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Sample records for earth metal complexes

  1. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  2. Rare Earth Metal Complexes of Bidentate Nitroxide Ligands: Synthesis and Electrochemistry.

    PubMed

    Kim, Jee Eon; Bogart, Justin A; Carroll, Patrick J; Schelter, Eric J

    2016-01-19

    We report rare earth metal complexes with tri- and bidentate ligands including strongly electron-donating nitroxide groups. The tridentate ligand 1,3,5-tris(2'-tert-butylhydroxylaminoaryl)benzene (H3arene-triNOx) was complexed to cerium(IV) in a 2:1 ligand-to-metal stoichiometry as Ce(Harene-triNOx)2 (1). Cyclic voltammetry of this compound showed stabilization of the tetravalent cerium cation with a Ce(IV/III) couple at E1/2 = -1.82 V versus Fc/Fc(+). On the basis of the uninvolvement of the third nitroxide group in the coordination chemistry with the cerium(IV) cation, the ligand system was redesigned toward a simpler bidentate mode, and a series of rare earth metal-arene-diNOx complexes were prepared with La(III), Ce(IV), Pr(III), Tb(III), and Y(III), [RE(arene-diNOx)2](-) ([2-RE](-), RE = La, Pr, Y, Tb) and Ce(IV)(arene-diNOx)2, where H2arene-diNOx = 1,3-bis(2'-tert-butylhydroxylaminoaryl)benzene. The core structures were isostructural throughout the series, with three nitroxide groups in η(2) binding modes and one κ(1) nitroxide group coordinated to the metal center in the solid state. In all cases except Ce(IV)(arene-diNOx)2, electrochemical analysis described two subsequent, ligand-based, quasi-reversible redox waves, indicating that a stable [N-O•] group was generated on the electrochemical time scale. Chemical oxidation of the terbium complex was performed, and isolation of the resulting complex, Tb(arene-diNOx)2·CH2Cl2 (3·CH2Cl2), confirmed the assignment of the cyclic voltammograms. Magnetic data showed no evidence of mixing between the Tb(III) states and the states of the open-shell ligand. PMID:26689656

  3. Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals.

    PubMed

    Huang, Wenliang; Diaconescu, Paula L

    2015-09-21

    Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes. PMID:26247323

  4. Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application.

    PubMed

    Trambitas, Alexandra G; Melcher, Daniel; Hartenstein, Larissa; Roesky, Peter W; Daniliuc, Constantin; Jones, Peter G; Tamm, Matthias

    2012-06-18

    Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity. PMID:22662762

  5. Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

    PubMed

    Thoi, V Sara; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2013-03-21

    Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products. PMID:23034627

  6. Synthesis and structural diversity of trivalent rare-earth metal diisopropylamide complexes.

    PubMed

    Spallek, Tatiana; Heß, Oliver; Meermann-Zimmermann, Melanie; Meermann, Christian; Klimpel, Michael G; Estler, Frank; Schneider, David; Scherer, Wolfgang; Tafipolsky, Maxim; Törnroos, Karl W; Maichle-Mössmer, Cäcilia; Sirsch, Peter; Anwander, Reiner

    2016-09-21

    A series of rare-earth metal diisopropylamide complexes has been obtained via salt metathesis employing LnCl3(THF)x and lithium (LDA) or sodium diisopropylamide (NDA) in n-hexane. Reactions with AM : Ln ratios ≥3 gave ate complexes (AM)Ln(NiPr2)4(THF)n (n = 1, 2; Ln = Sc, Y, La, Lu; AM = Li, Na) in good yields. For smaller rare-earth metal centres such as scandium and lutetium, a Li : Ln ratio = 2.5 accomplished ate-free tris(amido) complexes Ln(NiPr2)3(THF). The chloro-bridged dimeric derivatives [Ln(NiPr2)2(μ-Cl)(THF)]2 (Ln = Sc, Y, La, Lu) could be obtained in high yields for Li : Ln = 1.6-2. The product resulting from the Li : La = 1 : 1.6 reaction revealed a crystal structure containing two different molecules in the crystal lattice, [La(NiPr2)2(THF)(μ-Cl)]2·La(NiPr2)3(THF)2. Recrystallization of the chloro-bridged dimers led to the formation of the monomeric species Ln(NiPr2)2Cl(THF)2 (Ln = Sc, Lu) and La(NiPr2)3(THF)2. The reaction of YCl3 and LDA with Li : Y = 2 in the absence of THF gave a bimetallic ate complex LiY(NiPr2)4 with a chain-like structure. For scandium, the equimolar reactions with LDA or NDA yielded crystals of tetrametallic mono(amido) species, {[Sc(NiPr2)Cl2(THF)]2(LiCl)}2 and [Sc(NiPr2)Cl2(THF)]4, respectively. Depending on the Ln(iii) size, AM, and presence of a donor solvent, ate complexes (AM)Ln(NiPr2)4(THF)n show distinct dynamic behaviour as revealed by variable temperature NMR spectroscopy. The presence of weak LnCH(iPr) β-agostic interactions, as indicated by Ln-N-C angles <105°, is corroborated by DFT calculations and NBO analysis. PMID:27471799

  7. Reactivity of functionalized indoles with rare-earth metal amides. Synthesis, characterization and catalytic activity of rare-earth metal complexes incorporating indolyl ligands.

    PubMed

    Feng, Zhijun; Wei, Yun; Zhou, Shuangliu; Zhang, Guangchao; Zhu, Xiancui; Guo, Liping; Wang, Shaowu; Mu, Xiaolong

    2015-12-21

    The reactivity of several functionalized indoles 2-(RNHCH2)C8H5NH (R = C6H5 (1), (t)Bu (2), 2,6-(i)Pr2C6H3 (3)) with rare-earth metal amides is described. Reactions of 1 or 2 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 (RE = Eu, Yb) respectively produced the europium complexes [2-(C6H5N[double bond, length as m-dash]CH)C8H5N]2Eu[N(SiMe3)2] (4) and [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]Eu[N(SiMe3)2]2 (5), and the ytterbium complex [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]2Yb[N(SiMe3)2] (6), containing bidentate anionic indolyl ligands via dehydrogenation of the amine to the imine. In contrast, reactions of the more sterically bulky indole 3 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 afforded complexes [2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2](THF)2 (RE = Yb (7), Y (8), Er (9), Dy (10)) with the deprotonated indolyl ligand. While reactions of 3 with yttrium and ytterbium amides in refluxing toluene respectively gave the complexes [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]3Y (11) and [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]2Yb(II)(THF)2 (12), along with transformation of the amino group to the imino group, and also with a reduction of Yb(3+) to Yb(2+) in the formation of 12. Reactions of 3 with samarium and neodymium amides provided novel dinuclear complexes {[μ-η(5):η(1):η(1)-2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2]}2 (RE = Sm (13), Nd (14)) having indolyl ligands in μ-η(5):η(1):η(1) hapticities. The pathway for the transformation of the amino group to the imino group is proposed on the basis of the experimental results. The new complexes displayed excellent activity in the intramolecular hydroamination of aminoalkenes. PMID:26548974

  8. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.

    2012-11-01

    A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

  9. Mono(boratabenzene) rare-earth metal dialkyl complexes: synthesis, structure and catalytic behaviors for styrene polymerization.

    PubMed

    Wang, Xiufang; Leng, Xuebing; Chen, Yaofeng

    2015-03-28

    Four mono(boratabenzene) rare-earth metal dialkyl complexes, [(3,5-Me2-C5H3BR)Ln(CH2SiMe3)2(THF)] (1: R = NEt2, Ln = Sc; 2: R = NEt2, Ln = Lu; 3: R = Ph, Ln = Sc; 4: R = Ph, Ln = Lu), were synthesized efficiently via a one-pot strategy with Li[3,5-Me2-C5H3BR] (R = NEt2, Ph), LnCl3(THF)x (Ln = Sc, x = 3; Ln = Lu, x = 0), and LiCH2SiMe3. The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction. Variable-temperature NMR studies indicated that the energy barrier for the rotation of aminoboratabenzene in 1 (ΔG‡ ≈ 71 kJ mol−1) is higher than that of phenylboratabenzene in 3 (ΔG‡ ≈ 59 kJ mol−1). These mono(boratabenzene) rare-earth metal dialkyl complexes’ catalytic behaviors for styrene polymerization were investigated, and found that mono(boratabenzene) scandium dialkyl complexes show high catalytic activities for syndiotactic polymerization upon activation with cocatalysts. PMID:25714489

  10. Rare-earth-metal methyl, amide, and imide complexes supported by a superbulky scorpionate ligand.

    PubMed

    Schädle, Dorothea; Maichle-Mössmer, Cäcilia; Schädle, Christoph; Anwander, Reiner

    2015-01-01

    The reaction of monomeric [(Tp(tBu,Me) )LuMe2 ] (Tp(tBu,Me) =tris(3-Me-5-tBu-pyrazolyl)borate) with primary aliphatic amines H2 NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(Tp(tBu,Me) )LuMe(NHR)], the solid-state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(Tp(tBu,Me) )LnMe({μ2 -Me}AlMe3 )] (Ln=Y, Ho) reacted selectively and in high yield with H2 NR, according to methane elimination, to afford heterobimetallic complexes: [(Tp(tBu,Me) )Ln({μ2 -Me}AlMe2 )(μ2 -NR)] (Ln=Y, Ho). X-ray structure analyses revealed that the monomeric alkylaluminum-supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by (1) H and (13) C NMR spectroscopic studies at variable temperatures and (1) H-(89) Y HSQC NMR spectroscopy. Treatment of [(Tp(tBu,Me) )LnMe(AlMe4 )] with H2 NtBu gave dimethyl compounds [(Tp(tBu,Me) )LnMe2 ] as minor side products for the mid-sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative-scale amounts of complexes [(Tp(tBu,Me) )LnMe2 ] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(Tp(tBu,Me) )LnMe(AlMe4 )] with N,N,N',N'-tetramethylethylenediamine (tmeda). The solid-state structures of [(Tp(tBu,Me) )HoMe(AlMe4 )] and [(Tp(tBu,Me) )HoMe2 ] were analyzed by XRD. PMID:25392940

  11. Synthesis, structure, and spectroscopic and magnetic properties of mesomorphic octakis(hexylthio)-substituted phthalocyanine rare-earth metal sandwich complexes.

    PubMed

    Gürek, Ayse Gül; Basova, Tamara; Luneau, Dominique; Lebrun, Colette; Kol'tsov, Evgeny; Hassan, Aseel K; Ahsen, Vefa

    2006-02-20

    The syntheses of new bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes [(C6S)8-Pc]2M (M = Gd(III), Dy(III), and Sm(III)) (2-4, respectively) are described. These compounds are very soluble in most common organic solvents. They have been fully characterized using elemental analysis, infrared, UV-vis spectroscopy, and mass spectrometry. The crystal structures of compounds 2-4 have been determined by X-ray diffraction on a single crystal. They are isostructural and crystallize in the monoclinic space group (space group C2/c). Their lattice constants have been determined in the following order: (2) a = 31.629(4) Angstroms, b = 32.861(4) Angstroms, c = 20.482(2) Angstroms, beta = 126.922(2) degrees, V = 17019(3) Angstroms(3); (3) a = 31.595(2) Angstroms, b = 32.816(2) Angstroms, c = 20.481(1) Angstroms, beta = 127.005(1) degrees, V = 16958(2) Angstroms(3); (4) a = 31.563(2) Angstroms, b = 32.796(2) Angstroms, c = 20.481(1) Angstroms, beta = 127.032 degrees, V = 16924(2) Angstroms(3). The magnetic properties of compounds 2-4 were studied, and it was revealed that the lanthanide ions and the radical delocalized on the two phthalocyanine rings are weakly interacting. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. These phthalocyanine derivatives form columnar-hexagonal (Col(h)) mesophases. Thin films of bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes (2-4) were prepared by a spin-coating technique. Thermally induced molecular reorganization within films of bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes (2-4) was studied by the methods of ellipsometry, UV-vis absorption spectroscopy, and atomic force microscopy. Heat treatment produces molecular ordering, which is believed to be due to stacking interaction between neighboring phthalocyanine moieties. PMID:16471979

  12. Electronic structures and second hyperpolarizabilities of alkaline earth metal complexes end-capped with NA2 (A = H, Li, Na).

    PubMed

    Banerjee, Paramita; Nandi, Prasanta K

    2016-05-14

    The ground state structures and NLO properties of a number of alkaline earth metal complexes end-capped with NA2 groups (A = H, Li, Na) are calculated by employing the CAM-B3LYP, wB97XD and B2PLYP functionals along with MP2 and CCSD(T) for 6-311++G(d,p), 6-311++G(3df,3pd), aug-cc-pVTZ, aug-pc-2 and Hypol basis sets. The complexes are found to be significantly stable. The magnitude of second hyperpolarizability enhances appreciably with increase in the number of magnesium and calcium atoms in the chain, which has been indicated by the power law dependence γ = a + bn(c) with c values ranging from 2.4-4.3 for Mg and 2.4-3.7 for Ca complexes, respectively. The largest second-hyperpolarizability (10(9) au) is obtained for the complex Ca7(NNa2)2 at the CAM-B3LYP level. The two state model has been used to explain the variation of hyperpolarizabilities. PMID:27088138

  13. Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State.

    PubMed

    Volchkov, Valery V; Gostev, Fedor E; Shelaev, Ivan V; Nadtochenko, Viktor A; Dmitrieva, Svetlana N; Gromov, Sergey P; Alfimov, Mikhail V; Melnikov, Mikhail Ya

    2016-03-01

    Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown. The compounds investigated can be viewed as novel optical molecular sensors for alkali and alkaline-earth metal cations. The photoejection of a metal cation into the bulk was not observed. PMID:26670689

  14. Chemistry of soluble β-diketiminatoalkaline-earth metal complexes with M-X bonds (M=Mg, Ca, Sr; X=OH, Halides, H).

    PubMed

    Sarish, Sankaranarayana Pillai; Nembenna, Sharanappa; Nagendran, Selvarajan; Roesky, Herbert W

    2011-03-15

    Victor Grignard's Nobel Prize-winning preparation of organomagnesium halides (Grignard reagents) marked the formal beginning of organometallic chemistry with alkaline earth metals. Further development of this invaluable synthetic route, RX+Mg→RMgX, with the heavier alkaline earth metals (Ca and Sr) was hampered by limitations in synthetic methodologies. Moreover, the lack of suitable ligands for stabilizing the reactive target molecules, particularly with the more electropositive Ca and Sr, was another obstacle. The absence in the literature, until just recently, of fundamental alkaline earth metal complexes with M-H, M-F, and M-OH (where M is the Group 2 metal Mg, Ca, or Sr) bonds amenable for organometallic reactions is remarkable. The progress in isolating various unstable compounds of p-block elements with β-diketiminate ligands was recently applied to Group 2 chemistry. The monoanionic β-diketiminate ligands are versatile tools for addressing synthetic challenges, as amply demonstrated with alkaline earth complexes: the synthesis and structural characterization of soluble β-diketiminatocalcium hydroxide, β-diketiminatostrontium hydroxide, and β-diketiminatocalcium fluoride are just a few examples of our contribution to this area of research. To advance the chemistry beyond synthesis, we have investigated the reactivity and potential for applications of these species, for example, through the demonstration of dip coating surfaces with CaCO(3) and CaF(2) with solutions of the calcium hydroxide and calcium fluoride complexes, respectively. In this Account, we summarize some recent developments in alkaline earth metal complex chemistry, particularly of Mg, Ca, and Sr, through the utilization of β-diketiminate ligands. We focus on results generated in our laboratory but give due mention to work from other groups as well. We also highlight the closely related chemistry of the Group 12 element Zn, as well as the important chemistry developed by other groups

  15. Oligocyclopentadienyl transition metal complexes

    SciTech Connect

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  16. The low temperature radiolysis of cis-syn-cis-dicyclohexano-18-crown-6 complexes with alkaline earth metal nitrates: An evidence for energy transfer to the macrocyclic ligand

    NASA Astrophysics Data System (ADS)

    Zakurdaeva, O. A.; Nesterov, S. V.; Shmakova, N. A.; Sokolova, N. A.; Feldman, V. I.

    2015-10-01

    Formation of paramagnetic intermediates in macrocyclic complexes of cis-syn-cis-dicyclohexano-18-crown-6 (DCH18C6) with alkaline earth metal nitrates under X-rays irradiation was studied by EPR spectroscopy. NO32- dianions appear to be predominant intermediate species in the samples irradiated at 77 K at low doses (up to 40 kGy). This result was interpreted as an evidence for energy transfer within the complex from crown ether to nitrate anion. Increase in the absorbed dose from 40 kGy to 284 kGy results in built-up of a new EPR signal assigned to macrocyclic -CH2-ĊH-O- radicals produced from crown ether moieties. Thermal annealing of the irradiated macrocyclic complexes at 273 К led to fast decay of NO32- . This process was accompanied by a formation of -CH2-ĊH-O- radicals in secondary reactions. The nature of the metal cations coordinated in the macrocycle cavity had no appreciable effect on the composition of radical products and their post-radiation transformations.

  17. Rare-earth metal methylidene complexes with Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3 core structure.

    PubMed

    Schädle, Dorothea; Meermann-Zimmermann, Melanie; Maichle-Mössmer, Cäcilia; Schädle, Christoph; Törnroos, Karl W; Anwander, Reiner

    2015-11-01

    Trinuclear rare-earth metal methylidene complexes with a Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3 structural motif were synthesized by applying three protocols. Polymeric [LuMe3]n (1-Lu) reacts with the sterically demanding amine H[NSiMe3(Ar)] (Ar = C6H3iPr2-2,6) in tetrahydrofuran via methane elimination to afford isolable monomeric [NSiMe3(Ar)]LuMe2(thf)2 (4-Lu). The formation of trinuclear rare-earth metal tetramethyl methylidene complexes [NSiMe3(Ar)]3Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3(thf)3 (7-Ln; Ln = Y, Ho, Lu) via reaction of [LnMe3]n (1-Ln; Ln = Y, Ho, Lu) with H[NSiMe3(Ar)] is proposed to occur via an "intermediate" species of the type [NSiMe3(Ar)]LnMe2(thf)x and subsequent C-H bond activation. Applying Lappert's concept of Lewis base-induced methylaluminate cleavage, compounds [NSiMe3(Ar)]Ln(AlMe4)2 (5-Ln; Ln = Y, La, Nd, Ho) were converted into methylidene complexes 7-Ln (Ln = Y, Nd, Ho) in the presence of tetrahydrofuran. Similarly, tetramethylgallate complex [NSiMe3(Ar)]Y(GaMe4)2 (6-Y) could be employed as a synthesis precursor for 7-Y. The molecular composition of complexes 4-Ln, 5-Ln, 6-Y and 7-Ln was confirmed by elemental analyses, FTIR spectroscopy, (1)H and (13)C NMR spectroscopy (except for holmium derivatives) and single-crystal X-ray diffraction. The Tebbe-like reactivity of methylidene complex 7-Nd with 9-fluorenone was assessed affording oxo complex [NSiMe3(Ar)]3Nd3(μ3-O)(μ2-Me)4(thf)3 (8-Nd). The synthesis of 5-Ln yielded [NSiMe3(Ar)]2Ln(AlMe4) (9-Ln; Ln = La, Nd) as minor side-products, which could be obtained in moderate yields when homoleptic Ln(AlMe4)3 were treated with two equivalents of K[NSiMe3(Ar)]. PMID:26418665

  18. Rare-earth-metal dialkynyl dimethyl aluminates.

    PubMed

    Nieland, Anja; Mix, Andreas; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

    2013-06-17

    A new class of rare-earth-metal alkynyl complexes has been prepared. The reactions of the tris(tetramethylaluminate)s of lanthanum, praseodymium, samarium, yttrium, holmium, and thulium, [Ln(AlMe₄)₃], with phenylacetylene afforded compounds [Ln{(μ-C≡CPh)₂AlMe₂}₃] (Ln=La (1), Pr (2), Sm (3), Y (4), Ho (5), Tm (6)). All of these compounds have been characterized by NMR spectroscopy, X-ray crystallography, and by elemental analysis. NMR spectroscopic studies of the series of para- magnetic compounds [Ln(AlMe₄)₃] and [Ln{(μ-C≡CPh)₂AlMe₂}₃] have also been performed. PMID:23616205

  19. Synthesis, structure and reactivity of dinuclear rare earth metal bis(o-aminobenzyl) complexes bearing a 1,4-phenylenediamidinate co-ligand.

    PubMed

    Li, Meng; Hong, Jianquan; Chen, Zhenxia; Zhou, Xigeng; Zhang, Lixin

    2013-06-21

    A series of phenylenediamidinate rare earth metal complexes 1,4-C6H4[C(NR)2Ln(o-CH2C6H4NMe2)2]2 (R = 2,6-(i)Pr2-C6H3, Ln = Y (2a), Lu (2b), Sc (2c)) were synthesized by deprotonation of 1,4-C6H4[C(NR)(NHR)]2 (1) with two equivalents of n-BuLi followed by reacting with two equivalents of anhydrous LnCl3 and subsequently four equivalents of Li(o-CH2C6H4NMe2), or by protolysis of [Ln(o-CH2C6H4NMe2)3] with 0.5 equivalent of 1 in THF or toluene. Treatment of complexes 2a and 2b with four equivalents of phenyl isocyanate and phenyl isothiocyanate gave the corresponding insertion products 1,4-C6H4[C(NR)2Ln{OC(CH2C6H4NMe2-o)NPh}2(THF)]2 (Ln = Y (3a), Lu (3b)) and 1,4-C6H4[C(NR)2Ln{SC(CH2C6H4NMe2-o)NPh}2]2 (Ln = Y (4a), Lu (4b)), respectively. The structures of 1, 3b, and 4a were established by X-ray diffraction studies. Complexes 2 show high activity for rac-lactide and ε-caprolactone polymerization; for the former a synergistic effect between two metal centers is observed. PMID:23598898

  20. Synthesis of main group, rare-earth, and d{sup 0} metal complexes containing beta-hydrogen

    SciTech Connect

    Yan, Ka King

    2013-01-01

    A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)3 and KC(SiHMe2})3TMEDA are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)3 with potassium benzyl. KC(SiHMe2)3TMEDA crystallizes as a dimer with two types of three-center-two-electron KH- Si interactions. Homoleptic Ln(III) tris(silylalkyl) complexes containing β-SiH groups M{C(SiHMe2)3}3 (Ln = Y, Lu, La) are synthesized from salt elimination of the corresponding lanthanide halide and 3 equiv. of KC(SiHMe2)3. The related reactions with Sc yield bis(silylalkyl) ate-complexes containing either LiCl or KCl. The divalent calcium and ytterbium compounds M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2 or TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)3. The compounds M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2 or TMEDA) and La{C(SiHMe2)3}3 react with 1 equiv of B(C6F5)3 to give 1,3- disilacyclobutane {Me2Si-C(SiHMe2)2}2 and MC(SiHMe2)3HB(C6F5)3L, and La{C(SiHMe2)3}2HB(C6F5)3, respectively. The corresponding reactions of Ln{C(SiHMe2)3}3 (Ln = Y, Lu) give the β-SiH abstraction product [{(Me2HSi)3C}2LnC(SiHMe2)2SiMe2][HB(C6F5)3] (Ln = Y, Lu), but the silene remains associated with the Y or Lu center. The abstraction reactions of M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2or TMEDA) and Ln{C(SiHMe2)3}3 (Ln = Y, Lu, La) and 2 equiv of B(C6

  1. Antihuman Immunodeficiency Virus Type 1 (HIV-1) Activity of Rare Earth Metal Complexes of 4-Hydroxycoumarins in Cell Culture

    PubMed Central

    Manolov, Ilia; Raleva, Sevda; Genova, Petya; Savov, Alexey; Froloshka, Liliana; Dundarova, Daniela; Argirova, Radka

    2006-01-01

    The cerium Ce(III), lanthanum La(III), and neodymium Nd(III) complexes with 4-hydroxy-3-(3-oxo-1-phenylbutyl)-2H-1-benzopyran-2-one (warfarin) (W) and 3,3′-benzylidenebis[4-hydroxycoumarin] (1) were synthesized and studied for the first time for cytotoxicity (on MT-2 cells) and as anti-HIV agents under acute and chronic infection. The complexes were characterized by different physicochemical methods: mass spectrometry, 1H NMR, 13C NMR, and IR spectroscopy. The spectra of the complexes were interpreted on the basis of comparison with the spectrum of the free ligands. Anti-HIV effect of the complexes/ligands was measured in MT-2 cells by microtiter infection assay. Detection of endogenous reverse transcriptase (RT) activity and RT processivity by PCR indicative for proviral DNA synthesis demonstrated that anti-HIV activity has not been linked to early stages of viral replication. No effect on late steps of viral replication has been found using cells chronically producing HIV-1LAI virus. La(W) demonstrated anti-HIV activity (IC50=21.4 μM) close to maximal nontoxic concentration. Nd(W), Ce(1), and Nd(1) demonstrated limited anti-HIV potency, so none of the complexes seems appropriate to be used in clinic. Further targeting of HIV-1 inhibition by La(W) is under progress. PMID:17497016

  2. Iron complex-catalyzed ammonia-borane dehydrogenation. A potential route toward B-N-containing polymer motifs using earth-abundant metal catalysts.

    PubMed

    Baker, R Tom; Gordon, John C; Hamilton, Charles W; Henson, Neil J; Lin, Po-Heng; Maguire, Steven; Murugesu, Muralee; Scott, Brian L; Smythe, Nathan C

    2012-03-28

    Ammonia-borane (NH(3)BH(3), AB) has garnered interest as a hydrogen storage material due to its high weight percent hydrogen content and ease of H(2) release relative to metal hydrides. As a consequence of dehydrogenation, B-N-containing oligomeric/polymeric materials are formed. The ability to control this process and dictate the identity of the generated polymer opens up the possibility of the targeted synthesis of new materials. While precious metals have been used in this regard, the ability to construct such materials using earth-abundant metals such as Fe presents a more economical approach. Four Fe complexes containing amido and phosphine supporting ligands were synthesized, and their reactivity with AB was examined. Three-coordinate Fe(PCy(3))[N(SiMe(3))(2)](2) (1) and four-coordinate Fe(DEPE)[N(SiMe(3))(2)](2) (2) yield a mixture of (NH(2)BH(2))(n) and (NHBH)(n) products with up to 1.7 equiv of H(2) released per AB but cannot be recycled (DEPE = 1,2-bis(diethylphosphino)ethane). In contrast, Fe supported by a bidentate P-N ligand (4) can be used in a second cycle to afford a similar product mixture. Intriguingly, the symmetric analogue of 4 (Fe(N-N)(P-P), 3), only generates (NH(2)BH(2))(n) and does so in minutes at room temperature. This marked difference in reactivity may be the result of the chemistry of Fe(II) vs Fe(0). PMID:22428955

  3. Rare Earth Metals: Resourcefulness and Recovery

    NASA Astrophysics Data System (ADS)

    Wang, Shijie

    2013-10-01

    When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

  4. Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

    DOEpatents

    Ellis, T.W.; Schmidt, F.A.

    1995-08-01

    A method is described for treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation. 2 figs.

  5. Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

    DOEpatents

    Ellis, Timothy W.; Schmidt, Frederick A.

    1995-08-01

    Method of treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation.

  6. Selenophene transition metal complexes

    SciTech Connect

    White, C.J.

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the {eta}{sup 5}- and the {eta}{sup 1}(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The {sup 77}Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of {eta}{sup 1}(S)-bound thiophenes, {eta}{sup 1}(S)-benzothiophene and {eta}{sup 1}(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the {eta}{sup 1}(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh{sub 3})Re(2-benzothioenylcarbene)]O{sub 3}SCF{sub 3} was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the {eta}{sup 1}(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  7. Aminophosphonate metal complexes of biomedical potential.

    PubMed

    Tušek-Božić, L J

    2013-01-01

    Metals and their complexes with organic ligands have an important role in biochemical systems such as enzymatic catalysis, metal ion transfer across the cell membranes, treatment of malignancy, rheumatoid arthritis, ulcer and other types of diseases. Special attention is directed to metal complexes with ligands which are important in biological systems, as their incorporation into metallo-organic compounds offers much scope for design of potential metal-based agents that provide new opportunities in the medicinal chemistry. In view of this, derivatives of aminophosphonic acids, owing to their broad spectrum of biological activities and wide range of applications in the medicinal and agrochemical fields, are very attractive metal-ligand agents that might form biomedical important metal complexes. Thus, a number of aminophosphonate complexes of platinum group metals have been found to possess remarkable antitumor activity while complexes of some other transition and rare-earth metals like technetium, rhenium, samarium and gadolinium have been used either as therapeutic and diagnostic radiopharmaceuticals or as magnetic resonance imaging (MRI) contrast agents. In addition, the high phosphonate affinity towards bone and other calcified tissues may be utilized for the drug targeting based on synthesis of metal complexes linked to bioactive carrier systems, affording better modalities of attack to the site of pathology. In this review article, aminophosphonate metal-based compounds with potential biomedical applications are described. PMID:23432587

  8. First pentahaptofullerene metal complexes

    SciTech Connect

    Masaya, Sawamura; Iikura, Hitoshi; Nakamura, Eiichi

    1996-12-18

    Cyclopentadienyl metal complexes have played important roles in chemistry owing to their unique structures and functional activities. Here we report the synthesis and characterization of an entirely new class of cyclopentadienyl (Cp) metal complexes ({eta}{sup 5}-C{sub 60}Ph{sub 5})MLn (MLn = Li, K, Tl, and Cu.PEt{sub 3}). In these molecules, the five Cp carbons represent one pentagon of C{sub 60}, isolated from the remaining 50 sp{sup 2} carbon atoms by five surrounding sp{sup 3} carbon atoms each bearing a phenyl group. The X-ray crystal structure analysis of the thallium complex Tl({eta}{sup 5}-C{sub 60}Ph{sub 5}).2.5THF revealed its unique and esthetically pleasing C{sub 5} symmetrical molecular structure with the phenyl groups forming a chiral propeller array. The thallium atom is deeply buried in the cavity created by the phenyl groups, bonding to the five Cp carbons ({eta}{sup 5}-coordination) with an averaged Tl-C distance of 2.87 A. The key finding that we made in this research was a remarkable 5-fold addition of an organocopper reagent to C{sub 60}, which stands in contrast to the monoaddition reaction of Grignard or organolithium reagents. 10 refs., 1 fig.

  9. Synthesis, characterization and cytotoxicity of rare earth metal ion complexes of N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene, Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Shakir, Mohammad; Abbasi, Ambreen; Faraz, Mohammad; Sherwani, Asif

    2015-12-01

    Lanthanide complexes of La3+, Pr3+, Nd3+, Gd3+, Er3+ of general formula [Ln2 L(H2O)4(NO3)4](NO3)2·2H2O have been synthesized from Schiff base, N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene. The complexes were characterized by elemental analysis, molar conductance, UV-Vis, fluorescence, FT-IR,1H NMR, mass spectroscopy, EDX, SEM and thermal analysis. FT-IR spectral data suggested that ligand coordinate with metal ions through azomethine nitrogen and uncondensed amino group. Molar conductance data revealed 1:2 electrolytic nature of complexes. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (ligand:metal). Thephysico-chemical data suggested eight coordination number for Ln(III)Schiffbase complexes. SEM analysis shows morphological changes in the surfaces of complexes as compared to free ligand. Thermal decomposition profiles were consistent with proposed formulations. The anticancer activity of the complexes and theSchiffbase ligand has been studied towards human cervical cancer celllines (HeLa) and human breast cancer cell lines (MCF-7) and it was found that complexes exhibited greater activity than theSchiffbase.

  10. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  11. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    PubMed

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-01

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available. PMID:25413985

  12. Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Mono layers Probed by Sum-Frequency Generation Spectroscopy

    SciTech Connect

    Song, Woongmo; Vaknin, David; Kim, Doseok

    2013-02-25

    Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation La3+ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex Fe(OH)3 adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.

  13. Metal complex interactions with DNA.

    PubMed

    Pages, Benjamin J; Ang, Dale L; Wright, Elisé P; Aldrich-Wright, Janice R

    2015-02-28

    Increasing numbers of DNA structures are being revealed using biophysical, spectroscopic and genomic methods. The diversity of transition metal complexes is also growing, as the unique contributions that transition metals bring to the overall structure of metal complexes depend on the various coordination numbers, geometries, physiologically relevant redox potentials, as well as kinetic and thermodynamic characteristics. The vast range of ligands that can be utilised must also be considered. Given this diversity, a variety of biological interactions is not unexpected. Specifically, interactions with negatively-charged DNA can arise due to covalent/coordinate or subtle non-coordinate interactions such as electrostatic attraction, groove binding and intercalation as well as combinations of all of these modes. The potential of metal complexes as therapeutic agents is but one aspect of their utility. Complexes, both new and old, are currently being utilised in conjunction with spectroscopic and biological techniques to probe the interactions of DNA and its many structural forms. Here we present a review of metal complex-DNA interactions in which several binding modes and DNA structural forms are explored. PMID:25427534

  14. Synthesis of mono-amidinate-ligated rare-earth-metal bis(silylamide) complexes and their reactivity with [Ph3C][B(C6F5)4], AlMe3 and isoprene.

    PubMed

    Luo, Yunjie; Lei, Yinlin; Fan, Shimin; Wang, Yibin; Chen, Jue

    2013-03-21

    Amine elimination of rare-earth-metal tris(silylamide) complexes Ln[N(SiHMe(2))(2)](3)(THF)(x) (Ln = Sc, x = 1; Ln = Y, x = 2) with 1 equiv. of the amidines [PhC(N-2,6-R(2)C(6)H(3))(2)]H afforded a series of neutral mono(amidinate) rare-earth-metal bis(silylamide) complexes [PhC(N-2,6-R(2)C(6)H(3))(2)]Ln[N(SiHMe(2))(2)](2)(THF)(y) (R = Me, Ln = Sc, y = 0 (1); R = Me, Ln = Y, y = 1 (2); R = (i)Pr, Ln = Y, y = 1 (3)). Treatment of 1-3 with 1 equiv. of [Ph(3)C][B(C(6)F(5))(4)] in THF generated the corresponding cationic amidinate rare-earth-metal mono(silylamide) complexes [{PhC(N-2,6-R(2)C(6)H(3))(2)}Ln{N(SiHMe(2))(2)}(THF)(3)][B(C(6)F(5))(4)] (R = Me, Ln = Sc (4), Y (5); R = (i)Pr, Ln = Y (6)). When 1-3 were first activated with 1 equiv. of [Ph(3)C][B(C(6)F(5))(4)] in toluene, then treatment with THF gave the unexpected cationic amidinate rare-earth-metal amide complexes [{PhC(N-2,6-R(2)C(6)H(3))(2)}LnN{SiHMe(2)}{SiMe(2)N(SiHMe(2))(2)}(THF)(n)][B(C(6)F(5))(4)] (R = Me, Ln = Sc, n = 2 (7); R = Me, Ln = Y, n = 4 (8); R = (i)Pr, Ln = Y, n = 2 (9)). The reaction of 1-3 with excess AlMe(3) produced the heterometallic Ln/Al methyl complexes [PhC(N-2,6-R(2)C(6)H(3))(2)]Ln[(μ-Me)(2)AlMe(2)](2) (R = Me, Ln = Sc (10), Y (11); R = (i)Pr, Ln = Y (12)). All these complexes were well-characterized by elemental analysis, NMR spectroscopy and FT-IR spectroscopy. 2, 6 and 11 were further structurally authenticated by X-ray crystallography. The binary catalyst system of 1/[Ph(3)C][B(C(6)F(5))(4)] in toluene showed activity toward 3,4-selective polymerization of isoprene, whilst the tertiary catalyst systems of 1-3/[Ph(3)C][B(C(6)F(5))(4)]/AlMe(3) were highly active for cis-1,4-selective polymerization of isoprene. PMID:23340682

  15. METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

    DOEpatents

    Baker, R.D.; Hayward, B.R.

