannon, W. H.

1980-01-01

Until recently, the methods of geodetic positioning on the Earth were limited to a precision of roughly one part in 10 to the 6th power. At this level of precision, the Earth can be regarded as a rigid body since the largest departure of the Earth from rigidity is manifested in the strains of the Earth tides which are of the order of one part in 10 to the 7th power. Long baseline interferometry is expected to routinely provide global positioning to a precision of one part in 10 to the 8th power or better. At this level of precision, all parts of the Earth's surface must be regarded as being, at least potentially, in continual motion relative to the geocenter as a result of a variety of geophysical effects. The general implications of this phenomenon for the theory of the Earth's rotation is discussed. Particular attention is given to the question of the measurement of the 'Earth's rotation vector' on a deformable Earth.

U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

PubMed

Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-07-12

Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

Geochemistry of rare earth elements in minesoils from São Domingos mining district (Iberian Pyrite Belt)

NASA Astrophysics Data System (ADS)

Delgado, Joaquin; Perez-Lopez, Rafael; Nieto, Jose Miguel; Ayora, Carles

2010-05-01

The São Domingos mine is one of the most emblematic mining districts in the lower part of the Guadiana River Basin (SW of Iberian Peninsula). It is located in Portugal (about 5 km from the Spanish border), in the northern sector of the Iberian Pyrite Belt (IPB), one of the largest metallogenetic provinces of massive sulphides in the world. Although mining activity has ceased at present, the large-scale exploitation of this deposit between the second half of the XIX century and the first half of the XX century, has favoured the production of enormous waste dumps, where oxidation of pyrite and associated sulphides is resulting in the production of acid mine drainage (AMD). Mining wastes, minesoils, and acid mine drainage have been analyzed for their major ions and rare earth elements (REE) with the aim of understanding the REE mobility during sulphide weathering so that lanthanoid series can be used both as a proxy for the extent of water-rock interaction and as a tool for identifying impacts of AMD on natural ecosystems. Chemical speciation of REE in extracts from minesoils indicates that REE sulphate complexes (mainly LnSO4+) are the primary aqueous form (60-90%), and free ionic species (Ln3+, 10-40%) are the next most abundant form of soil water-soluble fraction and controls the REE speciation model. The REE from this fraction have NASC-normalized patterns with middle-REE (MREE) enriched signature compared to the light-REE (LREE) and heavy-REE (HREE), showing convex MREE-signatures and convexity index values of +1.29 +/- 1.13. These results are consistent with the typical REE fractionation patterns reported for AMD. Poorly crystalline iron oxyhydroxysulphates act as a source of labile MREE by dissolution and/or desorption processes and could explain the MREE-enriched signatures in solution.

Synthesis of Multicolor Core/Shell NaLuF4:Yb3+/Ln3+@CaF2 Upconversion Nanocrystals

PubMed Central

Li, Hui; Hao, Shuwei; Yang, Chunhui; Chen, Guanying

2017-01-01

The ability to synthesize high-quality hierarchical core/shell nanocrystals from an efficient host lattice is important to realize efficacious photon upconversion for applications ranging from bioimaging to solar cells. Here, we describe a strategy to fabricate multicolor core @ shell α-NaLuF4:Yb3+/Ln3+@CaF2 (Ln = Er, Ho, Tm) upconversion nanocrystals (UCNCs) based on the newly established host lattice of sodium lutetium fluoride (NaLuF4). We exploited the liquid-solid-solution method to synthesize the NaLuF4 core of pure cubic phase and the thermal decomposition approach to expitaxially grow the calcium fluoride (CaF2) shell onto the core UCNCs, yielding cubic core/shell nanocrystals with a size of 15.6 ± 1.2 nm (the core ~9 ± 0.9 nm, the shell ~3.3 ± 0.3 nm). We showed that those core/shell UCNCs could emit activator-defined multicolor emissions up to about 772 times more efficient than the core nanocrystals due to effective suppression of surface-related quenching effects. Our results provide a new paradigm on heterogeneous core/shell structure for enhanced multicolor upconversion photoluminescence from colloidal nanocrystals. PMID:28336867

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, Er) at high pressure

NASA Astrophysics Data System (ADS)

Turner, Katlyn M.; Tracy, Cameron L.; Mao, Wendy L.; Ewing, Rodney C.

2017-12-01

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln  =  Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn-O〉 bond in stannate pyrochlore is more covalent than the 〈B-O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18-40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite  +  weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B 0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B 0. Additionally, when normalized to r A

Postsynthesis Modification of a Metallosalen-Containing Metal-Organic Framework for Selective Th(IV)/Ln(III) Separation.

PubMed

Guo, Xiang-Guang; Qiu, Sen; Chen, Xiuting; Gong, Yu; Sun, Xiaoqi

2017-10-16

An uncoordinated salen-containing metal-organic framework (MOF) obtained through postsynthesis removal of Mn(III) ions from a metallosalen-containing MOF material has been used for selective separation of Th(IV) ion from Ln(III) ions in methanol solutions for the first time. This material exhibited an adsorption capacity of 46.345 mg of Th/g. The separation factors (β) of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Lu(III) were 10.7, 16.4, and 10.3, respectively.

The influence of A-site rare-earth for barium substitution on the chemical structure and ferroelectric properties of BZT thin films

NASA Astrophysics Data System (ADS)

Ostos, C.; Martínez-Sarrión, M. L.; Mestres, L.; Delgado, E.; Prieto, P.

2009-10-01

Rare-earth ( RE) doped Ba(Zr,Ti)O 3 (BZT) thin films were prepared by rf-magnetron sputtering from a Ba 0.90Ln0.067Zr 0.09Ti 0.91O 3 ( Ln=La, Nd) target. The films were deposited at a substrate temperature of 600 °C in a high oxygen pressure atmosphere. X-ray diffraction (XRD) patterns of RE-BZT films revealed a <001> epitaxial crystal growth on Nb-doped SrTiO 3, <001> and <011> growth on single-crystal Si, and a <111>-preferred orientation on Pt-coated Si substrates. Scanning electron microscopy (SEM) showed uniform growth of the films deposited, along with the presence of crystals of about half-micron size on the film's surface. Transmission electron microscopy (TEM) evidenced high crystalline films with thicknesses of about 100 nm for 30 min of sputtering. Electron-probe microanalysis (EPMA) corroborated the growth rate (3.0-3.5 nm/min) of films deposited on Pt-coated Si substrates. X-ray photoelectron spectroscopy (XPS), in depth profile mode, showed variations in photoelectron Ti 2 p doublet positions at lower energies with spin-orbital distances characteristic of BaTiO 3-based compounds. The XPS analysis revealed that lanthanide ions positioned onto the A-site of the BZT-perovskite structure increasing the MO 6-octahedra distortion ( M=Ti, Zr) and, thereby, modifying the Ti-O binding length. Polarization-electric field hysteresis loops on Ag/ RE-doped BZT/Pt capacitor showed good ferroelectric behavior and higher remanent polarization values than corresponding non-doped system.

Earth as an Extrasolar Planet: Earth Model Validation Using EPOXI Earth Observations

NASA Technical Reports Server (NTRS)

Robinson, Tyler D.; Meadows, Victoria S.; Crisp, David; Deming, Drake; A'Hearn, Michael F.; Charbonneau, David; Livengood, Timothy A.; Seager, Sara; Barry, Richard; Hearty, Thomas;

Earth as an Extrasolar Planet: Earth Model Validation Using EPOXI Earth Observations

NASA Astrophysics Data System (ADS)

Robinson, Tyler D.; Meadows, Victoria S.; Crisp, David; Deming, Drake; A'Hearn, Michael F.; Charbonneau, David; Livengood, Timothy A.; Seager, Sara; Barry, Richard K.; Hearty, Thomas; Hewagama, Tilak; Lisse, Carey M.; McFadden, Lucy A.; Wellnitz, Dennis D.

2011-06-01

The EPOXI Discovery Mission of Opportunity reused the Deep Impact flyby spacecraft to obtain spatially and temporally resolved visible photometric and moderate resolution near-infrared (NIR) spectroscopic observations of Earth. These remote observations provide a rigorous validation of whole-disk Earth model simulations used to better understand remotely detectable extrasolar planet characteristics. We have used these data to upgrade, correct, and validate the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional line-by-line, multiple-scattering spectral Earth model. This comprehensive model now includes specular reflectance from the ocean and explicitly includes atmospheric effects such as Rayleigh scattering, gas absorption, and temperature structure. We have used this model to generate spatially and temporally resolved synthetic spectra and images of Earth for the dates of EPOXI observation. Model parameters were varied to yield an optimum fit to the data. We found that a minimum spatial resolution of ∼100 pixels on the visible disk, and four categories of water clouds, which were defined by using observed cloud positions and optical thicknesses, were needed to yield acceptable fits. The validated model provides a simultaneous fit to Earth's lightcurve, absolute brightness, and spectral data, with a root-mean-square (RMS) error of typically less than 3% for the multiwavelength lightcurves and residuals of ∼10% for the absolute brightness throughout the visible and NIR spectral range. We have extended our validation into the mid-infrared by comparing the model to high spectral resolution observations of Earth from the Atmospheric Infrared Sounder, obtaining a fit with residuals of ∼7% and brightness temperature errors of less than 1 K in the atmospheric window. For the purpose of understanding the observable characteristics of the distant Earth at arbitrary viewing geometry and observing cadence, our validated forward model can be

Earth as an extrasolar planet: Earth model validation using EPOXI earth observations.

PubMed

Robinson, Tyler D; Meadows, Victoria S; Crisp, David; Deming, Drake; A'hearn, Michael F; Charbonneau, David; Livengood, Timothy A; Seager, Sara; Barry, Richard K; Hearty, Thomas; Hewagama, Tilak; Lisse, Carey M; McFadden, Lucy A; Wellnitz, Dennis D

2011-06-01

The EPOXI Discovery Mission of Opportunity reused the Deep Impact flyby spacecraft to obtain spatially and temporally resolved visible photometric and moderate resolution near-infrared (NIR) spectroscopic observations of Earth. These remote observations provide a rigorous validation of whole-disk Earth model simulations used to better understand remotely detectable extrasolar planet characteristics. We have used these data to upgrade, correct, and validate the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional line-by-line, multiple-scattering spectral Earth model. This comprehensive model now includes specular reflectance from the ocean and explicitly includes atmospheric effects such as Rayleigh scattering, gas absorption, and temperature structure. We have used this model to generate spatially and temporally resolved synthetic spectra and images of Earth for the dates of EPOXI observation. Model parameters were varied to yield an optimum fit to the data. We found that a minimum spatial resolution of ∼100 pixels on the visible disk, and four categories of water clouds, which were defined by using observed cloud positions and optical thicknesses, were needed to yield acceptable fits. The validated model provides a simultaneous fit to Earth's lightcurve, absolute brightness, and spectral data, with a root-mean-square (RMS) error of typically less than 3% for the multiwavelength lightcurves and residuals of ∼10% for the absolute brightness throughout the visible and NIR spectral range. We have extended our validation into the mid-infrared by comparing the model to high spectral resolution observations of Earth from the Atmospheric Infrared Sounder, obtaining a fit with residuals of ∼7% and brightness temperature errors of less than 1 K in the atmospheric window. For the purpose of understanding the observable characteristics of the distant Earth at arbitrary viewing geometry and observing cadence, our validated forward model can be

Earth as an Extrasolar Planet: Earth Model Validation Using EPOXI Earth Observations

PubMed Central

Meadows, Victoria S.; Crisp, David; Deming, Drake; A'Hearn, Michael F.; Charbonneau, David; Livengood, Timothy A.; Seager, Sara; Barry, Richard K.; Hearty, Thomas; Hewagama, Tilak; Lisse, Carey M.; McFadden, Lucy A.; Wellnitz, Dennis D.

2011-01-01

Abstract The EPOXI Discovery Mission of Opportunity reused the Deep Impact flyby spacecraft to obtain spatially and temporally resolved visible photometric and moderate resolution near-infrared (NIR) spectroscopic observations of Earth. These remote observations provide a rigorous validation of whole-disk Earth model simulations used to better understand remotely detectable extrasolar planet characteristics. We have used these data to upgrade, correct, and validate the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional line-by-line, multiple-scattering spectral Earth model. This comprehensive model now includes specular reflectance from the ocean and explicitly includes atmospheric effects such as Rayleigh scattering, gas absorption, and temperature structure. We have used this model to generate spatially and temporally resolved synthetic spectra and images of Earth for the dates of EPOXI observation. Model parameters were varied to yield an optimum fit to the data. We found that a minimum spatial resolution of ∼100 pixels on the visible disk, and four categories of water clouds, which were defined by using observed cloud positions and optical thicknesses, were needed to yield acceptable fits. The validated model provides a simultaneous fit to Earth's lightcurve, absolute brightness, and spectral data, with a root-mean-square (RMS) error of typically less than 3% for the multiwavelength lightcurves and residuals of ∼10% for the absolute brightness throughout the visible and NIR spectral range. We have extended our validation into the mid-infrared by comparing the model to high spectral resolution observations of Earth from the Atmospheric Infrared Sounder, obtaining a fit with residuals of ∼7% and brightness temperature errors of less than 1 K in the atmospheric window. For the purpose of understanding the observable characteristics of the distant Earth at arbitrary viewing geometry and observing cadence, our validated forward

Earth From Space: "Beautiful Earth's" Integration of Media Arts, Earth Science, and Native Wisdom in Informal Learning Environments

NASA Astrophysics Data System (ADS)

Casasanto, V.; Hallowell, R.; Williams, K.; Rock, J.; Markus, T.

2015-12-01

"Beautiful Earth: Experiencing and Learning Science in an Engaging Way" was a 3-year project funded by NASA's Competitive Opportunities in Education and Public Outreach for Earth and Space Science. An outgrowth of Kenji Williams' BELLA GAIA performance, Beautiful Earth fostered a new approach to teaching by combining live music, data visualizations and Earth science with indigenous perspectives, and hands-on workshops for K-12 students at 5 science centers. Inspired by the "Overview Effect," described by many astronauts who were awestruck by seeing the Earth from space and their realization of the profound interconnectedness of Earth's life systems, Beautiful Earth leveraged the power of multimedia performance to serve as a springboard to engage K-12 students in hands-on Earth science and Native wisdom workshops. Results will be presented regarding student perceptions of Earth science, environmental issues, and indigenous ways of knowing from 3 years of evaluation data.

Structural mechanism of the formation of mineral Na-tveitite-a new type of phase with a fluorite-derivative structure-in the NaF-CaF{sub 2}-(Y,Ln)F{sub 3} natural system

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

Golubev, A. M., E-mail: fluorides@ns.crys.ras.ru; Otroshchenko, L. P.; Sobolev, B. P.

2012-03-15

Relationships between the chemical compositions and structures of the mineral tveitite from the southern Norway pegmatites (with the idealized formula Ca{sub 14}Y{sub 5}F{sub 43}) and Na-tveitite from the Rov mountain (Keivy, Kola Peninsula) Na{sub 2.5}Ca{sub 10}Ln{sub 1.5}Y{sub 5}F{sub 42} are considered. According to the structural mechanism of its formation, Na-tveitite is a nanocomposite crystal based on the crystalline matrix Ca{sub 14}Y{sub 5}F{sub 43} with the ordered arrangement of {l_brace}Ca{sub 8}[CaY{sub 5}]F{sub 69}{r_brace} clusters which contain anionic {l_brace}F{sub 13}{r_brace} cuboctahedra with F{sup 1-} at the center. When Na-tveitite is formed, 29% of these clusters are statistically replaced by Na-'Y' clusters {l_brace}[Na{submore » 0.5}(Y,Ln){sub 0.5}]{sub 14}F{sub 64}{r_brace} with {l_brace}F{sub 8}{r_brace} cubes at the center (analogs of matrix fluorite groups {l_brace}Ca{sub 14}F{sub 64}{r_brace}). This replacement gives rise to composition-imperfect (Na, Ca, 'Y') cationic positions and occupancy-deficient F positions, which correspond to {l_brace}F{sub 13}{r_brace} cuboctahedra and the {l_brace}F{sub 8}{r_brace} cubes that replace them. The difference between Na-tveitite and fluorite phases M{sub 1-x}R{sub x}F{sub 2+x} is as follows: its matrix is the structure of the ordered phase (tveitite) into which Na-containing rare earth fragments of fluorite-type structure are incorporated instead of ordered-phase structural blocks (clusters).« less

Digital Earth - A sustainable Earth

NASA Astrophysics Data System (ADS)

Mahavir

2014-02-01

All life, particularly human, cannot be sustainable, unless complimented with shelter, poverty reduction, provision of basic infrastructure and services, equal opportunities and social justice. Yet, in the context of cities, it is believed that they can accommodate more and more people, endlessly, regardless to their carrying capacity and increasing ecological footprint. The 'inclusion', for bringing more and more people in the purview of development is often limited to social and economic inclusion rather than spatial and ecological inclusion. Economic investment decisions are also not always supported with spatial planning decisions. Most planning for a sustainable Earth, be at a level of rural settlement, city, region, national or Global, fail on the capacity and capability fronts. In India, for example, out of some 8,000 towns and cities, Master Plans exist for only about 1,800. A chapter on sustainability or environment is neither statutorily compulsory nor a norm for these Master Plans. Geospatial technologies including Remote Sensing, GIS, Indian National Spatial Data Infrastructure (NSDI), Indian National Urban Information Systems (NUIS), Indian Environmental Information System (ENVIS), and Indian National GIS (NGIS), etc. have potential to map, analyse, visualize and take sustainable developmental decisions based on participatory social, economic and social inclusion. Sustainable Earth, at all scales, is a logical and natural outcome of a digitally mapped, conceived and planned Earth. Digital Earth, in fact, itself offers a platform to dovetail the ecological, social and economic considerations in transforming it into a sustainable Earth.

Three isostructural one-dimensional Ln(III) chains with distorted cubane motifs showing dual fluorescence and slow magnetic relaxation/magnetocaloric effect.

PubMed

Li, Yan; Yu, Jia-Wen; Liu, Zhong-Yi; Yang, En-Cui; Zhao, Xiao-Jun

2015-01-05

Three new homometallic lanthanide complexes with mixed carboxylate-modified rigid ligands, [Ln(μ3-OH)(na)(pyzc)]n (na(-) = 1-naphtholate, pyzc(-) = 2-pyrazinecarboxylate, Ln = Dy (1), Yb (2), and Gd (3)), were solvothermally synthesized, and their structures and magnetic as well as photophysical properties were completely investigated. Complexes 1-3 are crystallographically isostructural, exhibiting linear chains with four bidentate bridging μ-COO(-) moieties encapsulated cubic {Ln4(μ3-OH)4}(8+) clusters repeatedly extended by 4-fold chelating-bridging-pyzc(-) connectors. Magnetically, the former two complexes with highly anisotropic Dy(III) and weak anisotropic Yb(III) ions in the distorted NO7 triangular dodecahedron coordination environment display field-induced slow relaxation of magnetization. Fitting the dynamic magnetic data to the Arrhenius law gives energy barrier ΔE/kB = 39.6 K and pre-exponential factor τo = 1.52 × 10(-8) s for 1 and ΔE/kB = 14.1 K and τo = 2.13 × 10(-7) s for 2. By contrast, complex 3 with isotropic Gd(III) ion and weak intracluster antiferromagnetic coupling shows a significant cryogenic magnetocaloric effect, with a maximum -ΔSm value of 30.0 J kg(-1) K(-1) at 2.5 K and 70 kOe. Additionally, the chromophoric na(-) and pyzc(-) ligands can serve as antenna groups, selectively sensitizing the Dy(III)- and Yb(III)-based luminescence of 1 and 2 in the UV-visible region by an intramolecular energy transfer process. Thus, complexes 1-3, incorporating field-induced slow magnetic magnetization and interesting luminescence together, can be used as composite magneto-optical materials. More importantly, these interesting results further demonstrate that the mixed-ligand system with rigid carboxylate-functionalized chromophores can be excellent candidates for the preparations of new bifunctional magneto-optical materials.

Monoclinic β-BaY2F8—a novel crystal simultaneously active for SRS and Ln3+-ion lasing

NASA Astrophysics Data System (ADS)

Kaminskii, A. A.; Lux, O.; Hanuza, J.; Rhee, H.; Eichler, H. J.; Zhang, J.; Tang, D.; Shen, D.; Yu, H.; Wang, J.; Yoneda, H.; Shirakawa, A.

2015-01-01

This paper presents the first investigation of stimulated Raman scattering (SRS) in the monoclinic fluoride crystal β-BaY2F8, which is known as a promising host-material for trivalent lanthanide (Ln3+) lasant ions. Picosecond laser excitation in the visible and near-IR spectral range at room temperature revealed the manifestation of nine SRS-promoting phonon modes, which are related to Ag and Bg vibrations of the crystal. Besides multi-phonon Stokes and anti-Stokes generation, we observed cross-cascaded χ(3) ↔ χ(3) processes involving different pairs of SRS-active phonons. A comparative estimation of the first Stokes steady-state Raman gain coefficients, both in the visible and near-IR region related to the most active SRS-phonon mode ωSRS1 ≈ 208 cm-1 of β-BaY2F8, was also performed. Furthermore, a brief review of the pioneering papers on laser action of Ln3+-ions doped in β-BaY2F8 single crystals and other known SRS-active fluoride crystals is given in tabular form.