    1963-01-01

    >This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

  16. Addressing the Complexity of the Earth System

    SciTech Connect

    Nobre, Carlos; Brasseur, Guy P.; Shapiro, Melvyn; Lahsen, Myanna; Brunet, Gilbert; Busalacchi, Antonio; Hibbard, Kathleen A.; Seitzinger, Sybil; Noone, Kevin; Ometto, Jean P.

    2010-10-01

    This paper highlights the role of the Earth-system biosphere and illustrates the complex: biosphere-atmosphere interactions in the Amazon Basin, changes in nitrogen cycling, ocean chemistry, and land use. It introduces three important requirements for accelerating the development and use of Earth system information. The first requirement is to develop Earth system analysis and prediction models that account for multi-scale physical, chemical and biological processes, including their interactions in the coupled atmosphere-ocean-land-ice system. The development of these models requires partnerships between academia, national research centers, and operational prediction facilities, and builds upon accomplishments in weather and climate predictions. They will highlight the regional aspects of global change, and include modules for water system, agriculture, forestry, energy, air quality, health, etc. The second requirement is to model the interactions between humans and the weather-climate-biogeochemical system. The third requirement is to introduce novel methodologies to account for societal drivers, impacts and feedbacks. This is a challenging endeavor requiring creative solutions and some compromising because human behavior cannot be fully represented within the framework of present-day physical prediction systems.

  17. Rare-earth metal bis(silylamide) complexes supported by mono-dentate arylamido ligand: synthesis, reactivity, and catalyst precursors in living cis-1,4-selective polymerization of isoprene.

    PubMed

    Shi, Liqin; Su, Qi; Chen, Jue; Li, Xiaonian; Luo, Yunjie

    2016-01-28

    The salt metathesis reaction of LnCl3 with 1 equivalent of arylamido lithium [2,6-(i)Pr2C6H3N(SiMe3)]Li followed by addition of 2 equivalents of LiN(SiHMe2)2 in THF at room temperature obtained neutral mono-arylamido-ligated rare-earth metal bis(silylamide) complexes [2,6-(i)Pr2C6H3N(SiMe3)]Ln[N(SiHMe2)2]2(THF) (Ln = Y (), Lu (), La ()) in good isolated yields. Treatment of with excess AlMe3 produced the mono(arylamido) Ln/Al heterotrinuclear methyl complexes [2,6-(i)Pr2C6H3N(SiMe3)]Ln[(μ-Me)2AlMe2]2 (Ln = Y (), Lu (), La ()) via amide-alkyl exchange. All these complexes were well-characterized by elemental analysis, NMR spectroscopy and FT-IR spectroscopy. , and were further structurally authenticated by X-ray crystallography. In the presence of [Ph3C][B(C6F5)4] and Al(i)Bu3, were highly active for cis-1,4-selective polymerization of isoprene, whereas /[Ph3C][B(C6F5)4]/Al(i)Bu3 promoted the polymerization in a living fashion. PMID:26674733

  18. Stability constants and thermodynamic data for complexes of 12-crown-4 with alkali metal and alkaline-earth cations in methanol solutions

    SciTech Connect

    Buschmann, H.

    1987-03-01

    The formation of 1:1- and 2:1-complexes of the crown ether 12C4 with mono- and bivalent cations was studied in methanol solutions by calorimetric, potentiometric and conductometric titrations. It is shown that not all donor atoms of the ligand 12C4 take part in complex formation. The accuracy of the three experimental methods are checked by comparing the results for the complexation of alkali ions with crown ether 18C6.

  19. Phisicochemistry of alkaline-earth metals oxides surface

    NASA Astrophysics Data System (ADS)

    Ekimova, Irina; Minakova, Tamara; Ogneva, Tatyana

    2016-01-01

    The surface state of alkaline-earth metals and magnesium oxides obtained by means of commercial and laboratory ways has been studied in this paper. A complex of methods has been used for identification, determination of a phase composition and morphology of the samples. The high basic character of surface centres has been shown with the help of pH-metry and adsorption of indicators methods. Acid-basic parameters (pHt, pHiis, etc.) can be used for the estimation of a general acid-basic state of metal oxides samples surface and for the supposition about different nature and strength of acid-basic centres as well as for the initial control in the process of acid basic properties of solid oxides surface properties evaluation.

  20. High fluorescence emission of carboxylic acid functionalized polystyrene/BaTiO{sub 3} nanocomposites and rare earth metal complexes: Preparation and characterization

    SciTech Connect

    Cao, X. T.; Showkat, A. M.; Wang, Z.; Lim, K. T.

    2015-03-30

    Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb{sup 3+}) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S’-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb{sup 3+} ions afforded fluorescent Tb{sup 3+} tagged aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-Tb{sup 3+}) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb{sup 3+}nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb{sup 3+} complexes were investigated by fluorescence spectroscopy.

  1. High fluorescence emission of carboxylic acid functionalized polystyrene/BaTiO3 nanocomposites and rare earth metal complexes: Preparation and characterization

    NASA Astrophysics Data System (ADS)

    Cao, X. T.; Showkat, A. M.; Wang, Z.; Lim, K. T.

    2015-03-01

    Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb3+) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S'-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb3+ ions afforded fluorescent Tb3+ tagged aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-Tb3+) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb3+nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb3+ complexes were investigated by fluorescence spectroscopy.

  2. Metal-metal bond lengths in complexes of transition metals*

    PubMed Central

    Pauling, Linus

    1976-01-01

    In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

  3. Molecular mechanics (MM3) calculations on benzocrown ether complexes of the alkali and alkaline earth cations

    SciTech Connect

    Yang, Linrong R.; Hay, B.P.

    1997-12-31

    The new metal-ligand feature of MM3 has been extended to benzocrown ether complexes of alkali and alkaline earth cations. Over 50 complexes were compared with the crystal structures retrieved from Cambridge Crystal Database. The results agree with experimental data. The averages of absolute deviations between experimental and calculated structural features are: metal-oxygen bond length, 0.03 {angstrom}; Metal-oxygen-carbon angles, 4.1{degrees}; and Metal-oxygen-carbon-carbon angles: 5.1{degrees}. Development of structure-function relationships is in progress.

  4. Near-Earth asteroids: Metals occurrence, extraction, and fabrication

    NASA Technical Reports Server (NTRS)

    Westfall, Richard

    1991-01-01

    Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

  5. Near-Earth asteroids: Metals occurrence, extraction, and fabrication

    NASA Astrophysics Data System (ADS)

    Westfall, Richard

    Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

  6. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare... production of rare earth metals and mischmetal by primary rare earth metals facilities......

  7. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare... production of rare earth metals and mischmetal by primary rare earth metals facilities......

  8. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare... production of rare earth metals and mischmetal by primary rare earth metals facilities......

  9. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare... production of rare earth metals and mischmetal by primary rare earth metals facilities......

  10. Method for treating rare earth-transition metal scrap

    DOEpatents

    Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

    1992-12-29

    Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

  11. Method for treating rare earth-transition metal scrap

    DOEpatents

    Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

    1992-12-29

    Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

  12. Hydrodynamic complexity in the Earth system

    NASA Astrophysics Data System (ADS)

    Peltier, W. Richard

    Geophysical fluid Dynamics (GFD), as a recognizably distinct subdiscipline in the geophysical sciences, was probably born in the continuing series of Summer Schools in GFD that began at the Woods Hole Oceanographic Institution over 20 years ago. The goal of these schools was to bring together relatively small groups of gifted graduate students with professional academics working in the areas of astrophysics, atmospheric science, geophysics, oceanography and other areas in which models based upon the concepts of classical hydrodynamics were coming to be seen as central to the understanding of a wide range of dynamical processes. The point of this effort was, and remains, to emphasize the commonality of physical process that underlies the behaviour of such apparently unrelated systems and thereby to stimulate the growth of a new group of theoretical geophysicists whose members are as comfortable in analyzing the behaviour of the infinite Reynold number flows that dominate the general circulation of the planetary atmosphere as they are in developing models of the zero Reynolds number flow associated with convection in the earth's mantle. The goal was, and remains, for example, to educate astrophysicists to understand that the double diffusive processes at work in magnetoconvection in the earth's core (say) have many similarities with the processes that operate in the oceanographically important heat-salt system; and similarly to educate oceanographers to understand that the process of Gulf Stream ring formation has everything to do with the process of occlusion of a frontal baroclinic wave in the atmosphere, etc. The summary of the present state and future promise of this young science, by Raymond Hyde, in the preceding paper of this volume, has provided an interesting view of some of the areas of present research that are liable to be most productive of new insights in the immediate future. By way of this invited response to what Dr. Hyde has written I thought I

  13. Method for synthesizing metal bis(borano) hypophosphite complexes

    DOEpatents

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  14. Rare-earth-metal nitridophosphates through high-pressure metathesis.

    PubMed

    Kloss, Simon David; Schnick, Wolfgang

    2015-09-14

    Developing a synthetic method to target an broad spectrum of unknown phases can lead to fascinating discoveries. The preparation of the first rare-earth-metal nitridophosphate LiNdP4 N8 is reported. High-pressure solid-state metathesis between LiPN2 and NdF3 was employed to yield a highly crystalline product. The in situ formed LiF is believed to act both as the thermodynamic driving force and as a flux to aiding single-crystal formation in dimensions suitable for crystal structure analysis. Magnetic properties stemming from Nd(3+) ions were measured by SQUID magnetometry. LiNdP4 N8 serves as a model system for the exploration of rare-earth-metal nitridophosphates that may even be expanded to transition metals. High-pressure metathesis enables the systematic study of these uncharted regions of nitride-based materials with unprecedented properties. PMID:26352033

  15. Rare Earth Metal/semiconductor Interfaces and Compounds

    NASA Astrophysics Data System (ADS)

    Nogami, Jun

    Interfaces formed at room temperature by incremental deposition of rare earth metals onto semiconductor substrates have been studied with surface sensitive soft X-ray photoelectron spectroscopy. The trends in core level lineshape and intensity with increasing metal coverage have been used to deduce an outline of the evolution and the final morphology of the interfacial region on a microscopic scale. Measurements were taken for Ytterbium (Yb) on Silicon (Si), Germanium, and Gallium Arsenide, and for Gadolinium (Gd) and Europium (Eu) on Silicon. The Yb/Si interface work was supported by comparable measurements of bulk Yb silicide samples of known composition and crystal structure. In a general sense, the behavior of all the systems studied is similar. At very low metal coverages, the metal atoms chemisorb and are weakly bonded to the substrate. The 4f core levels indicate that the metal-metal atom coordination is relatively low at this stage. The interaction with the substrate strengthens with increasing coverage, culminating in the formation of a strongly reacted phase at between 1 and 3 monolayers (ML). The strong reaction is limited to a narrow region at room temperature. At less than 10 ML coverage, the surface of the sample is almost indistinguishable from the pure metal. Details of the behavior such as the reactivity at low coverage, the compounds formed at the interface, the morphology at the surface at intermediate coverages, the final interfacial width, and the amount of substrate atom outdiffusion and surface segregation can all vary from system to system. It is in explaining the causes of some of these differences that insight about what governs the behavior of all of these rare earth metal/semiconductor systems has been obtained. The divalent metals (Yb, Eu) are significantly less reactive than trivalent Gd at sub-monolayer coverages. For the divalent metals the formation of a metal-rich phase is strongly favored in the reaction at the interface, whereas

  16. Rare earth-transition metal scrap treatment method

    DOEpatents

    Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.; Lincoln, L.P.

    1992-02-11

    Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. 3 figs.

  17. Rare earth-transition metal scrap treatment method

    DOEpatents

    Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.; Lincoln, Lanny P.

    1992-02-11

    Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets.

  18. Complexity in Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Dagotto, Elbio; Alvarez, Gonzalo; Moreo, Adriana

    2004-03-01

    Recent computational results in the context of models for manganites and cuprates will be briefly discussed. It is argued that correlations in quenched disorder -- needed to mimic cooperative Jahn-Teller effects -- are important to have colossal magnetoresistance in 3D. A related recently discussed metal-insulator transition induced by disorder in a one-orbital model with cooperative phonons is intuitively explained [1]. In addition, it is argued that colossal effects should be far more common than currently known, and they may appear in cuprate superconductors as well [2]. [1] J. Burgy et al., cond-mat/0308456; C. Sen, G. Alvarez, and E. Dagotto, preprint. [2] See also Adriana Moreo, invited talk, March APS 04; G. Alvarez, M. Mayr et al., preprint.

  19. Dynamical Correlation In Some Liquid Alkaline Earth Metals Near Melting

    NASA Astrophysics Data System (ADS)

    Thakore, B. Y.; Suthar, P. H.; Khambholja, S. G.; Gajjar, P. N.; Jani, A. R.

    2010-12-01

    The study of dynamical variables: velocity autocorrelation function (VACF) and power spectrum of liquid alkaline earth metals (Ca, Sr, and Ba) have been presented based on the static harmonic well approximation. The effective interatomic potential for liquid metals is computed using our well recognized model potential with the exchange correlation functions due to Hartree, Taylor, Ichimaru and Utsumi, Farid et al. and Sarkar et al. It is observed that the VACF computed using Sarkar et al. gives the good agreement with available molecular dynamics simulation (MD) results [Phys Rev. B 62, 14818 (2000)]. The shoulder of the power spectrum depends upon the type of local field correlation function used.

  20. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  1. Steady-state superradiance with alkaline-earth-metal atoms

    SciTech Connect

    Meiser, D.; Holland, M. J.

    2010-03-15

    Alkaline-earth-metal-like atoms with ultranarrow transitions open the door to a new regime of cavity quantum electrodynamics. That regime is characterized by a critical photon number that is many orders of magnitude smaller than what can be achieved in conventional systems. We show that it is possible to achieve superradiance in steady state with such systems. We discuss the basic underlying mechanisms as well as the key experimental requirements.

  2. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  3. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  4. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  5. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  6. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  7. Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

    NASA Astrophysics Data System (ADS)

    Takahashi, Yuriko

    Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

  8. Syntheses of new rare earth complexes with carboxymethylated polysaccharides and evaluation of their in vitro antifungal activities.

    PubMed

    Sun, Xiaobo; Jin, Xiaozhe; Pan, Wei; Wang, Jinping

    2014-11-26

    In the present paper, La, Eu and Yb were selected to represent light, middle and heavy rare earths to form complexes with polysaccharides through chelating coordination of carboxyl groups, which were added into polysaccharide chains by means of carboxymethylation. Their antifungal activities against plant pathogenic fungi were evaluated using growth rate method. These rare earth complexes exhibited various antifungal activities against the tested fungi, depending on rare earth elements, polysaccharide types and fungal species. Among these three metal elements (i.e. La, Eu and Yb), Yb formed the complexes with the most effective antifungal properties. Furthermore, the results showed that ligands of carboxymethylated polysaccharides played a key role in promoting cytotoxicity of the rare earth complexes. Carboxymethylated Ganoderma applanatum polysaccharide (CGAP) was found to be the most effective ligand to form complexes with antifungal activities, followed by carboxymethylated lentinan (CLNT) and carboxymethylated Momordica charantia polysaccharide (CMCP). PMID:25256475

  9. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    DOEpatents

    Wong, Stanislaus; Zhang, Fen

    2016-06-28

    The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

  10. Dirac Node Lines in Pure Alkali Earth Metals.

    PubMed

    Li, Ronghan; Ma, Hui; Cheng, Xiyue; Wang, Shoulong; Li, Dianzhong; Zhang, Zhengyu; Li, Yiyi; Chen, Xing-Qiu

    2016-08-26

    Beryllium is a simple alkali earth metal, but has been the target of intensive studies for decades because of its unusual electron behavior at surfaces. The puzzling aspects include (i) severe deviations from the description of the nearly free-electron picture, (ii) an anomalously large electron-phonon coupling effect, and (iii) giant Friedel oscillations. The underlying origins for such anomalous surface electron behavior have been under active debate, but with no consensus. Here, by means of first-principles calculations, we discover that this pure metal system, surprisingly, harbors the Dirac node line (DNL) that in turn helps to rationalize many of the existing puzzles. The DNL is featured by a closed line consisting of linear band crossings, and its induced topological surface band agrees well with previous photoemission spectroscopy observations on the Be (0001) surface. We further reveal that each of the elemental alkali earth metals of Mg, Ca, and Sr also harbors the DNL and speculate that the fascinating topological property of the DNL might naturally exist in other elemental metals as well. PMID:27610865

  11. Structure and Abundance of Nitrous Oxide Complexes in Earth's Atmosphere.

    PubMed

    Salmon, Steven R; de Lange, Katrina M; Lane, Joseph R

    2016-04-01

    We have investigated the lowest energy structures and binding energies of a series of atmospherically relevant nitrous oxide (N2O) complexes using explicitly correlated coupled cluster theory. Specifically, we have considered complexes with nitrogen (N2-N2O), oxygen (O2-N2O), argon (Ar-N2O), and water (H2O-N2O). We have calculated rotational constants and harmonic vibrational frequencies for the complexes and the constituent monomers. Statistical mechanics was used to determine the thermodynamic parameters for complex formation as a function of temperature and pressure. These results, in combination with relevant atmospheric data, were used to estimate the abundance of N2O complexes in Earth's atmosphere as a function of altitude. We find that the abundance of N2O complexes in Earth's atmosphere is small but non-negligible, and we suggest that N2O complexes may contribute to absorption of terrestrial radiation and be relevant for understanding the atmospheric fate of N2O. PMID:26983553

  12. Alkene epoxidation employing metal nitro complexes

    DOEpatents

    Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

    1982-07-15

    Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

  13. Stability of rare-earth complexes with acetylacetone and methaccrylic acid in aqueous solution

    SciTech Connect

    Panyushkin, V.T.; Akhrimenko, N.V.

    1995-09-01

    The stability constants for lanthanide (Ln) complexes with methacrylic acid (HL) (log{beta}{sub LnL}{sup Ln}), acetylacetone (HAA) (log{beta}{sub Ln(AA){sub 3}}{sup Ln}), and mixed-ligand complexes (log{beta}{sub LnL(AA){sub 2}}{sup Ln}), [Ln(III)=La, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb, Lu] in aqueous solution are determined by potentiometric titration at 25{degrees}C and {mu}=0.1 (KCl). A nonmonotonous change in the stability constants with an increase in the atomic number number of the rare-earth metal is found to occur.

  14. The structure of metallic complexes of polyacetylene with alkali metals

    NASA Astrophysics Data System (ADS)

    Baughman, R. H.; Murthy, N. S.; Miller, G. G.

    1983-07-01

    The crystal structures of sodium, potassium, rubidium, and cesium doped polyacetylene have been determined using crystal packing and x-ray diffraction analyses. Each of these metallic complexes is tetragonal, with the polyacetylene chains forming a host lattice in which the alkali metal ions are present in channels. Lithium appears to be too small to stabilize the channel structure and an amorphous structure is observed. Predicted unit cell parameters and x-ray diffraction intensities are in agreement with observed values. Similarities with the alkali metal doped graphite suggest that hybridization between carbon pz orbitals and metal s orbitals occurs. Such hybridization is expected to result in a high conductivity component normal to the chain direction. On the other hand, direct overlap between polymer chains appears small, since alkali metal columns separate polymer chains. Compositions calculated for the channel structures (from meridional diffraction spacings, the intensity of equatorial diffraction lines, measured volume expansion, and distances in model complexes) all range from y=0.12 to 0.18 for (CHMy)x, where M is sodium, potassium, rubidium, or cesium.

  15. Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media.

    PubMed

    Shao, Haiyan; Muduli, Subas K; Tran, Phong D; Soo, Han Sen

    2016-02-18

    New salicylaldimine nickel complexes, comprising only earth-abundant elements, have been developed for electrocatalytic hydrogen evolution in aqueous media. The second-sphere ether functionalities on the periphery of the complexes enhance the electrocatalytic activity in the presence of alkali metal cations. The electrocatalysts demonstrate improved performances especially in the economical and sustainable seawater reaction medium. PMID:26779580

  16. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    NASA Astrophysics Data System (ADS)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  17. Alkaline and alkaline earth metal phosphate halides and phosphors

    SciTech Connect

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  18. Metal complexes as "protein surface mimetics".

    PubMed

    Hewitt, Sarah H; Wilson, Andrew J

    2016-07-28

    A key challenge in chemical biology is to identify small molecule regulators for every single protein. However, protein surfaces are notoriously difficult to recognise with synthetic molecules, often having large flat surfaces that are poorly matched to traditional small molecules. In the surface mimetic approach, a supramolecular scaffold is used to project recognition groups in such a manner as to make multivalent non-covalent contacts over a large area of protein surface. Metal based supramolecular scaffolds offer unique advantages over conventional organic molecules for protein binding, including greater stereochemical and geometrical diversity conferred through the metal centre and the potential for direct assessment of binding properties and even visualisation in cells without recourse to further functionalisation. This feature article will highlight the current state of the art in protein surface recognition using metal complexes as surface mimetics. PMID:27353704

  19. Complexing of metal ions by humic substances

    SciTech Connect

    Bryan, N.D.; Zhang, Y.; Jones, M.N.

    1995-12-31

    The interaction of metal ions with humic substances is being studied using two different techniques. UV-scanning ultracentrifugation is being used to determine molecular weights and to investigate changes in aggregation brought about by metal ion complexation. The relationship between cation charge and conformation of the humic ligands is also being investigated. The complexation of actinide elements (U, Np, Pu, Am) by humic substances from soils contaminated by both natural processes and by low-level effluent releases is also being studied. Gel permeation chromatography has been used to show both that different fractions of humic substances vary greatly in their effectiveness as ligands and that different actinide elements associate with different fractions. These studies have also shown that uranium desorption is kinetically controlled by humic substances.

  20. Correlations in rare-earth transition-metal permanent magnets

    SciTech Connect

    Skomski, R. Manchanda, P.; Kashyap, A.

    2015-05-07

    It is investigated how electron-electron correlations affect the intrinsic properties of rare-earth transition-metal magnets. Focusing on orbital moment and anisotropy, we perform model calculations for 3d-4f alloys and density-functional theory (DFT) calculations for NdCo{sub 5}. On an independent-electron level, the use of a single Slater determinant with broken spin symmetry introduces Hund's rule correlations, which govern the behavior of rare-earth ions and of alloys described by the local spin density approximation (LSDA) and LSDA + U approximations to DFT. By contrast, rare-earth ions in intermetallics involve configuration interactions between two or more Slater determinants and lead to phenomena such as spin-charge distribution. Analyzing DFT as a Legendre transformation and using Bethe's crystal-field theory, we show that the corresponding density functionals are very different from familiar LSDA-type expressions and outline the effect of spin-charge separation on the magnetocrystalline anisotropy.

  1. Correlations in rare-earth transition-metal permanent magnets

    NASA Astrophysics Data System (ADS)

    Skomski, R.; Manchanda, P.; Kashyap, A.

    2015-05-01

    It is investigated how electron-electron correlations affect the intrinsic properties of rare-earth transition-metal magnets. Focusing on orbital moment and anisotropy, we perform model calculations for 3d-4f alloys and density-functional theory (DFT) calculations for NdCo5. On an independent-electron level, the use of a single Slater determinant with broken spin symmetry introduces Hund's rule correlations, which govern the behavior of rare-earth ions and of alloys described by the local spin density approximation (LSDA) and LSDA + U approximations to DFT. By contrast, rare-earth ions in intermetallics involve configuration interactions between two or more Slater determinants and lead to phenomena such as spin-charge distribution. Analyzing DFT as a Legendre transformation and using Bethe's crystal-field theory, we show that the corresponding density functionals are very different from familiar LSDA-type expressions and outline the effect of spin-charge separation on the magnetocrystalline anisotropy.

  2. Antiretroviral activity of thiosemicarbazone metal complexes.

    PubMed

    Pelosi, Giorgio; Bisceglie, Franco; Bignami, Fabio; Ronzi, Paola; Schiavone, Pasqualina; Re, Maria Carla; Casoli, Claudio; Pilotti, Elisabetta

    2010-12-23

    Thiosemicarbazones display a wide antimicrobial activity by targeting bacteria, fungi, and viruses. Here, we report our studies on the antiviral activity of two thiosemicarbazone metal complexes, [bis(citronellalthiosemicarbazonato)nickel(II)] and [aqua(pyridoxalthiosemicarbazonato)copper(II)] chloride monohydrate, against the retroviruses HIV-1 and HTLV-1/-2. Both compounds exhibit antiviral properties against HIV but not against HTLVs . In particular, the copper complex shows the most potent anti-HIV activity by acting at the post-entry steps of the viral cycle. PMID:21121632

  3. Metal-Metal Bonding in Uranium-Group 10 Complexes.

    PubMed

    Hlina, Johann A; Pankhurst, James R; Kaltsoyannis, Nikolas; Arnold, Polly L

    2016-03-16

    Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal

  4. Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

    DOEpatents

    Krikorian, Oscar H.; Curtis, Paul G.

    1992-01-01

    An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

  5. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary...

  6. Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

    PubMed

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-10-15

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra. PMID:25237839

  7. Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers.

    PubMed

    Soller, Benedikt S; Salzinger, Stephan; Rieger, Bernhard

    2016-02-24

    This review focuses on introducing and explaining the rare earth metal-mediated group transfer polymerization (REM-GTP) of polar monomers and is composed of three main sections: poly(vinylphosphonate)s, surface-initiated group transfer polymerization (SI-GTP), and extension to N-coordinating Michael-type monomers (2-vinylpridine (2VP), 2-isopropenyl-2-oxazoline (IPOx)). The poly(vinylphosphonate)s section is divided into two parts: radical, anionic, and silyl ketene acetal group transfer polymerization (SKA-GTP) of vinylphosphonates in comparison to REM-GTP, and properties of poly(vinylphosphonate)s. The mechanism of vinylphosphonate REM-GTP is discussed in detail for initiation and propagation including activation enthalpies ΔH(‡) and entropies ΔS(‡) according to the Eyring equation. SI-GTP is presented as a method for surface functionalization, and recent trends for 2VP and IPOx polymerization are summarized. This review will serve as a good resource or guideline for researchers who are currently working in the field of rare earth metal mediated polymerization catalysis as well as for those who are interested in beginning to employ rare earth metal complexes for the synthesis of new materials from polar monomers. PMID:26718632

  8. Trianionic pincer and pincer-type metal complexes and catalysts.

    PubMed

    O'Reilly, Matthew E; Veige, Adam S

    2014-09-01

    Trianionic pincer and pincer-type ligands are the focus of this review. Metal ions from across the periodic table, from main group elements, transition metals, and the rare earths, are combined with trianionic pincer ligands to produce some of the most interesting complexes to appear in the literature over the past decade. This review provides a comprehensive examination of the synthesis, characterization, properties, and catalytic applications of trianionic pincer metal complexes. Some of the interesting applications employing trianionic pincer and pincer-type complexes include: (1) catalyzed aerobic oxidation, (2) alkene isomerization, (3) alkene and alkyne polymerization, (4) nitrene and carbene group transfer, (5) fundamental transformations such as oxygen-atom transfer, (6) nitrogen-atom transfer, (7) O2 activation, (8) C-H bond activation, (9) disulfide reduction, and (10) ligand centered storage of redox equivalents (i.e. redox active ligands). Expansion of the architecture, type of donor atoms, chelate ring size, and steric and electronic properties of trianionic pincer ligands has occurred rapidly over the past ten years. This review is structured according to the type of pincer donor atoms that bind to the metal ion. The type of donor atoms within trianionic pincer and pincer-type ligands to be discussed include: NCN(3-), OCO(3-), CCC(3-), redox active NNN(3-), NNN(3-), redox active ONO(3-), ONO(3-), and SNS(3-). Since this is the first review of trianionic pincer and pincer-type ligands, an emphasis is placed on providing the reader with in-depth discussion of synthetic methods, characterization data, and highlights of these complexes as catalysts. PMID:24927219

  9. Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin.

    PubMed

    Zhang, Yuehong; Cao, Wei; Wang, Kang; Jiang, Jianzhuang

    2014-06-28

    Reaction of metal-free N-confused 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H2NTClPP) with metal-free 5,10,15,20-tetrakis[(4-tert-butyl)phenyl]porphyrin (H2TBPP) in the presence of M(III)(acac)3·nH2O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB) led to the isolation of heteroleptic bis(porphyrinato) rare earth compounds M(III)(HNTClPP)(TBPP) (M = La, Pr) (1, 2) in 6.7-10% yield. These represent the first examples of sandwich-type porphyrin rare earth double-decker complexes that involve N-confused porphyrin ligand. Different from their homoleptic bis(porphyrinato) rare earth double-decker counterparts HM(III)(TBPP)2 (M = La, Pr) (3, 4), the acidic proton in the heteroleptic analogues was revealed to localize at the inverted pyrrole nitrogen atom of the N-confused porphyrin ligand on the basis of NMR spectroscopic studies. Nevertheless, their heteroleptic bis(porphyrinato) sandwich molecular nature was confirmed on the basis of single crystal X-ray diffraction analysis over the praseodymium double-decker complex. PMID:24809442

  10. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  11. Ultrafast photophysics of transition metal complexes.

    PubMed

    Chergui, Majed

    2015-03-17

    The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

  12. Structural Characterisation of Complex Oxide & Rare Earth Manganite Thing Films by Microscopy

    NASA Astrophysics Data System (ADS)

    Jehanathan, Neerushana

    This PhD thesis presents the work on specific complex oxides and rare earth manganite thin films which were characterized mainly by transmission electron microscopy (TEM). The scientific results are divided in two main parts: the first part is devoted to the complex oxide films and the second to the rare earth manganite films. I. Complex oxides: The compositional influence of Cr, Al and Y on the microstructure of Mg-Cr-O, Mg-Al-O, Mg-Y-0 and Y-Al-O films synthesized by a reactive magnetron sputtering technique is reported. The study was based on a series of films with a range of compositions (metal ratios) deposited on Si substrates (without external substrate heating). The film thickness is about 1 μm (±200 nm). The effect of high temperatures (973 K to 1223 K) on the microstructural evolution of Mg-AlO, Mg-Cr-O and Y-Al-O films with specific metal ratios is also reported. II. Rare Earth Manganite Films: The microstructure and defect characterisation of hexagonal ReMnO3 (Re=Y, Tb, Dy, Ho and Er) thin films and multilayers is reported. The effect of off-stoichiometry on the microstructure of some hexagonal ReMnO3 (Re=Er, Dy and Ho) films with specific cationic ratios is also discussed. These thin films and multilayers were deposited on (111) YSZ and (111) Pt/TiO2/SiO 2/Si (stack) substrates by liquid injection metal organic chemical vapour deposition (MOCVD). The thickness of the films and multilayers is between 10 nm and 500 nm.

  13. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    DOE R&D Accomplishments Database

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  14. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  15. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  16. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  17. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  18. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  19. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  20. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  1. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  2. Methyl Complexes of the Transition Metals.

    PubMed

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity. PMID:26991740

  3. The Magnetic Ordering of Heavy Rare Earth Metals

    NASA Astrophysics Data System (ADS)

    Nordström, Lars

    1998-03-01

    The electronic and magnetic structures of the rare earth metals with hcp structure (Gd--Tm) are calculated by a full-potential LAPW method, which allows for non-collinear magnetism within the local approximation to spin-density functional theory. The 4f electrons are taken as localized, but their spin moment constrained as to fulfil Russel-Saunders coupling, polarizes the itinerant valence electrons. It is found that there are two competing magnetic structures; the ferromagnetic state, which dominates for the left-most elements (Gd and Tb), and a planar helical wave, which is found to have lowest energy for the last elements Er and Tm. In Ho the competition between the two leads to a compromise --- a helical cone. This trend is in accordance with the experimental situation. The mechanism behind the stabilization of the helical wave is confirmed to be an opening of a partial gap at the so-called ``webbing'' of the Fermi surface. This feature is found to exhibit nesting, a fact which is known both from earlier non-spin-polarized calculations and de Haas-van Alphen measurements. In contrast to prevailing models and earlier more primitive calculations, this nesting is found to exist for all elements, i.e. even for gadolinium. Instead, the magnitude of the spin splitting of the valence electrons due to the magnetic 4f states, is found to be an important quantity which has been missed out in the standard models for the magnetic structure of the rare earths.

  4. Metal complex polymers for electroluminescent applications

    SciTech Connect

    Tao, X.T.; Suzuki, H.; Zhang, Y.D.; Watanabe, T.; Miyata, S.; Wada, T.; Sasabe, H.

    1998-07-01

    The authors report the synthesis and characterization of a soluble metal complex polymer for electroluminescent (EL) applications. The polymer was prepared by the reaction of a zinc Schiff base with 4,4{prime}-diphenylmethane-diisocyanate. The polymer is amorphous and with glass transition temperature of 156 C and is soluble in common organic solvents such as chloroform, tetrahydrofuran (THF), and N-methylpyrrolidinone (NMP). The zinc Schiff base, and the polyurethane (PU) shows strong photoluminescence under a UV-lamp illumination. Single and double layer EL devices consisting ITO/hole transfer layer (HTL)/PU/AL have been fabricated and characterized. The results indicated that the complex polymer could act as both electron transport and emissive layers for EL devices.

  5. 40 CFR 721.10423 - Complex strontium aluminate, rare earth doped (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... earth doped (generic). 721.10423 Section 721.10423 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10423 Complex strontium aluminate, rare earth doped... substances identified generically as complex strontium aluminate, rare earth doped (PMNs P-12-22, P-12-23,...

  6. Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

    PubMed

    Yin, Jun; Hu, Ying; Yoon, Juyoung

    2015-07-21

    All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems. PMID:25317749

  7. High-temperature desulfurization of gasifier effluents with rare earth and rare earth/transition metal oxides

    SciTech Connect

    Dooley, Kerry M.; Kalakota, Vikram; Adusumilli, Sumana

    2011-02-11

    We have improved the application of mixed rare-earth oxides (REOs) as hot gas desulfurization adsorbents by impregnating them on stable high surface area supports and by the inclusion of certain transition metal oxides. We report comparative desulfurization experiments at high temperature (900 K) using a synthetic biomass gasifier effluent containing 0.1 vol % H2S, along with H2, CO2, and water. More complex REO sorbents outperform the simpler CeO2/La2O3 mixtures, in some cases significantly. Supporting REOs on Al2O3 (~20 wt % REO) or ZrO2 actually increased the sulfur capacities found after several cycles on a total weight basis. Another major increase in sulfur capacity took place when MnOx or FeOx is incorporated. Apparently most of the Mn or Fe is dispersed on or near the surface of the mixed REOs because the capacities with REOs greatly exceeded those of Al2O3-supported MnOx or FeOx alone at these conditions. In contrast, incorporating Cu has little effect on sulfur adsorption capacities. Both the REO and transition metal/REO adsorbents could be regenerated completely using air for at least five repetitive cycles.

  8. Preparation of decarboxylic-functionalized weak cation exchanger and application for simultaneous separation of alkali, alkaline earth and transition metals.

    PubMed

    Peng, Yahui; Gan, Yihui; He, Chengxia; Yang, Bingcheng; Guo, Zhimou; Liang, Xinmiao

    2016-06-01

    A novel weak cation exchanger (WCX) with dicarboxyl groups functionalized has been developed by clicking mercaptosuccinic acid onto silica gel. The simple synthesis starts with modification of silica gel with triethoxyvinylsilane, followed by efficient coupling vinyl-bonded silica with mercaptosuccinic acid via a "thiol-ene" click reaction. The obtained WCX demonstrated good separation and high selectivity towards common metals. Simultaneous separation of 10 alkali, alkaline earth and transition metals was achieved within 12min. Ion exchange and complex mechanism dominates the separation process. Its utility was demonstrated for determination of metals in tap water. PMID:27130093

  9. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    PubMed

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached. PMID:19886669

  10. Metal encapsulating carbon nanostructures from oligoalkyne metal complexes

    SciTech Connect

    Dosa, P.I.; Erben, C.; Iyer, V.S.; Vollhardt, K.P.C.; Wasser, I.M.

    1999-11-10

    Carbon nanotubes, onions, and related closed-shell carbon particles have commanded extensive recent attention because of their potential applications as unique electronic, magnetic, and mechanically robust materials. When filled with metals, such nanocapsules have additional promise as magnetic particles, contrasting agents, protecting cloaks, and catalysts and in other applications. Among the various methods for their preparation, the transition metal (especially Fe, Co, and Ni) catalyzed pyrolysis of small organic molecules has shown promise for larger scale production and in structural control. While the use of organometallic complexes as solid catalyst precursors or copyrolytic gaseous ingredients has been reported, all of these studies have been limited to gas-phase experiments at relatively high temperatures. There is very little literature that deals with the organic solid-state generation of carbon nanotubes. The latter suffers from extreme conditions, poor yields, or not readily modifiable starting materials. Development of synthetic organic approaches to closed shell large carbon structures is desirable but in its infancy. Here the authors present a significant step in its progress.

  11. Rare-earth metal prices in the USA ca. 1960 to 1994

    USGS Publications Warehouse

    Hedrick, J.B.

    1997-01-01

    Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

  12. Rare-earth metal prices in the USA ca. 1960 to 1994

    USGS Publications Warehouse

    Hedrick, James B.

    1997-01-01

    Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

  13. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process.

    PubMed

    Long, Jiang; Song, Hu; Jun, Xiang; Sheng, Su; Lun-Shi, Sun; Kai, Xu; Yao, Yao

    2012-07-01

    Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper. PMID:22525260

  14. Rare-earth transition-metal intermetallics: Structure-bonding-property relationships

    SciTech Connect

    Han, M.K.

    2006-05-06

    The explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding property relationships. The work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe{sub 13-x}Si{sub x} system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides Re{sub 2-x}Fe{sub 4}Si{sub 14-y} and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi{sub 2}: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb{sub 3}Zn{sub 3.6}Al{sub 7.4}: Partially ordered structure of Tb{sub 3}Zn{sub 3.6}Al{sub 7.4} compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn{sub 39}(Cr{sub x}Al{sub 1-x}){sub 81}: These layered structures are similar to icosahedral Mn-Al quasicrystalline

  15. Rare-Earth Transition-Metal Intermetallics: Structure-bonding-Property Relationships

    SciTech Connect

    Mi-Kyung Han

    2006-05-01

    Our explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding-property relationships. Our work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe{sub 13-x}Si{sub x} system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides RE{sub 2-x}Fe{sub 4}Si{sub 14-y} and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi{sub 2}: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb{sub 3}Zn{sub 3.6}Al{sub 7.4}: Partially ordered structure of Tb{sub 3}Zn{sub 3.6}Al{sub 7.4} compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn{sub 39}(Cr{sub x}Al{sub 1-x}){sub 81}: These layered structures are similar to icosahedral Mn-Al quasicrystalline

  16. Electrochromic bis(terpyridine)metal complex nanosheets.

    PubMed

    Takada, Kenji; Sakamoto, Ryota; Yi, Shi-Ting; Katagiri, Shunsuke; Kambe, Tetsuya; Nishihara, Hiroshi

    2015-04-15

    A series of electrochromic metal complex nanosheets comprising 1,3,5-tris(4-(2,2':6',2″-terpyridyl)phenyl)benzene or 1,3,5-tris((2,2':6',2″-terpyridyl)ethynyl)benzene and Fe(2+) or Co(2+) was synthesized. The preparation of multilayered nanosheets was achieved by liquid/liquid interfacial synthesis using an organic ligand solution and an aqueous metal-ion solution. The resultant nanosheet had a flat, smooth morphology and was several hundreds of nanometers thick. Upon its deposition on an indium tin oxide (ITO) electrode, the nanosheet underwent a reversible and robust redox reaction (Fe(3+)/Fe(2+) or Co(2+)/Co(+)) accompanied by a distinctive color change. Electrochromism was achieved in a solidified device composed of the nanosheet, a pair of ITO electrodes, and a polymer-supported electrolyte. The combination of Fe(2+) and Co(2+) nanosheets in one device-deposited on each ITO electrode-demonstrated dual-electrochromic behavior. PMID:25789415

  17. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    SciTech Connect

    Kanatzidis, Mercouri G.

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  18. Inverse Problems in Complex Models and Applications to Earth Sciences

    NASA Astrophysics Data System (ADS)

    Bosch, M. E.

    2015-12-01

    The inference of the subsurface earth structure and properties requires the integration of different types of data, information and knowledge, by combined processes of analysis and synthesis. To support the process of integrating information, the regular concept of data inversion is evolving to expand its application to models with multiple inner components (properties, scales, structural parameters) that explain multiple data (geophysical survey data, well-logs, core data). The probabilistic inference methods provide the natural framework for the formulation of these problems, considering a posterior probability density function (PDF) that combines the information from a prior information PDF and the new sets of observations. To formulate the posterior PDF in the context of multiple datasets, the data likelihood functions are factorized assuming independence of uncertainties for data originating across different surveys. A realistic description of the earth medium requires modeling several properties and structural parameters, which relate to each other according to dependency and independency notions. Thus, conditional probabilities across model components also factorize. A common setting proceeds by structuring the model parameter space in hierarchical layers. A primary layer (e.g. lithology) conditions a secondary layer (e.g. physical medium properties), which conditions a third layer (e.g. geophysical data). In general, less structured relations within model components and data emerge from the analysis of other inverse problems. They can be described with flexibility via direct acyclic graphs, which are graphs that map dependency relations between the model components. Examples of inverse problems in complex models can be shown at various scales. At local scale, for example, the distribution of gas saturation is inferred from pre-stack seismic data and a calibrated rock-physics model. At regional scale, joint inversion of gravity and magnetic data is applied

  19. Energetic characteristics of transition metal complexes.

    PubMed

    Wojewódka, Andrzej; Bełzowski, Janusz; Wilk, Zenon; Staś, Justyna

    2009-11-15

    Ten transition metal nitrate and perchlorate complexes of hydrazine and ethylenediamine were synthesized, namely [Cu(EN)(2)](ClO(4))(2), [Co(EN)(3)](ClO(4))(3), [Ni(EN)(3)](ClO(4))(2), [Hg(EN)(2)](ClO(4))(2), [Cr(N(2)H(4))(3)](ClO(4))(3), [Cd(N(2)H(4))(3)](ClO(4))(2), [Ni(N(2)H(4))(3)](NO(3))(2), [Co(N(2)H(4))(3)](NO(3))(3), [Zn(N(2)H(4))(3)](NO(3))(2), and [Cd(N(2)H(4))(3)](NO(3))(2) based on the lines of the literature reported methods. All of them were tested with applying underwater detonation test and further compared to the typical blasting explosives: RDX, HMX, TNT and PETN. From the above presented complexes [Ni(N(2)H(4))(3)](NO(3))(2) (called NHN) and [Co(N(2)H(4))(3)](NO(3))(3) (called CoHN) are known as primary explosives and can be used as the standard explosives. Explosion parameters, such as shock wave overpressure, shock wave energy equivalent and bubble energy equivalent, were determined. Evaluated energetic characteristics of the tested compounds are comparable to those of the classic high explosives and are even enhanced in some cases. PMID:19631466

  20. Structures and energetics of complexation of metal ions with ammonia, water, and benzene: A computational study.

    PubMed

    Sharma, Bhaskar; Neela, Y Indra; Narahari Sastry, G

    2016-04-30

    Quantum chemical calculations have been performed at CCSD(T)/def2-TZVP level to investigate the strength and nature of interactions of ammonia (NH3 ), water (H2 O), and benzene (C6 H6 ) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C6 H6 is observed for dicationic ions whereas the monocationic ions prefer to bind with NH3 . Density Functional Theory-Symmetry Adapted Perturbation Theory (DFT-SAPT) analysis has been employed at PBE0AC/def2-TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT-SAPT result shows that for the metal ion complexes with H2 O electrostatic component is the major contributor to the BE whereas, for C6 H6 complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH3 complexes, electrostatic component is dominant for s-block metal ions, whereas, for the d and p-block metal ion complexes both electrostatic and polarization components are important. The geometry (M(+) -N and M(+) -O distance for NH3 and H2 O complexes respectively, and cation-π distance for C6 H6 complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH3 , H2 O, and C6 H6 complexes shows that the charge transfer to metal ions is higher in case of C6 H6 complexes. PMID:26833683

  1. Chemical trend of pressure-induced metallization in alkaline earth hydrides

    SciTech Connect

    Zhang, Sijia; Chen, Xiao-Jia; Zhang, Rui-Qin; Lin, Hai-Qing

    2010-09-02

    The pressure-induced metallization of alkaline earth hydrides was systematically investigated using ab initio methods. While BeH{sub 2} and MgH{sub 2} present different semimetallic phases, CaH{sub 2}, SrH{sub 2}, and BaH{sub 2} share the same metallic phase (P6/mmm). The metallization pressure shows an attractive decrease with each increment of metal radius, and this trend is well correlated with both the electronegativity of alkaline earth metals and the band gap of alkaline earth hydrides at ambient pressure. Our results are consistent with current experimental data, and the obtained trend has significant implications for designing and engineering metallic hydrides for energy applications.

  2. Tris(pyrazolyl)methanides of the alkaline earth metals: influence of the substitution pattern on stability and degradation.

    PubMed

    Müller, Christoph; Koch, Alexander; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2015-01-20

    Trispyrazolylmethanides commonly act as strong tridentate bases toward metal ions. This expected coordination behavior has been observed for tris(3,4,5-trimethylpyrazolyl)methane (1a), which yields the alkaline-earth-metal bis[tris(3,4,5-trimethylpyrazolyl)methanides] of magnesium (1b), calcium (1c), strontium (1d), and barium (1e) via deprotonation of 1a with dibutylmagnesium and [Ae{N(SiMe3)2}2] (Ae = Mg, Ca, Sr, and Ba, respectively). Barium complex 1e degrades during recrystallization that was attempted from aromatic hydrocarbons and ethers. In these scorpionate complexes, the metal ions are embedded in distorted octahedral coordination spheres. Contrarily, tris(3-thienylpyrazolyl)methane (2a) exhibits a strikingly different reactivity. Dibutylmagnesium is unable to deprotonate 2a, whereas [Ae{N(SiMe3)2}2] (Ae = Ca, Sr, and Ba) smoothly metalates 2a. However, the primary alkaline-earth-metal bis[tris(3-thienylpyrazolyl)methanides] of Ca (2c), Sr (2d), and Ba (2e) represent intermediates and degrade under the formation of the alkaline-earth-metal bis(3-thienylpyrazolates) of calcium (3c), strontium (3d), and barium (3e) and the elimination of tetrakis(3-thienylpyrazolyl)ethene (4). To isolate crystalline compounds, 3-thienylpyrazole has been metalated, and the corresponding derivatives [(HPz(Tp))4Mg(Pz(Tp))2] (3b), dinuclear [(tmeda)Ca(Pz(Tp))2]2 (3c), mononuclear [(pmdeta)Sr(Pz(Tp))2] (3d), and [(hmteta)Ba(Pz(Tp))2] (3e) have been structurally characterized. Regardless of the applied stoichiometry, magnesiation of thienylpyrazole 3a with dibutylmagnesium yields [(HPz(Tp))4Mg(Pz(Tp))2] (3b), which is stabilized in the solid state by intramolecular N-H···N···H-N hydrogen bridges. The degradation of [Ae{C(Pz(R))3}2] (R = Ph and Tp) has been studied by quantum chemical methods, the results of which propose an intermediate complex of the nature [{(Pz(R))2C}2Ca{Pz(R)}2]; thereafter, the singlet carbenes ([:C(Pz(R))2]) dimerize in the vicinity of the alkaline

  3. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. PMID:26746588

  4. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a)...

  5. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses... dye (PMN P-94-499) is subject to reporting under this section for the significant new uses...

  6. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses... dye (PMN P-94-499) is subject to reporting under this section for the significant new uses...

  7. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses... dye (PMN P-94-499) is subject to reporting under this section for the significant new uses...

  8. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses... dye (PMN P-94-499) is subject to reporting under this section for the significant new uses...

  9. Activation of the C-H bond by metal complexes

    NASA Astrophysics Data System (ADS)

    Shilov, Aleksandr E.; Shul'pin, Georgiy B.

    1990-09-01

    Reactions involving the cleavage of C-H bonds by metal complexes in saturated and aromatic hydrocarbons and also in other compounds are examined. Some of these processes occur with formation of a carbon-metal bond, whilst in others the interaction of the complexes with the hydrocarbon takes place without direct contact between the metal atom and the C-H bonds. Metal compounds are widely used as initiators of the liquid-phase oxidation of hydrocarbons at relatively low temperatures. There is a prospect of creating new technologies for the chemical processing of petroleum and gas hydrocarbons, whereby they can be converted into valuable products, for example, into alcohols, ketones, and carboxylic acids, on the basis of processes involving metal complexes. The study of the metal complex activation of the C-H bond also makes it possible to understand and model the metalloenzyme-catalysed hydrocarbon oxidation reactions in the living cell. The bibliography includes 340 references.

  10. Complex seismic anisotropy in the Earth's inner core beneath Africa

    NASA Astrophysics Data System (ADS)

    Yu, W.; Wen, L.

    2006-05-01

    Seismic anisotropy in the top of the inner core is important to the understanding of the growth and dynamics of the Earth's inner core. The anisotropic structures beneath Africa in the top 80 km of the inner core were not well constrained, due to limited sampling coverage. Here, we analyze a large data-set of the PKiKP-PKIKP phases sampling the top 80 km of the inner core beneath Africa along various sampling directions. The differential travel times of the PKiKP-PKIKP phases sampling Africa reveal polar-equatorial differences. The differential travel times along polar paths are about 0-1.4 s larger than those along equatorial paths, suggesting the presence of anisotropy in velocity in the top 80 km of the inner core beneath Africa. The PKiKP-PKIKP phases along polar paths exhibit a complex lateral gradient from the East to the Middle Africa and a correlation of large (small) differential travel time with small (large) amplitude ratio. Largest differential travel times and smallest amplitude ratios are observed beneath the East Africa (Kenya, Tanzania, Mozambique), while small differential travel times and large amplitude ratios are observed beneath the Middle Africa (Democratic Republic of Congo, Congo, Gabon, Angola). The polar PKiKP-PKIKP waveforms are grouped based on the geographic sampling regions. We perform waveform modeling and iteratively search for the anisotropic velocity and attenuation models that explain the polar PKiKP-PKIKP waveforms in various groups. Most complexities observed in the PKiKP-PKIKP waveforms can be explained by the presence of uniform anisotropy, but with onset of the anisotropy occurring at various depths. The region beneath the East Africa can be explained by a uniform anisotropy model with a magnitude of about 1.7% and an average Q value of 250 present at the inner core boundary (ICB), while the region beneath the Middle Africa can be explained by a model with an isotropic layer in the top and a uniform anisotropy with a

  11. Process for preparing higher oxides of the alkali and alkaline earth metals

    NASA Technical Reports Server (NTRS)

    Sadhukhan, P.; Bell, A. (Inventor)

    1978-01-01

    High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

  12. Minerals yearbook, 1988. Rare-earth minerals and metals

    SciTech Connect

    Hedrick, J.B.; Templeton, D.A.

    1988-01-01

    Domestic production of rare-earth concentrates decreased in 1988. Foreign sources of processed rare earths obtained a slightly larger share of the U.S. market, while domestic exports saw a marked increase compared to 1987 levels. Rare earths were used in high-technology applications such as laser crystals, high-strength permanent magnets, optical fibers, magnetic resonance imaging (MRI) scanners, and high-temperature superconductors. Topics discussed in the report include domestic data coverage, legislation and government programs, environmental issues, domestic production, consumption and uses, stocks, prices, foreign trade, world capacity, world review--Australia, Brazil, Canada, China, Egypt, Greenland, Japan, Madagascar, Malaysia, Mozambique, Sri Lanka, Thailand--and technology.

  13. Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

    SciTech Connect

    Selle, J E

    1992-06-26

    Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.

  14. High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

    SciTech Connect

    Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.; Hope, Kevin M.

    2008-07-01

    High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalization in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)

  15. Synthesis and characterization of some transition metals polymer complexes

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Abdou, Azza E. H.; Ahmed, Wael M.

    2015-09-01

    Co2+, Ni2+, Cu2+, Cr3+, Mn2+ and Fe3+ complexes of Polyacrylamide are prepared and characterized by elemental analyses, IR, UV-Vis spectra, magnetic measurements, and thermal analyses. The data suggests octahedral geometry for all complexes. The thermal behavior of the complexes has been studied applying TG, DTA, and DSC techniques, and the thermodynamic parameters and mechanisms of the decompositions were evaluated. The ΔS# values of the decomposition steps of the metal complexes indicated that the activated fragments have more ordered structure than the undecomposed complexes. The thermal processes proceeded in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing 6(C2H5 N) and 6(CO), the metal complexes are ended with metal as a final product. Viscosity and Shale instability using liner swell meter were carried out. Comparisons of the experimental and theoretical IR spectra were also carried out besides some other theoretical calculations.

  16. Metal complexes of quinolone antibiotics and their applications: an update.

    PubMed

    Uivarosi, Valentina

    2013-01-01

    Quinolones are synthetic broad-spectrum antibiotics with good oral absorption and excellent bioavailability. Due to the chemical functions found on their nucleus (a carboxylic acid function at the 3-position, and in most cases a basic piperazinyl ring (or another N-heterocycle) at the 7-position, and a carbonyl oxygen atom at the 4-position) quinolones bind metal ions forming complexes in which they can act as bidentate, as unidentate and as bridging ligand, respectively. In the polymeric complexes in solid state, multiple modes of coordination are simultaneously possible. In strongly acidic conditions, quinolone molecules possessing a basic side nucleus are protonated and appear as cations in the ionic complexes. Interaction with metal ions has some important consequences for the solubility, pharmacokinetics and bioavailability of quinolones, and is also involved in the mechanism of action of these bactericidal agents. Many metal complexes with equal or enhanced antimicrobial activity compared to the parent quinolones were obtained. New strategies in the design of metal complexes of quinolones have led to compounds with anticancer activity. Analytical applications of complexation with metal ions were oriented toward two main directions: determination of quinolones based on complexation with metal ions or, reversely, determination of metal ions based on complexation with quinolones. PMID:24029748

  17. Equilibrium atomic properties of transition and rare-earth metals. (in Ukrainian)

    NASA Astrophysics Data System (ADS)

    Yakibchuk, P. M.

    Within the framework of the recently proposed nonlocal model potential the formulas for binding energy and equilibrium atomic radia of transition and rare--earth metals are received. Numerical calculation of the above characteristics for the 4d-transition metals is carried out for such an approach.

  18. Novel syntergistic agent for selective separation of yttrium from other rare earth metals

    SciTech Connect

    Miyata, Terufumi; Goto, Masahiro; Nakashio, Fumiyuki

    1995-06-01

    An oil-soluble synergistic agent has been developed for the selective separation of yttrium (Y) from the other rare earth metals. The synergistic agent is a polyaminocarboxylic acid alkylderivative and has interfacial activity like that of surfactants. Separation of yttrium from heavy rare earth metals (erbium (Er) and holmium (Ho)) in the presence of the synergistic agent was carried out with a 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester as a carrier using a hollow-fiber membrane extractor. The new agent shows a synergistic effect on the permeation rate of rare earth metals at the oil-water interface. By the addition of a small amount of the agent, the selectivity for yttrium from the two rare earth metals was enhanced remarkably, because of the permeation rate of Y was selectively decreased compared with those of Er and Ho. The synergistic effect is discussed from the viewpoint of the stability constant for rare earth metals and the interfacial activity of the synergistic agent. The difference in interaction between the synergistic agent and rare earth ions at the oil-water interface results in an increase in the separation efficiency.

  19. Electrical properties of transition metal hydrogen complexes in silicon

    SciTech Connect

    Weber, J.

    1998-12-31

    A summary is given on the electrical properties of transition-metal hydrogen complexes in silicon. Contrary to the general understanding, hydrogen leads not only to passivation of deep defect levels but also creates several new levels in the band gap due to electrically active transition-metal complexes. The author presents detailed data for Pt-H complexes and summarize briefly the results on the transition metals Ti, Co, Ni, Pd, and Ag. The introduction of hydrogen at room temperature by wet chemical etching, followed by specific annealing steps allows us to study the formation of the different complexes. In particular, depth profiles of the defect concentrations give an estimate of the number of hydrogen atoms involved in the complexes. Transition-metals binding up to four hydrogen atoms are identified.

  20. Quantitative parameters for the sequestering capacity of polyacrylates towards alkaline earth metal ions.

    PubMed

    De Stefano, Concetta; Gianguzza, Antonio; Piazzese, Daniela; Sammartano, Silvio

    2003-10-17

    The complex formation constants of polyacrylic (PAA) ligands (1.4complex species formation. The only species present in the system M-PAA (M=Ca(2+) or Mg(2+)) is ML(2): attempts to find species of different stoichiometry were unsuccessful. The stability dependence of this species on ionic strength, on the degree of neutralisation (alpha) and on PAA molecular weight is discussed using empirical equations. The formation constant, logbeta(2), is significantly higher for Ca(2+) than for Mg(2+): at I=0.1 mol l(-1) (NaCl), logN=1.8 and alpha=0.5, logbeta(2)(Ca)=4.43 and logbeta(2)(Mg)=4.24. The formation of polyacrylate-alkaline earth metal complexes is discussed in the light of sequestering effects in natural waters. PMID:18969177

  1. Correlation between volatility of rare-earth metals and encapsulation of their carbides in carbon nanocapsules

    SciTech Connect

    Saito, Yahachi; Okuda, Mitsumasa; Yoshikawa, Tadanobu ); Kasuya, Atsuo; Nishina, Yuichiro )

    1994-07-07

    Encapsulation of metals in multilayered graphitic capsules has been studied for all the rare-earth elements (Sc, Y, and Ln = La, Ce, ..., Lu) excluding Pm by using electric arc discharge. Electron microscopy and X-ray diffraction of carbonaceous products revealed that most of rare-earth metals (Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu) were encapsulated in the form of carbides, but the others, Sm, Eu, and Yb, were not. The metals in the former group that were encapsulated had vapor pressures definitely lower than those in the latter group. In the case of thulium (Tm), whose vapor pressure is intermediate between the two groups, only a trace amount of encapsulated carbide was formed. Correlation of volatility of metals with encapsulation was clearly found, suggesting that the volatility of a metal plays an important role in a process of the metal encapsulation. 25 refs., 4 figs., 1 tab.

  2. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

    NASA Astrophysics Data System (ADS)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

    2015-02-01

    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  3. Yttrium and rare earth stabilized fast reactor metal fuel

    DOEpatents

    Guon, Jerold; Grantham, LeRoy F.; Specht, Eugene R.

    1992-01-01

    To increase the operating temperature of a reactor, the melting point and mechanical properties of the fuel must be increased. For an actinide-rich fuel, yttrium, lanthanum and/or rare earth elements can be added, as stabilizers, to uranium and plutonium and/or a mixture of other actinides to raise the melting point of the fuel and improve its mechanical properties. Since only about 1% of the actinide fuel may be yttrium, lanthanum, or a rare earth element, the neutron penalty is low, the reactor core size can be reduced, the fuel can be burned efficiently, reprocessing requirements are reduced, and the nuclear waste disposal volumes reduced. A further advantage occurs when yttrium, lanthanum, and/or other rare earth elements are exposed to radiation in a reactor, they produce only short half life radioisotopes, which reduce nuclear waste disposal problems through much shorter assured-isolation requirements.

  4. [Advance of studies on bioactivity of flavonoid-metal complexes].

    PubMed

    Liu, Yanji; He, Xiaoyan; Zuo, Hua; Zhang, Qixiong; Li, Zhubo; Shi, Lunyong

    2012-07-01

    The flavonoid-metal complexes showed obviously stronger bioactivities such as antibiosis, antivirus, anti-inflammatory, anti-tumor and anti-free-radical, possibly because of the stronger binding force caused by the change in complex structure and accessibility to target spots, or the synergy effect between flavonoids and metallic ions. This essay summarizes studies on bioactivity and mechanism of flavonoid-metal complexes, in order to provide reference for in-depth study and development on effective constituents contained in flavonoid traditional Chinese medicines. PMID:23019867

  5. Metal-silicate partitioning during core formation on super-Earths

    NASA Astrophysics Data System (ADS)

    Schaefer, L. K.; Jacobsen, S. B.; Petaev, M. I.; Sasselov, D. D.; Remo, J. L.

    2015-12-01

    Separation of the Earth into a rocky mantle and metallic Fe core is a problem long studied in the planetary science community (e.g. [1]). The timing of core formation influences the abundances of the siderophile elements found in the Earth's mantle, and the mechanism of core formation influences the degree of chemical equilibration between the rocky mantle and the core at the time of metal separation. However, limited work has been done on formation of metallic cores and its effects on mantle chemistry in rocky planets larger than the Earth. Super-Earths, exoplanets with masses up to ~ 5 Earth masses and radii up to ~1.6-1.7 Earth radii, have significantly larger internal pressures and consequently higher internal temperatures than the Earth, therefore conclusions from Earth-centric studies of core formation may be erroneous. Partitioning coefficients for many of the relevant elements (e.g. Fe, Ni, Si, O, etc.) are available in the literature, but only to relatively low pressures. The relevant pressures for super-Earths are significantly larger. However, data on Fe-O-Ni-Si partitioning at pressures (200-500 GPa) and temperatures relevant to super-Earths have been measured by laser-induced shocks with the ZBL laser at Sandia National Laboratory with a method described in [2]. We will present a model which integrates this data with lower pressure partition coefficients from the literature (e.g. [3],[4],[5]), with special emphasis on Fe and O, to describe partitioning behavior at high pressures and discuss its implications for core size and composition on rocky super-Earths. [1] Ringwood, A.E. (1977) Geochem. J. 11, 111-135. [2] Remo, J.L., Petaev, M.I., Jacobsen, S. B. (2008) LPSC abstract, 1420. [3] Frost, D.J. et al. (2010) JGR, B02202. [4] Kombayashi, T. (2014) JGR, 4164-4177. [5] Rubie, D.C. et al. (2011) EPSL, 301, 31-42. [5

  6. Complex Electronic Structure of Rare Earth Activators in Scintillators

    SciTech Connect

    Aberg, D.; Yu, S. W.; Zhou, F.

    2015-10-27

    To aid and further the understanding of the microscopic mechanisms behind the scintillator nonproportionality that leads to degradation of the attainable energy resolution, we have developed theoretical and experimental algorithms and procedures to determine the position of the 4f energy levels of rare earth dopants relative to the host band edge states.

  7. Multiheteromacrocycles that complex metal ions. Sixth progress report, 1 May 1979-30 April 1980. [Hemispherands; spherands

    SciTech Connect

    Cram, D.J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate /sup 6/Li and /sup 7/Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  8. Antischistosomal Activity of Oxindolimine-Metal Complexes

    PubMed Central

    Dario, Bruno S.; Couto, Ricardo A. A.; Pinto, Pedro L. S.; da Costa Ferreira, Ana M.

    2015-01-01

    In recent years, a class of oxindole-copper and -zinc complex derivatives have been reported as compounds with efficient proapoptotic activity toward different tumor cells (e.g., neuroblastomas, melanomas, monocytes). Here we assessed the efficacy of synthesized oxindole-copper(II), -zinc(II), and -vanadyl (VO2+) complexes against adult Schistosoma mansoni worms. The copper(II) complexes (50% inhibitory concentrations of 30 to 45 μM) demonstrated greater antischistosomal properties than the analogous zinc and vanadyl complexes regarding lethality, reduction of motor activity, and oviposition. PMID:26239976

  9. Antischistosomal Activity of Oxindolimine-Metal Complexes.

    PubMed

    de Moraes, Josué; Dario, Bruno S; Couto, Ricardo A A; Pinto, Pedro L S; da Costa Ferreira, Ana M

    2015-10-01

    In recent years, a class of oxindole-copper and -zinc complex derivatives have been reported as compounds with efficient proapoptotic activity toward different tumor cells (e.g., neuroblastomas, melanomas, monocytes). Here we assessed the efficacy of synthesized oxindole-copper(II), -zinc(II), and -vanadyl (VO(2+)) complexes against adult Schistosoma mansoni worms. The copper(II) complexes (50% inhibitory concentrations of 30 to 45 μM) demonstrated greater antischistosomal properties than the analogous zinc and vanadyl complexes regarding lethality, reduction of motor activity, and oviposition. PMID:26239976

  10. Tetrazole-5-carboxylic acid based salts of earth alkali and transition metal cations.

    PubMed

    Hartdegen, Vera; Klapötke, Thomas M; Sproll, Stefan M

    2009-10-01

    The tetrazole-5-carboxylate anion was investigated as ligand for earth alkali metal and transition metal complexes. Therefore, the strontium 4a (*3 H(2)O, *2.75 H(2)O, *2.5 H(2)O), barium 4b (*3 H(2)O), copper 4c (*3.5 H(2)O, *4 H(2)O), manganese 4d (*4 H(2)O, *5 H(2)O), and silver tetrazol-5-carboxylate 4e (*1.56 H(2)O) were synthesized and characterized by vibrational spectroscopy (IR), and the crystal structures of 4a (*2.75 H(2)O, *2.5 H(2)O), 4b*3 H(2)O, 4c*4 H(2)O, and 4d*5 H(2)O were determined using single crystal X-ray diffraction. The thermal stability was investigated by DSC-measurements, and the sensitivity toward impact and friction was determined by BAM-standards. The copper, strontium, and barium tetrazole-5-carboxyate proved to be suitable thermal and physical stable colorants for pyrotechnic compositions. The crystal structure of the tetragonal modification of strontium tetrazole-5-carboxyate possesses channels along the c-axis, leading to a porous material. PMID:19780625

  11. Metal loading effect on rare earth element binding to humic acid: Experimental and modelling evidence

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Davranche, Mélanie; Gruau, Gérard; Dia, Aline

    2010-03-01

    The effect of metal loading on the binding of rare earth elements (REE) to humic acid (HA) was studied by combining ultrafiltration and Inductively Coupled Plasma Mass Spectrometry techniques. REE-HA complexation experiments were performed at pH 3 for REE/C molar ratios ranging from ca 4 × 10 -4 to 2.7 × 10 -2. Results show that the relative amount of REE bound to HA strongly increases with decreasing REE/C. A middle-REE (MREE) downward concavity is shown by patterns at high metal loading, whereas patterns at low metal loading display a regular increase from La to Lu. Humic Ion Model VI modelling are close to the experimental data variations, provided that (i) the ΔLK 2 parameter (i.e. the Model VI parameter taken into account the presence of strong but low density binding sites) is allowed to increase regularly from La to Lu (from 1.1 to 2.1) and (ii) the published log KMA values (i.e. the REE-HA binding constants specific to Model VI) are slightly modified, in particular with respect to heavy REE. Modelling approach provided evidence that logKdREE patterns with varying REE/C likely arises because REE binding to HA occurs through two types of binding sites in different density: (i) a few strong sites that preferentially complex the heavy REE and thus control the logKdREE atterns at low REE/C; (ii) a larger amount of weaker binding sites that preferentially complex the middle-REE and thus control the logKdREE pattern at high REE/C. Hence, metal loading exerts a major effect on HA-mediated REE binding, which could explain the diversity of published conditional constants for REE binding with HA. A literature survey suggests that the few strong sites activated at low REE/C could be multidentate carboxylic sites, or perhaps N-, or P-functional groups. Finally, an examination of the literature field data proposed that the described loading effect could account for much of the variation in REE patterns observed in natural organic-rich waters (DOC > 5 mg L -1 and 4

  12. SOLUBILITY AND MOBILITY OF TOXIC METALS UNDER COMPLEX CONDITIONS

    EPA Science Inventory

    EPA Identifier: F8P11069
    Title: Solubility and Mobility of Toxic Metals Under Complex Conditions
    Fellow (Principal Investigator): Brandi N. Clark
    Institution: University of Missouri - Rolla
    EPA GRANT Representative: Georgette Bod...

  13. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1997-03-04

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  14. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1997-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  15. Investigation of metal-polyelectrolyte complex toxicity.

    PubMed

    Karahan, Mesut; Mustafaeva, Zeynep; Koç, Rabia Çakır; Bağırova, Melahat; Allahverdiyev, Adil M

    2014-05-01

    Water-soluble binary and ternary copper complexes of polyelectrolytes were synthesized, and the toxicity of these complexes was tested in mouse fibroblast cell line (L929) in vitro. Both the binary and ternary complexes were prepared at the ratio of 0.4 mole copper(II) ions per monomer of acrylic acid and 0.5 mole copper(II) ions per monomer of methyl vinyl ether maleic anhydride, furthermore at the ratio of 1 and 2 mole bovine serum albumin per mole of polyacrylic acid and poly(methyl vinyl ether-co-maleic anhydride), respectively. Compared to binary copper(II)-polyelectrolyte complexes, these ternary complexes have been determined to be of least toxicity. PMID:22914259

  16. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities. PMID:17728178

  17. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  18. Electron Capture Dissociation of Trivalent Metal Ion-Peptide Complexes

    NASA Astrophysics Data System (ADS)

    Flick, Tawnya G.; Donald, William A.; Williams, Evan R.

    2013-02-01

    With electrospray ionization from aqueous solutions, trivalent metal ions readily adduct to small peptides resulting in formation of predominantly (peptide + MT - H)2+, where MT = La, Tm, Lu, Sm, Ho, Yb, Pm, Tb, or Eu, for peptides with molecular weights below ~1000 Da, and predominantly (peptide + MT)3+ for larger peptides. ECD of (peptide + MT - H)2+ results in extensive fragmentation from which nearly complete sequence information can be obtained, even for peptides for which only singly protonated ions are formed in the absence of the metal ions. ECD of these doubly charged complexes containing MT results in significantly higher electron capture efficiency and sequence coverage than peptide-divalent metal ion complexes that have the same net charge. Formation of salt-bridge structures in which the metal ion coordinates to a carboxylate group are favored even for (peptide + MT)3+. ECD of these latter complexes for large peptides results in electron capture by the protonation site located remotely from the metal ion and predominantly c/ z fragments for all metals, except Eu3+, which undergoes a one electron reduction and only loss of small neutral molecules and b/ y fragments are formed. These results indicate that solvation of the metal ion in these complexes is extensive, which results in the electrochemical properties of these metal ions being similar in both the peptide environment and in bulk water.

  19. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  20. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halophosphate mixed metal...

  1. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  2. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, Jr., Paul E.; Langdale, Wayne A.

    1997-01-01

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  3. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, P.E. Jr.; Langdale, W.A.

    1997-08-19

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  4. Compartmentation and complexation of metals in hyperaccumulator plants

    PubMed Central

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs. PMID:24065978

  5. Compartmentation and complexation of metals in hyperaccumulator plants.

    PubMed

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their "strange" behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs. PMID:24065978

  6. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  7. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  8. IUPAC-NIST Solubility Data Series. 94. Rare Earth Metal Iodides and Bromides in Water and Aqueous Systems. Part 2. Bromides

    NASA Astrophysics Data System (ADS)

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen; Voigt, Heidelore

    2013-03-01

    This work presents solubility data for rare earth metal bromides in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal bromide with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data and a brief discussion of the multicomponent systems. Because the ternary systems were almost never studied more than once, no critical evaluations of such data were possible. Only simple bromides (no complexes) are treated as the input substances in this work. The literature has been covered through the end of 2011.