Low-energy near Earth asteroid capture using Earth flybys and aerobraking

NASA Astrophysics Data System (ADS)

Tan, Minghu; McInnes, Colin; Ceriotti, Matteo

2018-04-01

Since the Sun-Earth libration points L1 and L2 are regarded as ideal locations for space science missions and candidate gateways for future crewed interplanetary missions, capturing near-Earth asteroids (NEAs) around the Sun-Earth L1/L2 points has generated significant interest. Therefore, this paper proposes the concept of coupling together a flyby of the Earth and then capturing small NEAs onto Sun-Earth L1/L2 periodic orbits. In this capture strategy, the Sun-Earth circular restricted three-body problem (CRTBP) is used to calculate target Lypaunov orbits and their invariant manifolds. A periapsis map is then employed to determine the required perigee of the Earth flyby. Moreover, depending on the perigee distance of the flyby, Earth flybys with and without aerobraking are investigated to design a transfer trajectory capturing a small NEA from its initial orbit to the stable manifolds associated with Sun-Earth L1/L2 periodic orbits. Finally, a global optimization is carried out, based on a detailed design procedure for NEA capture using an Earth flyby. Results show that the NEA capture strategies using an Earth flyby with and without aerobraking both have the potential to be of lower cost in terms of energy requirements than a direct NEA capture strategy without the Earth flyby. Moreover, NEA capture with an Earth flyby also has the potential for a shorter flight time compared to the NEA capture strategy without the Earth flyby.

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Panelists pose for a group photo at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and highlighted how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Upconverting and NIR emitting rare earth based nanostructures for NIR-bioimaging

NASA Astrophysics Data System (ADS)

Hemmer, Eva; Venkatachalam, Nallusamy; Hyodo, Hiroshi; Hattori, Akito; Ebina, Yoshie; Kishimoto, Hidehiro; Soga, Kohei

2013-11-01

In recent years, significant progress was achieved in the field of nanomedicine and bioimaging, but the development of new biomarkers for reliable detection of diseases at an early stage, molecular imaging, targeting and therapy remains crucial. The disadvantages of commonly used organic dyes include photobleaching, autofluorescence, phototoxicity and scattering when UV (ultraviolet) or visible light is used for excitation. The limited penetration depth of the excitation light and the visible emission into and from the biological tissue is a further drawback with regard to in vivo bioimaging. Lanthanide containing inorganic nanostructures emitting in the near-infrared (NIR) range under NIR excitation may overcome those problems. Due to the outstanding optical and magnetic properties of lanthanide ions (Ln3+), nanoscopic host materials doped with Ln3+, e.g. Y2O3:Er3+,Yb3+, are promising candidates for NIR-NIR bioimaging. Ln3+-doped gadolinium-based inorganic nanostructures, such as Gd2O3:Er3+,Yb3+, have a high potential as opto-magnetic markers allowing the combination of time-resolved optical imaging and magnetic resonance imaging (MRI) of high spatial resolution. Recent progress in our research on over-1000 nm NIR fluorescent nanoprobes for in vivo NIR-NIR bioimaging will be discussed in this review.In recent years, significant progress was achieved in the field of nanomedicine and bioimaging, but the development of new biomarkers for reliable detection of diseases at an early stage, molecular imaging, targeting and therapy remains crucial. The disadvantages of commonly used organic dyes include photobleaching, autofluorescence, phototoxicity and scattering when UV (ultraviolet) or visible light is used for excitation. The limited penetration depth of the excitation light and the visible emission into and from the biological tissue is a further drawback with regard to in vivo bioimaging. Lanthanide containing inorganic nanostructures emitting in the near

Make Earth science education as dynamic as Earth itself

NASA Astrophysics Data System (ADS)

Lautenbacher, Conrad C.; Groat, Charles G.

2004-12-01

The images of rivers spilling over their banks and washing away entire towns, buildings decimated to rubble by the violent shaking of the Earth's plates, and molten lava flowing up from inside the Earth's core are constant reminders of the power of the Earth. Humans are simply at the whim of the forces of Mother Nature—or are we? Whether it is from a great natural disaster, a short-term weather event like El Nino, or longer-term processes like plate tectonics, Earth processes affect us all. Yet,we are only beginning to scratch the surface of our understanding of Earth sciences. We believe the day will come when our understanding of these dynamic Earth processes will prompt better policies and decisions about saving lives and property. One key place to start is in America's classrooms.

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.

Antigenic Protein In Microgravity-Grown Human Mixed Mullerian Tumor (LN1) Cells Preserved In RNA Stabilizing Agent

NASA Technical Reports Server (NTRS)

Hammond, Dianne K.; Becker, Jeanne; Holubec, K.; Baker, T. L.; Love, J. E.

2004-01-01

Cells treated with RNAlater(TradeMark) have previously been shown to contain antigenic proteins that can be visualized using Western blot analysis. These proteins seem to be stable for several months when stored in RNA stabilizer at 4 C. Antigenic protein can be recovered from cells that have been processed using an Ambion RNAqueous(Registered TradeMark) kit to remove RNA. In this set of experiments, human mixed Mullerian tumor (LN1) cells grown on the International Space Station during Expedition 3 were examined for antigenic stability after removal of RNA. The cells were stored for three months in RNAlater(TradeMark) and RNA was extracted. The RNA filtrate Containing the protein was precipitated, washed, and suspended in buffer containing sodium dodecyl sulfate (SDS). Samples containing equal concentrations of protein were loaded onto SDS-polyacrylamide gels. Proteins were separated by electrophoresis and transferred by Western blot to polyvinylidene fluoride (PVDF) membrane. The Western blots were stained with an enhanced chemiluminescent ECL(Registered TradeMark)Plus detection kit (Amersham) and scanned using a Storm 840 gel image analyzer (Amersham, Molecular Dynamics). ImageQuant(Registered TradeMark)a software was used to quantify the densities of the protein bands. The ground control and flight LN1 cell samples showed a similar staining pattern over time with antibodies to vimentin, glyceraldehyde-3-phosphate dehydrogenase, and epithelial membrane antigens.

Characterisation of Ceramic-Coated 316LN Stainless Steel Exposed to High-Temperature Thermite Melt and Molten Sodium

NASA Astrophysics Data System (ADS)

Ravi Shankar, A.; Vetrivendan, E.; Shukla, Prabhat Kumar; Das, Sanjay Kumar; Hemanth Rao, E.; Murthy, S. S.; Lydia, G.; Nashine, B. K.; Mallika, C.; Selvaraj, P.; Kamachi Mudali, U.

2017-11-01

Currently, stainless steel grade 316LN is the material of construction widely used for core catcher of sodium-cooled fast reactors. Design philosophy for core catcher demands its capability to withstand corium loading from whole core melt accidents. Towards this, two ceramic coatings were investigated for its application as a layer of sacrificial material on the top of core catcher to enhance its capability. Plasma-sprayed thermal barrier layer of alumina and partially stabilised zirconia (PSZ) with an intermediate bond coat of NiCrAlY are selected as candidate material and deposited over 316LN SS substrates and were tested for their suitability as thermal barrier layer for core catcher. Coated specimens were exposed to high-temperature thermite melt to simulate impingement of molten corium. Sodium compatibility of alumina and PSZ coatings were also investigated by exposing samples to molten sodium at 400 °C for 500 h. The surface morphology of high-temperature thermite melt-exposed samples and sodium-exposed samples was examined using scanning electron microscope. Phase identification of the exposed samples was carried out by x-ray diffraction technique. Observation from sodium exposure tests indicated that alumina coating offers better protection compared to PSZ coating. However, PSZ coating provided better protection against high-temperature melt exposure, as confirmed during thermite melt exposure test.

ISS EarthKam: Taking Photos of the Earth from Space

ERIC Educational Resources Information Center

Haste, Turtle

2008-01-01

NASA is involved in a project involving the International Space Station (ISS) and an Earth-focused camera called EarthKam, where schools, and ultimately students, are allowed to remotely program the EarthKAM to take images. Here the author describes how EarthKam was used to help middle school students learn about biomes and develop their…

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Panelists discuss how research on early Earth could help guide our search for habitable planets orbiting other stars at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Photo Credit: (NASA/Aubrey Gemignani)

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. David H. Grinspoon, Senior Scientist, Planetary Science Institute, moderates a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and highlighted how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Partitioning of carbon between Fe-rich alloy melt and silicate melt in a magma ocean - Implications for the abundance and origin of volatiles in Earth, Mars, and the Moon

NASA Astrophysics Data System (ADS)

Chi, Han; Dasgupta, Rajdeep; Duncan, Megan S.; Shimizu, Nobumichi

2014-08-01

from 510 ± 53 to 5369 ± 217 and varies systematically as a function of P, T, fO2, water content, the composition of the silicate melt (expressed using NBO/T), and Ni content of alloy melt (XNi). The range of DCmetal/silicate measured in our study with carbonated and hydrogenated carbon species in silicate melt is similar to that reported in the literature for experiments where carbonyl complexes are the chief carbon species in silicate melts. A parameterization was derived using the data from this and existing studies such as lnDCmetal/silicate=a/T+b·P/T+c·ln(fO2)+d·(NBO/T)+e·ln(1-XNi)+f where a = -33,510, b = 1357, c = -0.596, d = -1.182, e = 4.15, f = 13.38, the temperature is in Kelvin, and the pressure is in gigapascal. Using this parameterization and the estimated conditions for the base of the MOs, the average DCmetal/silicate value for Earth, Mars, and the Moon can be predicted. The deep MO of Earth is predicted to cause the strongest depletion of its silicate carbon budget, closely followed by Mars with intermediate depth MO, and then the Moon with a shallow MO. We predict that the lunar mantle carbon budget, similar to that of the Earth’s present-day upper mantle, might have been set by equilibrium core-mantle fractionation in MO; whereas for Earth, later processes such as ingassing from a proto-atmosphere and late-stage accretion of volatile-rich material was necessary for delivery of carbon and other volatiles. Finally, the comparison of our measured and predicted value of DCmetal/silicate for terrestrial MO with similar constraints on DNmetal/silicate from the literature suggests that the apparent depletion of nitrogen relative to carbon for the bulk silicate Earth and the Earth’s upper mantle is unlikely to be caused by preferential partitioning of nitrogen to alloy melt during core formation.

Trivalent Rare-Earth-Metal Bis(trimethylsilyl)amide Halide Complexes by Targeted Oxidations.

PubMed

Bienfait, André M; Wolf, Benjamin M; Törnroos, Karl W; Anwander, Reiner

2018-05-07

In contrast to previously applied salt metathesis protocols the targeted rare-earth-metal compounds Ln[N(SiMe 3 ) 2 ] 2 (halogenido) were accessed by oxidation of Ln(II) silylamide precursors. Treatment of Sm[N(SiMe 3 ) 3 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 or 0.25 equiv of TeBr 4 in thf and crystallization thereof gave [Sm{N(SiMe 3 ) 2 } 2 (μ-X)(thf)] 2 (X = Cl, Br). A similar reaction/crystallization procedure performed with 0.5 equiv of 1,2-diiodoethane gave monomeric Sm[N(SiMe 3 ) 2 ] 2 I(thf) 2 . Switching to Yb[N(SiMe 3 ) 2 ] 2 (thf) 2 , the aforementioned oxidants generated monomeric five-coordinate complexes Yb[N(SiMe 3 ) 2 ] 2 X(thf) 2 (X = Cl, Br, I). The reaction of Eu[N(SiMe 3 ) 2 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 in thf yielded the separated ion pair [Eu{N(SiMe 3 ) 2 } 3 Cl][(thf) 5 Eu(μ-Cl) 2 Eu(thf) 5 ]. Performing the chlorination in n-hexane led to oxidation followed by rapid disproportionation into EuCl 3 (thf) x and Eu[N(SiMe 3 ) 2 ] 3 . The bromination reaction did not afford crystalline material, while the iodination gave crystals of divalent EuI 2 (thf) 5 . Use of trityl chloride (Ph 3 CCl) as the oxidant in thf accomplished the Eu(III) species [Eu{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 . In situ oxidation of putative [Tm{N(SiMe 3 ) 2 } 2 (thf) x ] using 0.5 equiv of C 2 Cl 6 in thf followed by crystallization from n-hexane led to the formation of a mixture of [Tm{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 and Tm[N(SiMe 3 ) 2 ] 3 . Switching the oxidant to 0.5 equiv of 1,2-diiodoethane and crystallizing from thf repeatedly afforded the bis-halogenated complex Tm[N(SiMe 3 ) 2 ]I 2 (thf) 3 .

Acceleration Processes in the Earth’s Magnetosphere.

DTIC Science & Technology

1985-05-17

R.L . , C.T. Russel I, and M.P . Auhry, Satcl Iik t li-, of mir(I T - spheric substorm (, Aiqu,,t 15, Itoh , 9. Ptinnm o ln ical r nde I of - storms...physics of auroral field lines, Nobel Symposium, Kiruna, Sweden, 1982. 2) T. Sato, Numerical study of magnetic reconnection mechanisms, AGU, Philadelphia

Digital Earth for Earth Sciences and Public Education

NASA Astrophysics Data System (ADS)

Foresman, T. W.

2006-12-01

Buckminster Fuller was an early advocate for better comprehension of the planet and its resources related to human affairs. A comprehensive vision was articulated by a US Vice President and quickly adopted by the world's oldest country China.. Digital Earth brings fresh perspective on the current state of affairs and connects citizens with scientists through the applications of 3D visualization, spinning globes, virtual Earths, and the current collaboration with Virtual Globes. The prowess of Digital Earth technology has been so successful in both understanding and communicating the more challenging topics for global change and climate change phenomena that China has assigned it priority status with the Ministry of Science and Technology and the Chinese Academy of Sciences. New Zealand has recently begun to adjust its national strategies for sustainability with the technologies of Digital Earth. A comprehensive coverage of the results compiled over the past seven years is presented to place a foundation for the science and engineering community to prepare to align with this compelling science enterprise as a fundamental new paradigm for the registration, storage, and access of science data and information through the emerging Digital Earth Exchange under protocols developed for the Digital Earth Reference Model.

Why Earth Science?

ERIC Educational Resources Information Center

Smith, Michael J.

2004-01-01

This article briefly describes Earth science. The study of Earth science provides the foundation for an understanding of the Earth, its processes, its resources, and its environment. Earth science is the study of the planet in its entirety, how its lithosphere, atmosphere, hydrosphere, and biosphere work together as systems and how they affect…

Crew Earth Observations

NASA Technical Reports Server (NTRS)

Runco, Susan

2009-01-01

Crew Earth Observations (CEO) takes advantage of the crew in space to observe and photograph natural and human-made changes on Earth. The photographs record the Earth's surface changes over time, along with dynamic events such as storms, floods, fires and volcanic eruptions. These images provide researchers on Earth with key data to better understand the planet.

Unique Resistance of I/LnJ Mice to a Retrovirus Is Due to Sustained Interferon γ–dependent Production of Virus-neutralizing Antibodies

PubMed Central

Purdy, Alexandra; Case, Laure; Duvall, Melody; Overstrom-Coleman, Max; Monnier, Nilah; Chervonsky, Alexander; Golovkina, Tatyana

2003-01-01

Selection of immune escape variants impairs the ability of the immune system to sustain an efficient antiviral response and to control retroviral infections. Like other retroviruses, mouse mammary tumor virus (MMTV) is not efficiently eliminated by the immune system of susceptible mice. In contrast, MMTV-infected I/LnJ mice are capable of producing IgG2a virus-neutralizing antibodies, sustain this response throughout their life, and secrete antibody-coated virions into the milk, thereby preventing infection of their progeny. Antibodies were produced in response to several MMTV variants and were cross-reactive to them. Resistance to MMTV infection was recessive and was dependent on interferon (IFN)-γ production, because I/LnJ mice with targeted deletion of the INF-γ gene failed to produce any virus-neutralizing antibodies. These findings reveal a novel mechanism of resistance to retroviral infection that is based on a robust and sustained IFN-γ–dependent humoral immune response. PMID:12538662

Earth Rotation

NASA Technical Reports Server (NTRS)

Dickey, Jean O.

1995-01-01

The study of the Earth's rotation in space (encompassing Universal Time (UT1), length of day, polar motion, and the phenomena of precession and nutation) addresses the complex nature of Earth orientation changes, the mechanisms of excitation of these changes and their geophysical implications in a broad variety of areas. In the absence of internal sources of energy or interactions with astronomical objects, the Earth would move as a rigid body with its various parts (the crust, mantle, inner and outer cores, atmosphere and oceans) rotating together at a constant fixed rate. In reality, the world is considerably more complicated, as is schematically illustrated. The rotation rate of the Earth's crust is not constant, but exhibits complicated fluctuations in speed amounting to several parts in 10(exp 8) [corresponding to a variation of several milliseconds (ms) in the Length Of the Day (LOD) and about one part in 10(exp 6) in the orientation of the rotation axis relative to the solid Earth's axis of figure (polar motion). These changes occur over a broad spectrum of time scales, ranging from hours to centuries and longer, reflecting the fact that they are produced by a wide variety of geophysical and astronomical processes. Geodetic observations of Earth rotation changes thus provide insights into the geophysical processes illustrated, which are often difficult to obtain by other means. In addition, these measurements are required for engineering purposes. Theoretical studies of Earth rotation variations are based on the application of Euler's dynamical equations to the problem of finding the response of slightly deformable solid Earth to variety of surface and internal stresses.

EarthChem and SESAR: Data Resources and Interoperability for EarthScope Cyberinfrastructure

NASA Astrophysics Data System (ADS)

Lehnert, K. A.; Walker, D.; Block, K.; Vinay, S.; Ash, J.

2008-12-01

Data management within the EarthScope Cyberinfrastructure needs to pursue two goals in order to advance and maximize the broad scientific application and impact of the large volumes of observational data acquired by EarthScope facilities: (a) to provide access to all data acquired by EarthScope facilities, and to promote their use by broad audiences, and (b) to facilitate discovery of, access to, and integration of multi-disciplinary data sets that complement EarthScope data in support of EarthScope science. EarthChem and SESAR, the System for Earth Sample Registration, are two projects within the Geoinformatics for Geochemistry program that offer resources for EarthScope CI. EarthChem operates a data portal that currently provides access to >13 million analytical values for >600,000 samples, more than half of which are from North America, including data from the USGS and all data from the NAVDAT database, a web-accessible repository for age, chemical and isotopic data from Mesozoic and younger igneous rocks in western North America. The new EarthChem GEOCHRON database will house data collected in association with GeoEarthScope, storing and serving geochronological data submitted by participating facilities. The EarthChem Deep Lithosphere Dataset is a compilation of petrological data for mantle xenoliths, initiated in collaboration with GeoFrame to complement geophysical endeavors within EarthScope science. The EarthChem Geochemical Resource Library provides a home for geochemical and petrological data products and data sets. Parts of the digital data in EarthScope CI refer to physical samples such as drill cores, igneous rocks, or water and gas samples, collected, for example, by SAFOD or by EarthScope science projects and acquired through lab-based analysis. Management of sample-based data requires the use of global unique identifiers for samples, so that distributed data for individual samples generated in different labs and published in different papers can be

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

An audience member asks the panelists a question at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Earth Science Europe "Is Earth Science Europe an interesting and useful construct?"

NASA Astrophysics Data System (ADS)

Ludden, John

2015-04-01

In 2014 we managed to have a group of earth scientists from across the spectrum: from academic, survey, industry and government, pull together to create the first output for Earth Science Europe http://www.bgs.ac.uk/earthScienceEurope/downloads/EarthScienceEuropeBrochure.pdf In this document we stated that Earth scientists need a united, authoritative voice to enhance the status and impact of Earth science across Europe. The feeling was that there were many diverse infrastructure and research initiatives spanning the terrestrial and oceanic realms and science ranged from historical geology to active dynamics on Earth, and that a level of coordination and mutual knowledge sharing was necessary. In addition to a better understanding of the Earth in general, we thought there was a need to have Earth Science Europe develop a strategic research capacity in geohazards, georesources and environmental earth sciences, through a roadmap addressing fundamental and societal challenges. This would involve a robust research infrastructure to deliver strategic goals, enabling inspirational research and promoting solutions to societal challenges. In this talk I will propose some next steps and discuss what this "authoritative voice" could look like and ask the question - "is Earth Science Europe and interesting and useful concept?"

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

PubMed

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

2017-12-12

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

Earth Reflectivity from Deep Space Climate Observatory (DSCOVR) Earth Polychromatic Camera (EPIC)

NASA Astrophysics Data System (ADS)

Song, W.; Knyazikhin, Y.; Wen, G.; Marshak, A.; Yan, G.; Mu, X.; Park, T.; Chen, C.; Xu, B.; Myneni, R. B.

2017-12-01

Earth reflectivity, which is also specified as Earth albedo or Earth reflectance, is defined as the fraction of incident solar radiation reflected back to space at the top of the atmosphere. It is a key climate parameter that describes climate forcing and associated response of the climate system. Satellite is one of the most efficient ways to measure earth reflectivity. Conventional polar orbit and geostationary satellites observe the Earth at a specific local solar time or monitor only a specific area of the Earth. For the first time, the NASA's Earth Polychromatic Imaging Camera (EPIC) onboard NOAA's Deep Space Climate Observatory (DSCOVR) collects simultaneously radiance data of the entire sunlit earth at 8 km resolution at nadir every 65 to 110 min. It provides reflectivity images in backscattering direction with the scattering angle between 168º and 176º at 10 narrow spectral bands in ultraviolet, visible, and near-Infrared (NIR) wavelengths. We estimate the Earth reflectivity using DSCOVR EPIC observations and analyze errors in Earth reflectivity due to sampling strategy of polar orbit Terra/Aqua MODIS and geostationary Goddard Earth Observing System-R series missions. We also provide estimates of contributions from ocean, clouds, land and vegetation to the Earth reflectivity. Graphic abstract shows enhanced RGB EPIC images of the Earth taken on July-24-2016 at 7:04GMT and 15:48 GMT. Parallel lines depict a 2330 km wide Aqua MODIS swath. The plot shows diurnal courses of mean Earth reflectance over the Aqua swath (triangles) and the entire image (circles). In this example the relative difference between the mean reflectances is +34% at 7:04GMT and -16% at 15:48 GMT. Corresponding daily averages are 0.256 (0.044) and 0.231 (0.025). The relative precision estimated as root mean square relative error is 17.9% in this example.