  9. IUPAC-NIST Solubility Data Series. 94. Rare Earth Metal Iodides and Bromides in Water and Aqueous Systems. Part 1. Iodides

    NASA Astrophysics Data System (ADS)

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

    2012-03-01

    This work presents solubility data for rare earth metal iodides in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal iodide with a corresponding critical evaluation. Every such evaluation contains a tabulated collection of all solubility results in water, a selection of suggested solubility data and a brief discussion of the multicomponent systems. Because the ternary systems were almost never studied more than once, no critical evaluations of such data were possible. Only simple iodides (no complexes) are treated as the input substances in this work. The literature has been covered through the middle of 2011.

  10. Yttrium and rare earth stabilized fast reactor metal fuel

    SciTech Connect

    Guon, J.; Grantham, L.F.; Specht, E.R.

    1992-05-12

    This patent describes an improved metal alloy reactor fuel consisting essentially of uranium, plutonium, and at least one element from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

  11. DNA binding and recognition by binuclear transition metal complexes

    NASA Astrophysics Data System (ADS)

    Liu, Changlin; Yan, Rui; Xu, Yan; Yu, Siwang; Liao, Zhanru; Li, Dongfeng; Xu, Hui-Bie F.

    2001-09-01

    The development of small molecules that can bind and recognize DNA with sequence- or stereo-specificity under physiological conditions has been attracting a great interest in chemistry and biochemistry. Here, spectroscopic characterization and gel electrophoresis methods have been utilized to investigate the DNA binding and recognition by a variety of binuclear transition metal complexes. The result indicate that the structures and charges of binuclear transition metal complexes, compositions of coordination spheres, central metal ions and their coordination unsaturation, and separations between two central metal atoms can exert significant effects on the DNA binding and recognition. If there are not intercalative ligands into DNA base pairs or kinetically substitutable ligands by DNA phosphate groups within coordination sphere, the coordination saturation and compact binuclear transition metal complexes weaker bind to DNA than the coordination unsaturation and extended ones to DNA. Since the different transtiometal ions exhibit different affinities to DNA phosphate oxygen atoms, the binding interactions between their binuclear complexes and DNA are controlled by the affinity. He binuclear complexes with one or more negative charges lead to a consequence that they can not efficient associate with DNA, because DNA phosphodiester backbone is negatively charged. Whenthe separations between two central transition metal atoms is more than the distance between two DNA base pairs, the binuclear complexes could bind and recognize the DNA sequence with two or more base pairs. The protonated and positively charged ligands can strengthen the DNA binding and recognition by these binuclear metal complexes. Based on such DNA binding and recognition principles, the binuclear zinc complex designed in the study preferentially bind and recognize the following DNA sequence on pBR322 DNA with binding constant K.

  12. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure.

    PubMed

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø

    2015-09-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children. PMID:25984984

  13. Evaluation of Grounding Impedance of a Complex Lightning Protective System Using Earth Ground Clamp Measurements and ATP Modeling

    NASA Technical Reports Server (NTRS)

    Mata, Carlos T.; Rakov, V. A.; Mata, Angel G.

    2010-01-01

    A new Lightning Protection System (LPS) was designed and built at Launch Complex 39B (LC39B), at the Kennedy Space Center (KSC), Florida, which consists of a catenary wire system (at a height of about 181 meters above ground level) supported by three insulators installed atop three towers in a triangular configuration. A total of nine downconductors (each about 250 meters long, on average) are connected to the catenary wire system. Each of the nine downconductors is connected to a 7.62-meter radius circular counterpoise conductor with six equally spaced 6-meter long vertical grounding rods. Grounding requirements at LC39B call for all underground and above ground metallic piping, enclosures, raceways, and cable trays, within 7.62 meters of the counterpoise, to be bounded to the counterpoise, which results in a complex interconnected grounding system, given the many metallic piping, raceways, and cable trays that run in multiple direction around LC39B. The complexity of this grounding system makes the fall of potential method, which uses multiple metallic rods or stakes, unsuitable for measuring the grounding impedances of the downconductors. To calculate the downconductors grounding impedance, an Earth Ground Clamp (a stakeless grounding resistance measuring device) and a LPS Alternative Transient Program (ATP) model are used. The Earth Ground Clamp is used to measure the loop impedance plus the grounding impedance of each downconductor and the ATP model is used to calculate the loop impedance of each downconductor circuit. The grounding impedance of the downconductors is then calculated by subtracting the ATP calculated loop impedances from the Earth Ground Clamp measurements.

  14. The σ-Capricornids complex of near-Earth objects

    NASA Astrophysics Data System (ADS)

    Babadzhanov, P. B.; Kokhirova, G. I.; Khamroev, U. Kh.

    2015-04-01

    The Earth-crossing asteroids 2008BO16, 2011EC41, and 2013CT36 have very similar orbits according to the Southworth and Hawkins DSH criterion. Their orbits are additionally classified as comet-like based on using the Tisserand parameter which is a standard tool used to distinction between asteroids and comets. The orbital evolution research shows that they cross the Earth's orbit four times over one cycle of the perihelion argument variations. Consequently, a meteoroid stream, possibly associated with them, may produce four meteor showers. Theoretic parameters of the predicted showers were calculated and identified with the observable nighttime σ-Capricornids and χ-Sagittariids, and daytime χ-Capricornids and Capricornids-Sagittariids meteor showers. The similar comet-like orbits and the linkage with the same meteoroid stream producing four active showers provide strong evidence that these asteroids have a common cometary origin. Earlier, it was demonstrated that the Earth-crossing asteroids (2101) Adonis and 1995CS, being a potentially hazardous asteroid (PHA), were recognized as dormant comets because of their linkage with the σ-Capricornids meteoroid stream. Thus, a conclusion was made, that either the considered objects are large pieces of the Adonis, or all five objects are extinct or dormant fragments of a larger comet that was the parent body of the σ-Capricornids meteoroid stream, and whose break-up occurred several tens of thousands years ago. During 2010-2011, three σ-Capricornids fireballs were captured by the Tajikistan fireball network. Taking into account the observations in Canada and the USA, the dynamic and physical properties of the σ-Capricornid meteoroids were identified. According to the estimated meteoroids bulk density a non-homogeneous compound of the σ-Capricornids shower comet-progenitor was suggested.

  15. Stability constants for the formation of rare earth-inorganic complexes as a function of ionic strength

    NASA Astrophysics Data System (ADS)

    Millero, Frank J.

    1992-08-01

    Recent studies have been made on the distribution of the rare earths (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in natural waters relative to their concentration in shales. These metals have also been used as models for the behavior of the trivalent actinides. The speciation of the rare earths in natural waters is modelled by using ionic interaction models which require reliable stability constants. In this paper the stability constants for the formation of lanthanide complexes ( k mx∗) with Cl -, NO 3-, SO 42-, OH -, HCO 3-, H 2PO 4-, HPO 42-, and CO 32- determined in NaClO 44 at various ionic strengths have been extrapolated to infinite dilution using the Pitzer interaction model. The activity coefficients for free ions ( γM, γx) needed for this extrapolation have been estimated from the Pitzer equations. The thermodynamic stability constants ( KMX) and activity coefficients of the various ion pairs ( γMX) were determined from In ( solK MX∗/γ Mγ x) = In K mx+ In (γ MX). The activity coefficients of the ion pairs have been used to determine Pitzer parameters ( BMX) for the rare earth complexes. The values of BMX were found to be the same for complexes of the same charge. These results make it possible to estimate the stability constants for the formation of rare earth complexes over a wide range of ionic strengths. The stability constants have been used to determine the speciation of the lanthanides in seawater and in brines. The carbonate complexes dominate for all natural waters where the carbonate alkalinity is greater than 0.001 eq/L at a pH near 8.

  16. π-Conjugated bis(terpyridine)metal complex molecular wires.

    PubMed

    Sakamoto, Ryota; Wu, Kuo-Hui; Matsuoka, Ryota; Maeda, Hiroaki; Nishihara, Hiroshi

    2015-11-01

    Bottom-up approaches have gained significant attention recently for the creation of nano-sized, ordered functional structures and materials. Stepwise coordination techniques, in which ligand molecules and metal sources are reacted alternatively, offer several advantages. Coordination bonds are stable, reversible, and self-assembling, and the resultant metal complex motifs may contain functionalities unique to their own characteristics. This review focuses on metal complex wire systems, specifically the bottom-up fabrication of linear and branched bis(terpyridine)metal complex wires on electrode surfaces. This system possesses distinct and characteristic electronic functionalities, intra-wire redox conduction and excellent long-range electron transport ability. This series of comprehensive studies exploited the customizability of bis(terpyridine)metal complex wires, including examining the influence of building blocks. In addition, simple yet effective electron transfer models were established for redox conduction and long-range electron transport. A fabrication technique for an ultra-long bis(terpyridine)metal complex wire is also described, along with its properties and functionalities. PMID:25864838

  17. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  18. A new metalation complex for organic synthesis and polymerization reactions

    NASA Technical Reports Server (NTRS)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  19. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

    1996-01-01

    Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  20. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, J.E.; Ellis, P.E. Jr.; Wagner, R.W.

    1996-01-02

    Transition metal complexes of Gable porphyrins are disclosed having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  1. Forcing Ferromagnetic Coupling Between Rare-Earth-Metal and 3d Ferromagnetic Films

    NASA Astrophysics Data System (ADS)

    Sanyal, Biplab; Antoniak, Carolin; Burkert, Till; Krumme, Bernhard; Warland, Anne; Stromberg, Frank; Praetorius, Christian; Fauth, Kai; Wende, Heiko; Eriksson, Olle

    2010-04-01

    Using density functional calculations, we have studied the magnetic properties of nanocomposites composed of rare-earth-metal elements in contact with 3d transition metals (Fe and Cr). We demonstrate the possibility to obtain huge magnetic moments in such nanocomposites, of order 10μB/rare-earth-metalatom, with a potential to reach the maximum magnetic moment of Fe-Co alloys at the top of the so-called Slater-Pauling curve. A first experimental proof of concept is given by thin-film synthesis of Fe/Gd and Fe/Cr/Gd nanocomposites, in combination with x-ray magnetic circular dichroism.

  2. Metal enhanced fluorescence in rare earth doped plasmonic core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Derom, S.; Berthelot, A.; Pillonnet, A.; Benamara, O.; Jurdyc, A. M.; Girard, C.; Colas des Francs, G.

    2013-12-01

    We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion’s excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

  3. Chiral benzamidinate ligands in rare-earth-metal coordination chemistry.

    PubMed

    Benndorf, Paul; Kratsch, Jochen; Hartenstein, Larissa; Preuss, Corinna M; Roesky, Peter W

    2012-11-01

    The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln = Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3)Sm], bis(amidinate) complexes [{Ln(PEBA)(2)(μ-Cl)}(2)] (Ln = Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2)(thf)(n)] (Ln = Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound. PMID:23015310

  4. One-dimensional rare earth compounds and complexes: preparation and improved photoluminescence properties.

    PubMed

    Song, Hongwei; Pan, Guohui; Bai, Xue; Li, Suwen; Yu, Hongquan; Zhang, Hui

    2008-03-01

    One-dimensional nanosized phosphors demonstrate special structural and photoluminescence properties, which have application potential in some optical fields. In this article, we present our recent progress on preparation and luminescence properties of some one-dimensional rare earth compounds and complexes, the core-shell oxide nanowires prepared by a two-step hydrothermal route, the nanowires of some inorganic compounds doped with rare earths and rare earth complexes/PVP composites prepared by the electrospinning method, and the rare earth complexes in the SBA-15 mesoporous molecule sieves. In these systems, some novel or improved photoluminescence properties are observed such as improved luminescence quantum yield, thermal stability and/or photostability, and depressed thermal effect in upconversion luminescence. PMID:18468146

  5. Complexed metals in hazardous waste: Limitations of conventional chemical oxidation

    SciTech Connect

    Diel, B.N.; Kuchynka, D.J.; Borchert, J.

    1994-12-31

    In the management of hazardous waste, more is known regarding the treatment of metals than about the fixation, destruction and/or immobilization of any other hazardous constituent group. Metals are the only hazardous constituents which cannot be destroyed, and so must be converted to their least soluble and/or reactive form to prevent reentry into the environment. The occurrence of complexed metals, e.g., metallocyanides, and/or chelated metals, e.g., M{center_dot}EDTA in hazardous waste streams presents formidable challenges to conventional waste treatment practices. This paper presents the results of extensive research into the destruction (chemical oxidation) of metallocyanides and metal-chelates, defines the utility and limitations of conventional chemical oxidation approaches, illustrates some of the waste management difficulties presented by such species, and presents preliminary data on the UV/H{sub 2}O{sub 2} photodecomposition of chelated metals.

  6. Earth

    NASA Technical Reports Server (NTRS)

    Carr, M. H.

    1984-01-01

    The following aspects of the planet Earth are discussed: plate tectonics, the interior of the planet, the formation of the Earth, and the evolution of the atmosphere and hydrosphere. The Earth's crust, mantle, and core are examined along with the bulk composition of the planet.

  7. Macrocyclic metal complexes for metalloenzyme mimicry and sensor development.

    PubMed

    Joshi, Tanmaya; Graham, Bim; Spiccia, Leone

    2015-08-18

    Examples of proteins that incorporate one or more metal ions within their structure are found within a broad range of classes, including oxidases, oxidoreductases, reductases, proteases, proton transport proteins, electron transfer/transport proteins, storage proteins, lyases, rusticyanins, metallochaperones, sporulation proteins, hydrolases, endopeptidases, luminescent proteins, iron transport proteins, oxygen storage/transport proteins, calcium binding proteins, and monooxygenases. The metal coordination environment therein is often generated from residues inherent to the protein, small exogenous molecules (e.g., aqua ligands) and/or macrocyclic porphyrin units found, for example, in hemoglobin, myoglobin, cytochrome C, cytochrome C oxidase, and vitamin B12. Thus, there continues to be considerable interest in employing macrocyclic metal complexes to construct low-molecular weight models for metallobiosites that mirror essential features of the coordination environment of a bound metal ion without inclusion of the surrounding protein framework. Herein, we review and appraise our research exploring the application of the metal complexes formed by two macrocyclic ligands, 1,4,7-triazacyclononane (tacn) and 1,4,7,10-tetraazacyclododecane (cyclen), and their derivatives in biological inorganic chemistry. Taking advantage of the kinetic inertness and thermodynamic stability of their metal complexes, these macrocyclic scaffolds have been employed in the development of models that aid the understanding of metal ion-binding natural systems, and complexes with potential applications in biomolecule sensing, diagnosis, and therapy. In particular, the focus has been on "coordinatively unsaturated" metal complexes that incorporate a kinetically inert and stable metal-ligand moiety, but which also contain one or more weakly bound ligands, allowing for the reversible binding of guest molecules via the formation and dissociation of coordinate bonds. With regards to mimicking

  8. New technology of extracting the amount of rare earth metals from the red mud

    NASA Astrophysics Data System (ADS)

    Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

    2016-01-01

    The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

  9. Tryptophan fluorescence quenching by alkaline earth metal cations in deionized bacteriorhodopsin.

    PubMed

    Wang, G; Wang, A J; Hu, K S

    2000-12-01

    Tryptophan quenching by the addition of alkaline earth metal cations to deionized bacteriorhodopsin suspensions was determined. The results show that the addition of cation primarily quenches fluorescence from surface tryptophan residues. The quenched intensity exhibits a 1/R dependence, where R is the ionic radius of the corresponding metal ion. This observation results from a stronger energy transfer coupling between the tryptophan and the retinal. The membrane curvature may be involved as a result of cations motion and correlated conformational changes. PMID:11332888

  10. First-principles study of He point-defects in HCP rare-earth metals

    SciTech Connect

    Li, Yang; Chen, Ru; Peng, SM; Long, XG; Wu, Z.; Gao, Fei; Zu, Xiaotao

    2011-05-01

    He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom is smaller than that of a substitutional He atom in all hcp rare-earth metals considered. Furthermore, the tetrahedral interstitial position is more favorable than an octahedral position for He defects. The results are compared with those from bcc and fcc metals.

  11. Complex Microfiltration Behavior of Metal Hydroxide Slurries

    SciTech Connect

    Shimskey, Rick W.; Schonewill, Philip P.; Daniel, Richard C.; Peterson, Reid A.

    2011-02-28

    Crossflow filtration is to be a key process in the treatment and disposal of approximately 60,000 metric tons of high-level waste stored at the Hanford Site in Richland, Washington. Pacific Northwest National Laboratory is assessing filter performance against waste simulant materials that mimic the chemical and physical properties of Hanford tank waste. Prior simulant studies indicate that waste filtration performance may be limited by pore and cake fouling. To limit the shutdown of waste treatment operations, the pre-treatment facility plans to recover filter flux loses from cake formation and filter fouling by frequently backpulsing the filter elements. The objective of the current research is to develop an understanding of the roles of cake and pore fouling and potential flux recovery through backpulsing of the filters for Hanford waste filtration operations. Metal hydroxide wastes were tested to examine the role of particle-filter interaction on filter performance.

  12. Complexes of metals with humus substances as natural biocolloids: mechanism and size

    NASA Astrophysics Data System (ADS)

    Dinu, Marina; Shkinev, Valery; Linnik, Vitaly

    2014-05-01

    Metal complexes with humus substances in the soil are natural biocolloids, which are characterized by the size of the nano- to milli grams. Physical state of the compound functional features humus substances (HS), the nature of metal - all these parameters define different mechanisms transportation of the metal in the soil profile. To assess changes in the composition humus substances complexes with metals and molecular weights humus substances used methods ultrotsentrifugation and filtration (<8 microns, <1.6 microns, <100 kDa), followed by analysis of the samples - ICP-MS electrochemical and chromatographic methods. Soil samples of gleepodzolic were selected in Hibin (Russia) by layers (0-50 cm) by 5 cm. According to the data within the layers ultrafiltration alkali metals do not stay in any of the fractions and to migrate as the ions (40-50 cm). Alkali- earth metals, on the contrary, delayed a layer ( 2-7 cm), most humified layer, explained by the appearance of active d- orbital of the metal cations, and their greater ability to form complexes than alkali metals. Aluminum content of elements of the subgroup represented by several peaks, mainly in the upper layers of the soil in those areas where the most represented type of fulvic humus substances. High concentration of iron in all studied soil layers. An exception is the 15-35 cm layer which contains humic substance in large quantities compared with fulvic acids, that may explain the decrease in the affinity of the metal to the functional groups and less strong sorption communication mechanism. Metal concentrations of nickel and cobalt are practically unchanged with soil depth. Indicating that almost the same ability to bind to humic and fulvic acids. In samples of 5-8 cm identified reduction of zinc and copper ions in the filtrates from 8 microns to 100 kDa. However, complexes with zinc ions of HS molecular weight less than 100 kDa in all filtrates predominates, particularly fulvic type complexes. Lead ions

  13. Synthesis and structures of transition metal pacman complexes of heteroditopic Schiff-base pyrrole macrocycles.

    PubMed

    Leeland, James W; Finn, Colin; Escuyer, Bérengère; Kawaguchi, Hiroyuki; Nichol, Gary S; Slawin, Alexandra M Z; Love, Jason B

    2012-12-01

    A series of polydentate dual-compartment, Schiff-base pyrrole macrocycles has been prepared through the straightforward Lewis acid catalysed [1 + 1] condensation reactions between ONO or O(5)-linked aryldiamines and dipyrromethane dialdehydes. These macrocycles display hydrogen-bond acceptor and donor properties and provide distinct N(4) and O(5)/ONO donor sets for metallation reactions, so forming alkali, alkaline earth, and transition metal complexes that were characterised spectroscopically and crystallographically. While the conformationally flexible O(5) donor set allows the formation of helical potassium salt structures, the transition metal complexes of all variants of these macrocycles invariably adopt wedged, Pacman-shaped structures in which the metal is bound in the pyrrole-imine N(4) donor set, so leaving the ONO/O(5) donor set pendant and apical. In some cases (V, Cr, and Co), this proximate combination of Lewis acid binding site and hydrogen bond acceptor facilitates the coordination of water within the molecular cleft; alternatively, direct interaction between the pendant arm and the metal is seen (e.g. Ti). Higher order [2 + 2] macrocycles were also prepared as minor, inseparable by-products of cyclisation, and Fe(2), Mn(2), and Co(2) complexes of these larger macrocycles were found to adopt binuclear helical structures by X-ray crystallography. PMID:23026851

  14. Aluminum/alkaline earth metal composites and method for producing

    DOEpatents

    Russell, Alan M; Anderson, Iver E; Kim, Hyong J; Freichs, Andrew E

    2014-02-11

    A composite is provided having an electrically conducting Al matrix and elongated filaments comprising Ca and/or Sr and/or Ba disposed in the matrix and extending along a longitudinal axis of the composite. The filaments initially comprise Ca and/or Sr and/or Ba metal or allow and then may be reacted with the Al matrix to form a strengthening intermetallic compound comprising Al and Ca and/or Sr and/or Ba. The composite is useful as a long-distance, high voltage power transmission conductor.

  15. Polymerization of 1,3-Conjugated Dienes with Rare-Earth Metal Precursors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhichao; Cui, Dongmei; Wang, Baoli; Liu, Bo; Yang, Yi

    This chapter surveys the publications except patents related to cis-1,4-, trans-1,4-, 3,4-regio-, and stereoselective polymerizations of 1,3-conjugated dienes with rare-earth metal-based catalytic systems during the past decade from 1999 to 2009. The concerned catalyst systems are classified into the conventional Ziegler-Natta catalysts, the modified Ziegler-Natta catalysts, and the single-site cationic systems composed of lanthanocene and noncyclopentadienyl precursors, respectively. For the conventional Ziegler-Natta catalysts of the most promising industry applicable recipe, the multicomponents based on lanthanide carboxylate or phosphate or alkoxide precursors, research works concern mainly about optimizing the catalyst preparation and polymerization techniques. Special emphases are put on the factors that influence the catalyst homogeneority, catalytic activity and efficiency, as well as cis-1,4-selectivity. Meanwhile, tailor-made lanthanide aryloxide and amide complexes are designed and fully characterized to mimic the conventional Ziegler-Natta catalysts, anticipated to elucidate the key processes, alkylation and cationization, for generating the active species. Regarding to the single-site catalytic systems generally comprising well-defined complexes containing lanthanide-carbon bonds, investigations cover their versatile catalytic activity and efficiency, and the distinguished regio- and stereoselectivity for both polymerization of dienes and copolymerization of dienes with alkenes. The correlation between the sterics and electronics of ligands and the molecular structures of the complexes and their catalytic performances are highlighted. The isolation of the probable active species in these polymerization processes from the stoichiometric reactions of the precursors with activators will be presented.

  16. Rare earth zirconium oxide buffer layers on metal substrates

    DOEpatents

    Williams, Robert K.; Paranthaman, Mariappan; Chirayil, Thomas G.; Lee, Dominic F.; Goyal, Amit; Feenstra, Roeland

    2001-01-01

    A laminate article comprises a substrate and a biaxially textured (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer over the substrate, wherein 0metal-organic decomposition. The laminate article can include a layer of YBCO over the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. A layer of CeO.sub.2 between the YBCO layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer can also be include. Further included can be a layer of YSZ between the CeO.sub.2 layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. The substrate can be a biaxially textured metal, such as nickel. A method of forming the laminate article is also disclosed.

  17. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    NASA Astrophysics Data System (ADS)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  18. Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

    NASA Astrophysics Data System (ADS)

    Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

    2009-10-01

    Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

  19. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the σ and π channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  20. Robust and Porous β-Diketiminate-Functionalized Metal-Organic Frameworks for Earth-Abundant-Metal-Catalyzed C-H Amination and Hydrogenation.

    PubMed

    Thacker, Nathan C; Lin, Zekai; Zhang, Teng; Gilhula, James C; Abney, Carter W; Lin, Wenbin

    2016-03-16

    We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal-organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp(3) C-H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp(3) C-H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity. Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations. PMID:26885768

  1. Shifted homologous relationships between the transplutonium and early rare-earth metals

    SciTech Connect

    Ward, J.W.

    1984-01-01

    The physico-chemical properties of the late actinide metals americium through einsteinium are compared with their rare-earth counterparts. Localization of the 5f electrons beginning at americium signals the appearance of true rare-earth-like properties, but the homologous relationship is shifted to place americium below praseodymium, einsteinium then below europium. The comparison of crystal structure, phase transitions, vapor pressures and heats of vaporization reveals remarkable similarities, especially for Sm-Cf and Eu-Es, where the stability of the divalent metal becomes established and divalent chemistry then follows. There is of course a major perturbation at the half-filled shell at curium, and it may be argued that americium is the anomaly in the so-called second rare-earth series. However, the response of americium, berkelium and californium under pressure reveals the true perturbation to be a thermodynamic one, occurring at curium.

  2. Electrochemical response of metal complexes in homogeneous solution under photoirradiation

    PubMed Central

    Fukatsu, Arisa; Kondo, Mio; Okamura, Masaya; Yoshida, Masaki; Masaoka, Shigeyuki

    2014-01-01

    The electrochemical detection of metal complexes in the photoexcited state is important for understanding photoinduced electron transfer (PET) processes, which play a central role in photo-energy conversion systems. In general, however, the redox potentials of excited states have been indirectly estimated by a combination of spectroscopic properties and ground-state redox potentials. To establish a simple method for directly determining the redox potentials of the photoexcited states of metal complexes, electrochemical measurements under several conditions were performed. The electrochemical response was largely influenced not only by the generation of photoexcited molecules but also by the convection induced by photoirradiation, even when the global temperature of the sample solution was unchanged. The suppression of these unfavourable electrochemical responses was successfully achieved by adopting well-established electrochemical techniques. Furthermore, as an initial demonstration, the photoexcited state of a Ru-based metal complex was directly detected, and its redox potential was determined using a thin layer electrochemical method. PMID:24937471

  3. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  4. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    DOEpatents

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  5. Magnetite-sulfide-metal complexes in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Haggerty, S. E.; Mcmahon, B. M.

    1979-01-01

    A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

  6. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

    PubMed Central

    Chen, Jinjie; Edelmann, Kevin; Wulfhekel, Wulf

    2015-01-01

    Summary We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium(III), onto metal surfaces of Cu(111), Ag(111) and Au(111) in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K) scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy. PMID:26733215

  7. Evaluating key parameters for the initiation of a Neoproterozoic Snowball Earth with a single Earth System Model of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Spiegl, T. C.; Paeth, H.; Frimmel, H. E.

    2015-04-01

    Even after more than two decades of intense research the main drivers for a potential Neoproterozoic Snowball Earth continue to be discussed controversially. In this study we present results from 37 sensitivity experiments that were performed with the Planet Simulator (PlaSim), an Earth System Model of intermediate complexity. In contrast to previous studies, in which only a limited number of potential climate-controlling parameters were assessed with different climate models, we tested our presumed key parameters within one single model. This approach makes it easier to compare the influence of the various parameters on extreme climate change as postulated for the Neoproterozoic Era. Furthermore we compare the results obtained to most recent high complexity state-of-the-art approaches. This comparison helps to estimate, which internal model interactions and physics are crucial for a Snowball Earth simulation and hence should be included into a model that is capable of realistically simulating a Neoproterozoic climate. To this effect we carried out simulations that involved reduced solar irradiation, land-sea distributions, atmospheric CO2 concentrations, relief of the land surface and length of day. In addition, we focus on different land surface albedo values, which were most likely exceptionally low and similar to the Martian albedo, and obliquity changes between 23.5° and 80°. Our findings suggest that changes in land surface albedo are a strong climate driver that can compensate a much lower Neoproterozoic total solar irradiance if it is combined with shifts in obliquity or atmospheric CO2 levels. We also obtained a critical threshold for increased obliquities beyond which a Snowball Earth situation turns into an extreme greenhouse climate with almost absent cryosphere, and furthermore, obliquity values that lead to a tropical ice age with sea ice spreading from the equator to high latitudes.

  8. Complex Seismic Anisotropy in the Earth's Inner Core Beneath Africa

    NASA Astrophysics Data System (ADS)

    Yu, W.; Wen, L.

    2005-12-01

    Seismic anisotropic velocity structure plays an important role in understanding the geodynamics and mineral physics in the Earth's inner core. Previous seismic studies using the PKiKP-PKIKP phase pairs have suggested no evidence for the presence of anisotropy in velocity in the top 80 km of the inner core. However, the sampling coverage of the PKiKP-PKIKP phase pairs in previous studies was limited, especially along the polar paths. Here we expand our PKiKP-PKIKP dataset by collecting the PKiKP-PKIKP waveforms sampling the inner core globally and along various sampling directions. Our data are selected from the Global Seismographic Network and many regional seismic networks: GEOSCOPE, GEOFON, the Canadian National Seismic Network (CNCN), the Oceanographic Hemisphere Project (OHP), Kazakhstan, and Kyrgyzstan. Our seismic observations show that there is indeed no difference in PKiKP-PKIKP differential travel time residual between the polar and equatorial paths in most regions of the inner core, suggesting no anisotropy in velocity in the top 80 km of the inner core in most regions. Our expanded collection of the PKiKP-PKIKP phases, however, reveals a clear polar-equatorial difference in differential travel time residual in a localized region in the western hemisphere beneath Africa. The PKiKP-PKIKP data sampling along the polar paths in this area of the inner core also exhibit strong lateral variations, requiring the thickness of isotropic layer varying from 10 km or less beneath Uganda and western Africa to 50 km beneath Cameron and Congo. We will show the seismic data grouped according to their sampling regions in the inner core and anisotropic velocity models in each of these regions by waveform modeling the PKiKP-PKIKP data, the PKP data observed at the caustics distance range (141°-145°), and the PKPbc-PKIKP data recorded at larger distances.

  9. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  10. Complexation-induced supramolecular assembly drives metal-ion extraction.

    PubMed

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. PMID:25169678

  11. Fluid dynamics experiments on impact-induced metal dispersion during Earth's accretion

    NASA Astrophysics Data System (ADS)

    Deguen, R.; Risso, F.; Landeau, M.; Olson, P.

    2015-12-01

    Much of the Earth was built by high-energy impacts of planetesimals and embryos, many of these impactors already differentiated, with metallic cores of their own. Geochemical data provide critical information on the timing of accretion and the prevailing physical conditions, but their interpretation depends critically on the degree of metal-silicate chemical equilibration and metal dispersion during core-mantle differentiation, which is poorly constrained. Efficient equilibration requires that the large volumes of iron derived from impactor cores mix with molten silicates down to scales small enough to allow fast metal-silicate mass transfer. Here we use fluid dynamics experiments to investigate the fate of the metal phase of a planetesimal or planetary embryo colliding with the proto-Earth. The degree of metal-dispersion and metal-silicate mixing are found to depend primarily on the Froude number of the impactor, with "small" impacts (having large Froude numbers) having a comparatively higher amount of dispersion and mixing than "large" impacts (moderate Froude numbers).

  12. Effects of inherent alkali and alkaline earth metallic species on biomass pyrolysis at different temperatures.

    PubMed

    Hu, Song; Jiang, Long; Wang, Yi; Su, Sheng; Sun, Lushi; Xu, Boyang; He, Limo; Xiang, Jun

    2015-09-01

    This work aimed to investigate effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass pyrolysis at different temperatures. The yield of CO, H2 and C2H4 was increased and that of CO2 was suppressed with increasing temperature. Increasing temperature could also promote depolymerization and aromatization reactions of active tars, forming heavier polycyclic aromatic hydrocarbons, leading to decrease of tar yields and species diversity. Diverse performance of inherent AAEMs at different temperatures significantly affected the distribution of pyrolysis products. The presence of inherent AAEMs promoted water-gas shift reaction, and enhanced the yield of H2 and CO2. Additionally, inherent AAEMs not only promoted breakage and decarboxylation/decarbonylation reaction of thermally labile hetero atoms of the tar but also enhanced thermal decomposing of heavier aromatics. Inherent AAEMs could also significantly enhance the decomposition of levoglucosan, and alkaline earth metals showed greater effect than alkali metals. PMID:26005925

  13. Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

    NASA Astrophysics Data System (ADS)

    Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun; Mann, Maxwell; Beach, Geoffrey S. D.

    2016-06-01

    We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead to spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.

  14. Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements

    SciTech Connect

    Hashida, Masaki; Sakabe, Shuji; Izawa, Yasukazu

    2011-03-15

    Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements (Sc, Y, and Gd) in the impact energy range of 30 to 1000 eV were measured for the first time. The experiments were performed with a crossed-beam apparatus that featured primary ion production by photoionization with a tunable dye laser. Comparing the cross sections of IIIa rare-earth-metal elements ({sigma}{sub Sc}, {sigma}{sub Y}, and {sigma}{sub Gd}) with those of alkali metals or helium {sigma}{sub 0}, we found that {sigma}{sub 0{approx_equal}{sigma}Sc}<{sigma}{sub Y}<{sigma}{sub Gd{approx_equal}}2{sigma}{sub 0}at an impact energy of 1000 eV.

  15. Luminescent molecular rods - transition-metal alkynyl complexes.

    PubMed

    Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

    2005-01-01

    A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes. PMID:22179333

  16. Properties- and applications of quasicrystals and complex metallic alloys.

    PubMed

    Dubois, Jean-Marie

    2012-10-21

    This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section. PMID:22933085

  17. The t-matrix resistivity of liquid rare earth metals using pseudopotential

    SciTech Connect

    Bhatia, Kamaldeep G.; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

    2015-06-24

    Present theoretical study of liquid metal resistivity of some trivalent (La,Ce,Gd) and divalent (Eu,Yb) rare earth metals using pseudopotential has been carried out employing Ziman’s weak scattering and transition matrix (t-matrix) approaches. Our computed results of liquid metal resistivity using t-matrix approach are better than resistivity computed using Ziman’s approach and are also in excellent agreement with experimental results and other theoretical findings. The present study confirms that for f-shell metals pseudopotential must be determined uniquely and t-matrix approach is more physical in comparison with Ziman’s nearly free electron approach. The present pseudopotential accounts s-p-d hybridization properly. Such success encourages us to study remaining liquid state properties of these metals.

  18. Bonding Model for Transition Metal and Rare Earth Monoxides and Laser Spectroscopy of Nickel-Oxide

    NASA Astrophysics Data System (ADS)

    Srdanov, Vojislav I.

    We discovered that, for the transition metal and the rare earth monoxide series, the sum of the ionization potential of the metal, the energy of the lowest ( ...np) configuration of the metal ion and the thermochemical dissociation energy of the molecule adds up to a constant number. The correlation is particularly striking for the rare earth monoxides where the standard deviation is less than 1%. Based on this correlation we developed a new bonding scheme common for both the transition metal and rare earth monoxides. We propose that the bonding is invariant within the series and consists of an ionic and a covalent contribution. In our model a covalent contribution to the bonding of the inner-core d and f orbitals is negligible. This is in contrast to the current paradigm regarding the significant role of the d orbitals in the bonding in the first and second row transition metal oxides. Our model also appears to be in conflict with the M^{2+} O^{2-} ligand-field bonding model currently accepted for the rare earth monoxides. Based on the empirical correlation and the proposed bonding mechanism, however, we give a number of predictions regarding yet unmeasured fundamental quantities of some of the oxides such as permanent dipole moments, dissociation energies and equilibrium bond distances. We also present the results of the first high resolution laser spectroscopic study of the NiO molecule. Several bands in the green spectral region were found to originate from the ground state of NiO; their analysis allowed us to determine the following fundamental parameters: Ground state symmetry: ^3Sigma^-; Vibrational frequency: omega_{ rm e} = 8.39.1 cm^{ -1}; Equilibrium distance: r_ {rm e} = 1.627 A. With this work the determination of the ground state parameters for the first row transition metal oxides is now complete.