Earth Observations

NASA Image and Video Library

2010-06-16

ISS024-E-006136 (16 June 2010) --- Polar mesospheric clouds, illuminated by an orbital sunrise, are featured in this image photographed by an Expedition 24 crew member on the International Space Station. Polar mesospheric, or noctilucent (?night shining?), clouds are observed from both Earth?s surface and in orbit by crew members aboard the space station. They are called night-shining clouds as they are usually seen at twilight. Following the setting of the sun below the horizon and darkening of Earth?s surface, these high clouds are still briefly illuminated by sunlight. Occasionally the ISS orbital track becomes nearly parallel to Earth?s day/night terminator for a time, allowing polar mesospheric clouds to be visible to the crew at times other than the usual twilight due to the space station altitude. This unusual photograph shows polar mesospheric clouds illuminated by the rising, rather than setting, sun at center right. Low clouds on the horizon appear yellow and orange, while higher clouds and aerosols are illuminated a brilliant white. Polar mesospheric clouds appear as light blue ribbons extending across the top of the image. These clouds typically occur at high latitudes of both the Northern and Southern Hemispheres, and at fairly high altitudes of 76?85 kilometers (near the boundary between the mesosphere and thermosphere atmospheric layers). The ISS was located over the Greek island of Kos in the Aegean Sea (near the southwestern coastline of Turkey) when the image was taken at approximately midnight local time. The orbital complex was tracking northeastward, nearly parallel to the terminator, making it possible to observe an apparent ?sunrise? located almost due north. A similar unusual alignment of the ISS orbit track, terminator position, and seasonal position of Earth?s orbit around the sun allowed for striking imagery of polar mesospheric clouds over the Southern Hemisphere earlier this year.

Acquisition/expulsion system for earth orbital propulsion system study. Volume 3: Cryogenic test

NASA Technical Reports Server (NTRS)

1973-01-01

A ground test program was conducted to verify several of the design methods and techniques that were used in designing cryogenic acquisition/expulsion systems. The testing of a 63.5-cm diameter DSL subscale model was particularly significant. Under these tests, the operational characteristics of the DSL concept were verified using LH2 and LN2. Demonstration of the gas free liquid expulsion characteristics was accomplished by expelling LH2 under -1 g using both GH2 and GHe pressurization. Loading of the acquisition/expulsion device was successfully accomplished using LH2 and LN2. The liquid free vapor venting performance of the model was limited because of the thermal stratification under the -1 g test conditions.

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. Phoebe Cohen, Professor of Geosciences, Williams College, speaks on a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. Christopher House, Professor of Geosciences, Pennsylvania State University, speaks on a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. Dawn Sumner, Professor of Geology, UC Davis, speaks on a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. Timothy Lyons, Professor of Biogeochemistry, UC Riverside, speaks on a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Effects of environment and frequency on the fatigue behavior of the spallation neutron source (SNS) target container material - 316 LN stainless steel

NASA Astrophysics Data System (ADS)

Tian, Hongbo

As the candidate target container material of the new Spallation Neutron Source (SNS) being designed and constructed at the Oak Ridge National Laboratory (ORNL), Type 316 low-carbon nitrogen-added (LN) stainless steel (SS) will operate in an aggressive environment, subjected to intense fluxes of high-energy protons and neutrons while exposed to liquid mercury. The current project is oriented toward materials studies regarding the effects of test environment and frequency on the fatigue behavior of 316 LN SS. In order to study the structural applications of this material and improve the fundamental understanding of the fatigue damage mechanisms, fatigue tests were performed in air and mercury environments at various frequencies and R ratios (R = sigma min/sigmamax, sigmamin and sigmamax are the applied minimum and maximum stresses, respectively). Fatigue data were developed for the structural design and engineering applications of this material. Specifically, high-cycle fatigue tests, fatigue crack-propagation tests, and ultrahigh cycle fatigue tests up to 10 9 cycles were conducted in air and mercury with test frequencies from 10 Hz to 700 Hz. Microstructure characterizations were performed using optical microscopy (OM), scanning-electron microscopy (SEM), and transmission-electron microscopy (TEM). It was found that mercury doesn't seem to have a large impact on the crack-initiation behavior of 316 LN SS. However, the crack-propagation mechanisms in air and mercury are different in some test conditions. Transgranular cracks seem to be the main mechanism in air, and intergranular in mercury. A significant specimen self-heating effect was found during high-cycle faituge. Theoretical calculation was performed to predict temperature responses of the material subjected to cyclic deformation. The predicted cyclic temperature evolution seems to be in good agreement with the experimental results.

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.

EarthLabs - Investigating Hurricanes: Earth's Meteorological Monsters

NASA Astrophysics Data System (ADS)

McDaris, J. R.; Dahlman, L.; Barstow, D.

2007-12-01

Earth science is one of the most important tools that the global community needs to address the pressing environmental, social, and economic issues of our time. While, at times considered a second-rate science at the high school level, it is currently undergoing a major revolution in the depth of content and pedagogical vitality. As part of this revolution, labs in Earth science courses need to shift their focus from cookbook-like activities with known outcomes to open-ended investigations that challenge students to think, explore and apply their learning. We need to establish a new model for Earth science as a rigorous lab science in policy, perception, and reality. As a concerted response to this need, five states, a coalition of scientists and educators, and an experienced curriculum team are creating a national model for a lab-based high school Earth science course named EarthLabs. This lab course will comply with the National Science Education Standards as well as the states' curriculum frameworks. The content will focus on Earth system science and environmental literacy. The lab experiences will feature a combination of field work, classroom experiments, and computer access to data and visualizations, and demonstrate the rigor and depth of a true lab course. The effort is being funded by NOAA's Environmental Literacy program. One of the prototype units of the course is Investigating Hurricanes. Hurricanes are phenomena which have tremendous impact on humanity and the resources we use. They are also the result of complex interacting Earth systems, making them perfect objects for rigorous investigation of many concepts commonly covered in Earth science courses, such as meteorology, climate, and global wind circulation. Students are able to use the same data sets, analysis tools, and research techniques that scientists employ in their research, yielding truly authentic learning opportunities. This month-long integrated unit uses hurricanes as the story line by

EarthExplorer

USGS Publications Warehouse

Houska, Treva

2012-01-01

The EarthExplorer trifold provides basic information for on-line access to remotely-sensed data from the U.S. Geological Survey Earth Resources Observation and Science (EROS) Center archive. The EarthExplorer (http://earthexplorer.usgs.gov/) client/server interface allows users to search and download aerial photography, satellite data, elevation data, land-cover products, and digitized maps. Minimum computer system requirements and customer service contact information also are included in the brochure.

Comparison of Low Earth Orbit and Geosynchronous Earth Orbits

NASA Technical Reports Server (NTRS)

Drummond, J. E.

1980-01-01

The technological, environmental, social, and political ramifications of low Earth orbits as compared to geosynchronous Earth orbits for the solar power satellite (SPS) are assessed. The capital cost of the transmitting facilities is dependent on the areas of the antenna and rectenna relative to the requirement of high efficiency power transmission. The salient features of a low orbit Earth orbits are discussed in terms of cost reduction efforts.

Partial Pressures for Several In-Se Compositions from Optical Absorbance of the Vapor

NASA Technical Reports Server (NTRS)

Brebrick, R. F.; Su, Ching-Hua

2001-01-01

The optical absorbance of the vapor phase over various In-Se compositions between 33.3-60.99 at.% Se and 673-1418 K was measured and used to obtain the partial pressures of Se2(g) and In2Se(g). The results are in agreement with silica Bourdon gauge measurements for compositions between 50-61 at.%, but significantly higher than those from Knudsen cell and simultaneous Knudsen-torsion cell measurements. It is found that 60.99 at.% Se lies outside the sesquiselenide homogeneity range and 59.98 at.% Se lies inside and is the congruently melting composition. The Gibbs energy of formation of the liquid from its pure liquid elements between 1000-1300 K is essentially independent of temperature and falls between -36 to -38 kJ per g atomic weight for 50 and 56% Se at 1200 and 1300 K.

Ancient Earth, Alien Earths Event

NASA Image and Video Library

2014-08-20

Dr. Shawn Domagal-Goldman, Research Space Scientist, NASA Goddard Space Flight Center, speaks on a panel at the “Ancient Earth, Alien Earths” Event at NASA Headquarters in Washington, DC Wednesday, August 20, 2014. The event was sponsored by NASA, the National Science Foundation (NSF), and the Smithsonian Institution and was moderated by Dr. David H. Grinspoon, Senior Scientist at the Planetary Science Institute. Six scientists discussed how research on early Earth could help guide our search for habitable planets orbiting other stars. Photo Credit: (NASA/Aubrey Gemignani)

Earth - South America (first frame of Earth Spin Movie)

NASA Technical Reports Server (NTRS)

1990-01-01

This color image of the Earth was obtained by Galileo at about 6:10 a.m. Pacific Standard Time on Dec. 11, 1990, when the spacecraft was about 1.3 million miles from the planet during the first of two Earth flybys on its way to Jupiter. The color composite used images taken through the red, green and violet filters. South America is near the center of the picture, and the white, sunlit continent of Antarctica is below. Picturesque weather fronts are visible in the South Atlantic, lower right. This is the first frame of the Galileo Earth spin movie, a 500- frame time-lapse motion picture showing a 25-hour period of Earth's rotation and atmospheric dynamics.

The Dynamic Earth.

ERIC Educational Resources Information Center

Siever, Raymond

1983-01-01

Discusses how the earth is a dynamic system that maintains itself in a steady state. Areas considered include large/small-scale earth motions, geologic time, rock and hydrologic cycles, and other aspects dealing with the changing face of the earth. (JN)

Building a Dashboard of the Planet with Google Earth and Earth Engine

NASA Astrophysics Data System (ADS)

Moore, R. T.; Hancher, M.

2016-12-01

In 2005 Google Earth, a popular 3-D virtual globe, was first released. Scientists immediately recognized how it could be used to tell stories about the Earth. From 2006 to 2009, the "Virtual Globes" sessions of AGU included innovative examples of scientists and educators using Google Earth, and since that time it has become a commonplace tool for communicating scientific results. In 2009 Google Earth Engine, a cloud-based platform for planetary-scale geospatial analysis, was first announced. Earth Engine was initially used to extract information about the world's forests from raw Landsat data. Since then, the platform has proven highly effective for general analysis of georeferenced data, and users have expanded the list of use cases to include high-impact societal issues such as conservation, drought, disease, food security, water management, climate change and environmental monitoring. To support these use cases, the platform has continuously evolved with new datasets, analysis functions, and user interface tools. This talk will give an overview of the latest Google Earth and Earth Engine functionality that allow partners to understand, monitor and tell stories about of our living, breathing Earth. https://earth.google.com https://earthengine.google.com

Student Geoscientists Explore the Earth during Earth Science Week 2005

ERIC Educational Resources Information Center

Benbow, Ann E.; Camphire, Geoff

2005-01-01

Taking place October 9-15, Earth Science Week 2005 will celebrate the theme "Geoscientists Explore the Earth." The American Geological Institute (AGI) is organizing the event, as always, to help people better understand and appreciate the Earth sciences and to encourage stewardship of the planet. This year, the focus will be on the wide range of…

Earth analysis methods, subsurface feature detection methods, earth analysis devices, and articles of manufacture

DOEpatents

West, Phillip B [Idaho Falls, ID; Novascone, Stephen R [Idaho Falls, ID; Wright, Jerry P [Idaho Falls, ID

2012-05-29

Earth analysis methods, subsurface feature detection methods, earth analysis devices, and articles of manufacture are described. According to one embodiment, an earth analysis method includes engaging a device with the earth, analyzing the earth in a single substantially lineal direction using the device during the engaging, and providing information regarding a subsurface feature of the earth using the analysis.

Earth analysis methods, subsurface feature detection methods, earth analysis devices, and articles of manufacture

DOEpatents

West, Phillip B [Idaho Falls, ID; Novascone, Stephen R [Idaho Falls, ID; Wright, Jerry P [Idaho Falls, ID

2011-09-27

Earth analysis methods, subsurface feature detection methods, earth analysis devices, and articles of manufacture are described. According to one embodiment, an earth analysis method includes engaging a device with the earth, analyzing the earth in a single substantially lineal direction using the device during the engaging, and providing information regarding a subsurface feature of the earth using the analysis.

Earth horizon modeling and application to static Earth sensors on TRMM spacecraft

NASA Technical Reports Server (NTRS)

Keat, J.; Challa, M.; Tracewell, D.; Galal, K.

1995-01-01

Data from Earth sensor assemblies (ESA's) often are used in the attitude determination (AD) for both spinning and Earth-pointing spacecraft. The ESA's on previous such spacecraft for which the ground-based AD operation was performed by the Flight Dynamics Division (FDD) used the Earth scanning method. AD on such spacecraft requires a model of the shape of the Earth disk as seen from the spacecraft. AD accuracy requirements often are too severe to permit Earth oblateness to be ignored when modeling disk shape. Section 2 of this paper reexamines and extends the methods for Earth disk shape modeling employed in AD work at FDD for the past decade. A new formulation, based on a more convenient Earth flatness parameter, is introduced, and the geometric concepts are examined in detail. It is shown that the Earth disk can be approximated as an ellipse in AD computations. Algorithms for introducing Earth oblateness into the AD process for spacecraft carrying scanning ESA's have been developed at FDD and implemented into the support systems. The Tropical Rainfall Measurement Mission (TRMM) will be the first spacecraft with AD operation performed at FDD that uses a different type of ESA - namely, a static one - containing four fixed detectors D(sub i) (i = 1 to 4). Section 3 of this paper considers the effect of Earth oblateness on AD accuracy for TRMM. This effect ideally will not induce AD errors on TRMM when data from all four D(sub i) are present. When data from only two or three D(sub i) are available, however, a spherical Earth approximation can introduce errors of 0.05 to 0.30 deg on TRMM. These oblateness-induced errors are eliminated by a new algorithm that uses the results of Section 2 to model the Earth disk as an ellipse.

Earth Science

NASA Image and Video Library

1992-07-18

Workers at Launch Complex 17 Pad A, Kennedy Space Center (KSC) encapsulate the Geomagnetic Tail (GEOTAIL) spacecraft (upper) and attached payload Assist Module-D upper stage (lower) in the protective payload fairing. GEOTAIL project was designed to study the effects of Earth's magnetic field. The solar wind draws the Earth's magnetic field into a long tail on the night side of the Earth and stores energy in the stretched field lines of the magnetotail. During active periods, the tail couples with the near-Earth magnetosphere, sometimes releasing energy stored in the tail and activating auroras in the polar ionosphere. GEOTAIL measures the flow of energy and its transformation in the magnetotail and will help clarify the mechanisms that control the imput, transport, storage, release, and conversion of mass, momentum, and energy in the magnetotail.

The Lifeworld Earth and a Modelled Earth

ERIC Educational Resources Information Center

Juuti, Kalle

2014-01-01

The goal of this paper is to study the question of whether a phenomenological view of the Earth could be empirically endorsed. The phenomenological way of thinking considers the Earth as a material entity, but not as an object as viewed in science. In the learning science tradition, tracking the process of the conceptual change of the shape of the…

Earth Observation

NASA Image and Video Library

2014-06-01

ISS040-E-006327 (1 June 2014) --- A portion of International Space Station solar array panels and Earth?s horizon are featured in this image photographed by an Expedition 40 crew member on the space station.

The Effects of Earth Science Programs on Student Knowledge and Interest in Earth Science

NASA Astrophysics Data System (ADS)

Wilson, A.

2016-12-01

Ariana Wilson, Chris Skinner, Chris Poulsen Abstract For many years, academic programs have been in place for the instruction of young students in the earth sciences before they undergo formal training in high school or college. However, there has been little formal assessment of the impacts of these programs on student knowledge of the earth sciences and their interest in continuing with earth science. On August 6th-12th 2016 I will attend the University of Michigan's annual Earth Camp, where I will 1) ascertain high school students' knowledge of earth science-specifically atmospheric structure and wind patterns- before and after Earth Camp, 2) record their opinions about earth science before and after Earth Camp, and 3) record how the students feel about how the camp was run and what could be improved. I will accomplish these things through the use of surveys asking the students questions about these subjects. I expect my results will show that earth science programs like Earth Camp deepen students' knowledge of and interest in earth science and encourage them to continue their study of earth science in the future. I hope these results will give guidance on how to conduct future learning programs and how to recruit more students to become earth scientists in the future.

Earth Science Information Center

USGS Publications Warehouse

,

1991-01-01

An ESIC? An Earth Science Information Center. Don't spell it. Say it. ESIC. It rhymes with seasick. You can find information in an information center, of course, and you'll find earth science information in an ESIC. That means information about the land that is the Earth, the land that is below the Earth, and in some instances, the space surrounding the Earth. The U.S. Geological Survey (USGS) operates a network of Earth Science Information Centers that sell earth science products and data. There are more than 75 ESIC's. Some are operated by the USGS, but most are in other State or Federal agencies. Each ESIC responds to requests for information received by telephone, letter, or personal visit. Your personal visit.

Earth meandering

NASA Astrophysics Data System (ADS)

Asadiyan, H.; Zamani, A.

2009-04-01

In this paper we try to put away current Global Tectonic Model to look the tectonic evolution of the earth from new point of view. Our new dynamic model is based on study of river meandering (RM) which infer new concept as Earth meandering(EM). In a universal gravitational field if we consider a clockwise spiral galaxy model rotate above Ninety East Ridge (geotectonic axis GA), this system with applying torsion field (likes geomagnetic field) in side direction from Rocky Mt. (west geotectonic pole WGP) to Tibetan plateau TP (east geotectonic pole EGP),it seems that pulled mass from WGP and pushed it in EGP due to it's rolling dynamics. According to this idea we see in topographic map that North America and Green land like a tongue pulled from Pacific mouth toward TP. Actually this system rolled or meander the earth over itself fractaly from small scale to big scale and what we see in the river meandering and Earth meandering are two faces of one coin. River transport water and sediments from high elevation to lower elevation and also in EM, mass transport from high altitude-Rocky Mt. to lower altitude Himalaya Mt. along 'S' shape geodetic line-optimum path which connect points from high altitude to lower altitude as kind of Euler Elastica(EE). These curves are responsible for mass spreading (source) and mass concentration (sink). In this regard, tiltness of earth spin axis plays an important role, 'S' are part of sigmoidal shape which formed due to intersection of Earth rolling with the Earth glob and actual feature of transform fault and river meandering. Longitudinal profile in mature rivers as a part of 'S' curve also is a kind of EE. 'S' which bound the whole earth is named S-1(S order 1) and cube corresponding to this which represent Earth fracturing in global scale named C-1(cube order 1 or side vergence cube SVC), C-1 is a biggest cycle of spiral polygon, so it is not completely closed and it has separation about diameter of C-7. Inside SVC we introduce cone

Defending Planet Earth: Near-Earth Object Surveys and Hazard Mitigation Strategies

NASA Technical Reports Server (NTRS)

2010-01-01

The United States spends approximately four million dollars each year searching for near-Earth objects (NEOs). The objective is to detect those that may collide with Earth. The majority of this funding supports the operation of several observatories that scan the sky searching for NEOs. This, however, is insufficient in detecting the majority of NEOs that may present a tangible threat to humanity. A significantly smaller amount of funding supports ways to protect the Earth from such a potential collision or "mitigation." In 2005, a Congressional mandate called for NASA to detect 90 percent of NEOs with diameters of 140 meters of greater by 2020. Defending Planet Earth: Near-Earth Object Surveys and Hazard Mitigation Strategies identifies the need for detection of objects as small as 30 to 50 meters as these can be highly destructive. The book explores four main types of mitigation including civil defense, "slow push" or "pull" methods, kinetic impactors and nuclear explosions. It also asserts that responding effectively to hazards posed by NEOs requires national and international cooperation. Defending Planet Earth: Near-Earth Object Surveys and Hazard Mitigation Strategies is a useful guide for scientists, astronomers, policy makers and engineers.

Discover Earth: Earth's Energy Budget or Can You Spare a Sun?

NASA Technical Reports Server (NTRS)

Gates, Tom; Peters, Dale E.; Steeley, Jeanne

1999-01-01

Discover Earth is a NASA-sponsored project for teachers of grades 5-12, designed to: enhance understanding of the Earth as an integrated system enhance the interdisciplinary approach to science instruction, and provide classroom materials that focus on those goals. Discover Earth is conducted by the Institute for Global Environmental Strategies in collaboration with Dr. Eric Barron, Director, Earth System Science Center, The Pennsylvania State University; and Dr. Robert Hudson, Chair, the Department of Meteorology, University of Maryland at College Park.