  19. Alkaline-Earth-Metal-Induced Liberation of Rare Allotropes of Elemental Silicon and Germanium from N-Heterocyclic Metallylenes.

    PubMed

    Blom, Burgert; Said, Amro; Szilvási, Tibor; Menezes, Prashanth W; Tan, Gengwen; Baumgartner, Judith; Driess, Matthias

    2015-09-01

    The synthesis and striking reactivity of the unprecedented N-heterocyclic silylene and germylene ("metallylene") alkaline-earth metal (Ae) complexes of the type [(η(5)-C5Me5)2Ae←:E(N(t)BuCH)2] (3, 4, and 7-9; Ae = Ca, E = Ge 3; Ae = Sr, E = Ge 4; Ae = Sr, E = Si 7; Ae = Ba, E = Si 8; Ae = Ba, E = Ge 9) are reported. All complexes have been characterized by spectroscopic means, and their bonding situations investigated by density functional theory (DFT) methods. Single-crystal X-ray diffraction analyses of examples revealed relatively long Si-Ae and Ge-Ae distances, respectively, indicative of weak E:→Ae (E = Si, Ge) dative bonds, further supported by the calculated Wiberg bond indices , which are rather low in all cases (∼0.5). Unexpectedly, the complexes undergo facile transformation to 1,4-diazabuta-1,3-diene Ae metal complexes of the type [(η(5)-C5Me5)2Ae(κ(2)-{N(t)Bu═CHCH═N(t)Bu})] (Ae = Sr 10, Ae = Ba 11) or in the case of calcium to the dinuclear complex [(η(5)-C5Me5)2Ca←:N((t)Bu)═CHCH═((t)Bu)N:→Ca(η(5)-C5Me5)2] (12) under concomitant liberation of elemental silicon and germanium. The formation of elemental silicon and germanium is proven by inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray spectroscopy. Notably, the decomposition of the Si(II)→Ba complex 8 produces allo-silicon, a rare allotropic form of elemental silicon. Similarly, the analogous Ge(II)→Ba complex 9, upon decomposition, forms tetragonal germanium, a dense and rare allotrope of elemental germanium. The energetics of this unprecedented alkaline-earth-metal-induced liberation of elemental silicon and germanium was additionally studied by DFT methods, revealing that the transformations are pronouncedly exergonic and considerably larger for the N-heterocyclic germylene complexes than those of the corresponding silicon analogues. PMID:26305163

  20. Understanding Student Cognition about Complex Earth System Processes Related to Climate Change

    NASA Astrophysics Data System (ADS)

    McNeal, K. S.; Libarkin, J.; Ledley, T. S.; Dutta, S.; Templeton, M. C.; Geroux, J.; Blakeney, G. A.

    2011-12-01

    The Earth's climate system includes complex behavior and interconnections with other Earth spheres that present challenges to student learning. To better understand these unique challenges, we have conducted experiments with high-school and introductory level college students to determine how information pertaining to the connections between the Earth's atmospheric system and the other Earth spheres (e.g., hydrosphere and cryosphere) are processed. Specifically, we include psychomotor tests (e.g., eye-tracking) and open-ended questionnaires in this research study, where participants were provided scientific images of the Earth (e.g., global precipitation and ocean and atmospheric currents), eye-tracked, and asked to provide causal or relational explanations about the viewed images. In addition, the students engaged in on-line modules (http://serc.carleton.edu/eslabs/climate/index.html) focused on Earth system science as training activities to address potential cognitive barriers. The developed modules included interactive media, hands-on lessons, links to outside resources, and formative assessment questions to promote a supportive and data-rich learning environment. Student eye movements were tracked during engagement with the materials to determine the role of perception and attention on understanding. Students also completed a conceptual questionnaire pre-post to determine if these on-line curriculum materials assisted in their development of connections between Earth's atmospheric system and the other Earth systems. The pre-post results of students' thinking about climate change concepts, as well as eye-tracking results, will be presented.

  1. Late transition metal. mu. -oxo and. mu. -imido complexes

    SciTech Connect

    Sharp, P.R.

    1990-01-01

    The synthesis and reactions of late-transition-metal oxo and imido complexes was explored. The deprotonation of platinum(II) hydroxo complexes yielded new oxo complexes. Attempted deprotonation of Cp*Rh(III) hydroxo complexes did not give oxo complexes but complex mixtures probably resulting from reduction of the Rh(III) center. The reaction of Na/Hg with (Cp*RhCl{sub 2}){sub 2} gave the very reactive Rh(II) dimer, (Cp*RhCl){sub 2}. Rhodium(I) imido complexes with the bis(dimethylphosphino)methane ligand were prepared and found to be similar to the previously prepared bis(diphenylphosphino)methane complexes. Attempts to prepare bis(diphenylphosphino)methylamine, bis(diphenylphosphino)phenylamine, PMe{sub e} and NO{sup +} analogues were not successful. Attempts to prepare Cp*Rh(III) imido complexes resulted in amido complexes and reduction. Rhodium (III) tris(3.5-dimethylpyrazoyl)borate analogues are reduction resistant but have not yet yielded imido complexes. The first imido complexes of Au were prepared by treating a Au oxo complex with amines or isocyanates. Dimeric Cp*Rh dioxygen and nitrosobenzene complexes were prepared by insertion into the Rh-Rh bond of (Cp*RhCl){sub 2}. The dioxygen complex activates a C-H bond of the Cp* ligand on treatment with PMe{sub 3}. Imido and oxo complexes nitrene and oxygen atom transfer product in reactions with CO. A novel electrophilic ring addition was observed with sterically protected aryl imido complexes. 15 refs.

  2. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  3. Coinage metal complexes supported by the tri- and tetraphosphine ligands.

    PubMed

    Dau, Minh Thuy; Shakirova, Julia R; Karttunen, Antti J; Grachova, Elena V; Tunik, Sergey P; Melnikov, Alexey S; Pakkanen, Tapani A; Koshevoy, Igor O

    2014-05-01

    A series of tri- and tetranuclear phosphine complexes of d(10) metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)2](3+) (M = Au (1), Cu (2), Ag (3)), [M4(PPPP)2](4+) (M = Ag (4), Au (5)), [AuAg3(PPPP)2](4+) (6), and [Au2Cu2(PPPP)2(NCMe)4](4+) (7), were characterized crystallographically. The trinuclear clusters 1-3 contain a linear metal core, while in the isostructural tetranuclear complexes 4-6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated Cu(I) ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation-desolvation. The complexes 1-3 and 5-7 exhibit room temperature luminescence in the solid state (Φem = 6-64%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered dσ* → pσ transitions. PMID:24750114

  4. Ultracold chemistry with alkali-metal-rare-earth molecules

    NASA Astrophysics Data System (ADS)

    Makrides, Constantinos; Hazra, Jisha; Pradhan, Gagan; Kendrick, Brian; González-Lezana, Thomás; Naduvalath, Balakrishnan; Petrov, Alexander; Kotochigova, Svetlana

    2015-05-01

    A first principles study of the dynamics of 6Li(2 S) +6 Li174Yb(2Σ+) -->6 Li2(1Σ+) +174 Yb(1 S) reaction is presented at cold and ultracold temperatures. The computations involve determination and analytic fitting of a three-dimensional potential energy surface for the Li2Yb system and quantum dynamics calculations of varying complexities, ranging from exact quantum dynamics within the close-coupling scheme, to statistical quantum treatment, and universal models. It is demonstrated that the two simplified methods yield zero-temperature limiting reaction rate coefficients in reasonable agreement with the full close-coupling calculations. The effect of the three-body term in the interaction potential is explored by comparing quantum dynamics results from a pairwise potential that neglects the three-body term to that derived from the full interaction potential. Inclusion of the three-body term in the close-coupling calculations was found to reduce the limiting rate coefficients by a factor of two. Research at Temple University is supported by MURI-ARO (W911NF-12-1-0476) grant.

  5. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  6. Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

    PubMed

    Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

    2013-06-15

    The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. PMID:23587931

  7. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  8. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGESBeta

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  9. Ultracold chemistry with alkali-metal-rare-earth molecules

    NASA Astrophysics Data System (ADS)

    Makrides, C.; Hazra, J.; Pradhan, G. B.; Petrov, A.; Kendrick, B. K.; González-Lezana, T.; Balakrishnan, N.; Kotochigova, S.

    2015-01-01

    A first principles study of the dynamics of 6Li(2S )+6Li174Yb(2Σ+)→6Li2(1Σ+) + 174Yb(1S ) reaction is presented at cold and ultracold temperatures. The computations involve determination and analytic fitting of a three-dimensional potential energy surface for the Li2Yb system and quantum dynamics calculations of varying complexities, ranging from exact quantum dynamics within the close-coupling scheme, to statistical quantum treatment, and universal models. It is demonstrated that the two simplified methods yield zero-temperature limiting reaction rate coefficients in reasonable agreement with the full close-coupling calculations. The effect of the three-body term in the interaction potential is explored by comparing quantum dynamics results from a pairwise potential that neglects the three-body term to that derived from the full interaction potential. Inclusion of the three-body term in the close-coupling calculations was found to reduce the limiting rate coefficients by a factor of two. The reaction exoergicity populates vibrational levels as high as v =19 of the 6Li2 molecule in the limit of zero collision energy. Product vibrational distributions from the close-coupling calculations reveal sensitivity to inclusion of three-body forces in the interaction potential. Overall, the results indicate that a simplified model based on the long-range potential is able to yield reliable values of the total reaction rate coefficient in the ultracold limit but a more rigorous approach based on statistical quantum or quantum close-coupling methods is desirable when product rovibrational distribution is required.

  10. Precious metals and rare earth elements in municipal solid waste--sources and fate in a Swiss incineration plant.

    PubMed

    Morf, Leo S; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Di Lorenzo, Fabian; Böni, Daniel

    2013-03-01

    In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process. PMID:23085306

  11. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2011-11-01

    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions [1]. The vibrational FT-IR (in KBr and ATR techniques) and 1H and 13C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg → Ba were compared with series of univalent metal Li → Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  12. Rare earth element recycling from waste nickel-metal hydride batteries.

    PubMed

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

    With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. PMID:25089667

  13. Fabrication of Superhydrophobic and Luminescent Rare Earth/Polymer complex Films.

    PubMed

    Wang, Zefeng; Ye, Weiwei; Luo, Xinran; Wang, Zhonggang

    2016-01-01

    The motivation of this work is to create luminescent rare earth/polymer films with outstanding water-resistance and superhydrophobicity. Specifically, the emulsion polymerization of styrene leads to core particles. Then core-shell-structured polymer nanoparticles are synthesized by copolymerization of styrene and acrylic acid on the core surface. The coordination reaction between carboxylic groups and rare earth ions (Eu(3+) and Tb(3+)) generates uniform spherical rare earth/polymer nanoparticles, which are subsequently complexed with PTFE microparticles to obtain micro-/nano-scaled PTFE/rare earth films with hierarchical rough morphology. The films exhibit large water contact angle up to 161° and sliding angle of about 6°, and can emit strong red and green fluorescence under UV excitation. More surprisingly, it is found that the films maintain high fluorescence intensity after submersed in water and even in aqueous salt solution for two days because of the excellent water repellent ability of surfaces. PMID:27086735

  14. Transition metal complexes of an isatinic quinolyl hydrazone

    PubMed Central

    2011-01-01

    Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring in the same compound. Quinoline ring has therapeutic and biological activities. On the other hand, isatin (1H-indole-2,3-dione) and its derivatives exhibit a wide range of biological activities. Also, the indole ring occurs in Jasmine flowers and Orange blossoms. Recently, the physiological and biological activities of quinolyl hydrazones arise from their tendency to form metal chelates with transition metal ions. In this context, we have reported to isolate, characterize and study the biological activity of some transition metal complexes of an isatinic quinolyl hydrazone; 3-[2-(4-methyl quinolin-2-yl)hydrazono] indolin-2-one. Results Mono- and binuclear as well as dimeric chelates were obtained from the reaction of a new isatinic quinolyl hydrazone with Fe(III), Co(II), Ni(II), Cu(II), VO(II) and Pd(II) ions. The ligand showed a variety of modes of bonding viz. (NNO)2-, (NO)- and (NO) per each metal ion supporting its ambidentate and flexidentate characters. The mode of bonding and basicity of the ligand depend mainly on the type of the metal cation and its counter anion. All the obtained Pd(II)- complexes have the preferable square planar geometry (D4h- symmetry) and depend mainly on the mole ratio (M:L). Conclusion The effect of the type of the metal ion for the same anion (Cl-) is obvious from either structural diversity of the isolated complexes (Oh, Td and D4h) or the various modes of bonding. The isatinic hydrazone uses its lactim form in all complexes (Cl-) except complex 5 (SO42-) in which it uses its lactam form. The obtained Pd(II)- complexes (dimeric, mono- and binuclear) are affected by the mole ratio (M:L) and have the square planar (D4h) geometry. Also, the antimicrobial activity is highly influenced by the nature of the metal ion and the order for S. aureus bacteria is as follows: Nickel(II) > Vanadyl(II) > Cobalt

  15. Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

    SciTech Connect

    Buschman, H.J.

    1986-06-01

    The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined from 2:1 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr/sup 2 +/ and Ba/sup 2 +/ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca/sup 2 +/, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.

  16. IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 1. Scandium Group (Sc, Y, La)

    SciTech Connect

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

    2014-03-15

    This work presents an assessment of solubility data for rare earth metal fluorides (generally of trivalent metals and of CeF{sub 4}) in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal fluoride with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data, and a brief discussion of the multicomponent systems. Because the ternary systems were seldom studied more than once, no critical evaluations of such data were possible. Only simple fluorides (no complexes or binary salts) are treated as the input substances in this report. The literature has been covered through the end of 2013.

  17. Efficient separation of transition metals from rare earths by an undiluted phosphonium thiocyanate ionic liquid.

    PubMed

    Rout, Alok; Binnemans, Koen

    2016-06-21

    The ionic liquid trihexyl(tetradecyl)phosphonium thiocyanate has been used for the extraction of the transition metal ions Co(ii), Ni(ii), Zn(ii), and the rare-earth ions La(iii), Sm(iii) and Eu(iii) from aqueous solutions containing nitrate or chloride salts. The transition metal ions showed a high affinity for the ionic liquid phase and were efficiently extracted, while the extraction efficiency of the rare-earth ions was low. This difference in extraction behavior enabled separation of the pairs Co(ii)/Sm(iii), Ni(ii)/La(iii) and Zn(ii)/Eu(iii). These separations are relevant for the recycling of rare earths and transition metals from samarium cobalt permanent magnets, nickel metal hydride batteries and lamp phosphors, respectively. The extraction of metal ions from a chloride or nitrate solution with a thiocyanate ionic liquid is an example of "split-anion extraction", where different anions are present in the aqueous and ionic liquid phase. Close to 100% loading was possible for Co(ii) and Zn(ii) up to a concentration of 40 g L(-1) of the transition metal salt in the initial aqueous feed solution, whereas the extraction efficiency for Ni(ii) gradually decreased with increase in the initial feed concentration. Stripping of Co(ii), Zn(ii) and Ni(ii) from the loaded ionic liquid phase was possible by a 15 wt% NH3 solution. The ionic liquid could reused after extraction and stripping. PMID:27243450

  18. Transport properties of liquid metals and viscosity of the earth's core

    NASA Astrophysics Data System (ADS)

    Poirier, J. P.

    1988-01-01

    Coefficients expressing transport properties of liquid metals (viscosity and diffusivity) can be scaled to the absolute melting temperature. A systematic review of the published experimental data leads to the conclusion that the effect of pressure on viscosity and diffusivity can be taken into account through its effect on the melting temperature. Hence the viscosity and diffusivity at the melting temperature are constants for a given metal. The viscosity of the earth's liquid core, near the inner core boundary, is probably close to 6 centipoises. It is suggested that the diffusivity of sulfur in the core is probably of the order of 0.0001 sq cm/sec.

  19. Vibration spectra of complexes of rare earth nitrate with some Schiff bases

    NASA Astrophysics Data System (ADS)

    Guofa, Liu

    1994-06-01

    Infrared and Raman spectra of complexes of rare earth nitrate with Schiff bases derived from vanillin (3-methoxy-4-hydroxy-benzaldehyde) or o-vanillin (2-hydroxy-3-methoxy-benzaldehyde) and p-toluidine, 1-naphthylamine, 2-naphthylamine are reported.

  20. Application of NASA management approach to solve complex problems on earth

    NASA Technical Reports Server (NTRS)

    Potate, J. S.

    1972-01-01

    The application of NASA management approach to solving complex problems on earth is discussed. The management of the Apollo program is presented as an example of effective management techniques. Four key elements of effective management are analyzed. Photographs of the Cape Kennedy launch sites and supporting equipment are included to support the discussions.

  1. Studying the volatility of pyrazolone complexes of rare-earth elements by means of Knudsen effusion

    NASA Astrophysics Data System (ADS)

    Lazarev, N. M.; Petrov, B. I.; Bochkarev, L. N.; Safronova, A. V.; Abakumov, G. A.; Arapova, A. V.; Bessonova, Yu. A.

    2014-08-01

    The temperature dependences of the pressure of saturated vapor of pyrazolone complexes of rare-earth elements Ln(PMIP)3 (where Ln = Y, Ho, Er, Tm, Lu; PMIP = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) are studied via Knudsen effusion, and the enthalpy of their sublimation is determined. Mass spectra and differential scanning calorimetry data are obtained.

  2. Kondo effect in alkaline-earth-metal atomic gases with confinement-induced resonances

    NASA Astrophysics Data System (ADS)

    Zhang, Ren; Zhang, Deping; Cheng, Yanting; Chen, Wei; Zhang, Peng; Zhai, Hui

    2016-04-01

    Alkaline-earth-metal atoms have a long-lived electronic excited state, and when atoms in this excited state are localized in the Fermi sea of ground-state atoms by an external potential, they serve as magnetic impurities, due to the spin-exchange interaction between the excited- and the ground-state atoms. This can give rise to the Kondo effect. However, in order to achieve this effect in current atomic gas experiments, it requires the Kondo temperature to be increased to a sizable portion of the Fermi temperature. In this paper we calculate the confinement-induced resonance (CIR) for the spin-exchanging interaction between the ground and the excited states of the alkaline-earth-metal atoms and propose that the spin-exchange interaction can be strongly enhanced by utilizing the CIR. We analyze this system by the renormalization-group approach and show that near a CIR, the Kondo temperature can be significantly enhanced.

  3. Electric relaxation processes in chemodynamics of aqueous metal complexes: from simple ligands to soft nanoparticulate complexants.

    PubMed

    van Leeuwen, Herman P; Buffle, Jacques; Town, Raewyn M

    2012-01-10

    The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles. PMID:22126743

  4. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    PubMed

    Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

    2015-01-01

    The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. PMID:26067934

  5. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  6. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  7. Optimization of film synthesized rare earth transition metal permanent magnet systems

    SciTech Connect

    Cadieu, F.J.

    1990-01-01

    This report reviews work on the optimization of film synthesized rare earth transition metal permanent magnet systems. Topics include: high coercivity in Sm-Fe-Ti-V, Sm-Fe-V, and two element systems; ThMn{sub 12} type pseudobinary SmFe{sub 12 {minus} X}T{sub X}; and sputter process control for the synthesis of precisely textured RE-TM magnetic films. (JL)

  8. Optimization of film synthesized rare earth transition metal permanent magnet systems

    SciTech Connect

    Cadieu, F.J.

    1992-01-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  9. Multicomponent analysis of mixed rare-earth metal ion solutions by the electronic tongue sensor system

    SciTech Connect

    Legin, A.; Kirsanov, D.; Rudnitskaya, A.; Rovny, S.; Logunov, M.

    2007-07-01

    Novel electrochemical sensors based on well-known extracting agents are developed. Sensors have shown high sensitivity towards a variety of rear earth metal ions in acidic media at pH=2. Multi-sensor system (electronic tongue) comprising newly developed sensors was successfully applied for the analysis of binary and ternary mixtures of Ce{sup 3+}, Nd{sup 3+}, Sm{sup 3+} and Gd{sup 3+} cations in different combinations. (authors)

  10. Properties of the triplet metastable states of the alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2004-11-01

    The static and dynamic properties of the alkaline-earth-metal atoms in their metastable state are computed in a configuration interaction approach with a semiempirical model potential for the core. Among the properties determined are the scalar and tensor polarizabilities, the quadrupole moment, some of the oscillator strengths, and the dispersion coefficients of the van der Waals interaction. A simple method for including the effect of the core on the dispersion parameters is described.

  11. Metal complexes of 4,5-dimethylpyrazole-3-carboxaldehyde phenylthiosemicarbazone

    NASA Astrophysics Data System (ADS)

    El-Dissouky, Ali

    Several new transition metal complexes derived from 4,5-dimethyl-3-carboxaldehyde phenyl- thiosemicarbazone, LH, have been synthesized. The complexes are of stoichiometry, [CoL 2]X, X = Cl -, Br -, ClO -4 or NO -3, [MnL 2] and [CuX nL m], X = Cl -, Br -, NCS - or N -3; n = 1 or 0; m = 1 or 2 and L = the anion of LH. All complexes have been characterized by elemental analysis, spectral (i.r., electronic, NMR, ESR) and magnetic measurements. The ligand acts as tridentate monobasic co-ordinated to the metal ion via azomethine, pyrazole (N 2) nitrogen atoms and the thiolo-sulphur. The ligand field and ESR parameters are used to interpret the nature of bonding of LH with the metal ion, ground state and the ligand field strength of LH and the various co-ordinated simple ions. The coupling constants of various co-ordinated nuclei with copper (II) are estimated from ESR spectra of copper (II) complexes.

  12. Alkaline earth metal ions mediated self-assembly in the presence of 1,10-phenanthroline, nitrate and tetrafluoroborate anions

    NASA Astrophysics Data System (ADS)

    Dimitrov, Georgi D.; Neykov, Mihail V.

    2007-10-01

    1,10-Phenanthroline (phen) was reacted with various combinations of two and in one of the cases with three alkaline earth metal cations taken in equimolar ratio. In all the competitive reactions it was obtained only one product free of any impurities, which is in accordance with the theory of self-assembly processes. The compound [Ca(phen) 2(H 2O) 2(NO 3)]NO 3 was synthesized in all the reactions where Ca 2+ was involved. In contrast, none of the reactions led to the preparation of a strontium complex. Two of the reactions, in which participated Be 2+, resulted in the compound (phen) 3(H +) 2(NO -3) 2. The second group of competitive reactions was carried out with 1,10-phenanthroline and a given alkaline earth metal cation in the presence of the anions NO 3- and BF 4-. These led to the compounds Mg(phen) 4(BF 4) 2(H 2O) 3, [Ca(phen) 2(H 2O) 2(NO 3)]BF 4, Sr(phen) 4(OH)(BF 4)(H 2O) and Ba(phen) 3.5(BF 4) 2(H 2O). All the newly synthesized substances were characterized by elemental analysis, IR- and FAB-mass-spectra.

  13. Volatile Single-Source Precursors for the Low-Temperature Preparation of Sodium-Rare Earth Metal Fluorides.

    PubMed

    Barry, Matthew C; Wei, Zheng; He, Tianyu; Filatov, Alexander S; Dikarev, Evgeny V

    2016-07-20

    Heterometallic single-source precursors for the preparation of sodium-rare earth metal fluorides are reported. Fluorinated β-diketonates NaRE(hfac)4 (RE = Y (1), Er (2), and Eu (3); hfac = hexafluoroacetylacetonate) have been obtained on a large scale, in high yield, via one-pot reaction that utilizes commercially available starting reagents. The solid-state structures of the title complexes consist of 1D polymeric chains with alternating [Na] and [RE(hfac)4] units. Compounds 1-3 are highly volatile and exhibit a fair stability in open air. Mass spectrometric investigation indicates the presence of heterometallic fragments in the gas phase. The presence of heterometallic species in solutions of coordinating solvents has also been confirmed. Decomposition of heterometallic precursors in argon atmosphere was shown to yield phase-pure sodium-rare earth metal fluorides. Low decomposition temperature effectively allows for a high degree of control over the formation of both kinetic α-phases and thermodynamic β-phases of target NaREF4 (RE = Y, Er, and Eu) materials. PMID:27232230

  14. The importance of the Maillard-metal complexes and their silicates in astrobiology

    NASA Astrophysics Data System (ADS)

    Liesch, Patrick J.; Kolb, Vera M.

    2007-09-01

    The Maillard reaction occurs when sugars and amino acids are mixed together in the solid state or in the aqueous solution. Since both amino acids and sugar-like compounds are found on meteorites, we hypothesized that they would also undergo the Maillard reaction. Our recent work supports this idea. We have shown previously that the water-insoluble Maillard products have substantial similarities with the insoluble organic materials from the meteorites. The Maillard organic materials are also part of the desert varnish on Earth, which is a dark, shiny, hard rock coating that contains iron and manganese and is glazed in silicate. Rocks that are similar in appearance to the desert varnish have been observed on the Martian surface. They may also contain the organic materials. We have undertaken study of the interactions between the Maillard products, iron and other metals, and silicates, to elucidate the role of the Maillard products in the chemistry of desert varnish and meteorites. Specifically, we have synthesized a series of the Maillard-metal complexes, and have tested their reactivity towards silicates. We have studied the properties of these Maillard-metal-silicate products by the IR spectroscopy. The astrobiological potential of the Maillard-metal complexes is assessed.

  15. Characterization of metal complexation in multiligand systems with lanthanide luminescence

    SciTech Connect

    Martinez, G.A.; Traina, S.J.; Logan, T.J.

    1998-08-01

    The effectiveness of an Eu{sup 3+} luminescence technique to describe metal complexation reactions in humic substances was evaluated. The molecular uncertainties intrinsic to humic substances were circumvented by using polyacrylic acid (PAA) and polyvinylsulfonic acid (PVS) as probes. An adequate determination of the Eu{sup 3+}-citrate affinity constant suggested that this technique could potentially be used to characterize metal binding reactions in polyelectrolytes. Various mixtures of PAA and PVS were then evaluated. The commonly adopted assumption of a single metal binding environment in those systems proved ineffective and resulted in a misleading representation of the Eu-PAA binding isotherm. The evidence indicates that prior knowledge about the number of binding environments, as well as their relative contribution to the overall sorption, is needed to describe metal binding on humic substances appropriately through this approach. The effect of metal competition on Eu{sup 3+} binding by a mixed polymer system (1:1 PAA:PVS) was also ascertained. The affinity series obtained (Cu{sup 2+} > Pb{sup 2+} {much_gt} Cd{sup 2+} {ge} Co{sup 2+} {approx_equal} Mg{sup 2+} {approx_equal} Ni{sup 2+} > Ca{sup 2+}) was similar to that frequently observed in humic substances, which reinforces the utility of these polymers as their surrogates in metal sorption studies.

  16. Inhomogeneous complexation of trace metals in water with organic nano-complexants

    NASA Astrophysics Data System (ADS)

    Dolgin, Bella; Bulatov, Valery; Hadar-Abuhatzira, Hodayah; Japarov, Julia; Schechter, Israel

    2011-12-01

    The complexation of heavy metals, such as Cd 2+ and Ni 2+, with organic complexants such as 1-(2-pyridylazo)-2-naphthol (PAN) and 1-(2-thiazolylazo)-2-naphthol (TAN) in water has been investigated. Under such conditions, both the reagents and the products form nano-particulates. These materials are important because their spectrum changes upon exposure to heavy metals and they may be used for design of new optical detectors. The kinetic schemes so far suggested for these complexation reactions are not valid for such experimental conditions, since they assume homogeneous behavior. We provide evidences to the inhomogeneous nature of these reactions. The complexation has been studied using TEM imaging, zeta-potentiometry, time-dependent particulate size analysis and time-dependent spectroscopy. Many of the experimental results are explained in terms of the nature of the nano-particulates of these two complexants. Several processes were identified, including crystal growing of the complexant, its reaction with metal ions in solution and on the surface area, chemical erosion of complexant crystallites and their decomposition, re-crystallization of the formed complexes and long term aggregation of both the complexant and the resulted complex. It was found that the needle-like nano-structures on the surface of the TAN particulates governs its reaction and particulate behavior. The known optimal complexation conditions, such as pH, and delay time are now understood in terms of the zeta-potential minima of the suspensions and in terms of the kinetic parameters. Also the interferences of some ions in the Ni-TAN complexation are now quantified and the kinetic data indicate the best delay time when the interfering effects are minimal.

  17. Enhancement of palladium-porphyrin room temperature phosphorescence by alkaline earth metal in deoxycholate aggregates solution.

    PubMed

    Wang, Ying-Te; Wang, Xiang-Wei; Zhang, Yong

    2011-01-01

    Room temperature phosphorescence (RTP) of three palladium (Pd)-phorphyrins in air-saturated solution of sodium deoxycholate (NaDC) aggregates was measured. RTP of Pd-meso-tetrakis (4-carboxyphenyl) porphyrin (Pd-TCPP) was obviously enhanced in NaDC-aggregates mediated by alkaline earth metal (AEM). Under the same experimental conditions, Ca(2+), Ba(2+) and Mg(2+) induced 200, 90 and 24 times greater enhancement in RTP of Pd-TCPP, respectively. It is ascribed to form the complex of NaDC-aggregate/AEM/Pd-TCPP in the system. The positively charged AEM has a strong capability of co-ordination with negatively charged carboxyl groups of NaDC and Pd-TCPP. The phosphor Pd-TCPP is confined in rigid NaDC-aggregates/AEM system by the coordination which decreases the probability of collision of phosphor with quenchers such as dissolved oxygen molecules and prolongs the lifetime of the phosphor on the triplet state. Long excited-state lifetimes resulted in great enhancement of Pd-TCPP phosphorescence. Observations by optical microscope showed that specific fan-like structures of NaDC were formed under the influence of AEM. Surface tension measurements supported a close interaction between Ca(2+) ions and anion aggregates of NaDC with 1:1 stoichiometric ratio. Due to its outstanding RTP behavior in NaDC-aggregates induced by Ca(2+), Pd-TCPP was used as a RTP probe to detect bovine serum albumin (BSA). A broad linear range from 1.0 × 10(-9) to 9.0 × 10(-7) g mL(-1) was obtained. Detection limit is 2.6 × 10(-11) g mL(-1), the relative standard deviation (n = 6) is 2.3% for 2.0 × 10(-9) g mL(-1) BSA. PMID:21438880

  18. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    SciTech Connect

    Dong, Qiang; Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin; Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro; Sato, Tsugio

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  19. Ultrafine Na-4-mica: uptake of alkali and alkaline earth metal cations by ion exchange.

    PubMed

    Kodama, Tatsuya; Ueda, Masahito; Nakamuro, Yumiko; Shimizu, Ken-ichi; Komarneni, Sridhar

    2004-06-01

    The cation exchange properties of alkali and alkaline earth metal cations at room temperature were investigated on an ultrafine, highly charged Na-4-mica (with the ideal mica composition Na4Mg6Al4Si4O20F4.xH2O). Ultrafine mica crystallites of 200 nm in size led to faster Sr2+ uptake kinetics in comparison to larger mica crystallites. The alkali metal ion (K+, Cs+, and Li+) exchange uptake was rapid, and complete exchange occurred within 30 min. For the alkaline earth metal ions Ba2+, Ca2+, and Mg2+, however, the exchange uptake required lengthy periods from 3 days to 4 weeks to be completed, similar to its Sr uptake, as previously reported. Kinetic models of the modified Freundlich and parabolic diffusion were examined for the experimental data on the Ba2+, Ca2+, and Mg2+ uptakes. The modified Freundlich model described well the Ba2+ ion uptake kinetics as well as that for the Sr2+ ion, while for the Ca2+ and Mg2+ ions the parabolic diffusion model showed better fitting. The alkali and alkaline earth ion exchange isotherms were also determined in comparison to the Sr2+ exchange isotherm. The thermodynamic equilibria for these cations were compared by using Kielland plots evaluated from the isotherms. PMID:15984251

  20. METAL PHTHALOCYANINES

    DOEpatents

    Frigerio, N.A.

    1962-03-27

    A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

  1. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    NASA Astrophysics Data System (ADS)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  2. Equilibrium modeling of trace metal transport from Duluth complex rockpile

    SciTech Connect

    Kelsey, P.D.; Klusman, R.W.; Lapakko, K.

    1996-12-31

    Geochemical modeling was used to predict weathering processes and the formation of trace metal-adsorbing secondary phases in a waste rock stockpile containing Cu-Ni ore mined from the Duluth Complex, MN. Amorphous ferric hydroxide was identified as a secondary phase within the pile, from observation and geochemical modeling of the weathering process. Due to the high content of cobalt, copper, nickel, and zinc in the primary minerals of the waste rock and in the effluent, it was hypothesized that the predicted and observed precipitant ferric hydroxide would adsorb small quantities of these trace metals. This was verified using sequential extractions and simulated using adsorption geochemical modeling. It was concluded that the trace metals were adsorbed in small quantities, and adsorption onto the amorphous ferric hydroxide was in decreasing order of Cu > Ni > Zn > Co. The low degree of adsorption was due to low pH water and competition for adsorption sites with other ions in solution.

  3. Mono- and Dinuclear Macrocyclic Calcium Complexes as Platforms for Mixed-Metal Complexes and Clusters.

    PubMed

    Connolly, Emma A; Leeland, James W; Love, Jason B

    2016-01-19

    Mono- and dinuclear calcium complexes of the Schiff-base macrocycles H4L have been prepared and characterized spectroscopically and crystallographically. In the formation of Ca(THF)2(H2L(1)), Ca2(THF)2(μ-THF)(L(1)), and Ca2(THF)4(L(2)), the ligand framework adopts a bowl-shaped conformation instead of the conventional wedge, Pacman-shaped structure as seen with the anthracenyl-hinged complex Ca2(py)5(L(3)). The mononuclear calcium complex Ca(THF)2(H2L(1)) reacts with various equivalents of LiN(SiMe3)2 to form calcium/alkali metal clusters and dinuclear transition metal complexes when reacted subsequently with transition metal salts. The dinuclear calcium complex Ca2(THF)2(μ-THF)(L(1)), when reacted with various equivalents of NaOH, is shown to act as a platform for the formation of calcium/alkali metal hydroxide clusters, displaying alternate wedged and bowl-shaped conformations. PMID:26709870

  4. [Photoluminescent and electroluminescent properties of a new rare earth terbium complex].

    PubMed

    Wang, Li; Zhang, Xi-qing; Lin, Peng; Xiong, De-pin; Huang, Shi-hua; Yu, Tian-zhi

    2004-06-01

    Pure green and narrowbandwidth emission from an organic electroluminescent device was presented by using arare earth terbium (III) complex as the emissive layer. The structure of the device was ITO/PVK/Tb/PBD/LiF/Al. It was proved that this new kind of rare earth complex has excellent photoluminescent and electroluminescent properties. The electroluminescent spectrum of the device was very similar to that of the terbium (III) complex film. The electroluminescent mechanism of the device was proposed by measuring and analyzing the spectra and electroluminescent property of the device. It is proposed that the excited carriers of PVK and PBD were captured by Tb3+ and light was emitted when the electrons and holes recombined at Tb3+. PMID:15766172

  5. Dynamics and Control in Complex Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Averitt, R. D.

    2014-07-01

    Advances in the synthesis, growth, and characterization of complex transition metal oxides coupled with new experimental techniques in ultrafast optical spectroscopy have ushered in an exciting era of dynamics and control in these materials. Experiments utilizing femtosecond optical pulses can initiate and probe dynamics of the spin, lattice, orbital, and charge degrees of freedom. Major goals include (a) determining how interaction and competition between the relevant degrees of freedom determine macroscopic functionality in transition metal oxides (TMOs) and (b) searching for hidden phases in TMOs by controlling dynamic trajectories in a complex and pliable energy landscape. Advances in creating intense pulses from the far-IR spectrum through the visible spectrum enable mode-selective excitation to facilitate exploration of these possibilities. This review covers recent developments in this emerging field and presents examples that include the cuprates, manganites, and vanadates.