Earth - South America First Frame of Earth Spin Movie

NASA Image and Video Library

1996-01-29

This color image of the Earth was obtained by NASA's Galileo at about 6:10 a.m. Pacific Standard Time on Dec. 11, 1990, when the spacecraft was about 1.3 million miles from the planet during the first of two Earth flybys on its way to Jupiter. The color composite used images taken through the red, green and violet filters. South America is near the center of the picture, and the white, sunlit continent of Antarctica is below. Picturesque weather fronts are visible in the South Atlantic, lower right. This is the first frame of the Galileo Earth spin movie, a 500- frame time-lapse motion picture showing a 25-hour period of Earth's rotation and atmospheric dynamics. A movie is availalble at http://photojournal.jpl.nasa.gov/catalog/PIA00114

Simulation of interference between Earth stations and Earth-orbiting satellites

NASA Technical Reports Server (NTRS)

Bishop, D. F.

1994-01-01

It is often desirable to determine the potential for radio frequency interference between earth stations and orbiting spacecraft. This information can be used to select frequencies for radio systems to avoid interference or it can be used to determine if coordination between radio systems is necessary. A model is developed that will determine the statistics of interference between earth stations and elliptical orbiting spacecraft. The model uses orbital dynamics, detailed antenna patterns, and spectral characteristics to obtain accurate levels of interference at the victim receiver. The model is programmed into a computer simulation to obtain long-term statistics of interference. Two specific examples are shown to demonstrate the model. The first example is a simulation of interference from a fixed-satellite earth station to an orbiting scatterometer receiver. The second example is a simulation of interference from earth-exploration satellites to a deep-space earth station.

New Technique for Cryogenically Cooling Small Test Articles

NASA Technical Reports Server (NTRS)

Rodriquez, Karen M.; Henderson, Donald J.

2011-01-01

Convective heat removal techniques to rapidly cool small test articles to Earth-Moon L2 temperatures of 77 K were accomplished through the use of liquid nitrogen (LN2). By maintaining a selected pressure range on the saturation curve, test articles were cooled below the LN2 boiling point at ambient pressure in less than 30 min. Difficulties in achieving test pressures while maintaining the temperature tolerance necessitated a modification to the original system to include a closed loop conductive cold plate and cryogenic shroud

Research Summary Number 36-14

DTIC Science & Technology

1962-05-01

probe up to the time of perihelion passage. Note from the two figures that for launching when the 1. Low- Energy Solar Trajectories Earth is near...vs C, (twice total geocentric energy per unit motion. Figure 2a shows a plot of the probe’s aphelion mass), where the outgoing geocentric asymptote...EARTH’S PER.-.. S60 z 3 - HELION 350 R, LAUNCH AT EARTH’S 0 ,LN AT RpLAUNCHCATAEARTH’S PHAPHE ION 60 2 2 0 " t . .. 250 L H LAUNCH AT EARTHS 0

The Not-So-Rare Earths.

ERIC Educational Resources Information Center

Muecke, Gunter K.; Moller, Peter

1988-01-01

Describes the characteristics of rare earth elements. Details the physical chemistry of rare earths. Reviews the history of rare earth chemistry and mineralogy. Discusses the mineralogy and crystallography of the formation of rare earth laden minerals found in the earth's crust. Characterizes the geologic history of rare earth elements. (CW)

Sun-Earth Day: Exposing the Public to Sun-Earth Connection Science

NASA Astrophysics Data System (ADS)

Thieman, J. R.; Lewis, E.; Cline, T.

2001-12-01

The year 2001 marked the first observance of Sun-Earth Day as an event to celebrate the strong interconnection of the life we have on Earth and the dependence of it on the dynamic influence of the Sun. The science of the Sun-Earth Connection has grown dramatically with new satellite and ground-based studies of the Sun and the Sun's extended "atmosphere" in which we live. Space weather is becoming a more common concept that people know can affect their lives. An understanding of the importance of the Sun's dynamic behavior and how this shapes the solar system and especially the Earth is the aim of Sun-Earth Day. The first Sun-Earth event actually took place over two days, April 27 and 28, 2001, in order to accommodate all the events which were planned both in the classroom on Friday the 27th and in more informal settings on Saturday the 28th. The Sun-Earth Connection Education Forum (SECEF) organized the creation of ten thousand packets of educational materials about Sun-Earth Day and distributed them mostly to teachers who were trained to use them in the classroom. Many packets, however, went to science centers, museums, and planetariums as resource materials for programs associated with Sun-Earth Day. Over a hundred scientists used the event as an opportunity to communicate their love of science to audiences in these informal settings. Sun-Earth Day was also greatly assisted by the Amateur Astronomical Society which used the event as a theme for their annual promotion of astronomy in programs given around the country. The Solar and Heliospheric Observatory (SOHO), a satellite mission jointly sponsored by NASA and the European Space Agency (ESA), used Sun-Earth Day in conjunction with the fifth anniversary celebration of SOHO as a basis for many programs and events, especially a large number of happenings in Europe. These included observing parties, art exhibits, demonstrations, etc. Examples of some of the innovative ways that Sun-Earth Day was brought into people

Early Earth(s) Across Time and Space

NASA Astrophysics Data System (ADS)

Mojzsis, S.

2014-04-01

The geochemical and cosmochemical record of our solar system is the baseline for exploring the question: "when could life appear on a world similar to our own?" Data arising from direct analysis of the oldest terrestrial rocks and minerals from the first 500 Myr of Earth history - termed the Hadean Eon - inform us about the timing for the establishment of a habitable silicate world. Liquid water is the key medium for life. The origin of water, and its interaction with the crust as revealed in the geologic record, guides our exploration for a cosmochemically Earth-like planets. From the time of primary planetary accretion to the start of the continuous rock record on Earth at ca. 3850 million years ago, our planet experienced a waning bolide flux that partially or entirely wiped out surface rocks, vaporized oceans, and created transient serpentinizing atmospheres. Arguably, "Early Earths" across the galaxy may start off as ice planets due to feeble insolation from their young stars, occasionally punctuated by steam atmospheres generated by cataclysmic impacts. Alternatively, early global environments conducive to life spanned from a benign surface zone to deep into crustal rocks and sediments. In some scenarios, nascent biospheres benefit from the exogenous delivery of essential bio-elements via leftovers of accretion, and the subsequent establishment of planetary-scale hydrothermal systems. If what is now known about the early dynamical regime of the Earth serves as any measure of the potential habitability of worlds across space and time, several key boundary conditions emerge. These are: (i) availability and long-term stability of liquid water; (ii) presence of energy resources; (iii) accessibility of organic raw materials; (iv) adequate inventory of radioisotopes to drive internal heating; (v) gross compositional parameters such as mantle/core mass ratio, and (vi) P-T conditions at or near the surface suitable for sustaining biological activity. Life could

M2+ Doping Induced Simultaneous Phase/Size Control and Remarkable Enhanced Upconversion Luminescence of NaLnF4 Probes for Optical-Guided Tiny Tumor Diagnosis.

PubMed

Li, Youbin; Li, Xiaolong; Xue, Zhenluan; Jiang, Mingyang; Zeng, Songjun; Hao, Jianhua

2017-05-01

Doping has played a vital role in constructing desirable hybrid materials with tunable functions and properties via incorporating atoms into host matrix. Herein, a simple strategy for simultaneously modifying the phase, size, and upconversion luminescence (UCL) properties of the NaLnF 4 (Ln = Y, Yb) nanocrystals by high-temperature coprecipitation through nonequivalent M 2+ doping (M = Mg 2+ , Co 2+ ) has been demonstrated. The phase transformation from cubic to hexagonal is readily achieved by doping M 2+ . Compared with Mg-free sample, a remarkable enhancement of overall UCL (≈27.5 times) is obtained by doping Mg 2+ . Interestingly, owing to the efficient UCL, red UCL-guided tiny tumor (down to 3 mm) diagnosis is demonstrated for the first time. The results open up a new way of designing high efficient UCL probe with combination of hexagonal phase and small size for tiny tumor detection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NASA Earth Day 2014

NASA Image and Video Library

2014-04-22

NASA Administrator Charles Bolden speaks to students who attended the NASA sponsored Earth Day event April 22, 2014 at Union Station in Washington, DC. NASA sponsored the Earth Day event as part of its "Earth Right Now" campaign, celebrating the launch of five Earth-observing missions in 2014. Photo Credit: (NASA/Aubrey Gemignani)

Isomorphous Substitution of Rare-Earth Elements in Lacunary Apatite Pb8Na2(PO4)6.

PubMed

Get'man, Evgeni I; Loboda, Stanislav N; Ignatov, Alexey V; Prisedsky, Vadim V; Abdul Jabar, Mohammed A B; Ardanova, Lyudmyla I

2016-03-07

The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity.

Discover Earth

NASA Technical Reports Server (NTRS)

1997-01-01

Discover Earth is a NASA-funded project for teachers of grades 5-12 who want to expand their knowledge of the Earth system, and prepare to become master teachers who promote Earth system science in their own schools, counties, and throughout their state. Participants from the following states are invited to apply: Connecticut, Delaware, Maine, Maryland, Massachusetts, New Hampshire, New Jersey, New York, Pennsylvania, Rhode Island, Vermont, and Washington, DC. Teachers selected for the project participate in a two-week summer workshop conducted at the University of Maryland, College Park; develop classroom-ready materials during the workshop for broad dissemination; conduct a minimum of two peer training activities during the coming school year; and participate in other enrichment/education opportunities as available and desired. Discover Earth is a team effort that utilizes expertise from a range of contributors, and balances science content with hands-on classroom applications.

Uderstanding Snowball Earth Deglaciation

NASA Astrophysics Data System (ADS)

Abbot, D. S.

2012-12-01

Earth, a normally clement planet comfortably in its star's habitable zone, suffered global or nearly global glaciation at least twice during the Neoproterozoic era (at about 635 and 710 million years ago). Viewed in the context of planetary evolution, these pan-global glaciations (Snowball Earth events) were extremely rapid, lasting only a few million years. The dramatic effect of the Snowball Earth events on the development of the planet can be seen through their link to rises in atmospheric oxygen and evolutionary innovations. These potential catastrophes on an otherwise clement planet can be used to gain insight into planetary habitability more generally. Since Earth is not currently a Snowball, a sound deglaciation mechanism is crucial for the viability of the Snowball Earth hypothesis. The traditional deglaciation mechanism is a massive build up of CO2 due to reduced weathering during Snowball Earth events until tropical surface temperatures reach the melting point. Once initiated, such a deglaciation might happen on a timescale of only dozens of thousands of years and would thrust Earth from the coldest climate in its history to the warmest. Therefore embedded in Snowball Earth events is an even more rapid and dramatic environmental change. Early global climate model simulations raised doubt about whether Snowball Earth deglaciation could be achieved at a CO2 concentration low enough to be consistent with geochemical data, which represented a potential challenge to the Snowball Earth hypothesis. Over the past few years dust and clouds have emerged as the essential missing additional processes that would allow Snowball Earth deglaciation at a low enough CO2 concentration. I will discuss the dust and cloud mechanisms and the modeling behind these ideas. This effort is critical for the broader implications of Snowball Earth events because understanding the specific deglaciation mechanism determines whether similar processes could happen on other planets.

The "Earth Physics" Workshops Offered by the Earth Science Education Unit

ERIC Educational Resources Information Center

Davies, Stephen

2012-01-01

Earth science has a part to play in broadening students' learning experience in physics. The Earth Science Education Unit presents a range of (free) workshops to teachers and trainee teachers, suggesting how Earth-based science activities, which show how we understand and use the planet we live on, can easily be slotted into normal science…

An Algorithm for Converting Static Earth Sensor Measurements into Earth Observation Vectors

NASA Technical Reports Server (NTRS)

Harman, R.; Hashmall, Joseph A.; Sedlak, Joseph

2004-01-01

An algorithm has been developed that converts penetration angles reported by Static Earth Sensors (SESs) into Earth observation vectors. This algorithm allows compensation for variation in the horizon height including that caused by Earth oblateness. It also allows pitch and roll to be computed using any number (greater than 1) of simultaneous sensor penetration angles simplifying processing during periods of Sun and Moon interference. The algorithm computes body frame unit vectors through each SES cluster. It also computes GCI vectors from the spacecraft to the position on the Earth's limb where each cluster detects the Earth's limb. These body frame vectors are used as sensor observation vectors and the GCI vectors are used as reference vectors in an attitude solution. The attitude, with the unobservable yaw discarded, is iteratively refined to provide the Earth observation vector solution.

Tidal Locking Of The Earth

NASA Astrophysics Data System (ADS)

Koohafkan, Michael

2006-05-01

The Moon's orbit and spin period are nearly synchronized, or tidally locked. Could the Moon's orbit and the Earth's spin eventually synchronize as well? The Moon's gravitational pull on the Earth produces tides in our oceans, and tidal friction gradually lengthens our days. Less obvious gravitational interactions between the Earth and Moon may also have effects on Earth's spin. The Earth is slightly distorted into an egg-like shape, and the torque exerted by the Moon on our equatorial bulge slowly changes the tilt of our spin axis. How do effects such as these change as the Moon drifts away from Earth? I will examine gravitational interactions between Earth and Moon to learn how they contribute to the deceleration of the Earth's rotation. My goal is to determine the amount of time it would take for the Earth's rotational speed to decelerate until the period of a single rotation matches the period of the Moon's orbit around Earth -- when the Earth is ``tidally locked'' with the Moon. I aim to derive a general mathematical expression for the rotational deceleration of the Earth due to Moon's gravitational influences.

Modeling of the Earth's gravity field using the New Global Earth Model (NEWGEM)

NASA Technical Reports Server (NTRS)

Kim, Yeong E.; Braswell, W. Danny

1989-01-01

Traditionally, the global gravity field was described by representations based on the spherical harmonics (SH) expansion of the geopotential. The SH expansion coefficients were determined by fitting the Earth's gravity data as measured by many different methods including the use of artificial satellites. As gravity data have accumulated with increasingly better accuracies, more of the higher order SH expansion coefficients were determined. The SH representation is useful for describing the gravity field exterior to the Earth but is theoretically invalid on the Earth's surface and in the Earth's interior. A new global Earth model (NEWGEM) (KIM, 1987 and 1988a) was recently proposed to provide a unified description of the Earth's gravity field inside, on, and outside the Earth's surface using the Earth's mass density profile as deduced from seismic studies, elevation and bathymetric information, and local and global gravity data. Using NEWGEM, it is possible to determine the constraints on the mass distribution of the Earth imposed by gravity, topography, and seismic data. NEWGEM is useful in investigating a variety of geophysical phenomena. It is currently being utilized to develop a geophysical interpretation of Kaula's rule. The zeroth order NEWGEM is being used to numerically integrate spherical harmonic expansion coefficients and simultaneously determine the contribution of each layer in the model to a given coefficient. The numerically determined SH expansion coefficients are also being used to test the validity of SH expansions at the surface of the Earth by comparing the resulting SH expansion gravity model with exact calculations of the gravity at the Earth's surface.

Earth Science

NASA Image and Video Library

1976-01-01

The LAGEOS I (Laser Geodynamics Satellite) was developed and launched by the Marshall Space Flight Center on May 4, 1976 from Vandenberg Air Force Base, California . The two-foot diameter satellite orbited the Earth from pole to pole and measured the movements of the Earth's surface.

Raising awareness for research on earth walls, and earth scientific aspects

NASA Astrophysics Data System (ADS)

van den Ancker, Hanneke; Jungerius, Pieter Dirk; Baas, Henk; Groenewoudt, Bert; Peen, Charlotte

2013-04-01

A conference to raise awareness In the Netherlands, little research on earth walls has been done. To improve attention for earth walls, a number of organisations, including Geoheritage NL, organized a conference at the RCE, the Cultural Heritage Agency of the Netherlands. The conference* presented a state-of-the-art of research done. The book with the presentations, and extra case studies added, was published in December 2012. The book concludes with a research action list, including earth science research, and can be downloaded freely from the internet. It has English summaries. The earth science aspects Historical earth walls do not only add cultural value to a landscape, but also geodiversity value. Apart from geomorphological aspects, the walls contain information about past land- and climate conditions: - They cover up a former topography, a past landscape. A relevant source of scientific information where lands are levelled, as is the case in many parts of The Netherlands; - The soil formation under the earth wall is a reference soil. The soil formation in the top of the wall gives insight in the rate of soil formation in relationship with the age and parent material of the wall; - The soil profiles of different age have ecological significance. Older walls with a more pronounced soil formation often hold forest flora that has disappeared from the surrounding environment, such as historical bush or tree species, autogenetic DNA material or a specific soil fauna; - The materials in the earth walls tell about the process of wall-building. Paleosols and sedimentary structures in the earth walls, in the gullies and colluvial fans along the walls contain information about past land management and climate. - The eroded appearance of the earth walls is part of their history, and contain information about past management and land conditions, has ecological relevance, for example for insects, and is often visually more interesting. Insight in the rates of erosion are

EarthChem: International Collaboration for Solid Earth Geochemistry in Geoinformatics

NASA Astrophysics Data System (ADS)

Walker, J. D.; Lehnert, K. A.; Hofmann, A. W.; Sarbas, B.; Carlson, R. W.

2005-12-01

The current on-line information systems for igneous rock geochemistry - PetDB, GEOROC, and NAVDAT - convincingly demonstrate the value of rigorous scientific data management of geochemical data for research and education. The next generation of hypothesis formulation and testing can be vastly facilitated by enhancing these electronic resources through integration of available datasets, expansion of data coverage in location, time, and tectonic setting, timely updates with new data, and through intuitive and efficient access and data analysis tools for the broader geosciences community. PetDB, GEOROC, and NAVDAT have therefore formed the EarthChem consortium (www.earthchem.org) as a international collaborative effort to address these needs and serve the larger earth science community by facilitating the compilation, communication, serving, and visualization of geochemical data, and their integration with other geological, geochronological, geophysical, and geodetic information to maximize their scientific application. We report on the status of and future plans for EarthChem activities. EarthChem's development plan includes: (1) expanding the functionality of the web portal to become a `one-stop shop for geochemical data' with search capability across databases, standardized and integrated data output, generally applicable tools for data quality assessment, and data analysis/visualization including plotting methods and an information-rich map interface; and (2) expanding data holdings by generating new datasets as identified and prioritized through community outreach, and facilitating data contributions from the community by offering web-based data submission capability and technical assistance for design, implementation, and population of new databases and their integration with all EarthChem data holdings. Such federated databases and datasets will retain their identity within the EarthChem system. We also plan on working with publishers to ease the assimilation

Structures and standard molar enthalpies of formation of a series of Ln(III)–Cu(II) heteronuclear compounds with pyrazine-2,3-dicarboxylic acid

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

Yang, Qi; Xie, Gang; Wei, Qing

2014-07-01

Fifteen lanthanide–copper heteronuclear compounds, formulated as [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 6}]·xH{sub 2}O (1–6(x=2), 8(x=3), 9–10(x=4)); [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 4}]·xH{sub 2}O (7, 12–13, 15(x=4), 14(x=5), 11(x=8)) (Ln(III)=La(1); Ce(2); Pr(3); Nd(4); Sm(5); Eu(6); Gd(7); Tb(8); Dy(9); Ho(10); Er(11); Tm(12); Yb(13); Lu(14); Y(15); H{sub 2}pzdc (C{sub 6}H{sub 4}N{sub 2}O{sub 4})=pyrazine-2,3-dicarboxylic acid) have been hydrothermally synthesized. All compounds were characterized by element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analyses confirm that all compounds are isostructural and feature a 3D brick-like framework structure with (4.6{sup 2}){sub 2}(4{sup 2}.6{sup 2}.8{sup 2})(6{sup 3}){sup 2}(6{sup 5}.8){sub 2} topology. Using 1 mol cm{supmore » −3} HCl(aq) as calorimetric solvent, with an isoperibol solution–reaction calorimeter, the standard molar enthalpies of formation of all compounds were determined by a designed thermochemical cycle. In addition, solid state luminescence properties of compounds 5, 6, 8 and 9 were studied in the solid state. - Graphical abstract: According to Hess' rule, the standard molar enthalpies of formation of Ln–Cu heterometallic coordination compounds were determined by a designed thermochemical cycle. - Highlights: • Fifteen lanthanide–copper heteronuclear isostructural compounds. • Structurally characterization by IR, X-ray diffraction and thermal analysis. • The standard molar enthalpy of formation. • Isoperibol solution–reaction calorimetry.« less

Di-Ethylhexylphthalate (DEHP) Modulates Cell Invasion, Migration and Anchorage Independent Growth through Targeting S100P in LN-229 Glioblastoma Cells

PubMed Central

Sims, Jennifer Nicole; Graham, Barbara; Pacurari, Maricica; Leggett, Sophia S.; Tchounwou, Paul B.; Ndebele, Kenneth

2014-01-01

Glioblastoma multiforme (GBM) is the most aggressive brain cancer with a median survival of 1–2 years. The treatment of GBM includes surgical resection, radiation and chemotherapy, which minimally extends survival. This poor prognosis necessitates the identification of novel molecular targets associated with glioblastoma. S100P is associated with drug resistance, metastasis, and poor clinical outcomes in many malignancies. The functional role of S100P in glioblastoma has not been fully investigated. In this study, we examined the role of S100P mediating the effects of the environmental contaminant, DEHP, in glioblastoma cells (LN-229) by assessing cell proliferation, apoptosis, anchorage independent growth, cell migration and invasion following DEHP exposure. Silencing S100P and DEHP treatment inhibited LN-229 glioblastoma cell proliferation and induced apoptosis. Anchorage independent growth study revealed significantly decreased colony formation in shS100P cells. We also observed reduced cell migration in cells treated with DEHP following S100P knockdown. Similar results were observed in spheroid formation and expansion. This study is the first to demonstrate the effects of DEHP on glioblastoma cells, and implicates S100P as a potential therapeutic target that may be useful as a drug response biomarker. PMID:24821384

Encapsulation of Ln(III) Ions/Dyes within a Microporous Anionic MOF by Post-synthetic Ionic Exchange Serving as a Ln(III) Ion Probe and Two-Color Luminescent Sensors.