  6. Blue metal complex pigments involved in blue flower color

    PubMed Central

    Takeda, Kosaku

    2006-01-01

    The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, “why is the cornflower blue and rose red when both flowers contain the same anthocyanin?” This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment. PMID:25792777

  7. Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities

    SciTech Connect

    Gutiérrez-Gutiérrez, Silvia C.; Coulon, Frédéric; Jiang, Ying; Wagland, Stuart

    2015-08-15

    Highlights: • Samples from multiple core drills were obtained from 4× landfill sites in the UK. • Each sample analysed for rare earth elements, critical metals and valuable metals. • Two stage microwave digestion method ensuring high yield. • High quantities of copper and aluminium were observed in the soil layers of landfill. • Across 4× landfills aluminium and copper present has a value of around $400 million. - Abstract: Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58 ± 6 mg kg{sup −1} for REEs comprising 44 ± 8 mg kg{sup −1} for light REEs, 11 ± 2 mg kg{sup −1} for heavy REEs and 3 ± 1 mg kg{sup −1} for Scandium (Sc) and 3 ± 1.0 mg kg{sup −1} of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are

  8. A simple, general route to 2-pyridylidene transition metal complexes.

    PubMed

    Roselló-Merino, Marta; Díez, Josefina; Conejero, Salvador

    2010-12-28

    Pyridinium 2-carboxylates decompose thermally in the presence of a variety of late transition metal precursors to yield the corresponding 2-pyridylidene-like complexes. The mild reaction conditions and structural diversity that can be generated in the heterocyclic ring make this method an attractive alternative for the synthesis of 2-pyridylidene complexes. IR spectra of the Ir(i) carbonyl compounds [IrCl(NHC)(CO)(2)] indicate that these N-heterocyclic carbene ligands are among the strongest σ-electron donors. PMID:21052586

  9. mer and fac isomerism in tris chelate diimine metal complexes.

    PubMed

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity. PMID:25600485

  10. Reductive dechlorination of trichloroethene mediated by humic-metal complexes

    SciTech Connect

    O`Loughlin, E.J.; Burris, D.R.; Delcomyn, C.A.

    1999-04-01

    Experiments were conducted to determine if transition metal-humic acid complexes can act as e{sup {minus}} transfer mediators in the reductive dechlorination of trichloroethene (TCE) using Ti(III) citrate as the bulk reductant. In the presence of Ni-Aldrich humic acid (AHA) complexes, TCE reduction was rapid, with complete removal of TCE in less than 23 h. Cu-AHA complexes were less effective as e{sup {minus}} mediators than Ni-AHA complexes; only 60% of TCE was reduced after 150 h. Partially dechlorinated intermediates were observed during TCE reduction; however, they were transitory, and at no time accounted for more than 2% of the initial TCE mass on a mole C basis. Ethane and ethene were the primary end products of TCE reduction; however, a suite of other non-chlorinated hydrocarbons consisting of methane and C{sub 3} to C{sub 6} alkanes and alkenes were also observed. The results suggest that humic-metal complexes may represent a previously unrecognized class of electron mediators in natural environments.

  11. Metal-Dioxygen and Metal-Dinitrogen Complexes: Where Are The Electrons?

    PubMed Central

    Holland, Patrick L.

    2011-01-01

    Transition-metal complexes of O2 and N2 play an important role in the environment, chemical industry, and metalloenzymes. This Perspective compares and contrasts the binding modes, reduction levels, and electronic influences on the nature of the bound O2 or N2 group in these complexes. The charge distribution between the metal and the diatomic ligand is variable, and different models for describing the adducts have evolved. In some cases, single resonance structures (e.g. M-superoxide = M–O2−) are accurate descriptions of the adducts. Recent studies have shown that the magnetic coupling in certain N22− complexes differs between resonance forms, and can be used to distinguish experimentally between resonance structures. On the other hand, many O2 and N2 complexes cannot be described well with a simple valence-bond model. Defining the situations where ambiguities occur is a fertile area for continued study. PMID:20361098

  12. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes

    SciTech Connect

    John, Kevin D; Martin, Richard L; Obrey, Steven J; Scott, Brian L

    2008-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  13. Integration of Paramagnetic Diruthenium Complexes into an Extended Chain by Heterometallic Metal-Metal Bonds with Diplatinum Complexes.

    PubMed

    Uemura, Kazuhiro; Uesugi, Naoyuki; Matsuyama, Akina; Ebihara, Masahiro; Yoshikawa, Hirofumi; Awaga, Kunio

    2016-07-18

    We successfully obtained a paramagnetic one-dimensional (1D) chain complex [{Ru2(O2CCH3)4}{Pt2(piam)2(NH3)4}2]n(PF6)4n·4nH2O (2; piam = pivalamidate) extended by metal-metal bonds. Compound 2 comprises two types of metal species, ruthenium and platinum, where an acetate-bridged dinuclear ruthenium complex (i.e., [Ru2]) and a pivalamidate-bridged platinum complex (i.e., [Pt2]) are connected by axial metal-metal bonds, forming an attractive quasi-1D infinite chain that can be expressed as -{[Pt2]-[Ru2]-[Pt2]}n-. Such axial metal-metal bonds are attributed to the interaction between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) along the z axis, where both the HOMO in [Pt2(II,II)] and the LUMO in [Ru2(II,II)] are σ* orbitals associated with metal cores. The crystal structure and X-ray photoelectron spectrum for 2 reveal that metal oxidation states are -{[Pt2(II,II)]-[Ru2(II,II)]-[Pt2(II,II)]}n-, where [Ru2(II,II)] can have an electronic configuration of σ(2)π(4)δ(2)δ*(2)π*(2) or σ(2)π(4)δ(2)π*(4). The magnetic susceptibility of 2 has a μeff [∝(χT)(1/2)] value of 2.77 μB per [Pt2(II,II)]-[Ru2(II,II)]-[Pt2(II,II)] unit at 300 K, showing that two unpaired electrons lie on π*(Ru2). Magnetic measurements performed at temperatures of 2-300 K indicate that S = 1 Ru2(II,II) units are weakly antiferromagnetically coupled (zJ = -1.4 cm(-1)) with a large zero-field splitting (D = 221 cm(-1)). PMID:27348516

  14. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    NASA Astrophysics Data System (ADS)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  15. Group 9 Metal Complexes of meso-Aryl-Substituted Rubyrin.

    PubMed

    Soya, Takanori; Osuka, Atsuhiro

    2015-07-20

    Invited for the cover of this issue are Takanori Soya and Atsuhiro Osuka at Kyoto University. The image depicts Group 9 metal (Co, Rh, and Ir) complexes of meso-aryl-substituted rubyrin and a meteorite approaching to the atmosphere. A large amount of Iridium is often contained in meteorites. Read the full text of the article at 10.1002/chem.201501080. PMID:26042817

  16. Dispersion coefficients for H and He interactions with alkali-metal and alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2003-12-01

    The van der Waals coefficients C{sub 6}, C{sub 8}, and C{sub 10} for H and He interactions with the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are determined from oscillator strength sum rules. The oscillator strengths were computed using a combination of ab initio and semiempirical methods. The dispersion parameters generally agree with close to exact variational calculations for Li-H and Li-He at the 0.1% level of accuracy. For larger systems, there is agreement with relativistic many-body perturbation theory estimates of C{sub 6} at the 1% level. These validations for selected systems attest to the reliability of the present dispersion parameters. About half the present parameters lie within the recommended bounds of the Standard and Certain compilation [J. Chem. Phys. 83, 3002 (1985)].

  17. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  18. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-31

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  19. Metal Complexes And Free Radical Toxins Produced By Pfiesteria Piscicida

    SciTech Connect

    Moeller, P.D.R.; Beauchesne, K.R.; Huncik, K.M.; Davis, W.C.; Christopher, S.J.; Riggs-Gelasco, P.; Gelasco, A.K.

    2009-06-03

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICPMS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  20. Metal Complexes and Free Radical Toxins Produced by Pfiesteria piscicida

    SciTech Connect

    Moeller,P.; Beauchesne, K.; Huncik, K.; Davis, W.; Christopher, S.; Riggs-Gelasco, P.; Gelasco, A.

    2007-01-01

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  1. Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities.

    PubMed

    Gutiérrez-Gutiérrez, Silvia C; Coulon, Frédéric; Jiang, Ying; Wagland, Stuart

    2015-08-01

    Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58±6mgkg(-1) for REEs comprising 44±8mgkg(-1) for light REEs, 11±2mgkg(-1) for heavy REEs and 3±1mgkg(-1) for Scandium (Sc) and 3±1.0mgkg(-1) of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are also recovered for reprocessing. PMID:25957938

  2. The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

    SciTech Connect

    Fondeur, F.F.

    2001-01-16

    This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

  3. How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

    NASA Astrophysics Data System (ADS)

    Kam, K.; Lemke, K.

    2014-12-01

    The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with

  4. Rare Earth Complex as Electron Trapper and Energy Transfer Ladder for Efficient Red Iridium Complex Based Electroluminescent Devices.

    PubMed

    Zhou, Liang; Li, Leijiao; Jiang, Yunlong; Cui, Rongzhen; Li, Yanan; Zhao, Xuesen; Zhang, Hongjie

    2015-07-29

    In this work, we experimentally demonstrated the new functions of trivalent rare earth complex in improving the electroluminescent (EL) performances of iridium complex by codoping trace Eu(TTA)3phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) into a light-emitting layer based on PQ2Ir(dpm) (iridium(III)bis(2-phenylquinoly-N,C(2'))dipivaloylmethane). Compared with a reference device, the codoped devices displayed higher efficiencies, slower efficiency roll-off, higher brightness, and even better color purity. Experimental results demonstrated that Eu(TTA)3phen molecules function as electron trappers due to its low-lying energy levels, which are helpful in balancing holes and electrons and in broadening recombination zone. In addition, the matched triplet energy of Eu(TTA)3phen is instrumental in facilitating energy transfer from host to emitter. Finally, highly efficient red EL devices with the highest current efficiency, power efficiency and brightness up to 58.98 cd A(-1) (external quantum efficiency (EQE) of 21%), 61.73 lm W(-1) and 100870 cd m(-2), respectively, were obtained by appropriately decreasing the doping concentration of iridium complex. At certain brightness of 1000 cd m(-2), EL current efficiency up to 51.94 cd A(-1) (EQE = 18.5%) was retained. Our investigation extends the application of rare earth complexes in EL devices and provides a chance to improve the device performances. PMID:26173649

  5. Pressure effects on hydrogen atoms near the metal plane in the HCP phase of rare-earth metal trihydrides

    NASA Astrophysics Data System (ADS)

    Tunghathaithip, N.; Pakornchote, T.; Phaisangittisakul, N.; Bovornratanaraks, T.; Pinsook, U.

    2016-04-01

    Rare-earth metal trihydrides, REH3 (RE=Sc, Y, La), in the hcp phase were investigated under high pressure by the ab initio method. We concentrated on the behavior of hydrogen atoms which is affected by pressure. Two-thirds of the hydrogen atoms near the metal plane (Hm) were found to displace away from the metal plane as pressure increases. The trajectory of these squeezed hydrogen atoms is from a site near the metal plane, and moves past the plane of the tetragonal sites, and heads toward the nearest octahedral site. However, the rate of displacement depends on the local environment. LaH3 exhibits the least impediment on the Hm displacement while YH3 and ScH3 exhibit stronger impediment. Furthermore, our calculated Raman and IR active modes are in general agreement with the experimental data. The displacement of Hm can be used to explain the behavior of the Ov peak in Raman spectra, where it exists at low pressure and disappears at higher pressure in YH3 and ScH3.

  6. Mechanics of metal-catecholate complexes: the roles of coordination state and metal types.

    PubMed

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  7. Complex demodulation in VLBI estimation of high frequency Earth rotation components

    NASA Astrophysics Data System (ADS)

    Böhm, S.; Brzeziński, A.; Schuh, H.

    2012-12-01

    The spectrum of high frequency Earth rotation variations contains strong harmonic signal components mainly excited by ocean tides along with much weaker non-harmonic fluctuations driven by irregular processes like the diurnal thermal tides in the atmosphere and oceans. In order to properly investigate non-harmonic phenomena a representation in time domain is inevitable. We present a method, operating in time domain, which is easily applicable within Earth rotation estimation from Very Long Baseline Interferometry (VLBI). It enables the determination of diurnal and subdiurnal variations, and is still effective with merely diurnal parameter sampling. The features of complex demodulation are used in an extended parameterization of polar motion and universal time which was implemented into a dedicated version of the Vienna VLBI Software VieVS. The functionality of the approach was evaluated by comparing amplitudes and phases of harmonic variations at tidal periods (diurnal/semidiurnal), derived from demodulated Earth rotation parameters (ERP), estimated from hourly resolved VLBI ERP time series and taken from a recently published VLBI ERP model to the terms of the conventional model for ocean tidal effects in Earth rotation recommended by the International Earth Rotation and Reference System Service (IERS). The three sets of tidal terms derived from VLBI observations extensively agree among each other within the three-sigma level of the demodulation approach, which is below 6 μas for polar motion and universal time. They also coincide in terms of differences to the IERS model, where significant deviations primarily for several major tidal terms are apparent. An additional spectral analysis of the as well estimated demodulated ERP series of the ter- and quarterdiurnal frequency bands did not reveal any significant signal structure. The complex demodulation applied in VLBI parameter estimation could be demonstrated a suitable procedure for the reliable reproduction of

  8. Acute metal toxicology of olfaction in coho salmon: behavior, receptors, and odor-metal complexation

    SciTech Connect

    Rehnberg, B.C.; Schreck, C.B.

    1986-04-01

    The objective of this research was to determine the acute toxicities of mercury (Hg), copper (Cu), and zinc (Zn) to coho salmon olfaction. The authors used a behavioral assay of olfaction based on an avoidance reaction to L-serine in a two-choice Y-trough. A second objective was to gain some understanding of the mechanism of metal-induced olfactory inhibition by observing how metals affect the binding of L-serine to its olfactory cell membrane receptor. They have also taken the novel approach of addressing olfactory toxicology from the perspective of the odor molecule by considering metal speciation and metal-serpine complexation chemistry on the basis of chemical equilibrium computations.

  9. Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel-metal-hydride batteries

    NASA Astrophysics Data System (ADS)

    Rodrigues, Luiz Eduardo Oliveira Carmo; Mansur, Marcelo Borges

    The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.2-10.9%), cobalt (5.1-5.5%), rare earth elements (15.3-29.0%) and cadmium (2.8%). The presence of cadmium reveals that some Ni-Cd batteries are possibly labeled as NiMH ones. The leaching of nickel and cobalt from the NiMH battery powder with sulfuric acid is efficient; operating variables temperature and concentration of H 2O 2 has no significant effect for the conditions studied. A mixture of rare earth elements is separated by precipitation with NaOH. Finally, solvent extraction with D2EHPA (di-2-ethylhexyl phosphoric acid) followed by Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) can separate cadmium, cobalt and nickel from the leach liquor. The effect of the main operating variables of both leaching and solvent extraction steps are discussed aiming to maximize metal separation for recycling purposes.

  10. Extractive properties towards rare-earth metal ions of calix[4]arenes substituted at the narrow rim by phosphoryl and amide groups

    SciTech Connect

    Yaftian, M.R.; Burgard, M.; Wieser, C.; Dieleman, C.B.; Matt, D.

    1998-08-01

    The extractive properties of the cone and partial-cone isomers of 5,11,17,23-tetra-tert-butyl-25,27-bis(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphinoylmethoxy)calix[4]arene (cone-1 and partial-cone-1) in 1,2-dichloroethane towards rare-earth metal ions in nitrate media at 25 C were investigated. The analysis of the extraction equilibrium obtained from a mixture of four rare-earths (La, Eu, Er and Y) revealed that the extracted species have a 1:1 metal/ligand ratio for both ligands. The intra-group separation efficiencies of the ligands have been evaluated in a competitive extraction process of 11 rare-earth metal ions (La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb and Y). Significantly higher extractive properties were found for cone-1 with respect to partial-cone-1, suggesting the crucial role of the phosphoryl groups in the complexation of the rare-earth ions.

  11. Metal-dithiocarbamate complexes: chemistry and biological activity.

    PubMed

    Hogarth, Graeme

    2012-10-01

    Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors. PMID:22931592

  12. Water clusters in mixed ionic complexes with metal dipicolinate anions

    NASA Astrophysics Data System (ADS)

    Das, Babulal; Baruah, Jubaraj B.

    2013-02-01

    Formations of three different types of hydrogen-bonded water clusters in the interstices of mixed ionic complexes with metal dipicolinate anions are reported. In the complex [Co(phen)2(H2O)2][Zn(dpa)2]ṡ7H2O (1) (where phen = 1,10-phenanthroline, dpa = dipicolinate), both the cation and anion is hydrophilic in nature, exhibits an unusual 2D infinite cyclic water decamers (H2O)10 stabilized by four identical zinc dipicolinato complex anions. Modulating the cationic unit to a hydrophobic environment by replacing the aqua ligand with 2,2'-bipyridine ligand the water cluster can be modified. The complex [Ni(phen)2ṡbpy][Co(dpa)2]ṡ8H2O (2) (where bpy = 2,2'-bipyridine) has unprecedented discrete hydrogen bonded hexadecameric (H2O)16 water clusters encapsulated between eight anionic units. A rare wavelike infinite water chain (H2O)n is observed in complex [Co(phen)3][Mn(dpa)2]ṡ12H2O (3), in this case the water chain fills the interstitial space created by packing of large hydrophilic anionic units and hydrophobic cationic units. The reported clusters are indefinitely stable in their respective complex at ambient temperature, but the water loss is irreversible when thermally decomposed.

  13. Preparation of molecule-based magnets from metal thiocyanate complexes

    NASA Astrophysics Data System (ADS)

    Shurdha, Endrit

    2011-07-01

    The study of magnetism has enabled many technological applications that are ubiquitous in our daily life. Presently, most of the magnetic applications use metal/metal oxide magnets, which are readily available. In the last few decades, research has focused on a new class of magnetic materials, molecule-based magnets. This class of materials has diverse physical and chemical properties, which can be controlled by synthetic methods. Utilizing a variety of metals and ligands, researchers can control and fine tune various aspects of these magnetic materials, such as structural connections and possibly magnetic properties. Tetracyanoethylene (TCNE) is widely used in the preparation of molecule-based magnets due to its unique electronic and connectivity properties. TCNE has multiple binding sites, which gives it a diverse range of structural connectivity. Also, TCNE can be reduced easily to form a radical anion, which facilitates spin communication between metal centers allowing isolation of magnetically ordered systems such as V(TCNE)2 (a room temperature molecule-based magnet). M-TCNE magnets are prepared from solvated MII complexes or a metal carbonyl and TCNE in dichloromethane. The reaction involves the oxidation of the MII to MIII and the reduction of TCNE. More coordinating solvents used to prepare TCNE molecule-based magnets facilitate the dimerization of the radical TCNE, which does not allow for long-range ordering. The work presented herein will show the synthesis of MII thiocyanate complexes and their reaction with TCNE radical anion to yield M(TCNE)[C4(CN)8]1/2, which is obtained through ligand substitution between TCNE and thiocyanate. The development of new MII thiocyanate complexes through MII(NCMe)x(BF4)2 (x = 4, 6) in acetone, acetonitrile, and tetrahydrofuran will be the focus of Chapter 2. Also, in Chapter 2, structural and magnetic characterization will be discussed. Few of the metal thiocyanate complexes exhibit antiferromagnetic ordering at

  14. Metal–Metal Bonding in Uranium–Group 10 Complexes

    PubMed Central

    2016-01-01

    Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I

  15. [Green electroluminescence generated from a new rare earth complex: Tb(asprin)3phen].

    PubMed

    Duan, N; Zhang, X; Gao, X; Liu, S; Xu, X; Tao, D; Xu, Y; Wu, J

    2001-06-01

    Pure Green and narrow bandwidth emission from organic electroluminescent device was presented by using a new rare earth complex Tb(asprin)3phen as emissive layer. The structure of the device was ITO/PVK:Tb(asprin)3phen/Al, where PVK was used to improve the film-forming ability and conductivity of Tb(asprin)3phen. The electroluminescent property of the device was studied. It proved that this new kind of rare earth complex has excellent optoluminescent and electroluminescent properties. The electroluminescent mechanism of the device was proposed by measuring and analyzing the emission and excitation spectra of the emissive layer. The excitation spectrum of Tb(asprin)3phen-dispersed PVK film was very similar to that of the PVK. We proposed that the excited carriers of PVK and Tb(asprin)3phen were captured by Tb3+ and light was emitted when the electrons and holes recombined at Tb3+. PMID:12947642

  16. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    NASA Astrophysics Data System (ADS)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  17. Controlling the metal insulator transition using the ferroelectric field effect in rare earth nickelates

    NASA Astrophysics Data System (ADS)

    Marshall, Matthew; Disa, Ankit; Kumah, Divine; Chen, Hanghui; Ismail-Beigi, Sohrab; Walker, Fred; Ahn, Charles

    2013-03-01

    A ferroelectric field effect transistor (FE-FET) modulates conductivity in a non-volatile manner by electrostatically accumulating and depleting charge carriers at the interface between a conducting channel and ferroelectric gate. The rare earth nickelate LaNiO3 is metallic in bulk, while other rare earth nickelates, such as NdNiO3, exhibit metal-insulator transitions and anti-ferromagnetic behavior in the bulk. Here, we show that by coupling the ferroelectric polarization of Pb0.8Zr0.2TiO3 (PZT) to the carriers in a nickelate, we can dynamically induce a metal- insulator transition in ultra-thin films of LaNiO3, and induce large changes in the MIT transition temperature in NdNiO3. Density functional theory is used to determine changes in the physical and electronic Ni-O-Ni bond angle of the nickelate at the interface between PZT and LaNiO3. The effect of the ferroelectric polarization is to decrease the Ni-O-Ni bond angle from 180 degrees and increase the carrier effective mass. Related to this change in electronic structure, we observe a change in resistivity of approximately 80% at room temperature for an ultra-thin 3 unit cell thick film of LaNiO3. Work supported by FENA and the NSF under MRSEC DMR 1119826.

  18. Moderate pressure synthesis of rare earth nickelate with metal-insulator transition using polymeric precursors

    NASA Astrophysics Data System (ADS)

    Napierala, C.; Lepoittevin, C.; Edely, M.; Sauques, L.; Giovanelli, F.; Laffez, P.; VanTedeloo, G.

    2010-07-01

    Rare earth nickelates exhibit a reversible metal-semiconductor phase transition that is, in the infrared range, responsible for a thermo-optical contrast. The state of the art synthesis of these compounds usually requires high oxygen pressure to stabilize Ni in the oxidation state 3 +. In this work, using polymeric precursor associated with moderate pressure annealing, we show that it is possible to obtain fully oxidized rare earth nickelate with metal-insulator transition. Using thermogravimetric analysis, X-ray diffraction and transmission electronic microscopy we compare different samples synthesized at different oxygen pressures and demonstrate their structural similarity. Thermo-optical properties were measured, in the infrared range, using reflectance measurements and confirmed the metal-insulator transition at 60 °C in both samples.TEM observations lead to the conclusion that the structure commonly obtained at 175 bar is perfectly observed in the 20 bar sample without major structural defects. The two samples exhibit a thermochromic behavior and thermo-optical properties of the two samples are equivalent.

  19. High-pressure metallization of FeO and implications for the earth's core

    NASA Technical Reports Server (NTRS)

    Knittle, Elise; Jeanloz, Raymond

    1986-01-01

    The phase diagram of FeO has been experimentally determined to pressures of 155 GPa and temperatures of 4000 K using shock-wave and diamond-cell techniques. A metallic phase of FeO is observed at pressures greater than 70 GPa and temperatures exceeding 1000 K. The metallization of FeO at high pressures implies that oxygen can be present as the light alloying element of the earth's outer core, in accord with the geochemical predictions of Ringwood (1977 and 1979). The high pressures necessary for this metallization suggest that the core has acquired its composition well after the initial stages of the earth's accretion. Direct experimental observations at elevated pressures and temperatures indicate that core-forming alloy can react chemically with oxides such as those forming the mantle. The core and mantle may never have reached complete chemical equilibrium, however. If this is the case, the core-mantle boundary is likely to be a zone of active chemical reactions.

  20. Structural models for alkali-metal complexes of polyacetylene

    NASA Astrophysics Data System (ADS)

    Murthy, N. S.; Shacklette, L. W.; Baughman, R. H.

    1990-02-01

    Structural models for a stage-2 complex are proposed for polyacetylene doped with less than about 0.1 potassium or rubidium atoms per carbon. These structures utilize as a basic motif an alkali-metal column surrounded by four planar-zig-zag polyacetylene chains, a structure found at the highest dopant levels. In the new stage-2 structures, each polyacetylene chain neighbors only one alkali-metal column, so the phase contains four polymer chains per alkali-metal column. Basic structural aspects for stage-1 and stage-2 structures are now established for both potassium- and rubidium-doped polyacetylene. X-ray-diffraction and electrochemical data show that undoped and doped phases coexist at low dopant concentrations (<0.06 K atom per C). X-ray-diffraction data, down to a Bragg spacing of 1.3 Å, for polyacetylene heavily doped with potassium (0.125-0.167 K atom per C) is fully consistent with our previously proposed stage-1 tetragonal unit cell containing two polyacetylene chains per alkali-metal column. There is no evidence for our samples requiring a distortion to a monoclinic unit cell as reported by others for heavily doped samples. The nature of structural transformations and the relationship between structure and electronic properties are discussed for potassium-doped polyacetylene.

  1. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  2. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  3. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  4. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-01-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: [3]Li+, [3]Na+, [4]K+, [4]Rb+, [6]Cs+, [3]Be2+, [4]Mg2+, [6]Ca2+, [6]Sr2+ and [6]Ba2+, but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of [6]Na+, the ratio U eq(Na)/U eq(bonded anions) is partially correlated with 〈[6]Na+—O2−〉 (R 2 = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li+ in [4]- and [6]-coordination, Na+ in [4]- and [6

  5. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

  6. Extent of metal-silicate disequilibrium during accretion and early differentiation of the Earth

    NASA Astrophysics Data System (ADS)

    Rubie, D. C.; Nimmo, F.; Morbidelli, A.; Frost, D. J.

    2012-12-01

    Earth, Mars, Venus and Mercury accreted on a timescale of 10-100 My through a series of violent collisions with planetesimals and embryos. The high energy of such impacts was sufficient to cause deep magma ocean formation which facilitated the segregation of metal and silicate liquids. Planetary cores thus formed as a multistage process that was inseparable from the accretion process. In order to better understand the formation and early differentiation of the terrestrial planets, we are integrating a multistage core-formation model with N-body accretion simulations. Constraints on model parameters are the compositions of the Earth's primitive mantle and, to a lesser extent, the mantles of Mars and Mercury which may be FeO rich and FeO-poor respectively. We use a least-squares minimization to optimise 4 model parameters. Elements currently considered include Si, O, Ni, Co, W, Nb, Cr, Ta and V. We concentrate on recent N-body simulations that result in an approximately Earth-mass planet at ~1 AU. In order to satisfy the model constraints, accretion has to be heterogeneous, with embryos and planetesimals originating in the inner part of the solar system (e.g. <1.5 AU) being highly reduced and those from further out being more oxidised. Metal-silicate equilibration pressures are high (e.g. ~0.75 x evolving CMB pressures). The model enables estimations of (1) the extent to which the metallic cores of impactors emulsify and equilibrate in a magma ocean and (2) the fraction of magma oceans that are involved in the equilibration process for both impacting planetesimals and embryos. Both estimates are crucial for interpreting Hf-W age determinations. Best results are obtained when the fraction of silicate mantle/magma ocean that interacts chemically with the metallic cores of impactors is limited and lies in the range 0.003 to 0.1, depending on the size of the impactor and magma ocean depth. The degree of incomplete metal equilibration depends on the extent to which the

  7. Chemical bonding of hydrogen molecules to transition metal complexes

    SciTech Connect

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 3} = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H{sub 2} exchanges easily with D{sub 2}. This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 2} were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig.

  8. Complex metal borohydrides: multifunctional materials for energy storage and conversion.

    PubMed

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world's energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future. PMID:27384871

  9. Exciton complexes in low dimensional transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Thilagam, A.

    2014-08-01

    We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton.

  10. Exciton complexes in low dimensional transition metal dichalcogenides

    SciTech Connect

    Thilagam, A.

    2014-08-07

    We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton.

  11. Coordination Programming of Two-Dimensional Metal Complex Frameworks.

    PubMed

    Maeda, Hiroaki; Sakamoto, Ryota; Nishihara, Hiroshi

    2016-03-22

    Since the discovery of graphene, two-dimensional materials with atomic thickness have attracted much attention because of their characteristic physical and chemical properties. Recently, coordination nanosheets (CONASHs) came into the world as new series of two-dimensional frameworks, which can show various functions based on metal complexes formed by numerous combinations of metal ions and ligands. This Feature Article provides an overview of recent progress in synthesizing CONASHs and in elucidating their intriguing electrical, sensing, and catalytic properties. We also review recent theoretical studies on the prediction of the unique electronic structures, magnetism, and catalytic ability of materials based on CONASHs. Future prospects for applying CONASHs to novel applications are also discussed. PMID:26915925

  12. Complex metal borohydrides: multifunctional materials for energy storage and conversion

    NASA Astrophysics Data System (ADS)

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world’s energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  13. Metal complex modified azo polymers for multilevel organic memories

    NASA Astrophysics Data System (ADS)

    Ma, Yong; Chen, Hong-Xia; Zhou, Feng; Li, Hua; Dong, Huilong; Li, You-Yong; Hu, Zhi-Jun; Xu, Qing-Feng; Lu, Jian-Mei

    2015-04-01

    Multilevel organic memories have attracted considerable interest due to their high capacity of data storage. Despite advances, the search for multilevel memory materials still remains a formidable challenge. Herein, we present a rational design and synthesis of a class of polymers containing an azobenzene-pyridine group (PAzo-py) and its derivatives, for multilevel organic memory storage. In this design, a metal complex (M(Phen)Cl2, M = Cu, Pd) is employed to modify the HOMO-LUMO energy levels of azo polymers, thereby converting the memory state from binary to ternary. More importantly, this approach enables modulating the energy levels of azo polymers by varying the coordination metal ions. This makes the achievement of high performance multilevel memories possible. The ability to tune the bandgap energy of azo polymers provides new exciting opportunities to develop new materials for high-density data storage.Multilevel organic memories have attracted considerable interest due to their high capacity of data storage. Despite advances, the search for multilevel memory materials still remains a formidable challenge. Herein, we present a rational design and synthesis of a class of polymers containing an azobenzene-pyridine group (PAzo-py) and its derivatives, for multilevel organic memory storage. In this design, a metal complex (M(Phen)Cl2, M = Cu, Pd) is employed to modify the HOMO-LUMO energy levels of azo polymers, thereby converting the memory state from binary to ternary. More importantly, this approach enables modulating the energy levels of azo polymers by varying the coordination metal ions. This makes the achievement of high performance multilevel memories possible. The ability to tune the bandgap energy of azo polymers provides new exciting opportunities to develop new materials for high-density data storage. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00871a

  14. Investigations of charge-separation processes in metal complexes

    SciTech Connect

    Crosby, G.A.

    1991-02-18

    The major thrust of the research has been the quantification of the excited states of inorganic complexes that display potential for mediating charge-separation processes. Investigations of copper(1) mixed-ligand complexes have been completed. Non-equilibrated emitting states have been assigned. Chemical tuning of the emission energy by modifying the basicity of the donor ligand on the metal has been achieved. Structure-property relationships have been defined for crystalline complexes of zinc containing both diimine and monothiol ligands. Correlation of the spectral shifts with the rotations of the thiol phenyl rings in different crystal phases has been shown by comparing with extended Huckel calculations and x-ray structures. Complexes of zinc containing diimine and dithiol ligands are shown to be polynuclear species. A trinuclear species can be forced to assume a binuclear structure by incorporating other non-coordinating ligands into the lattice. The transformation is accompanied by substantial photophysical changes. Syntheses and x-ray structure determinations of platinum(2) complexes containing diimine ligands only, both diimine and dithiol ligands, and dithiol ligands only have been completed. An unusual platinum(3) bis(dithiol) species has been obtained and its structure determined. Investigations of the emission spectra of bis(bipyridine)platinum(2) have revealed the existence of multiple emitting states with both ligand-localized and charge- transfer characteristics.

  15. Surface location of alkaline-earth-metal-atom impurities on helium nanodroplets

    NASA Astrophysics Data System (ADS)

    Ren, Yanfei; Kresin, Vitaly V.

    2007-10-01

    There has been notable uncertainty regarding the degree of solvation of alkaline-earth-metals atoms, especially Mg, in free He4 nanodroplets. We have measured the electron energy dependence of the ionization yield of picked-up atoms. There is a qualitative shape difference between the yield curves of species solvated in the middle of the droplet and species located in the surface region; this difference arises from the enhanced role played by the Penning ionization process in the latter case. The measurements demonstrate that Mg, Ca, Sr, and Ba all reside at or near the droplet surface.

  16. Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

    DOEpatents

    Epperly, William R.; Deane, Barry C.; Brunson, Roy J.

    1982-01-01

    An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

  17. Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

    SciTech Connect

    Brunson, R.J.; Deane, B.C.; Epperly, W.R.

    1982-06-01

    An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

  18. Surface location of alkaline-earth-metal-atom impurities on helium nanodroplets

    SciTech Connect

    Ren Yanfei; Kresin, Vitaly V.

    2007-10-15

    There has been notable uncertainty regarding the degree of solvation of alkaline-earth-metals atoms, especially Mg, in free {sup 4}He nanodroplets. We have measured the electron energy dependence of the ionization yield of picked-up atoms. There is a qualitative shape difference between the yield curves of species solvated in the middle of the droplet and species located in the surface region; this difference arises from the enhanced role played by the Penning ionization process in the latter case. The measurements demonstrate that Mg, Ca, Sr, and Ba all reside at or near the droplet surface.

  19. Oxygen activation with transition metal complexes in aqueous solution

    SciTech Connect

    Bakac, Andreja

    2010-04-12

    Coordination to transition-metal complexes changes both the thermodynamics and kinetics of oxygen reduction. Some of the intermediates (superoxo, hydroperoxo, and oxo species) are close analogues of organic oxygen-centered radicals and peroxides (ROO{sm_bullet}, ROOH, and RO{sm_bullet}). Metal-based intermediates are typically less reactive, but more persistent, than organic radicals, which makes the two types of intermediates similarly effective in their reactions with various substrates. The self-exchange rate constant for hydrogen-atom transfer for the couples Cr{sub aq}OO{sup 2+}/Cr{sub aq}OOH{sup 2+} and L{sup 1}(H{sub 2}O)RhOO{sup 2+}/L{sup 1}(H{sub 2}O)RhOOH{sup 2+} was estimated to be 10{sup 1 {+-} 1} M{sup -1} s{sup -1}. The use of this value in the simplified Marcus equation for the Cr{sub aq}O{sup 2+}/Cr{sub aq}OOH{sup 2+} cross reaction provided an upper limit k{sub CrO,CrOH} {le} 10{sup (-2{+-}1)} M{sup -1} s{sup -1} for Cr{sub aq}O{sup 2+}/Cr{sub aq}OH{sup 2+} self-exchange. Even though superoxo complexes react very slowly in bimolecular self-reactions, extremely fast cross reactions with organic counterparts, i.e., acylperoxyl radicals, have been observed. Many of the intermediates generated by the interaction of O{sub 2} with reduced metal complexes can also be accessed by alternative routes, both thermal and photochemical.