PubMed

Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Feng, Jing; Song, Shu-Yan; Zhang, Hong-Jie

2015-06-26

A new anionic framework {[Me2NH2]0.125[In0.125(H2L)0.25]⋅xDMF}n (1) with one-dimensional (1D) channels along the c axis of about 13.06×13.06 Å(2), was solvothermally synthesized and well characterized. Post-synthetic cation exchange of 1 with Eu(3+), Tb(3+), Dy(3+), Sm(3+) afforded lanthanide(III)-loaded materials, Ln(3+)@1, with different luminescent behavior, indicating that compound 1 could be used as a potential luminescent probe toward different lanthanide(III) ions. Additionally, compound 1 exhibits selective adsorption ability toward cationic dyes. Moreover, the RhB@1 realized the probing of different organic solvent molecules by tuning the energy transfer efficiency between two different emissions, especially for sensing DMF. This work highlights the practical application of luminescent guest@MOFs as sensors, and it paves the way toward other one/multi-color luminescent host-guest systems by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional PEG-PAMAM-tetraphosphonate capped NaLnF₄ nanoparticles and their colloidal stability in phosphate buffer.

PubMed

Zhao, Guangyao; Tong, Lemuel; Cao, Pengpeng; Nitz, Mark; Winnik, Mitchell A

2014-06-17

Developing surface coatings for NaLnF4 nanoparticles (NPs) that provide long-term stability in solutions containing competitive ions such as phosphate remains challenging. An amine-functional polyamidoamine tetraphosphonate (NH2-PAMAM-4P) as a multidentate ligand for these NPs has been synthesized and characterized as a ligand for the surface of NaGdF4 and NaTbF4 nanoparticles. A two-step ligand exchange protocol was developed for introduction of the NH2-PAMAM-4P ligand on oleate-capped NaLnF4 NPs. The NPs were first treated with methoxy-poly(ethylene glycol)-monophosphoric acid (M(n) = 750) in tetrahydrofuran. The mPEG750-OPO3-capped NPs were stable colloidal solutions in water, where they could be ligand-exchanged with NH2-PAMAM-4P. The surface amine groups on the NPs were available for derivatization to attach methoxy-PEG (M(n) = 2000) and biotin-terminated PEG (M(n) = 2000) chains. The surface coverage of ligands on the NPs was examined by thermal gravimetric analysis, and by a HABA analysis for biotin-containing NPs. Colloidal stability of the NPs was examined by dynamic light scattering. NaGdF4 and NaTbF4 NPs capped with mPEG2000-PAMAM-4P showed colloidal stability in DI water and in phosphate buffer (10 mM, pH 7.4). A direct comparison with NaTbF4 NPs capped with a mPEG2000-lysine-based tetradentate ligand that we reported previously (Langmuir 2012, 28, 12861-12870) showed that both ligands provided long-term stability in phosphate buffer, but that the lysine-based ligand provided better stability in phosphate-buffered saline.

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.

Enhanced ferromagnetic order in Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} featuring canted [MnO{sub 4}]{sub ∞} spin chains of mixed-valent Mn(III)/Mn(IV). Aliovalent substitution of the Sr{sub 4−x}Ln{sub x}Mn{sup III}{sub 2+x}Mn{sup IV}{sub 1−x}O{sub 3}(GeO{sub 4}){sub 3} solid-solution

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

West, J. Palmer; Sulejmanovic, Dino; Becht, Gregory

2013-10-15

Crystals of Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0; x∼0.15 for Ln=La, Pr, Nd, Sm. Eu, Gd, Dy; x∼0.3 for Ln=Gd) were isolated upon using high-temperature, solid-state methods in molten-salt media. These compounds are isostructural with the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} (Ln=La, Sm, Gd) series that contains the same [MnO{sub 4}]{sub ∞} spin chains. The synthesis of the Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0) phase was carried out by a double aliovalent substitution with respect to the Sr{sup 2+} and Ge{sup 4+} ions that replace Na{sup +}/Ln{sup 3+} and As{sup 5+} in Na{sub 3}LnMn{submore » 3}O{sub 3}(AsO{sub 4}){sub 3}, respectively. The title series contains mixed-valent Mn(III)/Mn(IV) and shows a limited range of solid solution, both of which were not observed in the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series. To form the Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} solid solution, one of the Sr{sup 2+} sites, i.e., the original Ln-site in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, is partially substituted by Ln{sup 3+} in a statistical disorder of Sr{sub 1−x}/Ln{sub x}. Initial magnetic investigations of selected derivatives reveal higher ferromagnetic ordering temperatures than those reported for the Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series, presumably attributed to a lesser degree of canting as a result of introducing non-Jahn–Teller Mn{sup 4+} ions. Also intriguing is the observation of multiple anomalies at low temperatures which appear to be of electronic origins. - Graphical abstract: Sr{sub 4−x}Ln{sub x}Mn(III){sub 2+x}Mn(IV){sub 1−x}O{sub 3}(GeO{sub 4}){sub 3}. Display Omitted - Highlights: • Double aliovalent substitution: Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} with respect to Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}. • Solid solution with respect to statistical disorder of Sr{sub 1−x}Ln

EarthEd Online: Open Source Online Software to Support Large Courses

NASA Astrophysics Data System (ADS)

Prothero, W. A.

2003-12-01

The purpose of the EarthEd Online software project is to support a modern instructional pedagogy in a large, college level, earth science course. It is an ongoing development project that has evolved in a large general education oceanography course over the last decade. Primary goals for the oceanography course are to support learners in acquiring a knowledge of science process, an appreciation for the relevance of science to society, and basic content knowledge. In order to support these goals, EarthEd incorporates: a) integrated access to various kinds of real earth data (and links to web-based data browsers), b) online discussions, live chat, with integrated graphics editing, linking, and upload, c) online writing, reviewing, and grading, d) online homework assignments, e) on demand grade calculation, and f) instructor grade entry and progress reports. The software was created using Macromedia Director. It is distributed to students on a CDROM and updates are downloaded and installed automatically. Data browsers for plate tectonics relevant data ("Our Dynamic Planet"), a virtual exploration of the East Pacific Rise, the World Ocean Atlas-98, and a fishing simulation game are integrated with the EarthEd software. The system is modular which allows new capabilities, such as new data browsers, to be added. Student reactions to the software are positive overall. They are especially appreciative of the on demand grade computation capability. The online writing, commenting and grading is particularly effective in managing the large number of papers that get submitted. The TA's grade the papers, but the instructor can provide feedback to them as they grade the papers, and a record is maintained of all comments and rubric item grades. Commenting is made easy by simply "dragging" a selection of pre-defined comments into the student's text. Scoring is supported by an integrated scoring rubric. All assignments, rubrics, etc. are configured in text files that are downloaded

Earth Global Reference Atmospheric Model (Earth-GRAM) GRAM Virtual Meeting

NASA Technical Reports Server (NTRS)

White, Patrick

2017-01-01

What is Earth-GRAM? Provide monthly mean and standard deviation for any point in atmosphere; Monthly, Geographic, and Altitude Variation. Earth-GRAM is a C++ software package; Currently distributed as Earth-GRAM 2016. Atmospheric variables included: pressure, density, temperature, horizontal and vertical winds, speed of sound, and atmospheric constituents. Used by engineering community because of ability to create dispersions inatmosphere at a rapid runtime; Often embedded in trajectory simulation software. Not a forecast model. Does not readily capture localized atmospheric effects.

EarthServer: Cross-Disciplinary Earth Science Through Data Cube Analytics

NASA Astrophysics Data System (ADS)

Baumann, P.; Rossi, A. P.

2016-12-01

The unprecedented increase of imagery, in-situ measurements, and simulation data produced by Earth (and Planetary) Science observations missions bears a rich, yet not leveraged potential for getting insights from integrating such diverse datasets and transform scientific questions into actual queries to data, formulated in a standardized way.The intercontinental EarthServer [1] initiative is demonstrating new directions for flexible, scalable Earth Science services based on innovative NoSQL technology. Researchers from Europe, the US and Australia have teamed up to rigorously implement the concept of the datacube. Such a datacube may have spatial and temporal dimensions (such as a satellite image time series) and may unite an unlimited number of scenes. Independently from whatever efficient data structuring a server network may perform internally, users (scientist, planners, decision makers) will always see just a few datacubes they can slice and dice.EarthServer has established client [2] and server technology for such spatio-temporal datacubes. The underlying scalable array engine, rasdaman [3,4], enables direct interaction, including 3-D visualization, common EO data processing, and general analytics. Services exclusively rely on the open OGC "Big Geo Data" standards suite, the Web Coverage Service (WCS). Conversely, EarthServer has shaped and advanced WCS based on the experience gained. The first phase of EarthServer has advanced scalable array database technology into 150+ TB services. Currently, Petabyte datacubes are being built for ad-hoc and cross-disciplinary querying, e.g. using climate, Earth observation and ocean data.We will present the EarthServer approach, its impact on OGC / ISO / INSPIRE standardization, and its platform technology, rasdaman.References: [1] Baumann, et al. (2015) DOI: 10.1080/17538947.2014.1003106 [2] Hogan, P., (2011) NASA World Wind, Proceedings of the 2nd International Conference on Computing for Geospatial Research

Earth Science Education Plan: Inspire the Next Generation of Earth Explorers

NASA Technical Reports Server (NTRS)

2004-01-01

The Education Enterprise Strategy, the expanding knowledge of how people learn, and the community-wide interest in revolutionizing Earth and space science education have guided us in developing this plan for Earth science education. This document builds on the success of the first plan for Earth science education published in 1996; it aligns with the new framework set forth in the NASA Education Enterprise Strategy; it recognizes the new educational opportunities resulting from research programs and flight missions; and it builds on the accomplishments th'at the Earth Science Enterprise has made over the last decade in studying Earth as a system. This document embodies comprehensive, practicable plans for inspiring our children; providing educators with the tools they need to teach science, technology, engineering, and mathematics (STEM); and improving our citizens' scientific literacy. This plan describes an approach to systematically sharing knowledge; developing the most effective mechanisms to achieve tangible, lasting results; and working collaboratively to catalyze action at a scale great enough to ensure impact nationally and internationally. This document will evolve and be periodically reviewed in partnership with the Earth science education community.

Beautiful Earth: Inspiring Native American students in Earth Science through Music, Art and Science

NASA Astrophysics Data System (ADS)

Casasanto, V.; Rock, J.; Hallowell, R.; Williams, K.; Angell, D.; Beautiful Earth

2011-12-01

The Beautiful Earth program, awarded by NASA's Competitive Opportunities in Education and Public Outreach for Earth and Space Science (EPOESS), is a live multi-media performance at partner science centers linked with hands-on workshops featuring Earth scientists and Native American experts. It aims to inspire, engage and educate diverse students in Earth science through an experience of viewing the Earth from space as one interconnected whole, as seen through the eyes of astronauts. The informal education program is an outgrowth of Kenji Williams' BELLA GAIA Living Atlas Experience (www.bellagaia.com) performed across the globe since 2008 and following the successful Earth Day education events in 2009 and 2010 with NASA's DLN (Digital Learning Network) http://tinyurl.com/2ckg2rh. Beautiful Earth takes a new approach to teaching, by combining live music and data visualizations, Earth Science with indigenous perspectives of the Earth, and hands-on interactive workshops. The program will utilize the emotionally inspiring multi-media show as a springboard to inspire participants to learn more about Earth systems and science. Native Earth Ways (NEW) will be the first module in a series of three "Beautiful Earth" experiences, that will launch the national tour at a presentation in October 2011 at the MOST science museum in collaboration with the Onandaga Nation School in Syracuse, New York. The NEW Module will include Native American experts to explain how they study and conserve the Earth in their own unique ways along with hands-on activities to convey the science which was seen in the show. In this first pilot run of the module, 110 K-12 students with faculty and family members of the Onandaga Nations School will take part. The goal of the program is to introduce Native American students to Earth Sciences and STEM careers, and encourage them to study these sciences and become responsible stewards of the Earth. The second workshop presented to participants will be the

Effect of surface polishing and vacuum firing on electron stimulated desorption from 316LN stainless steel

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

Malyshev, Oleg B., E-mail: oleg.malyshev@stfc.ac.uk; Hogan, Benjamin T.; Pendleton, Mark

2014-09-01

The reduction of thermal outgassing from stainless steel by surface polishing or vacuum firing is well-known in vacuum technology, and the consequent use of both techniques allows an even further reduction of outgassing. The aim of this study was to identify the effectiveness of surface polishing and vacuum firing for reducing electron-stimulated desorption (ESD) from 316LN stainless steel, which is a frequently used material for particle accelerator vacuum chambers and components. It was found that, unlike for thermal outgassing, surface polishing does not reduce the ESD yield and may even increase it, while vacuum firing of nonpolished sample reduces onlymore » the H{sub 2} ESD yield by a factor 2.« less

Dehydrogenation of secondary amines: synthesis, and characterization of rare-earth metal complexes incorporating imino- or amido-functionalized pyrrolyl ligands.

PubMed

Li, Qinghai; Zhou, Shuangliu; Wang, Shaowu; Zhu, Xiancui; Zhang, Lijun; Feng, Zhijun; Guo, Liping; Wang, Fenhua; Wei, Yun

2013-02-28

The dehydrogenation of pyrrolyl-functionalized secondary amines initiated by rare-earth metal amides was systematically studied. Reactions of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with pyrrolyl-functionalized secondary amines 2-(t)BuNHCH(2)-5-R-C(4)H(2)NH (R = H (1), R = (t)Bu (2)) led to dehydrogenation of the secondary amines with isolation of imino-functionalized pyrrolyl rare-earth metal complexes [2-(t)BuN=CH-5-R-C(4)H(2)N](2)REN(SiMe(3))(2) (R = H, RE = Y (3a), Dy (3b), Yb (3c), Eu (3d); R = (t)Bu, RE = Y (4a), Dy (4b), Er (4c)). The mixed ligands erbium complex [2-(t)BuNCH(2)-5-(t)Bu-C(4)H(2)N]Er[2-(t)BuN=CH-5-(t)BuC(4)H(2)N](2)ClLi(2)(THF) (4c') was isolated in a short reaction time for the synthesis of complex 4c. Reaction of the deuterated pyrrolyl-functionalized secondary amine 2-((t)BuNHCHD)C(4)H(3)NH with yttrium amide [(Me(3)Si)(2)N](3)Y(μ-Cl)Li(THF)(3) further proved that pyrrolyl-amino ligands were transferred to pyrrolyl-imino ligands. Treatment of 2-((t)BuNHCH(2))C(4)H(3)NH (1) with excess (Me(3)Si)(2)NLi gave the only pyrrole deprotonated product {[η(5):η(2):η(1)-2-((t)BuNHCH(2))C(4)H(3)N]Li(2)N(SiMe(3))(2)}(2) (5), indicating that LiN(SiMe(3))(2) could not dehydrogenate the secondary amines to imines and rare-earth metal ions had a decisive effect on the dehydrogenation. The reaction of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with 1 equiv. of more bulky pyrrolyl-functionalized secondary amine 2-[(2,6-(i)Pr(2)C(6)H(3))NHCH(2)](C(4)H(3)NH) (6) in toluene afforded the only amine and pyrrole deprotonated dinuclear rare-earth metal amido complexes {(μ-η(5):η(1)):η(1)-2-[(2,6-(i)Pr(2)C(6)H(3))NCH(2)]C(4)H(3)N]LnN(SiMe(3))(2)}(2) (RE = Nd (7a), Sm (7b), Er (7c)), no dehydrogenation of secondary amine to imine products were observed. On the basis of experimental results, a plausible mechanism for the dehydrogenation of secondary amines to imines was proposed.

Galileo 1989 VEEGA trajectory design. [Venus-Earth-Earth-Gravity-Assist

NASA Technical Reports Server (NTRS)

D'Amario, Louis A.; Byrnes, Dennis V.; Johannesen, Jennie R.; Nolan, Brian G.

1989-01-01

The new baseline for the Galileo Mission is a 1989 Venus-earth-earth gravity-assist (VEEGA) trajectory, which utilizes three gravity-assist planetary flybys in order to reduce launch energy requirements significantly compared to other earth-Jupiter transfer modes. The launch period occurs during October-November 1989. The total flight time is about 6 years, with November 1995 as the most likely choice for arrival at Jupiter. Optimal 1989 VEEGA trajectories have been generated for a wide range of earth launch dates and Jupiter arrival dates. Launch/arrival space contour plots are presented for various trajectory parameters, including propellant margin, which is used to measure mission performance. The accessible region of the launch/arrival space is defined by propellant margin and launch energy constraints; the available launch period is approximately 1.5 months long.

Rare earth elements in coastal sediments of the northern Galician shelf: Influence of geological features

NASA Astrophysics Data System (ADS)

Prego, Ricardo; Caetano, Miguel; Bernárdez, Patricia; Brito, Pedro; Ospina-Alvarez, Natalia; Vale, Carlos

2012-03-01

The Northern coast of Galicia, NW Iberian Peninsula, exhibits a variety of geological features: Ortegal allochthonous complex, Ollo-de-Sapo autochthonous domain and massifs of Bares, Barqueiro and San-Ciprian. In order to examine the influence of terrestrial lithologies on coastal sediments, 103 samples were collected in the Rias of Ortigueira, Barqueiro and Viveiro, their neighbouring shelf and the estuaries of Mera, Sor and Landro rivers. Aluminium, Fe, Sc, particulate inorganic and organic carbon and rare earth elements (REE) were determined in the <2 mm fraction. In addition, calcite, muscovite, quartz and riebeckite minerals were identified and quantified in 33 selected samples. The distributions of riebeckite and Fe reflect the influence of Ortegal complex on the coastal areas around the Cape Ortegal. The highest concentrations of ΣREE were found in fine sediments from confined inner parts of the Rias (up to 233 mg kg-1), while most of the sands contained 11-70 mg kg-1. ΣREE normalised to European Shale (ES) highlights the relative abundance of lanthanides (ΣREEN>6) near Cape Ortegal and the innermost ria zones. The ratio between light and heavy REE (L/H) showed lower values (4-11) around Cape Ortegal and the shelf while higher ratios (15-23) were detected in west of the Cape Estaca-de-Bares and in the inner Viveiro Ria due to elevated contributions of La and Ce. The L/H values normalised to ES reflects the importance of HREE in the adjacent area to Ortegal Complex (LN/HN<0.8) and the LREE (LN/HN>1.4) in the inner estuaries and west Cape Estaca-de-Bares. The highest REE individual ES normalised were measured in fine-grained sediments of the Mera and Sor estuaries. Sediments from the eastern shelf of Cape Ortegal presented enhanced ratios only for HREE. These results indicate that distribution of REE in the northern Galician region is highly depending on the neighbouring lithological pattern, contrasting with the situation found in the western Galician

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

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

Abdelbaky, Mohammed S.M.; Amghouz, Zakariae, E-mail: amghouz.uo@uniovi.es; Servicios Científico-Técnicos, University of Oviedo—CINN, Oviedo 33006

) attract tremendous attention due to the unique characteristic of lanthanide cations, such as variable coordination numbers and geometries which often lead to novel complex structures, and also to their magnetic and photoluminescence properties. Herein, three LOFs formulated as [Ln{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (Ln=Y, Yb) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] have been obtained by hydrothermal method and characterized, and the photoluminescence properties of the Eu and Tb doped compounds are discussed. - Highlights: • Three novel LnOFs has been synthesized and characterized. • Crystal structures are based on tetranuclear cuban-like [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pYb and 25pY-1 are based on isolated [Ln{sub 4}(OH){sub 4}]{sup 8+} clusters. • 25pY-2 is based on infinite inorganic chains built up from [Y{sub 4}(OH){sub 4}]{sup 8+} clusters. • Photoluminescence studies show strong red and green light emissions.« less

Earth Wisdom.