  20. Molecular electrocatalysts for oxidation of hydrogen using earth-abundant metals: shoving protons around with proton relays.

    PubMed

    Bullock, R Morris; Helm, Monte L

    2015-07-21

    Sustainable, carbon-neutral energy is needed to supplant the worldwide reliance on fossil fuels in order to address the persistent problem of increasing emissions of CO2. Solar and wind energy are intermittent, highlighting the need to develop energy storage on a huge scale. Electrocatalysts provide a way to convert between electrical energy generated by renewable energy sources and chemical energy in the form of chemical bonds. Oxidation of hydrogen to give two electrons and two protons is carried out in fuel cells, but the typical catalyst is platinum, a precious metal of low earth abundance and high cost. In nature, hydrogenases based on iron or iron/nickel reversibly oxidize hydrogen with remarkable efficiencies and rates. Functional models of these enzymes have been synthesized with the goal of achieving electrocatalytic H2 oxidation using inexpensive, earth-abundant metals along with a key feature identified in the [FeFe]-hydrogenase: an amine base positioned near the metal. The diphosphine ligands P(R)2N(R')2 (1,5-diaza-3,7-diphosphacyclooctane with alkyl or aryl groups on the P and N atoms) are used as ligands in Ni, Fe, and Mn complexes. The pendant amines facilitate binding and heterolytic cleavage of H2, placing the hydride on the metal and the proton on the amine. The pendant amines also serve as proton relays, accelerating intramolecular and intermolecular proton transfers. Electrochemical oxidations and deprotonations by an exogeneous amine base lead to catalytic cycles for oxidation of H2 (1 atm) at room temperature for catalysts derived from [Ni(P(Cy)2N(R')2)2](2+), Cp(C6F5)Fe(P(tBu)2N(Bn)2)H, and MnH(P(Ph)2N(Bn)2)(bppm)(CO) [bppm = (PAr(F)2)2CH2]. In the oxidation of H2 catalyzed by [Ni(P(Cy)2N(R')2)2](2+), the initial product observed experimentally is a Ni(0) complex in which two of the pendant amines are protonated. Two different pathways can occur from this intermediate; deprotonation followed by oxidation occurs with a lower overpotential than

  1. Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C-N bond formation reactions.

    PubMed

    Zhao, Bei; Xiao, Yang; Yuan, Dan; Lu, Chengrong; Yao, Yingming

    2016-03-01

    Based on three bisamide proligands H2Ln (n = 1–3) (H2L1 = [(Me3C6H2CONHCH2)2CH2], H2L2 = [(Me3C6H2CONHCH2)2C(CH3)2], H2L3 = [Me3C6H2CONH(CH2)2]2NCH3), eight bis(amidato) trivalent rare-earth metal amides {LnRE[N(TMS)2]}2 (n = 1, RE = La (1), Sm (2), Nd (3), Y (4); n = 2, RE = La (5), Nd (6);n = 3, RE = La (7), Nd (8); TMS = SiMe3) were successfully synthesized by treatment of H2Ln with RE[N(TMS)2]3 in a 1 : 1 molar ratio. Complexes 3, and 5–8 were characterized by single-crystal X-ray diffraction, and NMR characterization was carried out for the La complexes 1, 5, 7 and the Y complex 4. These complexes exhibited high catalytic activities in both the direct amidation of aldehydes and the addition of amines with carbodiimine. It was found that the bis(amidato) rare earth metal amides bearing different linkers have different effects on the transformations and lanthanum and neodymium complexes performed better than others. PMID:26906617

  2. APPROACHING THE HARTREE-FOCK LIMIT FOR ORGANOTRANSITION METAL COMPLEXES

    SciTech Connect

    Schaefer, III., Henry F.

    1980-09-01

    In theoretical studies of the electronic structure of organometallic complexes, the choice of basis set is critical, much more so than for analogous studies of molecules containing only H, C, N, and O. This problem is discussed in light of structural predictions for the transition metal hydrides MH, MH{sub 2}, and MH{sub 4}, for the fluorides MF{sub 2} and MF{sub 3}, for Ni(CO){sub 4}, Ni(C{sub 2}H{sub 4}){sub 3}, (CO){sub 3}NiCH{sub 2} , and Ni(C{sub 5}H{sub 5}){sub 2}.

  3. Long tailed cage amines: Synthesis, metal complexation, and structure

    SciTech Connect

    Dittrich, Birger; Harrowfield, Jack M.; Koutsantonis, George A.; Nealon, Gareth L.; Skelton, Brian W.

    2011-12-09

    The generation of amphiphiles derived from macrobicyclic hexamines of the 'sarcophagine' class can be prepared through efficient and selective reactions involving the reductive alkylation, using long-chain aldehydes, of amino-functionalized sarcophagines when bound to Cu(II) or Mg(II). The Mg(II) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of one of the free (protonated) ligands and some of their complexes.

  4. Hybridization wave as the cause of the metal-insulator transition in rare earth nickelates

    NASA Astrophysics Data System (ADS)

    Park, Hyowon; Marianetti, Chris A.; Millis, Andrew J.

    2012-02-01

    The metal-insulator transition driven by varying rare earth (Re) ion in ReNiO3 has been a longstanding challenge to materials theory. Experimental evidence suggesting charge order is seemingly incompatible with the strong Mott-Hubbard correlations characteristic of transition metals. We present density functional, Hartree-Fock and Dynamical Mean field calculations showing that the origin of the insulating phase is a hybridization wave, in which a two sublattice ordering of the oxygen breathing mode produces two Ni sites with almost identical Ni d-charge densities but very different magnetic moments and other properties. The high temperature crystal structure associated with smaller Re ions such as Lu is shown to be more susceptible to the distortion than the high temperature structure associated with larger Re ions such as La.

  5. The contents of alkali and alkaline earth metals in soils of the southern Cis-Ural region

    NASA Astrophysics Data System (ADS)

    Asylbaev, I. G.; Khabirov, I. K.

    2016-01-01

    The contents and distribution patterns of alkali and alkaline earth metals in soils and rocks of the southern Cis-Ural region were studied. A database on the contents of these metals was developed, the soils were classified with respect to their provision with these metals, and corresponding schematic maps showing their distribution in soils of the region were compiled. It was found that the contents of these metals decrease from east to west (from the Yuryuzan-Aisk Piedmont Plain to the Ufa Plateau and to the Belebeevsk Upland), and their distribution patterns change. Among alkali metals, the highest accumulation in the soils is typical of potassium, sodium, and cesium; among alkaline earth metals, of strontium and barium.

  6. Infra-red spectroscopic characteristics of naphthalocyanine in bis(naphthalocyaninato) rare earth complexes peripherally substituted with thiophenyl derivatives

    NASA Astrophysics Data System (ADS)

    Li, Xiaobo; Mao, Yajun; Xiao, Chi; Lu, Fanli

    2015-04-01

    The infra-red (IR) spectroscopic data for a series of eleven rare earth double-deckers MIII[Nc(SPh)8]2 (M = Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er) have been collected and systematically investigated. For MIII[Nc(SPh)8]2, typical IR marker bands for the naphthalocyanine anion radical [Nc(SPh)8]rad - were observed at 1317-1325 cm-1 as the most intense absorption bands, which can be attributed to the pyrrole stretching. As for Ce[Nc(SPh)8]2, the typical IR marker band was also observed at 1317 cm-1, which shows that the cerium complex exists as the form of CeIII[Nc(SPh)8]2-[Nc(SPh)8]rad -. In addition, both the Q-bands of electronic absorption spectra and the typical IR absorption bands of naphthalocyanine radical anion [Nc(SPh)8]rad - move to the high energy as the decrease of rare earth metal ionic radius. These facts suggest that the π-π electron interaction in these double-deckers becomes stronger along with the lanthanide contraction.

  7. A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State.

    PubMed

    Chapman, Michael R; Henkelis, Susan E; Kapur, Nikil; Nguyen, Bao N; Willans, Charlotte E

    2016-08-01

    Synthetic methods to prepare organometallic and coordination compounds such as Schiff-base complexes are diverse, with the route chosen being dependent upon many factors such as metal-ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal-salen/salan complexes which comprise diverse metal-ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (M(II/III/IV) where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol-switch is described which allows access to analytically pure Fe(II/III)-salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers Mn(II/IV)-salen complexes in high yield. PMID:27547645

  8. Photophysical investigation of palladium(II) ortho-metalated complexes

    SciTech Connect

    Craig, C.A.; Watts, R.J. )

    1989-01-25

    Syntheses and structural characterizations of four complexes of Pd(II) with ortho-metalated 2-phenylpyridinate (ppy{sup minus}) are reported. These complexes include a parent dimer, (Pd(ppy)Cl){sub 2}, and three derivative monomers, (Pd(ppy)(bpy))Cl, (Pd(ppy)(en))Cl, and (Pd(ppy)(CO)Cl), whereby = 2,2'-bipyridine and en = ethylenediamine. Photophysical characterizations of these species indicate low-energy absorption bands ({approximately}360 nm) and emission bands at 77 K ({approximately}460 nm) that are assigned to transitions located on the ppy{sup {minus}} ligand. Some evidence for low-energy charge-transfer states is found in trends in luminescence lifetimes. 2 tabs., 5 figs., 21 refs.

  9. Metal Complexes of meso-meso Linked Corrole Dimers.

    PubMed

    Ooi, Shota; Tanaka, Takayuki; Osuka, Atsuhiro

    2016-09-01

    Cobalt, gallium, silver, and copper complexes of 5,5'-linked corrole dimer 1 and 10,10'-linked corrole dimer 2 were synthesized by metalations with Co(OAc)2·4H2O, GaCl3, AgOAc, and Cu(OAc)2·H2O, respectively, in good yields. The structures of cobalt(III), gallium(III), and silver(III) complexes have been unambiguously revealed by X-ray diffraction analysis. Their optical and electrochemical properties have been studied, which revealed different electronic interactions between the two corrole units depending upon the positions of meso-meso linkage and axial-ligand coordination modes. PMID:27533780

  10. Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

    SciTech Connect

    Morf, Leo S.; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Lorenzo, Fabian Di; Böni, Daniel

    2013-03-15

    Highlights: ► We carefully addressed all the very valuable comments and suggestions of the reviewers. ► We also have shortened the size of the paper and tried simplify it substantially, as requested by the reviewers (introduction 25% reduced!). ► We have decided to take the chance and have replaced the data for the “additional” elements (Cu, Cd, Zn, Pb, Sn, Cr, Ni, Fe, Al) of the earlier MFA (Morf, 2011) with data that belong to the samples of this study. ► We are convinced that with the revision the paper has significantly improved in quality and attractiveness. - Abstract: In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are

  11. Simulation of the mobility of metal - EDTA complexes in groundwater: The influence of contaminant metals

    USGS Publications Warehouse

    Friedly, J.C.; Kent, D.B.; Davis, J.A.

    2002-01-01

    Reactive transport simulations were conducted to model chemical reactions between metal - EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz - sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium - EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created bythe sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal - hydroxypolymer coatings on the aquifer sediments by the metal - EDTA complexes was kinetically restricted. All other reactions, including metal - EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal - EDTA complexes was less important than the fact that these reactions are rate controlled. Results

  12. Radical AdoMet enzymes in complex metal cluster biosynthesis.

    PubMed

    Duffus, Benjamin R; Hamilton, Trinity L; Shepard, Eric M; Boyd, Eric S; Peters, John W; Broderick, Joan B

    2012-11-01

    Radical S-adenosylmethionine (AdoMet) enzymes comprise a large superfamily of proteins that engage in a diverse series of biochemical transformations through generation of the highly reactive 5'-deoxyadenosyl radical intermediate. Recent advances into the biosynthesis of unique iron-sulfur (FeS)-containing cofactors such as the H-cluster in [FeFe]-hydrogenase, the FeMo-co in nitrogenase, as well as the iron-guanylylpyridinol (FeGP) cofactor in [Fe]-hydrogenase have implicated new roles for radical AdoMet enzymes in the biosynthesis of complex inorganic cofactors. Radical AdoMet enzymes in conjunction with scaffold proteins engage in modifying ubiquitous FeS precursors into unique clusters, through novel amino acid decomposition and sulfur insertion reactions. The ability of radical AdoMet enzymes to modify common metal centers to unusual metal cofactors may provide important clues into the stepwise evolution of these and other complex bioinorganic catalysts. This article is part of a Special Issue entitled: Radical SAM enzymes and Radical Enzymology. PMID:22269887

  13. Three-photon process for producing a degenerate gas of metastable alkaline-earth-metal atoms

    NASA Astrophysics Data System (ADS)

    Barker, D. S.; Pisenti, N. C.; Reschovsky, B. J.; Campbell, G. K.

    2016-05-01

    We present a method for creating a quantum degenerate gas of metastable alkaline-earth-metal atoms. This has yet to be achieved due to inelastic collisions that limit evaporative cooling in the metastable states. Quantum degenerate samples prepared in the 1S0 ground state can be rapidly transferred to either the 3P2 or 3P0 state via a coherent three-photon process. Numerical integration of the density-matrix evolution for the fine structure of bosonic alkaline-earth-metal atoms shows that transfer efficiencies of ≃90 % can be achieved with experimentally feasible laser parameters in both Sr and Yb. Importantly, the three-photon process can be set up such that it imparts no net momentum to the degenerate gas during the excitation, which will allow for studies of metastable samples outside the Lamb-Dicke regime. We discuss several experimental challenges to successfully realizing our scheme, including the minimization of differential ac Stark shifts between the four states connected by the three-photon transition.

  14. A high pressure low temperature study on rare earth compounds: Semiconductor to metal transition

    NASA Astrophysics Data System (ADS)

    Neuenschwander, J.; Wachter, P.

    1990-01-01

    This work studies the pressure induced semiconductor to metal transition (SMT) in several rare earth compounds. This SMT is accompanied by a valence instability. Single crystalline semiconducting TmSe 1- xTe x, Tm 1- xEu xSe and SmS 1- xSe x alloys are investigated under high pressure at low temperatures. Measurements of electrical resistivity, magnetic susceptibility, neutron diffraction, volume and optical properties are presented and discussed. A very unusual peak structure in the resistivity-pressure relation of TmSe 1- xTe x at low temperatures is observed. A discussion of the novel feature involves the concept of the excitonic insulator and f-d hybridization. The magnetic behavior of the Tm and Eu based compounds is significantly influenced by the SMT. This is thought to be mainly due to the additional coupling between the rare earth moments via free carriers which are present in the metallic state. In SmS 1- xSe x a considerable softening of the lattice is observed before the valence transition occurs. It is speculated that Poisson's ratio might become negative already in the semiconducting state.

  15. A high pressure low temperature study on rare earth compounds: Semiconductor to metal transition

    NASA Astrophysics Data System (ADS)

    Neuenschwander, J.; Wachter, P.

    1989-12-01

    This work studies the pressure induced semiconductor to metal transition (SMT) in several rare earth compounds. This SMT is accompanied by a valence instability. Single crystalline semiconducting TmSe1-xTex, Tm1-xEuxSe and SmS1-xSex alloys are investigated under high pressure at low temperatures. Measurements of electrical resistivity, magnetic susceptibility, neutron diffraction, volume and optical properties are presented and discussed. A very unusual peak structure in the resistivity-pressure relation of TmSe1-xTex at low temperatures is observed. A discussion of the novel feature involves the concept of the excitonic insulator and f-d hybridization. The magnetic behavior of the Tm and Eu based compounds is significantly influenced by the SMT. This is thought to be mainly due to the additional coupling between the rare earth moments via free carriers which are present in the metallic state. In SmS1-xSex a considerable softening of the lattice is observed before the valence transition occurs. It is speculated that Poisson's ratio might become negative already in the semiconducting state.

  16. Matrix diffusion of some alkali- and alkaline earth-metals in granitic rock

    SciTech Connect

    Johansson, H.; Byegaard, J.; Skarnemark, G.; Skaalberg, M.

    1997-12-31

    Static through-diffusion experiments were performed to study the diffusion of alkali- and alkaline earth-metals in fine-grained granite and medium-grained Aespoe-diorite. Tritiated water was used as an inert reference tracer. Radionuclides of the alkali- and alkaline earth-metals (mono- and divalent elements which are not influenced by hydrolysis in the pH-range studied) were used as tracers, i.e., {sup 22}Na{sup +}, {sup 45}Ca{sup 2+} and {sup 85}Sr{sup 2+}. The effective diffusivity and the rock capacity factor were calculated by fitting the breakthrough curve to the one-dimensional solution of the diffusion equation. Sorption coefficients, K{sub d}, that were derived from the rock capacity factor (diffusion experiments) were compared with K{sub d} determined in batch experiments using crushed material of different size fractions. The results show that the tracers were retarded in the same order as was expected from the measured batch K{sub d}. Furthermore, the largest size fraction was the most representative when comparing batch K{sub d} with K{sub d} evaluated from the diffusion experiments. The observed effective diffusivities tended to decrease with increasing cell lengths, indicating that the transport porosity decreases with increasing sample lengths used in the diffusion experiments.

  17. Ab initio calculation of molecular field interactions in rare-earth transition-metal intermetallics (invited)

    NASA Astrophysics Data System (ADS)

    Brooks, M. S. S.; Gasche, T.; Auluck, S.; Nordström, L.; Severin, L.; Trygg, J.; Johansson, B.

    1991-11-01

    The interaction, KRM, between the rare-earth 4f moment and the transition-metal 3d moments in rare-earth transition-metal intermetallics is shown to depend upon the R-5d moment, which is due to 3d-5d hybridization, and local 4f-5d exchange integrals. Both the R-5d moment and KRM may be calculated ab initio from the local spin-density approximation to density functional theory in self-consistent energy-band calculations with the localized 4f-moments fixed at their Russel-Saunders values. Detailed examples are given for the RFe2 (R=Gd-Yb) series. The exchange integrals are similar to those entering into the density functional version of Stoner theory and their energy dependence must be treated carefully. The calculated local exchange integrals are shown to be related to the molecular fields derived from spin Hamiltonians, hence to the spin-wave spectra. Reasonable agreement with values of the molecular fields extracted from inelastic neutron scattering and high field susceptibility measurements is obtained.

  18. The atmospheric circulation of the super Earth GJ 1214b: Dependence on composition and metallicity

    SciTech Connect

    Kataria, T.; Showman, A. P.; Fortney, J. J.; Marley, M. S.; Freedman, R. S.

    2014-04-20

    We present three-dimensional atmospheric circulation models of GJ 1214b, a 2.7 Earth-radius, 6.5 Earth-mass super Earth detected by the MEarth survey. Here we explore the planet's circulation as a function of atmospheric metallicity and atmospheric composition, modeling atmospheres with a low mean molecular weight (MMW; i.e., H{sub 2}-dominated) and a high MMW (i.e., water- and CO{sub 2}-dominated). We find that atmospheres with a low MMW have strong day-night temperature variations at pressures above the infrared photosphere that lead to equatorial superrotation. For these atmospheres, the enhancement of atmospheric opacities with increasing metallicity lead to shallower atmospheric heating, larger day-night temperature variations, and hence stronger superrotation. In comparison, atmospheres with a high MMW have larger day-night and equator-to-pole temperature variations than low MMW atmospheres, but differences in opacity structure and energy budget lead to differences in jet structure. The circulation of a water-dominated atmosphere is dominated by equatorial superrotation, while the circulation of a CO{sub 2}-dominated atmosphere is instead dominated by high-latitude jets. By comparing emergent flux spectra and light curves for 50× solar and water-dominated compositions, we show that observations in emission can break the degeneracy in determining the atmospheric composition of GJ 1214b. The variation in opacity with wavelength for the water-dominated atmosphere leads to large phase variations within water bands and small phase variations outside of water bands. The 50× solar atmosphere, however, yields small variations within water bands and large phase variations at other characteristic wavelengths. These observations would be much less sensitive to clouds, condensates, and hazes than transit observations.

  19. The Atmospheric Circulation of the Super Earth GJ 1214b: Dependence on Composition and Metallicity

    NASA Astrophysics Data System (ADS)

    Kataria, T.; Showman, A. P.; Fortney, J. J.; Marley, M. S.; Freedman, R. S.

    2014-04-01

    We present three-dimensional atmospheric circulation models of GJ 1214b, a 2.7 Earth-radius, 6.5 Earth-mass super Earth detected by the MEarth survey. Here we explore the planet's circulation as a function of atmospheric metallicity and atmospheric composition, modeling atmospheres with a low mean molecular weight (MMW; i.e., H2-dominated) and a high MMW (i.e., water- and CO2-dominated). We find that atmospheres with a low MMW have strong day-night temperature variations at pressures above the infrared photosphere that lead to equatorial superrotation. For these atmospheres, the enhancement of atmospheric opacities with increasing metallicity lead to shallower atmospheric heating, larger day-night temperature variations, and hence stronger superrotation. In comparison, atmospheres with a high MMW have larger day-night and equator-to-pole temperature variations than low MMW atmospheres, but differences in opacity structure and energy budget lead to differences in jet structure. The circulation of a water-dominated atmosphere is dominated by equatorial superrotation, while the circulation of a CO2-dominated atmosphere is instead dominated by high-latitude jets. By comparing emergent flux spectra and light curves for 50× solar and water-dominated compositions, we show that observations in emission can break the degeneracy in determining the atmospheric composition of GJ 1214b. The variation in opacity with wavelength for the water-dominated atmosphere leads to large phase variations within water bands and small phase variations outside of water bands. The 50× solar atmosphere, however, yields small variations within water bands and large phase variations at other characteristic wavelengths. These observations would be much less sensitive to clouds, condensates, and hazes than transit observations.

  20. Manganese Complexes of 1,3,5-triaza-7-phosphaadamantane (PTA): The First Nitrogen Bound Transition Metal Complex of PTA

    SciTech Connect

    Frost,B.; Bautista, C.; Huang, R.; Shearer, J.

    2006-01-01

    The structures of two manganese(II) complexes of 1,3,5-triaza-7-phosphaadamantane (PTA) reveal the first transition-metal complexes of PTA in which the metal preferentially coordinates to a nitrogen and not the phosphorus of PTA. The coordination environment about the manganese was probed using X-ray crystallography (solid state) and EXAFS spectroscopy (solution).

  1. Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

    NASA Astrophysics Data System (ADS)

    Tang, Jianwu; Johannesson, Karen H.

    2010-12-01

    The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH 3COO -) or strong (i.e., CO32-) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE

  2. Determination of equilibrium constants of alkaline earth metal ion chelates with Dowex A-1 chelating resin.

    PubMed

    Harju, L; Krook, T

    1995-03-01

    A complexation chemistry model is applied to chelating ion-exchange systems and a method is presented for the determination of equilibrium constants for metal ion chelates with these resins. Protonation constants for the iminodiacetic based chelating resin Dowex A-1 were determined from potentiometric pH-data. Equilibrium constants were determined for 1:1 beryllium, magnesium, calcium, strontium and barium chelates with the resin in a wide pH range by measuring the concentrations of respective metal ions in the aqueous phase with direct current plasma atomic emission spectrometry (DCP-AES). A batch technique was used for the equilibrium experiments. At pH below 7 protonated 1:1 species were also found to be formed with the resin. From the obtained equilibrium constants, theoretical distribution coefficients were calculated as function of pH for respective metal ion resin system. PMID:18966248

  3. Strong metal-support interaction between mononuclear and polynuclear transition metal complexes and oxide supports which dramatically affects catalytic activity

    SciTech Connect

    Hucul, D.A.; Brenner, A.

    1981-03-05

    The interaction of carbonyl complexes with catalyst supports, primarily ..gamma..-alumina, has been studied by temperature-programmed decomposition. In all cases, including cluster complexes and complexes of noble metals, after heating to 600/sup 0/C in flowing He the catalysts are significantly oxidized due to a redox reaction between surface hydroxyl groups and the initially zero-valent metal. Contrary reports are probably incorrect and likely reflect the insensitivity of the experimental techniques used. For all but the most thermally unstable complexes, the oxidation occurs during the latter stages of decarbonylation indicating that there is no significant accumulation of bare zero-valent metal. Hence, decomposition does not in general provide a direct route to supported metals and, contrary to some claims, molecular cluster complexes cannot necessarily be used as precursors to supported metal clusters. Further, knowledge of this redox reaction is critical for understanding patterns of activity and for the development of improved catalysts.

  4. Complexities of high temperature metal fatigue: Some steps toward understanding

    NASA Technical Reports Server (NTRS)

    Manson, S. S.; Halford, G. R.

    1983-01-01

    After pointing out many of the complexities that attend high temperature metal fatigue beyond those already studied in the sub-creep range, a description of the micromechanisms of deformation and fracture is presented for several classes of materials that were studied over the past dozen years. Strainrange Partitioning (SRP) is used as a framework for interpreting the results. Several generic types of behavior were observed with regard both to deformation and fracture and each is discussed in the context of the micromechanisms involved. Treatment of cumulative fatigue damage and the possibility of ""healing'' of damage in successive loading loops, has led to a new interpretation of the Interaction Damage Rule of SRP. Using the concept of ""equivalent micromechanistic damage'' -- that the same damage on a microscopic scale is induced if the same hysteresis loops are generated, element for element -- it turns out the Interaction Damage Rule essentially compounds a number of variants of hysteresis loops, all of which have the same damage according to SRP concepts, into a set of loops each containing only one of the generic SRP strainranges. Thus the damage associcated with complex loops comprising several types of strainrange is analyzed by considering a combination of loops each containing only one type of strainrange. This concept is expanded to show how several independent loops can combine to ""heal'' creep damage in a complex loading history.

  5. Composite of liposome and metal complexes: Toward creating a new chemical reaction space

    NASA Astrophysics Data System (ADS)

    Koshiyama, Tomomi; Ohba, Masaaki

    2015-12-01

    The purpose of our research is to construct a novel functional space by fixation of various metal complexes into the liposome space. For the functionalization of liposome surface, we designed lipophilic metal complexes and succeeded in the fixation of various metal complexes such as oxidation catalysts. In addition, reactivities of metal complexes on the liposome surface were optimized by controlling their surrounding environment using various types of phospholipids. Furthermore, we succeeded in the incorporation of coordination polymers in inner water phase of liposomes using antibiotic ion channel, and the composites showed absorption of metal ions through antibiotic ion channels.

  6. π-Extended dipyrrins capable of highly fluorogenic complexation with metal ions

    PubMed Central

    Filatov, Mikhail A.; Lebedev, Artem Y.; Mukhin, Sergei N.; Vinogradov, Sergei A.; Cheprakov, Andrei V.

    2010-01-01

    Synthesis and properties of a new family of π-extended dipyrrins, capable of forming brightly fluorescent complexes with metal ions, are reported. The metal complexes posses tunable spectral bands and exhibit different emission properties depending on the mode of metal coordination. PMID:20583759

  7. Excited-state properties of a triply ortho-metalated iridium(III) complex

    SciTech Connect

    King, K.A.; Spellane, P.J.; Watts, R.J.

    1985-03-06

    The characterization of the ground and luminescent excited states of a triply ortho-metalated complex of ppy, fac-Ir(ppy)/sub 3/ (ppy = 2-phenylpyridine) is effected. This complex, which is the first triply ortho-metalated ppy species to be characterized, is one of the strongest transition-metal photoreductants thus far reported. 20 references, 2 figures.

  8. Proton-coupled electron transfer with photoexcited metal complexes.

    PubMed

    Wenger, Oliver S

    2013-07-16

    Proton-coupled electron transfer (PCET) plays a crucial role in many enzymatic reactions and is relevant for a variety of processes including water oxidation, nitrogen fixation, and carbon dioxide reduction. Much of the research on PCET has focused on transfers between molecules in their electronic ground states, but increasingly researchers are investigating PCET between photoexcited reactants. This Account describes recent studies of excited-state PCET with d(6) metal complexes emphasizing work performed in my laboratory. Upon photoexcitation, some complexes release an electron and a proton to benzoquinone reaction partners. Others act as combined electron-proton acceptors in the presence of phenols. As a result, we can investigate photoinduced PCET involving electron and proton transfer in a given direction, a process that resembles hydrogen-atom transfer (HAT). In other studies, the photoexcited metal complexes merely serve as electron donors or electron acceptors because the proton donating and accepting sites are located on other parts of the molecular PCET ensemble. We and others have used this multisite design to explore so-called bidirectional PCET which occurs in many enzymes. A central question in all of these studies is whether concerted proton-electron transfer (CPET) can compete kinetically with sequential electron and proton transfer steps. Short laser pulses can trigger excited-state PCET, making it possible to investigate rapid reactions. Luminescence spectroscopy is a convenient tool for monitoring PCET, but unambiguous identification of reaction products can require a combination of luminescence spectroscopy and transient absorption spectroscopy. Nevertheless, in some cases, distinguishing between PCET photoproducts and reaction products formed by simple photoinduced electron transfer (ET) (reactions that don't include proton transfer) is tricky. Some of the studies presented here deal directly with this important problem. In one case study we

  9. Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

    PubMed

    Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-02-12

    The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. PMID:26762546

  10. Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

    1992-01-01

    Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

  11. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    SciTech Connect

    Curry, J. J.; Henins, A.; Hardis, J. E.; Estupinan, E. G.; Lapatovich, W. P.; Shastri, S. D.

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  12. Recovery of Rare Earths, Precious Metals and Other Critical Materials from Geothermal Waters with Advanced Sorbent Structures

    SciTech Connect

    Pamela M. Kinsey

    2015-09-30

    The work evaluates, develops and demonstrates flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The selected organic and inorganic sorbent materials demonstrated high performance for collection of trace REEs, precious and valuable metals. The nanostructured materials typically performed better than commercially available sorbents. Data contains organic and inorganic sorbent removal efficiency, Sharkey Hot Springs (Idaho) water chemsitry analysis, and rare earth removal efficiency from select sorbents.

  13. Adsorption of alkali and alkaline-earth metal atoms on the reconstructed graphene-like BN single sheet

    NASA Astrophysics Data System (ADS)

    Hao, Jun-Hua; Wang, Zheng-Jia; Wang, Yu-Fang; Yin, Yu-Hua; Jiang, Run; Jin, Qing-Hua

    2015-12-01

    A graphene-like BN single sheet with absorbed alkali and alkaline-earth metal atoms have been investigated by using a first-principles method within the framework of density functional theory (DFT). The electronic structure of BN sheet with adsorbed metal atoms is mainly determined by the metal electronic state which is near to the Fermi level owing to the wide band gap of pure BN sheet. So, we calculated the adsorption energy, charge transfer and work function after the metal adsorbed on BN sheet. We found that the interaction between the metal atoms and BN surface was very strong, and the stable adsorption site for all the adsorbed atoms concluded was high-coordination surface site (H-center) rather than the surface dangling bond sites from the perspective of simple bond-counting arguments. Our results indicate that the interaction of BN sheet with metal atoms could help in the development of metallic nanoscale devices.

  14. Modeling platinum group metal complexes in aqueous solution.

    PubMed

    Lienke, A; Klatt, G; Robinson, D J; Koch, K R; Naidoo, K J

    2001-05-01

    We construct force fields suited for the study of three platinum group metals (PGM) as chloranions in aqueous solution from quantum chemical computations and report experimental data. Density functional theory (DFT) using the local density approximation (LDA), as well as extended basis sets that incorporate relativistic corrections for the transition metal atoms, has been used to obtain equilibrium geometries, harmonic vibrational frequencies, and atomic charges for the complexes. We found that DFT calculations of [PtCl(6)](2-).3H(2)O, [PdCl(4)](2-).2H(2)O, and [RhCl(6)](3-).3H(2)O water clusters compared well with molecular mechanics (MM) calculations using the specific force field developed here. The force field performed equally well in condensed phase simulations. A 500 ps molecular dynamics (MD) simulation of [PtCl(6)](2-) in water was used to study the structure of the solvation shell around the anion. The resulting data were compared to an experimental radial distribution function derived from X-ray diffraction experiments. We found the calculated pair correlation functions (PCF) for hexachloroplatinate to be in good agreement with experiment and were able to use the simulation results to identify and resolve two water-anion peaks in the experimental spectrum. PMID:11327912

  15. Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

    DOE PAGESBeta

    Ford, Peter C.

    2001-01-01

    Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO.his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls.hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

  16. Formation and dynamics of "waterproof" photoluminescent complexes of rare earth ions in crowded environment.

    PubMed

    Ignatova, Tetyana; Blades, Michael; Duque, Juan G; Doorn, Stephen K; Biaggio, Ivan; Rotkin, Slava V

    2014-12-28

    Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5×-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel. PMID:25379879

  17. NEW RARE EARTH ELEMENT ABUNDANCE DISTRIBUTIONS FOR THE SUN AND FIVE r-PROCESS-RICH VERY METAL-POOR STARS

    SciTech Connect

    Sneden, Christopher; Lawler, James E.; Den Hartog, Elizabeth A.; Cowan, John J.; Ivans, Inese I. E-mail: jelawler@wisc.edu E-mail: cowan@nhn.ou.edu

    2009-05-15

    We have derived new abundances of the rare earth elements Pr, Dy, Tm, Yb, and Lu for the solar photosphere and for five very metal-poor, neutron-capture r-process-rich giant stars. The photospheric values for all five elements are in good agreement with meteoritic abundances. For the low-metallicity sample, these abundances have been combined with new Ce abundances from a companion paper, and reconsideration of a few other elements in individual stars, to produce internally consistent Ba, rare earth, and Hf (56 {<=} Z {<=} 72) element distributions. These have been used in a critical comparison between stellar and solar r-process abundance mixes.