ERIC Educational Resources Information Center

Van Matre, Steve

1985-01-01

In our human-centered ignorance and arrogance we are rapidly destroying the earth. We must start helping people understand the big picture of ecological concepts. What these concepts mean for our own lives and how we must begin to change our lifestyles in order to live more harmoniously with the earth. (JHZ)

Earth observation images taken as part of the EarthKAM educational program

NASA Image and Video Library

2000-02-13

S99-E-5267 (13 February 2000) --- City of El Paso, Texas, and Ciudad Juarez, Chihuahua, Mexico and the Rio Grande River, which separates them. An electronic still camera (ESC), mounted in one of Endeavour's aft flight deck windows, is recording imagery of hundreds of Earth targets for the EarthKAM project. Students across the United States and in France, Germany and Japan are taking photos throughout the STS-99 mission. And they are using these new photos, plus all the images already available in the EarthKAM system, to enhance their classroom learning in Earth and space science, social studies, geography, mathematics and more. For general EarthKAM information and more images from this flight, go to http://www.earthkam.ucsd.edu/

Towards Big Earth Data Analytics: The EarthServer Approach

NASA Astrophysics Data System (ADS)

Baumann, Peter

2013-04-01

Big Data in the Earth sciences, the Tera- to Exabyte archives, mostly are made up from coverage data whereby the term "coverage", according to ISO and OGC, is defined as the digital representation of some space-time varying phenomenon. Common examples include 1-D sensor timeseries, 2-D remote sensing imagery, 3D x/y/t image timeseries and x/y/z geology data, and 4-D x/y/z/t atmosphere and ocean data. Analytics on such data requires on-demand processing of sometimes significant complexity, such as getting the Fourier transform of satellite images. As network bandwidth limits prohibit transfer of such Big Data it is indispensable to devise protocols allowing clients to task flexible and fast processing on the server. The EarthServer initiative, funded by EU FP7 eInfrastructures, unites 11 partners from computer and earth sciences to establish Big Earth Data Analytics. One key ingredient is flexibility for users to ask what they want, not impeded and complicated by system internals. The EarthServer answer to this is to use high-level query languages; these have proven tremendously successful on tabular and XML data, and we extend them with a central geo data structure, multi-dimensional arrays. A second key ingredient is scalability. Without any doubt, scalability ultimately can only be achieved through parallelization. In the past, parallelizing code has been done at compile time and usually with manual intervention. The EarthServer approach is to perform a samentic-based dynamic distribution of queries fragments based on networks optimization and further criteria. The EarthServer platform is comprised by rasdaman, an Array DBMS enabling efficient storage and retrieval of any-size, any-type multi-dimensional raster data. In the project, rasdaman is being extended with several functionality and scalability features, including: support for irregular grids and general meshes; in-situ retrieval (evaluation of database queries on existing archive structures, avoiding data

Earth Science

NASA Image and Video Library

1994-09-02

This image depicts a full view of the Earth, taken by the Geostationary Operational Environment Satellite (GOES-8). The red and green charnels represent visible data, while the blue channel represents inverted 11 micron infrared data. The north and south poles were not actually observed by GOES-8. To produce this image, poles were taken from a GOES-7 image. Owned and operated by the National Oceanic and Atmospheric Administration (NOAA), GOES satellites provide the kind of continuous monitoring necessary for intensive data analysis. They circle the Earth in a geosynchronous orbit, which means they orbit the equatorial plane of the Earth at a speed matching the Earth's rotation. This allows them to hover continuously over one position on the surface. The geosynchronous plane is about 35,800 km (22,300 miles) above the Earth, high enough to allow the satellites a full-disc view of the Earth. Because they stay above a fixed spot on the surface, they provide a constant vigil for the atmospheric triggers for severe weather conditions such as tornadoes, flash floods, hail storms, and hurricanes. When these conditions develop, the GOES satellites are able to monitor storm development and track their movements. NASA manages the design and launch of the spacecraft. NASA launched the first GOES for NOAA in 1975 and followed it with another in 1977. Currently, the United States is operating GOES-8, positioned at 75 west longitude and the equator, and GOES-10, which is positioned at 135 west longitude and the equator. (GOES-9, which malfunctioned in 1998, is being stored in orbit as an emergency backup should either GOES-8 or GOES-10 fail. GOES-11 was launched on May 3, 2000 and GOES-12 on July 23, 2001. Both are being stored in orbit as a fully functioning replacement for GOES-8 or GOES-10 on failure.

Tracking silica in Earth's upper mantle using new sound velocity data for coesite to 5.8 GPa and 1073 K: Tracking Silica in Earth's Upper Mantle

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

Chen, Ting; Liebermann, Robert C.; Zou, Yongtao

The compressional and shear wave velocities for coesite have been measured simultaneously up to 5.8 GPa and 1073 K by ultrasonic interferometry for the first time. The shear wave velocity decreases with pressure along all isotherms. The resulting contrasts between coesite and stishovite reach ~34% and ~45% for P and S wave velocities, respectively, and ~64% and ~75% for their impedance at mantle conditions. The large velocity and impedance contrasts across coesite-stishovite transition imply that to generate the velocity and impedance contrasts observed at the X-discontinuity, only a small amount of silica would be required. The velocity jump dependences onmore » silica, d(lnVP)/d(SiO2) = 0.38 (wt %)-1 and d(lnVS)/d(SiO2) = 0.52 (wt %)-1, are utilized to place constraints on the amount of silica in the upper mantle and provide a geophysical approach to track mantle eclogite materials and ancient subducted oceanic slabs.« less

NASA Earth Day 2014

NASA Image and Video Library

2014-04-22

NASA Administrator Charles Bolden poses for a quick selfie with students who attended the NASA sponsored Earth Day event April 22, 2014 at Union Station in Washington, DC. NASA announced the "Global Selfie" event as part of its "Earth Right Now" campaign, celebrating the launch of five Earth-observing missions in 2014. All selfies posted to social media with the hashtag "GlobalSelfie" will be included in a mosaic image of Earth. Photo Credit: (NASA/Aubrey Gemignani)

Earth Science Informatics - Overview

NASA Technical Reports Server (NTRS)

Ramapriyan, H. K.

2015-01-01

Over the last 10-15 years, significant advances have been made in information management, there are an increasing number of individuals entering the field of information management as it applies to Geoscience and Remote Sensing data, and the field of informatics has come to its own. Informatics is the science and technology of applying computers and computational methods to the systematic analysis, management, interchange, and representation of science data, information, and knowledge. Informatics also includes the use of computers and computational methods to support decision making and applications. Earth Science Informatics (ESI, a.k.a. geoinformatics) is the application of informatics in the Earth science domain. ESI is a rapidly developing discipline integrating computer science, information science, and Earth science. Major national and international research and infrastructure projects in ESI have been carried out or are on-going. Notable among these are: the Global Earth Observation System of Systems (GEOSS), the European Commissions INSPIRE, the U.S. NSDI and Geospatial One-Stop, the NASA EOSDIS, and the NSF DataONE, EarthCube and Cyberinfrastructure for Geoinformatics. More than 18 departments and agencies in the U.S. federal government have been active in Earth science informatics. All major space agencies in the world, have been involved in ESI research and application activities. In the United States, the Federation of Earth Science Information Partners (ESIP), whose membership includes nearly 150 organizations (government, academic and commercial) dedicated to managing, delivering and applying Earth science data, has been working on many ESI topics since 1998. The Committee on Earth Observation Satellites (CEOS)s Working Group on Information Systems and Services (WGISS) has been actively coordinating the ESI activities among the space agencies. Remote Sensing; Earth Science Informatics, Data Systems; Data Services; Metadata

ACCESS Earth: Promoting Accessibility to Earth System Science for Students with Disabilities

NASA Astrophysics Data System (ADS)

Locke, S. M.; Cohen, L.; Lightbody, N.

2001-05-01

ACCESS Earth is an intensive summer institute for high school students with disabilities and their teachers that is designed to encourage students with disabilities to consider careers in earth system science. Participants study earth system science concepts at a Maine coastal estuary, using Geographic Information Systems, remote sensing, and field observations to evaluate the impacts of climate change, sea level rise, and development on coastal systems. Teachers, students, and scientists work together to adapt field and laboratory activities for persons with disabilities, including those with mobility and visual impairments. Other sessions include demonstrations of assistive technology, career discussions, and opportunities for students to meet with successful scientists with disabilities from throughout the U.S. The summer institute is one of several programs in development at the University of Southern Maine to address the problem of underrepresentation of people with disabilities in the earth sciences. Other projects include a mentoring program for high school students, a web-based clearinghouse of resources for teaching earth sciences to students with disabilities, and guidebooks for adaptation of popular published earth system science curricula for disabled learners.

Google Earth and Geo Applications: A Toolset for Viewing Earth's Geospatial Information

NASA Astrophysics Data System (ADS)

Tuxen-Bettman, K.

2016-12-01

Earth scientists measure and derive fundamental data that can be of broad general interest to the public and policy makers. Yet, one of the challenges that has always faced the Earth science community is how to present their data and findings in an easy-to-use and compelling manner. Google's Geo Tools offer an efficient and dynamic way for scientists, educators, journalists and others to both access data and view or tell stories in a dynamic three-dimensional geospatial context. Google Earth in particular provides a dense canvas of satellite imagery on which can be viewed rich vector and raster datasets using the medium of Keyhole Markup Language (KML). Through KML, Google Earth can combine the analytical capabilities of Earth Engine, collaborative mapping of My Maps, and storytelling of Tour Builder and more to make Google's Geo Applications a coherent suite of tools for exploring our planet.https://earth.google.com/https://earthengine.google.com/https://mymaps.google.com/https://tourbuilder.withgoogle.com/https://www.google.com/streetview/

Influence of slip-surface geometry on earth-flow deformation, Montaguto earth flow, southern Italy

USGS Publications Warehouse

Guerriero, L.; Coe, Jeffrey A.; Revellio, P.; Grelle, G.; Pinto, F.; Guadagno, F.

2016-01-01

We investigated relations between slip-surface geometry and deformational structures and hydrologic features at the Montaguto earth flow in southern Italy between 1954 and 2010. We used 25 boreholes, 15 static cone-penetration tests, and 22 shallow-seismic profiles to define the geometry of basal- and lateral-slip surfaces; and 9 multitemporal maps to quantify the spatial and temporal distribution of normal faults, thrust faults, back-tilted surfaces, strike-slip faults, flank ridges, folds, ponds, and springs. We infer that the slip surface is a repeating series of steeply sloping surfaces (risers) and gently sloping surfaces (treads). Stretching of earth-flow material created normal faults at risers, and shortening of earth-flow material created thrust faults, back-tilted surfaces, and ponds at treads. Individual pairs of risers and treads formed quasi-discrete kinematic zones within the earth flow that operated in unison to transmit pulses of sediment along the length of the flow. The locations of strike-slip faults, flank ridges, and folds were not controlled by basal-slip surface topography but were instead dependent on earth-flow volume and lateral changes in the direction of the earth-flow travel path. The earth-flow travel path was strongly influenced by inactive earth-flow deposits and pre-earth-flow drainages whose positions were determined by tectonic structures. The implications of our results that may be applicable to other earth flows are that structures with strikes normal to the direction of earth-flow motion (e.g., normal faults and thrust faults) can be used as a guide to the geometry of basal-slip surfaces, but that depths to the slip surface (i.e., the thickness of an earth flow) will vary as sediment pulses are transmitted through a flow.

Chiral Silver-Lanthanide Metal-Organic Frameworks Comprised of One-Dimensional Triple Right-Handed Helical Chains Based on [Ln7(μ3-OH)8]13+ Clusters.

PubMed

Guo, Yan; Zhang, Lijuan; Muhammad, Nadeem; Xu, Yan; Zhou, Yunshan; Tang, Fang; Yang, Shaowei

2018-02-05

Three new isostructural chiral silver-lanthanide heterometal-organic frameworks [Ag 3 Ln 7 (μ 3 -OH) 8 (bpdc) 6 (NO 3 ) 3 (H 2 O) 6 ](NO 3 )·2H 2 O [Ln = Eu (1), Tb (2, Sm (3); H 2 bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid] based on heptanuclear lanthanide clusters [Ln 7 (μ 3 -OH) 8 ] 13+ comprised of one-dimensional triple right-handed helical chains were hydrothermally synthesized. Various means such as UV-vis spectroscopy, IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric/differential thermal analysis were used to characterize the compounds, wherein compound 3 was crystallographically characterized. In the structure of compound 3, eight μ 3 -OH - groups link seven Sm 3+ ions, forming a heptanuclear cluster, [Sm 7 (μ 3 -OH) 8 ] 13+ , and the adjacent [Sm 7 (μ 3 -OH) 8 ] 13+ clusters are linked by the carboxylic groups of bpdc 2- ligands, leading to the formation of a one-dimensional triple right-handed helical chain. The adjacent triple right-handed helical chains are further joined together by coordinating the pyridyl N atoms of the bpdc 2- ligands with Ag + , resulting in a chiral three-dimensional silver(I)-lanthanide(III) heterometal-organic framework with one-dimensional channels wherein NO 3 - anions and crystal lattice H 2 O molecules are trapped. The compounds were studied systematically with respect to their photoluminescence properties and energy-transfer mechanism, and it was found that H 2 bpdc (the energy level for the triplet states of the ligand H 2 bpdc is 21505 cm -1 ) can sensitize Eu 3+ luminescence more effectively than Tb 3+ and Sm 3+ luminescence because of effective energy transfer from bpdc 2- to Eu 3+ under excitation in compound 1.

Earth - Moon Conjunction

NASA Technical Reports Server (NTRS)

1992-01-01

On December 16, 1992, 8 days after its encounter with Earth, the Galileo spacecraft looked back from a distance of about 6.2 million kilometers (3.9 million miles) to capture this remarkable view of the Moon in orbit about Earth. The composite photograph was constructed from images taken through visible (violet, red) and near-infrared (1.0-micron) filters. The Moon is in the foreground; its orbital path is from left to right. Brightly colored Earth contrasts strongly with the Moon, which reacts only about one-third as much sunlight as our world. To improve the visibility of both bodies, contrast and color have been computer enhanced. At the bottom of Earth's disk, Antarctica is visible through clouds. The Moon's far side can also be seen. The shadowy indentation in the Moon's dawn terminator--the boundary between its dark and lit sides--is the South Pole-Aitken Basin, one of the largest and oldest lunar impact features. This feature was studied extensively by Galileo during the first Earth flyby in December 1990.

NASA Sun Earth

NASA Image and Video Library

2017-12-08

CME blast and subsequent impact at Earth -- This illustration shows a CME blasting off the Sun’s surface in the direction of Ea CME blast and subsequent impact at Earth -- This illustration shows a CME blasting off the Sun’s surface in the direction of Earth. This left portion is composed of an EIT 304 image superimposed on a LASCO C2 coronagraph. Two to four days later, the CME cloud is shown striking and beginning to be mostly deflected around the Earth’s magnetosphere. The blue paths emanating from the Earth’s poles represent some of its magnetic field lines. The magnetic cloud of plasma can extend to 30 million miles wide by the time it reaches earth. These storms, which occur frequently, can disrupt communications and navigational equipment, damage satellites, and even cause blackouts. (Objects in the illustration are not drawn to scale.) Credit: NASA/GSFC/SOHO/ESA To learn more go to the SOHO website: sohowww.nascom.nasa.gov/home.html To learn more about NASA's Sun Earth Day go here: sunearthday.nasa.gov/2010/index.php

Controlled processing of (Gd,Ln)2O3:Eu (Ln = Y, Lu) red phosphor particles and compositional effects on photoluminescence

NASA Astrophysics Data System (ADS)

Lu, Bin; Li, Ji-Guang; Sakka, Yoshio

2013-12-01

Synthesis of (Gd0.95-xLnxEu0.05)2O3 (Ln = Y and Lu, x = 0-0.95) powders via ammonium hydrogen carbonate (AHC) precipitation has been systematically studied. The best synthesis parameters are found to be an AHC/total cation molar ratio of 4.5 and an ageing time of 3 h. The effects of Y3+ and Lu3+ substitution for Gd3+, on the nucleation kinetics of the precursors and structural features and optical properties of the oxides, have been investigated. The results show that (i) different nucleation kinetics exist in the Gd-Y-Eu and Gd-Lu-Eu ternary systems, which lead to various morphologies and particle sizes of the precipitated precursors. The (Gd,Y)2O3:Eu precursors display spherical particle morphologies and the particle sizes increase along with more Y3+ addition. The (Gd,Lu)2O3:Eu precursors, on the other hand, are hollow spheres and the particle sizes increase with increasing Lu3+ incorporation, (ii) the resultant oxide powders are ultrafine, narrow in size distribution, well dispersed and rounded in particle shape, (iii) lattice parameters of the two kinds of oxide solid solutions linearly decrease at a higher Y3+ or Lu3+ content. Their theoretical densities linearly decrease with increasing Y3+ incorporation, but increase along with more Lu3+ addition and (iv) the two kinds of phosphors exhibit typical red emissions at ˜613 nm and their charge-transfer bands blue shift at a higher Y3+ or Lu3+ content. Photoluminescence/photoluminescence excitation intensities and external quantum efficiency are found to decrease with increasing value of x, and the fluorescence lifetime mainly depends on the specific surface areas of the powders.

NASA Earth Day 2014

NASA Image and Video Library

2014-04-22

NASA Astronaut John Mace Grunsfeld takes a quick selfie with astronauts at the International Space Station at the NASA sponsored Earth Day event April 22, 2014 at Union Station in Washington, DC. NASA announced the "Global Selfie" event as part of its "Earth Right Now" campaign, celebrating the launch of five Earth-observing missions in 2014. All selfies posted to social media with the hashtag "GlobalSelfie" will be included in a mosaic image of Earth. Photo Credit: (NASA/Aubrey Gemignani)

Curiosity Mars Rover First Image of Earth and Earth Moon

NASA Image and Video Library

2014-02-06

The two bodies in this portion of an evening-sky view by NASA Mars rover Curiosity are Earth and Earth moon. The rover Mast Camera Mastcam imaged them in the twilight sky of Curiosity 529th Martian day, or sol Jan. 31, 2014.

Earthing: health implications of reconnecting the human body to the Earth's surface electrons.

PubMed

Chevalier, Gaétan; Sinatra, Stephen T; Oschman, James L; Sokal, Karol; Sokal, Pawel

2012-01-01

Environmental medicine generally addresses environmental factors with a negative impact on human health. However, emerging scientific research has revealed a surprisingly positive and overlooked environmental factor on health: direct physical contact with the vast supply of electrons on the surface of the Earth. Modern lifestyle separates humans from such contact. The research suggests that this disconnect may be a major contributor to physiological dysfunction and unwellness. Reconnection with the Earth's electrons has been found to promote intriguing physiological changes and subjective reports of well-being. Earthing (or grounding) refers to the discovery of benefits-including better sleep and reduced pain-from walking barefoot outside or sitting, working, or sleeping indoors connected to conductive systems that transfer the Earth's electrons from the ground into the body. This paper reviews the earthing research and the potential of earthing as a simple and easily accessed global modality of significant clinical importance.

Earthing: Health Implications of Reconnecting the Human Body to the Earth's Surface Electrons

PubMed Central

Chevalier, Gaétan; Sinatra, Stephen T.; Oschman, James L.; Sokal, Karol; Sokal, Pawel

2012-01-01

Environmental medicine generally addresses environmental factors with a negative impact on human health. However, emerging scientific research has revealed a surprisingly positive and overlooked environmental factor on health: direct physical contact with the vast supply of electrons on the surface of the Earth. Modern lifestyle separates humans from such contact. The research suggests that this disconnect may be a major contributor to physiological dysfunction and unwellness. Reconnection with the Earth's electrons has been found to promote intriguing physiological changes and subjective reports of well-being. Earthing (or grounding) refers to the discovery of benefits—including better sleep and reduced pain—from walking barefoot outside or sitting, working, or sleeping indoors connected to conductive systems that transfer the Earth's electrons from the ground into the body. This paper reviews the earthing research and the potential of earthing as a simple and easily accessed global modality of significant clinical importance. PMID:22291721

Next-generation Digital Earth

PubMed Central

Goodchild, Michael F.; Guo, Huadong; Annoni, Alessandro; Bian, Ling; de Bie, Kees; Campbell, Frederick; Craglia, Max; Ehlers, Manfred; van Genderen, John; Jackson, Davina; Lewis, Anthony J.; Pesaresi, Martino; Remetey-Fülöpp, Gábor; Simpson, Richard; Skidmore, Andrew; Wang, Changlin; Woodgate, Peter

2012-01-01

A speech of then-Vice President Al Gore in 1998 created a vision for a Digital Earth, and played a role in stimulating the development of a first generation of virtual globes, typified by Google Earth, that achieved many but not all the elements of this vision. The technical achievements of Google Earth, and the functionality of this first generation of virtual globes, are reviewed against the Gore vision. Meanwhile, developments in technology continue, the era of “big data” has arrived, the general public is more and more engaged with technology through citizen science and crowd-sourcing, and advances have been made in our scientific understanding of the Earth system. However, although Google Earth stimulated progress in communicating the results of science, there continue to be substantial barriers in the public’s access to science. All these factors prompt a reexamination of the initial vision of Digital Earth, and a discussion of the major elements that should be part of a next generation. PMID:22723346

People and the Earth

NASA Astrophysics Data System (ADS)

Rogers, John James William; Feiss, P. Geoffrey

1998-03-01

People and the Earth examines the numerous ways in which this planet enhances and limits our lifestyles. Written with wit and remarkable insight, and illustrated with numerous case histories, it provides a balanced view of the complex environmental issues facing our civilization. The authors look at the geologic restrictions on our ability to withdraw resources--food, water, energy, and minerals--from the earth, the effect human activity has on the earth, and the lingering damage caused by natural disasters. People and the Earth examines the basic components of our interaction with this planet, provides a lucid, scientific discussion of each issue, and speculates on what the future may hold. It provides the fundamental concepts that will enable us to make wise and conscientious choices on how to live our day-to-day lives. People and the Earth is an ideal introductory textbook and will also appeal to anyone concerned with our evolving relationship to the earth.

Next-generation Digital Earth.

PubMed

Goodchild, Michael F; Guo, Huadong; Annoni, Alessandro; Bian, Ling; de Bie, Kees; Campbell, Frederick; Craglia, Max; Ehlers, Manfred; van Genderen, John; Jackson, Davina; Lewis, Anthony J; Pesaresi, Martino; Remetey-Fülöpp, Gábor; Simpson, Richard; Skidmore, Andrew; Wang, Changlin; Woodgate, Peter

2012-07-10

A speech of then-Vice President Al Gore in 1998 created a vision for a Digital Earth, and played a role in stimulating the development of a first generation of virtual globes, typified by Google Earth, that achieved many but not all the elements of this vision. The technical achievements of Google Earth, and the functionality of this first generation of virtual globes, are reviewed against the Gore vision. Meanwhile, developments in technology continue, the era of "big data" has arrived, the general public is more and more engaged with technology through citizen science and crowd-sourcing, and advances have been made in our scientific understanding of the Earth system. However, although Google Earth stimulated progress in communicating the results of science, there continue to be substantial barriers in the public's access to science. All these factors prompt a reexamination of the initial vision of Digital Earth, and a discussion of the major elements that should be part of a next generation.

Galileo's Earth-Moon portrait

NASA Astrophysics Data System (ADS)

Simarski, Lynn Teo

Research reported at an AGU session on Galileo's Earth/Moon flyby refined the spacecraft's distinctive portrait of the Earth-Moon system. The Galileo team presented dramatic new views of the Earth and Moon taken last December. Andrew P. Ingersoll showed a color movie of the rotating Earth, made through spectral filters with which Galileo viewed the Earth almost continuously for 25 hours.Galileo also made finely tuned observations of vegetation and clouds, using three very closely spaced spectral wavelengths in the near-infrared, explained W. Reid Thompson. In the resulting images, Argentinian grassland and Brazilian rain forest are clearly distinguished, demonstrating the applicability of this technique for routine monitoring of deforestation, shifts in vegetation due to climate, and other phenomena. Thompson suggested that this capability could be used on the Earth Observing System. One of the spectral bands may also have potential for monitoring cloud condensation, as it appears to differentiate actively condensing, vapor-heavy clouds from higher and drier clouds.

Earth impedance model for through-the-earth communication applications with electrodes

NASA Astrophysics Data System (ADS)

Bataller, Vanessa; MuñOz, Antonio; Gaudó, Pilar Molina; Mediano, Arturo; Cuchí, José A.; Villarroel, José L.

2010-12-01

Through-the-earth (TTE) communications are relevant in applications such as caving, tunnel and cave rescue, mining, and subsurface radiolocation. The majority of the TTE communication systems use ground electrodes as load antenna. Wires, electrode contact, and earth impedances are the major contributors to the impedance observed by the transmitter. In this paper, state-of-art models found in the literature are reviewed, and an improved method to measure the earth impedance is presented. The paper also proposes an optimal circuit model for earth impedance between electrodes as a function of frequency, as a consequence of the particular conditions of the application. The model is validated with measurements for different soil conditions, showing a good agreement between empirical data and the simulation results.

Synthesis and magneto-structural studies on a new family of carbonato bridged 3d-4f complexes featuring a [CoLn(CO3)] (Ln = La, Gd, Tb, Dy and Ho) core: slow magnetic relaxation displayed by the cobalt(ii)-dysprosium(iii) analogue.

PubMed

Majee, Mithun Chandra; Towsif Abtab, Sk Md; Mondal, Dhrubajyoti; Maity, Manoranjan; Weselski, Marek; Witwicki, Maciej; Bieńko, Alina; Antkowiak, Michał; Kamieniarz, Grzegorz; Chaudhury, Muktimoy

2018-03-06

A new family of [3 + 3] hexanuclear 3d-4f complexes [(μ 3 -CO 3 ){Co II Ln III L(μ 3 -OH)(OH 2 )} 3 ]-(ClO 4 )·mC 2 H 5 OH·nH 2 O (1-5) [Ln = La (1), Gd (2), Tb (3), Dy (4), and Ho (5)] have been prepared in moderate to high yields (62-78%) following a self-assembly reaction between the ligand 6,6',6''-(nitrilotris(methylene))tris-(2-methoxy-4-methylphenol) (H 3 L), Co(OAc) 2 ·4H 2 O and the lanthanide ion precursors in the mandatory presence of tetrabutylammonium hydroxide. During the reaction, atmospheric carbon dioxide is fixed in the product molecule as a bridging carbonato ligand which connects all the three lanthanide centers of this molecular assembly through a rare η 2 :η 2 :η 2 -μ 3 mode of bridging as revealed from X-ray crystallography. The metal centers in all these compounds, except the Gd III analogue (2), are coupled in antiferromagnetic manner while the nature of coupling in the CoGd complex is ferromagnetic. DFT calculations revealed that this ferromagnetic interaction occurs most likely by the Co II -Gd III superexchange, mediated via the bridging oxygen atoms. Only the Co II -Dy III compound (4) displayed a slow relaxation of the magnetization at a very low temperature as established by AC susceptibility measurements. The data provides an estimation of the activation energy U/k B = 9.2 K and the relaxation time constant τ 0 = 1.0 × 10 -7 s.

Earth observing satellite: Understanding the Earth as a system

NASA Technical Reports Server (NTRS)

Soffen, Gerald

1990-01-01

There is now a plan for global studies which include two very large efforts. One is the International Geosphere/Biosphere Program (IGBP) sponsored by the International Council of Scientific Unions. The other initiative is Mission to Planet Earth, an unbrella program for doing three kinds of space missions. The major one is the Earth Observation Satellite (EOS). EOS is large polar orbiting satellites with heavy payloads. Two will be placed in orbit by NASA, one by the Japanese and one or two by ESA. The overall mission measurement objectives of EOS are summarized: (1) the global distribution of energy input to and energy output from the Earth; (2) the structure, state variables, composition, and dynamics of the atmosphere from the ground to the mesopause; (3) the physical and biological structure, state, composition, and dynamics of the land surface, including terrestrial and inland water ecosystems; (4) the rates, important sources and sinks, and key components and processes of the Earth's biogeochemical cycles; (5) the circulation, surface temperature, wind stress, sea state, and the biological activity of the oceans; (6) the extent, type, state, elevation, roughness, and dynamics of glaciers, ice sheets, snow and sea ice, and the liquid equivalent of snow in the global cryosphere; (7) the global rates, amounts, and distribution of precipitation; and (8) the dynamic motions of the Earth (geophysics) as a whole, including both rotational dynamics and the kinematic motions of the tectonic plates.

Earth Science Informatics - Overview

NASA Technical Reports Server (NTRS)

Ramapriyan, H. K.

2017-01-01

Over the last 10-15 years, significant advances have been made in information management, there are an increasing number of individuals entering the field of information management as it applies to Geoscience and Remote Sensing data, and the field of informatics has come to its own. Informatics is the science and technology of applying computers and computational methods to the systematic analysis, management, interchange, and representation of science data, information, and knowledge. Informatics also includes the use of computers and computational methods to support decision making and applications. Earth Science Informatics (ESI, a.k.a. geoinformatics) is the application of informatics in the Earth science domain. ESI is a rapidly developing discipline integrating computer science, information science, and Earth science. Major national and international research and infrastructure projects in ESI have been carried out or are on-going. Notable among these are: the Global Earth Observation System of Systems (GEOSS), the European Commissions INSPIRE, the U.S. NSDI and Geospatial One-Stop, the NASA EOSDIS, and the NSF DataONE, EarthCube and Cyberinfrastructure for Geoinformatics. More than 18 departments and agencies in the U.S. federal government have been active in Earth science informatics. All major space agencies in the world, have been involved in ESI research and application activities. In the United States, the Federation of Earth Science Information Partners (ESIP), whose membership includes over 180 organizations (government, academic and commercial) dedicated to managing, delivering and applying Earth science data, has been working on many ESI topics since 1998. The Committee on Earth Observation Satellites (CEOS)s Working Group on Information Systems and Services (WGISS) has been actively coordinating the ESI activities among the space agencies.

The Earth & Moon

NASA Image and Video Library

1998-06-04

During its flight, NASA’s Galileo spacecraft returned images of the Earth and Moon. Separate images of the Earth and Moon were combined to generate this view. http://photojournal.jpl.nasa.gov/catalog/PIA00342

A carbon dioxide radiance model of the earth planet using the conical earth sensor data

NASA Astrophysics Data System (ADS)

Deng, Loulou; Mei, Zhiwu; Tu, Zhijun; Yuan, Jun; He, Ting; Wei, Yi

2013-10-01

Climate Modeling results show that about 50% of the Earth's outgoing radiation and 75% of the atmospheric outgoing radiation are contained in the far infrared. Generally the earth is considered as a 220~230 K blackbody, and the peak breadth of the Earth's outgoing radiation is around the wavelength of 10 micron. The atmospheric outgoing radiation are contained with five spectral intervals: the water vapor band from 6.33 to 6.85 microns, the ozone band from 8.9 to 10.1microns, the atmospheric window from 10.75 to 11.75 microns, the carbon dioxide band from 14 to 16 microns, and finally the rotational water vapor band from 21 to 125 microns. The properties of the carbon dioxide band is stable than other bands which has been chosen for the work Spectrum of the earth sensors. But the radiation energy of carbon dioxide band is variety and it is a function of latitude, season and weather conditions. Usually the luminance of the Earth's radiation (14 to 16 μm) is from 3 to 7 W/m2Sr. Earth sensor is an important instrument of the Attitude and Orbit Control System (AOCS), and it is sensitive to the curve of the earth's and atmospheric outgoing radiation profile to determine the roll and pitch angles of satellite which are relative to nadir vector. Most earth sensors use profile data gathered form Project Scanner taken in August and December 1966. The earth sensor referred in this paper is the conical scanning earth sensor which is mainly used in the LEO (Low Earth Orbit) satellite. A method to determine the luminance of earth's and atmospheric outgoing radiation (carbon dioxide) using the earth sensor is discussed in this paper. When the conical scanning sensor scan form the space to the earth, a pulse is produced and the pulse breadth is scale with the infrared radiation luminance. Then the infrared radiation luminance can be calculated. A carbon dioxide radiance model of the earth's and atmospheric outgoing radiation is obtained according the luminance data about with

Melting in super-earths.

PubMed

Stixrude, Lars

2014-04-28

We examine the possible extent of melting in rock-iron super-earths, focusing on those in the habitable zone. We consider the energetics of accretion and core formation, the timescale of cooling and its dependence on viscosity and partial melting, thermal regulation via the temperature dependence of viscosity, and the melting curves of rock and iron components at the ultra-high pressures characteristic of super-earths. We find that the efficiency of kinetic energy deposition during accretion increases with planetary mass; considering the likely role of giant impacts and core formation, we find that super-earths probably complete their accretionary phase in an entirely molten state. Considerations of thermal regulation lead us to propose model temperature profiles of super-earths that are controlled by silicate melting. We estimate melting curves of iron and rock components up to the extreme pressures characteristic of super-earth interiors based on existing experimental and ab initio results and scaling laws. We construct super-earth thermal models by solving the equations of mass conservation and hydrostatic equilibrium, together with equations of state of rock and iron components. We set the potential temperature at the core-mantle boundary and at the surface to the local silicate melting temperature. We find that ancient (∼4 Gyr) super-earths may be partially molten at the top and bottom of their mantles, and that mantle convection is sufficiently vigorous to sustain dynamo action over the whole range of super-earth masses.

Magnetic relaxation behavior of lanthanide substituted Dawson-type tungstoarsenates

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

Liu Lizhen; Li Fengyan; Xu Lin, E-mail: linxu@nenu.edu.c

2010-02-15

Two new polyoxometalate compounds [(CH{sub 3}){sub 4}N]{sub 8}[Ln(H{sub 2}O){sub 8}]{sub 2}[(alpha{sub 2}-As{sub 2}W{sub 17}O{sub 61})Ln(H{sub 2}O){sub 2}]{sub 2}.nH{sub 2}O (Ln=Er (1), Dy (2)) have been prepared by the trivacant Dawson-type anion [alpha-As{sub 2}W{sub 15}O{sub 56}]{sup 12-} and trivalent rare earth ion and characterized by single-crystal X-ray diffraction, IR spectra, thermogravimetric and electrochemical analyses. The centrosymmetric polyoxoanion, {l_brace}[(alpha{sub 2}-As{sub 2}W{sub 17}O{sub 61})Ln(H{sub 2}O){sub 2}]{sub 2}{r_brace}{sup 14-}, bounded to each other via Ln{sup 3+} connecting to terminal W-O oxygen atoms. Furthermore, the polyoxoanions are linked by [Ln(H{sub 2}O){sub 8}]{sup 3+} to form an extensive 3D supramolecular network structure depending on hydrogen bond.more » The magnetic properties of the two compounds have been studied by measuring their magnetic susceptibilities in the temperature range 2.0-300.0 K, indicating the depopulation of the stark components at low temperature and/or very weak antiferromagnetic interactions between magnetic centers. Low-temperature ac magnetic susceptibility measurements reveal a slow magnetic relaxation behavior for 2. - Graphical abstract: Two polyoxometalate compounds [(CH{sub 3}){sub 4}N]{sub 8}[Ln(H{sub 2}O){sub 8}]{sub 2}[(alpha{sub 2}-As{sub 2}W{sub 17}O{sub 61})Ln(H{sub 2}O){sub 2}]{sub 2}.nH{sub 2}O (Ln=Er (1), Dy (2)) have been prepared. The dynamic magnetic measurements for 2 display a slow relaxation of magnetization, showing a frequency-dependent susceptibility.« less

Development of educational programs using Dagik Earth, a four dimensional display of the Earth and planets

NASA Astrophysics Data System (ADS)

Saito, A.; Akiya, Y.; Yoshida, D.; Odagi, Y.; Yoshikawa, M.; Tsugawa, T.; Takahashi, M.; Kumano, Y.; Iwasaki, S.

2010-12-01

We have developed a four-dimensional display system of the Earth and planets to use in schools, science centers, and research institutes. It can display the Earth and planets in three-dimensional way without glasses, and the time variation of the scientific data can be displayed on the Earth and planets image. The system is named Dagik Earth, and educational programs using Dagik Earth have been developed for schools and science centers. Three dimensional displays can show the Earth and planets in exact form without any distortion, which cannot be achieved with two-dimensional display. Furthermore it can provide a sense of reality. There are several systems for the three-dimensional presentation of the Earth, such as Science on a sphere by NOAA, and Geocosmos by Miraikan, Japan. Comparing these systems, the advantage of Dagik Earth is portability and affordability. The system uses ordinary PC and PC projector. Only a spherical screen is the special equipment of Dagik Earth. Therefore Dagik Earth is easy to use in classrooms. Several educational programs have been developed and carried out in high schools, junior high schools, elementary schools and science centers. Several research institutes have used Dagik Earth in their public outreach programs to demonstrate their novel scientific results to public in an attractive way of presentation. A community of users and developers of Dagik Earth is being formed in Japan. In the presentation, the outline of Dagik Earth and the educational programs using Dagik Earth will be presented. Its future plan will also be discussed.

Earth Day 2017

NASA Image and Video Library

2017-12-08

Happy Earth Day! Explore the diverse colors, unique shapes and striking patterns of our very favorite planet, Earth - as only NASA can see it. Credit: NASA/Goddard #nasagoddard NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

Functional PEG–PAMAM-Tetraphosphonate Capped NaLnF4 Nanoparticles and their Colloidal Stability in Phosphate Buffer

PubMed Central

2015-01-01

Developing surface coatings for NaLnF4 nanoparticles (NPs) that provide long-term stability in solutions containing competitive ions such as phosphate remains challenging. An amine-functional polyamidoamine tetraphosphonate (NH2-PAMAM-4P) as a multidentate ligand for these NPs has been synthesized and characterized as a ligand for the surface of NaGdF4 and NaTbF4 nanoparticles. A two-step ligand exchange protocol was developed for introduction of the NH2-PAMAM-4P ligand on oleate-capped NaLnF4 NPs. The NPs were first treated with methoxy-poly(ethylene glycol)-monophosphoric acid (Mn = 750) in tetrahydrofuran. The mPEG750-OPO3-capped NPs were stable colloidal solutions in water, where they could be ligand-exchanged with NH2-PAMAM-4P. The surface amine groups on the NPs were available for derivatization to attach methoxy-PEG (Mn = 2000) and biotin-terminated PEG (Mn = 2000) chains. The surface coverage of ligands on the NPs was examined by thermal gravimetric analysis, and by a HABA analysis for biotin-containing NPs. Colloidal stability of the NPs was examined by dynamic light scattering. NaGdF4 and NaTbF4 NPs capped with mPEG2000–PAMAM-4P showed colloidal stability in DI water and in phosphate buffer (10 mM, pH 7.4). A direct comparison with NaTbF4 NPs capped with a mPEG2000-lysine-based tetradentate ligand that we reported previously (Langmuir2012, 28, 12861−1287022906305) showed that both ligands provided long-term stability in phosphate buffer, but that the lysine-based ligand provided better stability in phosphate-buffered saline. PMID:24898128

Earth - Pacific Ocean

NASA Image and Video Library

1996-01-29

This color image of the Earth was obtained by NASA’s Galileo spacecraft early Dec. 12, 1990, when the spacecraft was about 1.6 million miles from the Earth. http://photojournal.jpl.nasa.gov/catalog/PIA00123

Accretion of the Earth.

PubMed

Canup, Robin M

2008-11-28

The origin of the Earth and its Moon has been the focus of an enormous body of research. In this paper I review some of the current models of terrestrial planet accretion, and discuss assumptions common to most works that may require re-examination. Density-wave interactions between growing planets and the gas nebula may help to explain the current near-circular orbits of the Earth and Venus, and may result in large-scale radial migration of proto-planetary embryos. Migration would weaken the link between the present locations of the planets and the original provenance of the material that formed them. Fragmentation can potentially lead to faster accretion and could also damp final planet orbital eccentricities. The Moon-forming impact is believed to be the final major event in the Earth's accretion. Successful simulations of lunar-forming impacts involve a differentiated impactor containing between 0.1 and 0.2 Earth masses, an impact angle near 45 degrees and an impact speed within 10 per cent of the Earth's escape velocity. All successful impacts-with or without pre-impact rotation-imply that the Moon formed primarily from material originating from the impactor rather than from the proto-Earth. This must ultimately be reconciled with compositional similarities between the Earth and the Moon.

Early Earth slab stagnation

NASA Astrophysics Data System (ADS)

Agrusta, R.; Van Hunen, J.

2016-12-01

At present day, the Earth's mantle exhibits a combination of stagnant and penetrating slabs within the transition zone, indicating a intermittent convection mode between layered and whole-mantle convection. Isoviscous thermal convection calculations show that in a hotter Earth, the natural mode of convection was dominated by double-layered convection, which may imply that slabs were more prone to stagnate in the transition zone. Today, slab penetration is to a large extent controlled by trench mobility for a plausible range of lower mantle viscosity and Clapeyron slope of the mantle phase transitions. Trench mobility is, in turn, governed by slab strength and density and upper plate forcing. In this study, we systematically investigate the slab-transition zone internation in the Early Earth, using 2D self-consistent numerical subduction models. Early Earth's higher mantle temperature facilitates decoupling between the plates and the underlying asthenosphere, and may result in slab sinking almost without trench retreat. Such behaviour together with a low resistance of a weak lower mantle may allow slabs to penetrate. The ability of slab to sink into the lower mantle throughout Earth's history may have important implications for Earth's evolution: it would provide efficient mass and heat flux through the transition zone therefore provide an efficient way to cool and mix the Earth's mantle.

Venus, Earth, Xenon

NASA Astrophysics Data System (ADS)

Zahnle, K. J.

2013-12-01

Xenon has been regarded as an important goal of many proposed missions to Venus. This talk is intended to explain why. Despite its being the heaviest gas found in natural planetary atmospheres, there is more evidence that Xe escaped from Earth than for any element apart from helium: (i) Atmospheric Xe is very strongly mass fractionated (at about 4% per amu) from any known solar system source. This suggests fractionating escape that preferentially left the heavy Xe isotopes behind. (ii) Xe is underabundant compared to Kr, a lighter noble gas that is not strongly mass fractionated in air. (iii) Radiogenic Xe is strongly depleted by factors of several to ~100 compared to the quantities expected from radioactive decay of primordial solar system materials. In these respects Xe on Mars is similar to Xe on Earth, but with one key difference: Xe on Mars is readily explained by a simple process like hydrodynamic escape that acts on an initially solar or meteoritic Xe. This is not so for Earth. Earth's Xe cannot be derived by an uncontrived mass fractionating process acting on any known type of Solar System Xe. Earth is a stranger, made from different stuff than any known meteorite or Mars or even the Sun. Who else is in Earth's family? Comets? We know nothing. Father Zeus? Data from Jupiter are good enough to show that jovian Xe is not strongly mass-fractionated but not good enough to determine whether Jupiter resembles the Earth or the Sun. Sister Venus? Noble gas data from Venus are incomplete, with Kr uncertain and Xe unmeasured. Krypton was measured by several instruments on several spacecraft. The reported Kr abundances are discrepant and were once highly controversial. These discrepancies appear to have been not so much resolved as forgotten. Xenon was not detected on Venus. Upper limits were reported for the two most abundant xenon isotopes 129Xe and 132Xe. From the limited data it is not possible to tell whether Venus's affinities lie with the solar wind, or with

NASA's mission to planet Earth: Earth observing system

NASA Technical Reports Server (NTRS)

1993-01-01

The topics covered include the following: global climate change; radiation, clouds, and atmospheric water; the ocean; the troposphere - greenhouse gases; land cover and the water cycle; polar ice sheets and sea level; the stratosphere - ozone chemistry; volcanoes; the Earth Observing System (EOS) - how NASA will support studies of global climate change?; research and assessment - EOS Science Investigations; EOS Data and Information System (EOSDIS); EOS observations - instruments and spacecraft; a national international effort; and understanding the Earth System.

Magnetic interactions and magnetic anisotropy in exchange coupled 4f-3d systems: a case study of a heterodinuclear Ce3+-Fe3+ cyanide-bridged complex.

PubMed

Sorace, Lorenzo; Sangregorio, Claudio; Figuerola, Albert; Benelli, Cristiano; Gatteschi, Dante

2009-01-01

We report here a detailed single-crystal EPR and magnetic study of a homologous series of complexes of the type Ln-M (Ln = La(III), Ce(III); M = Fe(III), Co(III)). We were able to obtain a detailed picture of the low-lying levels of Ce(III) and Fe(III) centres through the combined use of single-crystal EPR and magnetic susceptibility data. We show that classical ligand field theory can be of great help in rationalising the energies of the low-lying levels of both the transition-metal and rare-earth ions. The combined analysis of single-crystal EPR and magnetic data of the coupled system Ce-Fe confirmed the great complexity of the interactions involving rare-earth elements. With little uncertainty, it turned out clearly that the description of the interaction involving the lowest lying spin levels requires the introduction of the isotropic, anisotropic and antisymmetric terms.

Earth's earliest atmospheres.

PubMed

Zahnle, Kevin; Schaefer, Laura; Fegley, Bruce

2010-10-01

Earth is the one known example of an inhabited planet and to current knowledge the likeliest site of the one known origin of life. Here we discuss the origin of Earth's atmosphere and ocean and some of the environmental conditions of the early Earth as they may relate to the origin of life. A key punctuating event in the narrative is the Moon-forming impact, partly because it made Earth for a short time absolutely uninhabitable, and partly because it sets the boundary conditions for Earth's subsequent evolution. If life began on Earth, as opposed to having migrated here, it would have done so after the Moon-forming impact. What took place before the Moon formed determined the bulk properties of the Earth and probably determined the overall compositions and sizes of its atmospheres and oceans. What took place afterward animated these materials. One interesting consequence of the Moon-forming impact is that the mantle is devolatized, so that the volatiles subsequently fell out in a kind of condensation sequence. This ensures that the volatiles were concentrated toward the surface so that, for example, the oceans were likely salty from the start. We also point out that an atmosphere generated by impact degassing would tend to have a composition reflective of the impacting bodies (rather than the mantle), and these are almost without exception strongly reducing and volatile-rich. A consequence is that, although CO- or methane-rich atmospheres are not necessarily stable as steady states, they are quite likely to have existed as long-lived transients, many times. With CO comes abundant chemical energy in a metastable package, and with methane comes hydrogen cyanide and ammonia as important albeit less abundant gases.

Earth Science Informatics - Overview

NASA Technical Reports Server (NTRS)

Ramapriyan, H. K.

2017-01-01

Over the last 10-15 years, significant advances have been made in information management, there are an increasing number of individuals entering the field of information management as it applies to Geoscience and Remote Sensing data, and the field of informatics has come to its own. Informatics is the science and technology of applying computers and computational methods to the systematic analysis, management, interchange, and representation of science data, information, and knowledge. Informatics also includes the use of computers and computational methods to support decision making and applications. Earth Science Informatics (ESI, a.k.a. geoinformatics) is the application of informatics in the Earth science domain. ESI is a rapidly developing discipline integrating computer science, information science, and Earth science. Major national and international research and infrastructure projects in ESI have been carried out or are on-going. Notable among these are: the Global Earth Observation System of Systems (GEOSS), the European Commissions INSPIRE, the U.S. NSDI and Geospatial One-Stop, the NASA EOSDIS, and the NSF DataONE, EarthCube and Cyberinfrastructure for Geoinformatics. More than 18 departments and agencies in the U.S. federal government have been active in Earth science informatics. All major space agencies in the world, have been involved in ESI research and application activities. In the United States, the Federation of Earth Science Information Partners (ESIP), whose membership includes over 180 organizations (government, academic and commercial) dedicated to managing, delivering and applying Earth science data, has been working on many ESI topics since 1998. The Committee on Earth Observation Satellites (CEOS)s Working Group on Information Systems and Services (WGISS) has been actively coordinating the ESI activities among the space agencies.The talk will present an overview of current efforts in ESI, the role members of IEEE GRSS play, and discuss

Direct and indirect capture of near-Earth asteroids in the Earth-Moon system

NASA Astrophysics Data System (ADS)

Tan, Minghu; McInnes, Colin; Ceriotti, Matteo

2017-09-01

Near-Earth asteroids have attracted attention for both scientific and commercial mission applications. Due to the fact that the Earth-Moon L1 and L2 points are candidates for gateway stations for lunar exploration, and an ideal location for space science, capturing asteroids and inserting them into periodic orbits around these points is of significant interest for the future. In this paper, we define a new type of lunar asteroid capture, termed direct capture. In this capture strategy, the candidate asteroid leaves its heliocentric orbit after an initial impulse, with its dynamics modeled using the Sun-Earth-Moon restricted four-body problem until its insertion, with a second impulse, onto the L2 stable manifold in the Earth-Moon circular restricted three-body problem. A Lambert arc in the Sun-asteroid two-body problem is used as an initial guess and a differential corrector used to generate the transfer trajectory from the asteroid's initial obit to the stable manifold associated with Earth-Moon L2 point. Results show that the direct asteroid capture strategy needs a shorter flight time compared to an indirect asteroid capture, which couples capture in the Sun-Earth circular restricted three-body problem and subsequent transfer to the Earth-Moon circular restricted three-body problem. Finally, the direct and indirect asteroid capture strategies are also applied to consider capture of asteroids at the triangular libration points in the Earth-Moon system.

Earth Orientation - Naval Oceanography Portal

Science.gov Websites

section Advanced Search... Sections Home Time Earth Orientation Astronomy Meteorology Oceanography Ice You are here: Home › USNO › Earth Orientation USNO Logo USNO Navigation Earth Orientation Products GPS -based Products VLBI-based Products EO Information Center Publications about Products Software Info Earth

Earthing Spiritual Literacy: How to Link Spiritual Development and Education to a New Earth Consciousness?

ERIC Educational Resources Information Center

King, Ursula

2010-01-01

This article discusses the development of spiritual literacy in relation to a new consciousness of the Earth and what Thomas Berry calls "Earth literacy". It draws on the metaphor of "earthing" to argue for a close link between spiritual literacy and Earth literacy, considered of great importance for both personal spiritual…

Not So Rare Earth? New Developments in Understanding the Origin of the Earth and Moon

NASA Technical Reports Server (NTRS)

Righter, Kevin

2007-01-01

A widely accepted model for the origin of the Earth and Moon has been a somewhat specific giant impact scenario involving an impactor to proto-Earth mass ratio of 3:7, occurring 50-60 Ma after T(sub 0), when the Earth was only half accreted, with the majority of Earth's water then accreted after the main stage of growth, perhaps from comets. There have been many changes to this specific scenario, due to advances in isotopic and trace element geochemistry, more detailed, improved, and realistic giant impact and terrestrial planet accretion modeling, and consideration of terrestrial water sources other than high D/H comets. The current scenario is that the Earth accreted faster and differentiated quickly, the Moon-forming impact could have been mid to late in the accretion process, and water may have been present during accretion. These new developments have broadened the range of conditions required to make an Earth-Moon system, and suggests there may be many new fruitful avenues of research. There are also some classic and unresolved problems such as the significance of the identical O isotopic composition of the Earth and Moon, the depletion of volatiles on the lunar mantle relative to Earth's, the relative contribution of the impactor and proto-Earth to the Moon's mass, and the timing of Earth's possible atmospheric loss relative to the giant impact.

Exploring Spaceship Earth

ERIC Educational Resources Information Center

McInnis, Noel F.

1973-01-01

Describes various activities to understand the nature of the earth as a spaceship and its impact on human life. A figure depicting a holocoenotic environmental complex is given which can be used to illustrate various interacting forces on earth. (PS)

The Group on Earth Observations and the Global Earth Observation System of Systems

NASA Astrophysics Data System (ADS)

Achache, J.

2006-05-01

The Group on Earth Observations (GEO) is leading a worldwide effort to build a Global Earth Observation System of Systems (GEOSS) over the next 10 years. The GEOSS vision, articulated in its 10-Year Implementation Plan, represents the consolidation of a global scientific and political consensus: the assessment of the state of the Earth requires continuous and coordinated observation of our planet at all scales. GEOSS aims to achieve comprehensive, coordinated and sustained observations of the Earth system in order to improve monitoring of the state of the Earth; increase understanding of Earth processes; and enhance prediction of the behaviour of the Earth system. After the World Summit on Sustainable Development in 2002 highlighted the urgent need for coordinated observations relating to the state of the Earth, GEO was established at the Third Earth Observation Summit in February 2005 and the GEOSS 10-Year Implementation Plan was endorsed. GEO currently involves 60 countries; the European Commission; and 43 international organizations and has begun implementation of the GEOSS 10-Year Implementation Plan. GEO programme activities cover nine societal benefit areas (Disasters; Health; Energy; Climate; Water; Weather; Ecosystems; Agriculture; Biodiversity) and five transverse or crosscutting elements (User Engagement; Architecture; Data Management; Capacity Building; Outreach). All these activities have as their final goal the establishment of the "system of systems" which will yield a broad range of basic societal benefits, including the reduction of loss of life and property from tsunamis, hurricanes, and other natural disasters; improved water resource and energy management; and improved understanding of environmental factors significant to public health. As a "system of systems", GEOSS will work with and build upon existing national, regional, and international systems to provide comprehensive, coordinated Earth observations from thousands of instruments worldwide

PREFACE: 2013 International Conferences on Geological, Geographical, Aerospace and Earth Sciences (AeroEarth 2013)

NASA Astrophysics Data System (ADS)

2014-03-01

The 2013 International Conferences on Geological, Geographical, Aerospace and Earth Sciences (AeroEarth 2013), was held at the Swiss Bell Mangga Besar, Jakarta, Indonesia, on 23 December 2013. The AeroEarth conference aims to bring together researchers, engineers and scientists in the domain of interest from around the world. AeroEarth 2013 promotes interaction between the theoretical, experimental, and applied communities, so that high-level exchange is achieved in new and emerging areas within Earth Science. Through research and development, earth scientists have the power to preserve the planet's different resource domains by providing expert opinion and information about the forces which make life possible on Earth. We would like to express our sincere gratitude to all in the Technical Program Committee who have reviewed the papers and developed a very interesting Conference Program as well as the invited and plenary speakers. This year, we received 91 papers and after rigorous review, 17 papers were accepted. The participants come from 8 countries. There are 3 (three) Plenary Sessions and two invited Speakers. It is an honour to present this volume of IOP Conference Series: Earth and Environmental Science (EES) and we deeply thank the authors for their enthusiastic and high-grade contribution. Finally, we would like to thank the conference chairmen, the members of the steering committee, the organizing committee, the organizing secretariat and the financial support from the conference sponsors that allowed the success of AeroEarth 2013. The AeroEarth 2013 Proceedings Editors Dr. Ford Lumban Gaol Dr. Benfano Soewito Dr. Amit Desai Further information on the invited plenary speakers and photographs from the conference can be found in the pdf.

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 .

Modeling the Earth system in the Mission to Planet Earth era

NASA Technical Reports Server (NTRS)

Unninayar, Sushel; Bergman, Kenneth H.

1993-01-01

A broad overview is made of global earth system modeling in the Mission to Planet Earth (MTPE) era for the multidisciplinary audience encompassed by the Global Change Research Program (GCRP). Time scales of global system fluctuation and change are described in Section 2. Section 3 provides a rubric for modeling the global earth system, as presently understood. The ability of models to predict the future state of the global earth system and the extent to which their predictions are reliable are covered in Sections 4 and 5. The 'engineering' use of global system models (and predictions) is covered in Section 6. Section 7 covers aspects of an increasing need for improved transform algorithms and better methods to assimilate this information into global models. Future monitoring and data requirements are detailed in Section 8. Section 9 covers the NASA-initiated concept 'Mission to Planet Earth,' which employs space and ground based measurement systems to provide the scientific basis for understanding global change. Section 10 concludes this review with general remarks concerning the state of global system modeling and observing technology and the need for future research.

Sun-Earth Scientists and Native Americans Collaborate on Sun-Earth Day

NASA Astrophysics Data System (ADS)

Ng, C. Y.; Lopez, R. E.; Hawkins, I.

2004-12-01

Sun-Earth Connection scientists have established partnerships with several minority professional societies to reach out to the blacks, Hispanics and Native American students. Working with NSBP, SACNAS, AISES and NSHP, SEC scientists were able to speak in their board meetings and national conferences, to network with minority scientists, and to engage them in Sun-Earth Day. Through these opportunities and programs, scientists have introduced NASA research results as well indigenous views of science. They also serve as role models in various communities. Since the theme for Sun-Earth Day 2005 is Ancient Observatories: Timeless Knowledge, scientists and education specialists are hopeful to excite many with diverse backgrounds. Sun-Earth Day is a highly visible annual program since 2001 that touches millions of students and the general public. Interviews, classroom activities and other education resources are available on the web at sunearthday.nasa.gov.

PREFACE: 3rd International Conference on Geological, Geographical, Aerospace and Earth Science 2015 (AeroEarth 2015)

NASA Astrophysics Data System (ADS)

Gaol, F. L.

2016-02-01

The 3rd International Conferences on Geological, Geographical, Aerospaces and Earth Sciences 2015 (AeroEarth 2015), was held at The DoubleTree Hilton, Jakarta, Indonesia during 26 - 27 September 2015. The 1st AeoroEarth was held succefully in Jakarta in 2013. The success continued to The 2nd AeroEarth 2014 that was held in Kuta Bali, Indonesia. The publications were published by EES IOP in http://iopscience.iop.org/1755-1315/19/1 and http://iopscience.iop.org/1755-1315/23/1 respectively. The AeroEarth 2015 conference aims to bring together researchers, engineers and scientists from around the world. Through research and development, Earth's scientists have the power to preserve the planet's different resource domains by providing expert opinion and information about the forces which make life possible on Earth. The theme of AeroEarth 2015 is ''Earth and Aerospace Sciences : Challenges and Opportunities'' Earth provides resources and the exact conditions to make life possible. However, with the advent of technology and industrialization, the Earth's resources are being pushed to the brink of depletion. Non-sustainable industrial practices are not only endangering the supply of the Earth's natural resources, but are also putting burden on life itself by bringing about pollution and climate change. A major role of earth science scholars is to examine the delicate balance between the Earth's resources and the growing demands of industrialization. Through research and development, earth scientists have the power to preserve the planet's different resource domains by providing expert opinion and information about the forces which make life possible on Earth. We would like to express our sincere gratitude to all in the Technical Program Committee who have reviewed the papers and developed a very interesting Conference Program as well as the invited and plenary speakers. This year, we received 78 papers and after rigorous review, 18 papers were accepted. The participants

Baltic Earth - Earth System Science for the Baltic Sea Region

NASA Astrophysics Data System (ADS)

Meier, Markus; Rutgersson, Anna; Lehmann, Andreas; Reckermann, Marcus

2014-05-01

The Baltic Sea region, defined as its river catchment basin, spans different climate and population zones, from a temperate, highly populated, industrialized south with intensive agriculture to a boreal, rural north. It encompasses most of the Scandinavian Peninsula in the west; most of Finland and parts of Russia, Belarus, and the Baltic states in the east; and Poland and small parts of Germany and Denmark in the south. The region represents an old cultural landscape, and the Baltic Sea itself is among the most studied sea areas of the world. Baltic Earth is the new Earth system research network for the Baltic Sea region. It is the successor to BALTEX, which was terminated in June 2013 after 20 years and two successful phases. Baltic Earth stands for the vision to achieve an improved Earth system understanding of the Baltic Sea region. This means that the research disciplines of BALTEX continue to be relevant, i.e. atmospheric and climate sciences, hydrology, oceanography and biogeochemistry, but a more holistic view of the Earth system encompassing processes in the atmosphere, on land and in the sea as well as in the anthroposphere shall gain in importance in Baltic Earth. Specific grand research challenges have been formulated, representing interdisciplinary research questions to be tackled in the coming years. A major means will be scientific assessments of particular research topics by expert groups, similar to the BACC approach, which shall help to identify knowledge gaps and develop research strategies. Preliminary grand challenges and topics for which Working Groups have been installed include: • Salinity dynamics in the Baltic Sea • Land-Sea biogeochemical feedbacks in the Baltic Sea region • Natural hazards and extreme events in the Baltic Sea region • Understanding sea level dynamics in the Baltic Sea • Understanding regional variability of water and energy exchange • Utility of Regional Climate Models • Assessment of Scenario Simulations

In situ hydrothermal syntheses, structures and photoluminescent properties of four novel metal-organic frameworks constructed by lanthanide (Ln=Ce(III), Pr(III), Eu(III)) and Cu(I) metals with flexible dicarboxylate acids and piperazine-based ligands

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

Ay, Burak; Karaca, Serkan; Yildiz, Emel, E-mail: eeyildiz@cu.edu.tr

2016-01-15

Four novel metal-organic frameworks,[Cu{sub 2}Cl{sub 2}(pyrz)]{sub n} (1) and (H{sub 2}pip){sub n}[Ln{sub 2}(pydc){sub 4}(H{sub 2}O){sub 2}]{sub n} (Ln=Ce (2), Pr (3) and Eu (4), H{sub 2}pzdc=2,3-pyrazinedicarboxylic acid, pyrz=pyrazine, H{sub 2}pydc=2,6-pyridinedicarboxylic acid, H{sub 2}pip=piperazine) have been synthesized under hydrothermal conditions and characterized by the elemental analysis, ICP, Far IR (FIR), FT-IR spectra, TGA, single crystal X-ray diffraction analysis and powder X-ray diffraction (PXRD). Compound 1 is two-dimensional containing Cl-Cu-Cl sites, while the lanthanide complexes contain one-dimensional infinite Ln–O-Ln chains. All the complexes show high thermal stability. The complexes 1–3 exhibit luminescence emission bands at 584, 598 and 614 nm at roommore » temperature when excited at 300 nm. Complex 4 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four novel metal-organic frameworks have been synthesized under hydrothermal conditions. Thermal and luminescent properties of the compounds have been investigated.« less

Rotation of a Moonless Earth

NASA Technical Reports Server (NTRS)

Lissauer, Jack J.; Barnes, Jason W.; Chambers, John E.

2013-01-01

We numerically explore the obliquity (axial tilt) variations of a hypothetical moonless Earth. Previous work has shown that the Earth's Moon stabilizes Earth's obliquity such that it remains within a narrow range, between 22.1 deg and 24.5 deg. Without lunar influence, a frequency-map analysis by Laskar et al. showed that the obliquity could vary between 0 deg. and 85 deg. This has left an impression in the astrobiology community that a large moon is necessary to maintain a habitable climate on an Earth-like planet. Using a modified version of the orbital integrator mercury, we calculate the obliquity evolution for moonless Earths with various initial conditions for up to 4 Gyr. We find that while obliquity varies significantly more than that of the actual Earth over 100,000 year timescales, the obliquity remains within a constrained range, typically 20-25 deg. in extent, for timescales of hundreds of millions of years. None of our Solar System integrations in which planetary orbits behave in a typical manner show obliquity accessing more than 65% of the full range allowed by frequency-map analysis. The obliquities of moonless Earths that rotate in the retrograde direction are more stable than those of pro-grade rotators. The total obliquity range explored for moonless Earths with rotation periods shorter than 12 h is much less than that for slower-rotating moonless Earths. A large moon thus does not seem to be needed to stabilize the obliquity of an Earth-like planet on timescales relevant to the development of advanced life.

Biosignatures of early earths

NASA Technical Reports Server (NTRS)

Pilcher, Carl B.

2003-01-01

A major goal of NASA's Origins Program is to find habitable planets around other stars and determine which might harbor life. Determining whether or not an extrasolar planet harbors life requires an understanding of what spectral features (i.e., biosignatures) might result from life's presence. Consideration of potential biosignatures has tended to focus on spectral features of gases in Earth's modern atmosphere, particularly ozone, the photolytic product of biogenically produced molecular oxygen. But life existed on Earth for about 1(1/2) billion years before the buildup of atmospheric oxygen. Inferred characteristics of Earth's earliest biosphere and studies of modern microbial ecosystems that share some of those characteristics suggest that organosulfur compounds, particularly methanethiol (CH(3)SH, the sulfur analog of methanol), may have been biogenic products on early Earth. Similar production could take place on extrasolar Earth-like planets whose biota share functional chemical characteristics with Earth life. Since methanethiol and related organosulfur compounds (as well as carbon dioxide) absorb at wavelengths near or overlapping the 9.6-microm band of ozone, there is potential ambiguity in interpreting a feature around this wavelength in an extrasolar planet spectrum.

Biosignatures of early earths.

PubMed

Pilcher, Carl B

2003-01-01

A major goal of NASA's Origins Program is to find habitable planets around other stars and determine which might harbor life. Determining whether or not an extrasolar planet harbors life requires an understanding of what spectral features (i.e., biosignatures) might result from life's presence. Consideration of potential biosignatures has tended to focus on spectral features of gases in Earth's modern atmosphere, particularly ozone, the photolytic product of biogenically produced molecular oxygen. But life existed on Earth for about 1(1/2) billion years before the buildup of atmospheric oxygen. Inferred characteristics of Earth's earliest biosphere and studies of modern microbial ecosystems that share some of those characteristics suggest that organosulfur compounds, particularly methanethiol (CH(3)SH, the sulfur analog of methanol), may have been biogenic products on early Earth. Similar production could take place on extrasolar Earth-like planets whose biota share functional chemical characteristics with Earth life. Since methanethiol and related organosulfur compounds (as well as carbon dioxide) absorb at wavelengths near or overlapping the 9.6-microm band of ozone, there is potential ambiguity in interpreting a feature around this wavelength in an extrasolar planet spectrum.