  18. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  19. Resonant Ultrasound Studies of Complex Transition Metal Oxides

    SciTech Connect

    Dr. Henry Bass; Dr. J. R. Gladden

    2008-08-18

    Department of Energy EPSCoR The University of Mississippi Award: DE-FG02-04ER46121 Resonant Ultrasound Spectroscopy Studies of Complex Transition Metal Oxides The central thrust of this DOE funded research program has been to apply resonant ultrasound spectroscopy (RUS), an elegant and efficient method for determining the elastic stiffness constants of a crystal, to the complex and poorly understood class of materials known as transition metal oxides (TMOs). Perhaps the most interesting and challenging feature of TMOs is their strongly correlated behavior in which spin, lattice, and charge degrees of freedom are strongly coupled. Elastic constants are a measure of the interatomic potentials in a crystal and are thus sensitive probes into the atomic environment. This sensitivity makes RUS an ideal tool to study the coupling of phase transition order parameters to lattice strains. The most significant result of the project has been the construction of a high temperature RUS apparatus capable of making elastic constant measurements at temperatures as high as 1000 degrees Celsius. We have designed and built novel acoustic transducers which can operate as high as 600 degrees Celsius based on lithium niobate piezoelectric elements. For measurement between 600 to 1000 C, a buffer rod system is used in which the samples under test and transducers are separated by a rod with low acoustic attenuation. The high temperature RUS system has been used to study the charge order (CO) transition in transition metal oxides for which we have discovered a new transition occurring about 35 C below the CO transition. While the CO transition exhibits a linear coupling between the strain and order parameter, this new precursor transition shows a different coupling indicating a fundamentally different mechanism. We have also begun a study, in collaboration with the Jet Propulsion Laboratory, to study novel thermoelectric materials at elevated temperatures. These materials include silicon

  20. Antimony film sensor for sensitive rare earth metal analysis in environmental samples.

    PubMed

    Makombe, Martin; van der Horst, Charlton; Silwana, Bongiwe; Iwuoha, Emmanuel; Somerset, Vernon

    2016-07-01

    A sensor for the adsorptive stripping voltammetric determination of rare earth elements has been developed. The electrochemical procedure is based on the oxidation of the rare earth elements complexed with alizarin complexone at a glassy carbon electrode that was in situ modified with an antimony film, during an anodic scan from -0.2 V to 1.1 V (vs. Ag/AgCl) and deposition potential of -0.1 V (vs. Ag/AgCl). The factors influencing the adsorptive stripping capability were optimised, including the complexing agent concentration, plating concentration of antimony and deposition time. The detection of rare earth elements (La, Ce and Pr) were realised in 0.08 M sodium acetate (pH = 5.8) solution as supporting electrolyte, with 2 × 10(-6) M alizarin complexone and 1.0 mg L(-1) antimony solution. Under the optimised conditions, a deposition time of 360 s was obtained and a linear response was observed between 1 and 25 µg L(-1). The reproducibility of the voltammetric measurements was found to be within 5.0% RSD for 12 replicate measurements of cerium(III) concentration of 5 µg L(-1) using the same electrode surface. The detection limits obtained using stripping analysis was 0.06, 0.42 and 0.71 μg L(-1) for Ce(III), La(III) and Pr(III), respectively. The developed sensor has been successfully applied for the determination of cerium, lanthanum and praseodymium in municipal tap water samples. PMID:27065049

  1. Preparation and luminescence properties of phosphors of rare earth complexes based on polyoxotungstates

    SciTech Connect

    Wen, He-Rui; Lu, Xiao-Neng; Liao, Jin-Sheng; Zhang, Cai-Wei; You, Hang-Ying; Liu, Cai-Ming

    2015-08-15

    Highlights: • Three new phosphors of rare earth complexes based on polyoxotungstates were synthesized. • [Eu(PW{sub 11}O{sub 39}){sub 2}]{sup 11−} (1) emits red light which used as potential red light materials. • [Sm(PW{sub 11}O{sub 39}){sub 2}] {sup 11−} (2) emits strong orange-red light at 598.7 nm. • [Dy(PW{sub 11}O{sub 39}){sub 2}] {sup 11−} (3) emits white light which used as potential white light materials. - Abstract: Three new phosphors of rare earth complexes based on polyoxotungstates, K{sub 3}Cs{sub 8}[Eu(PW{sub 11}O{sub 39}){sub 2}]·11H{sub 2}O (1), K{sub 3}Cs{sub 8}[Sm(PW{sub 11}O{sub 39}){sub 2}]·10H{sub 2}O (2), and K{sub 5}Cs{sub 6}[Dy(PW{sub 11}O{sub 39}){sub 2}]·15H{sub 2}O (3) have been prepared and characterized. The crystallographic analyses reveal that these compounds consist of two monovacant keggin anions [PW{sub 11}O{sub 39}]{sup 7−} connected by a rare earth ion in a sandwich structure. The investigations of photoluminescence properties show that phosphor 1 emits strong red light at 614 and 702 nm, 2 emits strong orange-red light at 598.7 nm, and 3 exists two strong emissions at 479 nm (blue) and 574 nm (orange). The luminescence properties suggest that the 1 can be applied as the potential red-emitting crystal phosphor, and the 3 may be regarded as a potential white light material for LEDs.

  2. Rare earth-transition metal-magnesium compounds-An overview

    SciTech Connect

    Rodewald, Ute Ch.; Chevalier, Bernard Poettgen, Rainer

    2007-05-15

    Intermetallic rare earth-transition metal-magnesium compounds play an important role as precipitations in modern light weight alloys and as host materials for hydrogen storage applications. Recent results on the crystal chemistry, the chemical bonding peculiarities, physical properties, and hydrogenation behavior of these materials are reviewed. - Graphical abstract: View of the Sm{sub 4}RhMg crystal structure approximately along the direction. Samarium, rhodium, and magnesium atoms are drawn as medium gray, filled (hidden in the trigonal prisms), and open circles, respectively. The three-dimensional network of corner-sharing RhSm{sub 6} trigonal prisms and the Mg{sub 4} tetrahedra are emphasized. The Sm1 atoms do not participate in the network of condensed trigonal prisms.

  3. Properties of metastable alkaline-earth-metal atoms calculated using an accurate effective core potential

    SciTech Connect

    Santra, Robin; Christ, Kevin V.; Greene, Chris H.

    2004-04-01

    The first three electronically excited states in the alkaline-earth-metal atoms magnesium, calcium, and strontium comprise the (nsnp){sup 3}P{sub J}{sup o}(J=0,1,2) fine-structure manifold. All three states are metastable and are of interest for optical atomic clocks as well as for cold-collision physics. An efficient technique--based on a physically motivated potential that models the presence of the ionic core--is employed to solve the Schroedinger equation for the two-electron valence shell. In this way, radiative lifetimes, laser-induced clock shifts, and long-range interaction parameters are calculated for metastable Mg, Ca, and Sr.

  4. Coercivity of domain wall motion in thin films of amorphous rare earth-transition metal alloys

    NASA Technical Reports Server (NTRS)

    Mansuripur, M.; Giles, R. C.; Patterson, G.

    1991-01-01

    Computer simulations of a two dimensional lattice of magnetic dipoles are performed on the Connection Machine. The lattice is a discrete model for thin films of amorphous rare-earth transition metal alloys, which have application as the storage media in erasable optical data storage systems. In these simulations, the dipoles follow the dynamic Landau-Lifshitz-Gilbert equation under the influence of an effective field arising from local anisotropy, near-neighbor exchange, classical dipole-dipole interactions, and an externally applied field. Various sources of coercivity, such as defects and/or inhomogeneities in the lattice, are introduced and the subsequent motion of domain walls in response to external fields is investigated.

  5. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    NASA Astrophysics Data System (ADS)

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-01

    Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

  6. Magnetization and compensation temperature in transition metal -- rare earth multilayers: a mean-field approach

    NASA Astrophysics Data System (ADS)

    Tornau, E. E.; Šmakov, J.; Lapinskas, S.; Rosengren, A.

    1998-03-01

    Mean-field theory is used to explain the magnetization as a function of layer thickness in transition metal -- rare earth multilayers. Long-range dipole interactions are included along with FM nearest neighbor interactions within the layers and AF nearest neighbor interactions at the interface. The obtained dependencies of saturation magnetization and compensation temperature on layer thickness agree with experimental data on Tb/Co multilayers( L. Ertl, G. Endl, and H. Hoffmann, J. Magn. Magn. Mater. 113, 227 (1992).). The saturation magnetization is constant for very thin films (the behavior characteristic to Tb - Co alloys) but it decreases with increase of layer thickness. At thick enough films the magnetization starts to increase again confirming the importance of the long - range forces. The compensation temperature also decreases with layer thickness. The proposed theory is extended to calculate the magnetization of FM/AFM layers with a spacer layer in between.

  7. Permanent electric dipole moments of alkaline-earth-metal monofluorides: Interplay of relativistic and correlation effects

    NASA Astrophysics Data System (ADS)

    Prasannaa, V. S.; Sreerekha, S.; Abe, M.; Bannur, V. M.; Das, B. P.

    2016-04-01

    The interplay of the relativistic and correlation effects in the permanent electric dipole moments of the X 2Σ+ electronic ground states of the alkaline-earth-metal monofluorides (BeF, MgF, CaF, SrF, and BaF) has been studied using a relativistic coupled cluster method. The calculations were carried out using double, triple, and quadruple zeta basis sets, and with no core orbitals frozen. The results are compared with those of other calculations available in the literature and with experiments. The correlation trends in the permanent electric dipole moments of these molecules are discussed in detail. This information will be useful in throwing light on the interplay between relativistic and correlation effects of other properties that are relevant to fundamental physics.

  8. Binary rare earth element-Ni/Co metallic glasses with distinct β-relaxation behaviors

    SciTech Connect

    Zhu, Z. G.; Wang, Z.; Wang, W. H.

    2015-10-21

    We report the formation of a series of rare earth element (RE)-Ni/Co binary metallic glasses (MGs) with unusual distinct β-relaxation peak compared with that of most of the reported MGs which usually exhibit as an excess wing or a shoulder. The β-relaxation behavior of RE-Ni/Co MGs is sensitive to the composition and the atomic radii of the RE and can be tuned through changing the fraction of RE-Ni (or Co) atomic pairs. The novel RE-Ni/Co MGs with distinct β-relaxation can serve as model system to investigate the nature of the β-relaxation as well as its relations with other physical and mechanical properties of MGs.

  9. Low-energy description of the metal-insulator transition in the rare-earth nickelates

    NASA Astrophysics Data System (ADS)

    Subedi, Alaska; Peil, Oleg E.; Georges, Antoine

    2015-02-01

    We propose a simple theoretical description of the metal-insulator transition of rare-earth nickelates. The theory involves only two orbitals per nickel site, corresponding to the low-energy antibonding eg states. In the monoclinic insulating state, bond-length disproportionation splits the manifold of eg bands, corresponding to a modulation of the effective on-site energy. We show that, when subject to a local Coulomb repulsion U and Hund's coupling J , the resulting bond-disproportionated state is a paramagnetic insulator for a wide range of interaction parameters. Furthermore, we find that when U -3 J is small or negative, a spontaneous instability to bond disproportionation takes place for large enough J . This minimal theory emphasizes that a small or negative charge-transfer energy, a large Hund's coupling, and a strong coupling to bond disproportionation are the key factors underlying the transition. Experimental consequences of this theoretical picture are discussed.

  10. Calculation of the lowest electronic excitations of the alkaline earth metals using the relativistic polarization propagator

    NASA Astrophysics Data System (ADS)

    Brandt, Sven; Pernpointner, Markus

    2015-07-01

    In this work we use the recently implemented four-component polarization propagator for accurate single excitation calculations of alkaline earth metals and compare our results to experimental data. Various approximations to the Dirac-Coulomb Hamiltonian are additionally tested. In Ca spin-orbit coupling already leads to noticeable zero field splitting, which gradually increases for the heavier homologs finally invalidating the singlet and triplet state characterizations. For all systems we observe a very good agreement with experimental transition energies in the considered energy range. For Sr, Ba and Ra non-relativistic approaches already exhibit unacceptable deviations in the reproduction of transition energies and spectral structure. The obtained excited final states are analyzed in terms of atomic donor and acceptor orbital contributions. Our results stress the necessity to use relativistic implementations of the polarization propagator for an accurate description of both electron correlation and relativistic effects contributing to excitation spectra of heavy systems.

  11. Magnetic Exchange Couplings in Transition Metal Complexes from DFT

    NASA Astrophysics Data System (ADS)

    Peralta, Juan

    In this talk I will review our current efforts for the evaluation of magnetic exchange couplings in transition metal complexes from density functional theory. I will focus on the performance of different DFT approximations, including a variety of hybrid density functionals, and show that hybrid density functionals containing approximately 30% Hartree-Fock type exchange are in general among the best choice in terms of accuracy. I will also describe a novel computational method to evaluate exchange coupling parameters using analytic self-consistent linear response theory. This method avoids the explicit evaluation of energy differences, which can become impractical for large systems. Our approach is based on the evaluation of the transversal magnetic torque between two magnetic centers for a given spin configuration using explicit constraints of the local magnetization direction via Lagrange multipliers. This method is applicable in combination with any modern density functional with a noncollinear spin generalization and can be utilized as a ``black-box''. I will show proof-of-concept calculations in frustrated Fe7IIIdisk-shaped clusters, and dinuclear CuII, FeIII, and heteronuclear complexes. NSF DMR-1206920.

  12. On the existence of near-Earth-object meteoroid complexes producing meteorites

    NASA Astrophysics Data System (ADS)

    Trigo-Rodriguez, J.; Madiedo, J.; Williams, I.

    2014-07-01

    It is generally thought that meteorites are formed as a result of collisions within the main belt of asteroids [1]. They are delivered onto Earth-crossing orbits because of the effects of orbital resonances, primarily with Jupiter. About 15 meteorites are known where their passage through the atmosphere was observed and recorded, allowing the parameters of the pre-encounter orbit to be derived [2]. The cosmic-ray-exposure ages (CREAs) are suggesting that most meteorites have been exposed to cosmic rays for tens of millions of years (Myrs) [3], re-enforcing the belief that the process of modifying the orbit from being near-circular in the main belt to highly elliptical as an Earth-crossing orbit was a gradual process like the effects of resonance. However, there is growing evidence that some meteorite could originate directly from the near-Earth-object (NEO) population. A good example of this is the recent discovery of rare primitive groups in the Antarctic, an example being Elephant Moraine (EET) 96026: a C4/5 carbonaceous chondrite with a measured cosmic ray exposure age of only 0.28 Ma [4]. Here, we focus on recent dynamic links that have been established between meteorite-dropping bolides and NEOs that support the idea of short-life meteoroid streams that can generate meteoroids on Earth. The fact that such streams can exist allows rocky material from potentially-hazardous asteroids (PHA) to be sampled and investigated in the laboratory. The existence of meteoroid streams capable of producing meteorites has been proposed following the determination of accurate meteoroid orbits of fireballs obtained by the Canadian Meteorite Observation and Recovery Project (MORP) [5]. Some asteroids in the Earth's vicinity are undergoing both dynamical and collisional evolution on very short timescales [6]. Many of these objects are crumbly bodies that originated from the collisions between main-belt asteroids during their life-time. An obvious method of forming these complexes

  13. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  14. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

    SciTech Connect

    Khan, Sami; Varanasi, Kripa K.; Azimi, Gisele; Yildiz, Bilge

    2015-02-09

    Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ∼3 and a water contact angle of ∼15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (∼2.2) and becomes hydrophobic (contact angle of ∼104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

  15. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

    NASA Astrophysics Data System (ADS)

    Khan, Sami; Azimi, Gisele; Yildiz, Bilge; Varanasi, Kripa K.

    2015-02-01

    Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ˜3 and a water contact angle of ˜15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (˜2.2) and becomes hydrophobic (contact angle of ˜104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

  16. Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

    NASA Astrophysics Data System (ADS)

    Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

    1993-07-01

    Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in

  17. Metal complex-based electron-transfer mediators in dye-sensitized solar cells

    DOEpatents

    Elliott, C. Michael; Sapp, Shawn A.; Bignozzi, Carlo Alberto; Contado, Cristiano; Caramori, Stefano

    2006-03-28

    This present invention provides a metal-ligand complex and methods for using and preparing the same. In particular, the metal-ligand complex of the present invention is of the formula: L.sub.a-M-X.sub.b where L, M, X, a, and b are those define herein. The metal-ligand complexes of the present invention are useful in a variety of applications including as electron-transfer mediators in dye-sensitized solar cells and related photoelectrochromic devices.

  18. Antimicrobial Activity of Metal & Metal Oxide Nanoparticles Interfaced With Ligand Complexes Of 8-Hydroxyquinoline And α-Amino Acids

    NASA Astrophysics Data System (ADS)

    Bhanjana, Gaurav; Kumar, Neeraj; Thakur, Rajesh; Dilbaghi, Neeraj; Kumar, Sandeep

    2011-12-01

    Antimicrobial nanotechnology is a recent addition to the fight against disease causing organisms, replacing heavy metals and toxins. In the present work, mixed ligand complexes of metals like zinc, silver etc. and metal oxide have been synthesized using 8-hydroxyquinoline (HQ) as a primary ligand and N-and/O-donor amino acids such as L-serine, L-alanine, glycine, cysteine and histidine as secondary ligands. These complexes were characterized using different spectroscopic techniques. The complexes were tested for antifungal and antibacterial activity by using agar well diffusion bioassay.

  19. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect

    Guodong Du

    2004-12-19

    products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of {alpha}-ketols to {alpha}-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  20. Application of flowing stream techniques to water analysis Part III. Metal ions: alkaline and alkaline-earth metals, elemental and harmful transition metals, and multielemental analysis.

    PubMed

    Miró, Manuel; Estela, José Manuel; Cerdà, Víctor

    2004-05-28

    In the earlier parts of this series of reviews [1,2], the most relevant flowing stream techniques (namely, segmented flow analysis, continuous flow analysis, flow injection (FI) analysis, sequential injection (SI) analysis, multicommuted flow injection analysis and multisyringe flow injection analysis) applied to the determination of several core inorganic parameters for water quality assessment, such as nutrients and anionic species including nitrogen, sulfur and halogen compounds, were described. In the present paper, flow techniques are presented as powerful analytical tools for the environmental monitoring of metal ions (alkaline and alkaline-earth metals, and elemental and harmful transition metals) as well as to perform both multielemental and speciation analysis in water samples. The potentials of flow techniques for automated sample treatment involving on-line analyte separation and/or pre-concentration are also discussed in the body of the text, and demonstrated for each individual ion with a variety of strategies successfully applied to trace analysis. In this context, the coupling of flow methodologies with atomic spectrometric techniques such as flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICPMS) or hydride-generation (HG)/cold-vapor (CV) approaches, launching the so-called hyphenated techniques, is specially worth mentioning. PMID:18969420

  1. Alkali and alkaline earth metallic (AAEM) species leaching and Cu(II) sorption by biochar.

    PubMed

    Li, Mi; Lou, Zhenjun; Wang, Yang; Liu, Qiang; Zhang, Yaping; Zhou, Jizhi; Qian, Guangren

    2015-01-01

    Alkali and alkaline earth metallic (AAEM) species water leaching and Cu(II) sorption by biochar prepared from two invasive plants, Spartina alterniflora (SA) and water hyacinth (WH), were explored in this work. Significant amounts of Na and K can be released (maximum leaching for Na 59.0 mg g(-1) and K 79.9 mg g(-1)) from SA and WH biochar when they are exposed to contact with water. Cu(II) removal by biochar is highly related with pyrolysis temperature and environmental pH with 600-700 °C and pH of 6 showing best performance (29.4 and 28.2 mg g(-1) for SA and WH biochar). Cu(II) sorption exerts negligible influence on Na/K/Mg leaching but clearly promotes the release of Ca. Biochars from these two plant species provide multiple benefits, including nutrient release (K), heavy metal immobilization as well as promoting the aggregation of soil particles (Ca) for soil amelioration. AAEM and Cu(II) equilibrium concentrations in sorption were analyzed by positive matrix factorization (PMF) to examine the factors underlying the leaching and sorption behavior of biochar. The identified factors can provide insightful understanding on experimental phenomena. PMID:25194478

  2. Core and shallow-core d- to f-shell excitations in rare-earth metals

    NASA Astrophysics Data System (ADS)

    Bradley, J. A.; Moore, K. T.; van der Laan, G.; Bradley, J. P.; Gordon, R. A.

    2011-11-01

    We report on the results of probing the light lanthanide metals Ce, Pr, and Nd with inelastic x-ray and electron scattering. Aberration-corrected transmission electron microscope-based electron spectroscopy and nonresonant inelastic x-ray scattering are shown to be in a high degree of accord and here serve as complementary probes of electronic structure. The high resolution and high signal-to-noise electron technique allows for the measurement of the complex and subtle excitation spectra in the lanthanide metals, validating the applicability of the screened trivalent atomic model used for these materials. In addition, the momentum transfer dependence of the x-ray scattering is extracted and compared against atomic calculations for the most tightly bound excitonic resonances, which provides a direct test of the predicted atomic radial wave functions.

  3. DPP dyes as ligands in transition-metal complexes.

    PubMed

    Lorenz, Ingo-Peter; Limmert, Michael; Mayer, Peter; Piotrowski, Holger; Langhals, Heinz; Poppe, Martin; Polborn, Kurt

    2002-09-01

    The DPP dyes (=diketopyrrolopyrrole) 1 are deprotonated to give the corresponding dianions 2. These are treated with two moles of the transition-metal complexes [L(n)MX]=[(Ph(3)P)(2)MX] (M=Cu, Ag; X=Cl, NO(3)), [(Ph(3)P)AuCl], [(Et(3)P)AuCl], [(tBuNC)AuCl], [(Ph(3)P)(2)PdCl(2)], and [(Ph(3)P)(2)PtCl(2)] to give the novel bismetalated DPP dyes [L(n)MN[C(3)R(1)(O)](2)NML(n)] (4-10). In comparison with the starting materials, these compounds show better solubilities, high fluorescence quantum yields (Phi > or = 80 %), and bathochromic absorptions. The compounds 4 c, 5 a, 6 b, 6 c, 6 e, 7 c, and 8 c were characterized by X-ray crystallography. The copper and silver atoms in 4 c and 5 a are trigonal planar and are surrounded by the P atoms of the phosphane ligands and the N atom of the DPP dianion 2. Both metals are somewhat forced out-of-plane, and the P(2)M plane and the phenyl planes of R1 are twisted by > or = 70 degrees and < or = 25 degrees, respectively, towards the chromophore plane. The gold atoms in 6-8 are linearly coordinated to one N and one P (6 b, c, e, 7 c) or one C atom (8 c), respectively. The gold atoms are only slightly pressed out-of-plane, and the P substituents are staggered so that there is enough space for the planarization of R(1) into the plane of the chromophore. Compound 8 c shows intermolecular d(10)-d(10) interactions between Au(I) centers of different molecules, and these interactions lead to infinite chains of parallel orientated molecules in a gauche conformation of neighbors (torsion angle=150 degrees) in the crystal. PMID:12360946

  4. Thermodynamic, Magnetic, and Superconductivity Properties of Selected Rare Earth - Transition Metal Compounds.

    NASA Astrophysics Data System (ADS)

    Higgins, Bill Edward

    Selected material problems relating to R _2T_{14}B (R = rare earth T = transition metal) and RBa_2 Cu_3O_{ rm x} type materials are studied. Properties central to a basic understanding of desirable characteristics of the material were chosen for study and methods for improving the characteristics devised. Common to both systems is an investigation of the metal gas reactions which each compound undergoes. In R_2T_ {14}B, oxidation is destructive of the material and ways to minimize it, including substitution of chromium at the transition metal site, are developed. Second, the temperature dependence of coercivity in R_2 T_{14}B was shown to depend on the temperature dependence of anisotropy. Materials with a stable temperature dependence of coercivity designed on the basis of this relationship were prepared, and characterized. Finally, the potential of R_2T _{14}B for use as magnetooptic recording media is considered. The R_2 T_{14}B family is promising for this application as it has a large Kerr rotation among other desirable properties. In the RBa_2Cu _3O_{rm x} system oxygen content is important to superconducting properties. Oxygen uptake kinetics are measured for YBa _2Cu_3O _{rm x} as well as Y _{0.5}Na_{0.5 }Ba_2Cu_3 O_{rm x}, YBa_2Cu_{2.5 }Fe_{0.5}O _{rm x} and the Y _{rm 1-y}La _{rm y}Ba_2 Cu_3O_{ rm x} family. Substitution at the rare earth site is found to have little effect on the activation energy of the oxygenation reaction, but substitution at the chain copper site, such as in YBa_2 Cu_{2.5}Fe _{0.5}O_{rm x}, is found to cause a large decrease in the activation energy of oxygen uptake. In addition, the Y_{rm 1-y}La_{rm y} Ba_2Cu_3O _{rm x} system was studied, in order to determine the reason for the anomalously low superconducting transition temperature of LaBa _2Cu_3O_ {rm x} when it is prepared by conventional means. It is likely that the reduced transition temperature comes from disorder of the barium and lanthanum.

  5. Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

    NASA Astrophysics Data System (ADS)

    Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

    2014-03-01

    We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the

  6. Extraction of rare-earth metal(III) nitrates by neutral organophosphorus compounds from concentrated aqueous salt solutions

    SciTech Connect

    Pyartman, A.K.; Puzikov, E.A.

    1995-07-20

    Equations describing isotherms of extraction of rare-earth metal(III) nitrates by neutral organo-phosphorus compounds over a wide range of component concentrations in aqueous and organic phases have been proposed. Constants of phase extraction and empirical parameters characterizing the influence of organic phase composition on the activity coefficients of the components have been presented.

  7. Electric dipole polarizabilities at imaginary frequencies for hydrogen, the alkali-metal, alkaline-earth, and noble gas atoms

    SciTech Connect

    Derevianko, Andrei Porsev, Sergey G. Babb, James F.

    2010-05-15

    The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline-earth atoms, and the noble gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

  8. Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

    PubMed

    Cheng, Jinghui; Zhou, Xiangge; Xiang, Haifeng

    2015-11-01

    Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors. PMID:26375420

  9. ExploreNEOs. V. AVERAGE ALBEDO BY TAXONOMIC COMPLEX IN THE NEAR-EARTH ASTEROID POPULATION

    SciTech Connect

    Thomas, C. A.; Trilling, D. E.; Emery, J. P.; Mueller, M.; Delbo, M.; Morbidelli, A.; Hora, J. L.; Fazio, G.; Smith, H. A.; Spahr, T. B.; Benner, L. A. M.; Chesley, S.; Mainzer, A.; Bhattacharya, B.; Bottke, W. F.; Harris, A. W.; Mommert, M.; Penprase, B.; Stansberry, J. A.

    2011-09-15

    Examining the albedo distribution of the near-Earth object (NEO) population allows for a better understanding of the relationship between absolute (H) magnitude and size, which impacts calculations of the size frequency distribution and impact hazards. Examining NEO albedos also sheds light on the differences between the NEO and Main Belt populations. We combine albedo results from the ExploreNEOs Warm Spitzer Exploration Science program with taxonomic classifications from the literature, publicly available data sets, and new observations from our concurrent spectral survey to derive the average albedos for C-, D-, Q-, S-, V-, and X-complex NEOs. Using a sample size of 118 NEOs, we calculate average albedos of 0.29{sup +0.05}{sub -0.04}, 0.26{sup +0.04}{sub -0.03}, and 0.42{sup +0.13}{sub -0.11} for the Q-, S-, and V-complexes, respectively. The averages for the C- and D-complexes are 0.13{sup +0.06}{sub -0.05} and 0.02{sup +0.02}{sub -0.01}, but these averages are based on a small number of objects (five and two, respectively) and will improve with additional observations. We use albedos to assign X-complex asteroids to one of the E-, M-, or P-types. Our results demonstrate that the average albedos for the C-, S-, V-, and X-complexes are higher for NEOs than the corresponding averages observed in the Main Belt.

  10. Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce γ-Valerolactone.

    PubMed

    Gowda, Ravikumar R; Chen, Eugene Y-X

    2016-01-01

    Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into γ-valerolactone in up to 93% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs. PMID:26735911

  11. Earth-Facing Antenna Characterization in a Complex Ground Plane/Multipath Rich Environment

    NASA Technical Reports Server (NTRS)

    Welch, Bryan W.; Piasecki, Marie T.

    2015-01-01

    The Space Communications and Navigation (SCAN) Testbed was a Software Defined Radio (SDR)-based payload launched to the International Space Station (ISS) in July of 2012. The purpose of the SCAN Testbed payload was to investigate the applicability of SDRs to NASA space missions in an operational space environment, which means that a proper model for system performance in said operational space environment is a necessary condition. The SCAN Testbed has line-of-sight connections to various ground stations with its S-Band Earth-facing Near-Earth Network Low Gain Antenna (NEN-LGA). Any previous efforts to characterize the NEN-LGA proved difficult, therefore, the NASA Glenn Research Center built its own S-Band ground station, which became operational in 2015, and has been successfully used to characterize the NEN-LGAs in-situ pattern measurements. This methodology allows for a more realistic characterization of the antenna performance, where the pattern oscillation induced by the complex ISS ground plane, as well as shadowing effects due to ISS structural blockage are included into the final performance model. This paper describes the challenges of characterizing an antenna pattern in this environment. It will also discuss the data processing, present the final antenna pattern measurements and derived model, as well as discuss various lessons learned.

  12. Earth-Facing Antenna Characterization in Complex Ground Plane/Multipath Rich Environment

    NASA Technical Reports Server (NTRS)

    Welch, Bryan W.; Piasecki, Marie T.

    2015-01-01

    The Space Communications and Navigation (SCAN) Testbed was a Software Defined Radio (SDR)-based payload launched to the International Space Station (ISS) in July of 2012. The purpose of the SCAN Testbed payload was to investigate the applicability of SDRs to NASA space missions in an operational environment, which means that a proper model for system performance in said operational space environment is a necessary condition. The SCAN Testbed has line-of-sight connections to various ground stations with its S-Band Earth-facing Near-Earth-Network Low Gain Antenna (NEN-LGA). Any previous efforts to characterize the NEN-LGA proved difficult, therefore, the NASA Glenn Research Center built its own S-Band ground station, which became operational in 2015, and has been used successfully to characterize the NEN-LGA's in-situ pattern measurements. This methodology allows for a more realistic characterization of the antenna performance, where the pattern oscillation induced by the complex ISS ground plane, as well as shadowing effects due to ISS structural blockage are included into the final performance model. This paper describes the challenges of characterizing an antenna pattern in this environment. It will also discuss the data processing, present the final antenna pattern measurements and derived model, as well as discuss various lessons learned

  13. The Earth's entropy production budget as simulated by a climate system model of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Kleidon, A.; Fraedrich, K.; Lunkeit, F.; Jansen, H.

    2003-04-01

    The Earth is an open thermodynamic system far from equilibrium. It has been suggested that processes within such systems evolve to states of maximum entropy production. Here we report on the entropy production budget of the climate system as simulated by the intermediate complexity climate model PUMA, which consists of an atmospheric general circulation model of coarse resolution, a land surface representation, and a mixed-layer ocean model. We expanded the model to explicitly calculate entopy production for absorption of solar and terrestrial radiation, turbulent fluxes of sensible and latent heat, atmospheric and oceanic heat transport, and entropy production associated with biotic productivity. We present the general methodology, the entropy production budget for the present-day climatic mean, and the sensitivity to vegetation related land surface characteristics.

  14. Digermylene Oxide Stabilized Group 11 Metal Iodide Complexes.

    PubMed

    Yadav, Dhirendra; Siwatch, Rahul Kumar; Sinhababu, Soumen; Karwasara, Surendar; Singh, Dharmendra; Rajaraman, Gopalan; Nagendran, Selvarajan

    2015-12-01

    Use of a substituted digermylene oxide as a ligand has been demonstrated through the isolation of a series of group 11 metal(I) iodide complexes. Accordingly, the reactions of digermylene oxide [{(i-Bu)2ATIGe}2O] (ATI = aminotroponiminate) (1) with CuI under different conditions afforded [({(i-Bu)2ATIGe}2O)2(Cu4I4)] (2) with a Cu4I4 octahedral core, [({(i-Bu)2ATIGe}2O)2(Cu3I3)] (3) with a Cu3I3 core, and [{(i-Bu)2ATIGe}2O(Cu2I2)(C5H5N)2] (4) with a butterfly-type Cu2I2 core. The reactions of compound 1 with AgI and AuI produced [({(i-Bu)2ATIGe}2O)2(Ag4I4)] (5) with a Ag4I4 octahedral core and [{(i-Bu)2ATIGe}2O(Au2I2)] (6) with a Au2I2 core, respectively. The presence of metallophilic interactions in these compounds is shown through the single-crystal X-ray diffraction and atom-in-molecule (AIM) studies. Preliminary photophysical studies on compound 6 are also carried out. PMID:26558406

  15. Extraction kinetics of rare earth metals with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester using a hollow fiber membrane extractor

    SciTech Connect

    Kubota, Fukiko; Goto, Masahiro; Nakashio, Fumiyuki; Hano, Tadashi

    1995-03-01

    A kinetic study concerning chemical complexation-based solvent extraction of rare earth metals with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester dissolved as an extractant in n-heptane was carried out using a microporous hydrophobic hollow fiber membrane extractor. The effects of concentration of chemical species in aqueous and organic feed solutions on the apparent permeabilities of metal species for extraction and stripping, respectively, were investigated to clarify the permeation mechanism. From the experimental results it was predicted that the permeation rate is controlled by diffusion of the chemical species in aqueous and organic phases and by interfacial chemical reaction. The experimental data were analyzed by the diffusion model accompanied with an interfacial reaction, taking into account the velocity distributions of the aqueous and organic phases through the inner and outer sides of the hollow fiber.

  16. Capillary electrophoresis application in metal speciation and complexation characterization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

  17. A parallel Atmosphere-Ocean Global Circulation Model of intermediate complexity for Earth system climate research

    NASA Astrophysics Data System (ADS)

    Silva, T. A.; Schmittner, A.

    2007-12-01

    We present the evolution of an Earth System model of intermediate complexity featuring an ocean global circulation model to include a fully coupled 3D primitive equations atmospheric model. The original Earth System climate model, UVic ESCM (Weaver et al. 2001), uses an ocean global circulation model coupled to a one layer atmospheric energy-moisture balance model. It also comprises a viscous-plastic rheology sea ice model, a mechanical land ice model, land surface, oceanic and terrestrial carbon models and a simple 3D marine ecosystem model (Schmittner et al. 2005). A spectral atmospheric, model, PUMA (Fraedrich et al. 2005), was coupled to the UVic ESCM to provide an atmosphere with nonlinear dynamics in target resolutions of T21, T31 and T42, as required. The coupling with the atmosphere, which involves data transfer, preprocessing and interpolation, is done through the OASIS3 coupler. During a run there are 2 + 2N parallel processes: the UVic ESCM, the Oasis3 coupler and the PUMA model with its domain split across 2N processes. The choice of N allows to balance more or less complex configurations of UVic model (e.g. higher level marine ecosystem model or number of biogeochemical tracers) with the atmospheric model at different resolutions, in order to maintain computational efficiency. The relatively simple parameterizations make this new atmosphere-ocean global circulation model much faster than a state-of-the-art Atmosphere-Ocean Global Circulation Model, and so optimally geared for decadal to millennial scale integrations. The latter require special care with the conservation of fluxes during coupling. A second order conservative interpolation method was applied (Jones 1999) and this is compared with the use of typical non-conservative methods.

  18. A major light rare-earth element (LREE) resource in the Khanneshin carbonatite complex, southern Afghanistan

    USGS Publications Warehouse

    Tucker, Robert D.; Belkin, Harvey E.; Schulz, Klaus J.; Peters, Stephen G.; Horton, Forrest; Buttleman, Kim; Scott, Emily R.

    2012-01-01

    The rapid rise in world demand for the rare-earth elements (REEs) has expanded the search for new REE resources. We document two types of light rare-earth element (LREE)-enriched rocks in the Khanneshin carbonatite complex of southern Afghanistan: type 1 concordant seams of khanneshite-(Ce), synchysite-(Ce), and parisite-(Ce) within banded barite-strontianite alvikite, and type 2 igneous dikes of coarse-grained carbonatite, enriched in fluorine or phosphorus, containing idiomorphic crystals of khanneshite-(Ce) or carbocernaite. Type 1 mineralized barite-strontianite alvikite averages 22.25 wt % BaO, 4.27 wt % SrO, and 3.25 wt % ∑ LREE2O3 (sum of La, Ce, Pr, and Nd oxides). Type 2 igneous dikes average 14.51 wt % BaO, 5.96 wt % SrO, and 3.77 wt % ∑ LREE2O3. A magmatic origin is clearly indicated for the type 2 LREE-enriched dikes, and type 1 LREE mineralization probably formed in the presence of LREE-rich hydrothermal fluid. Both types of LREE mineralization may be penecontemporaneous, having formed in a carbonate-rich magma in the marginal zone of the central vent, highly charged with volatile constituents (i.e., CO2, F, P2O5), and strongly enriched in Ba, Sr, and the LREE. Based on several assumptions, and employing simple geometry for the zone of LREE enrichment, we estimate that at least 1.29 Mt (million metric tonnes) of LREE2O3 is present in this part of the Khanneshin carbonatite complex.

  19. Regional projections of climate change using an Earth system model of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Sobie, S. R.; Murdock, T. Q.

    2011-12-01

    Earth system models of intermediate complexity have been generally employed in experiments studying global temperature changes, carbon-cycle responses and millennial-scale climate variability. Their reduced computational demands mean many different greenhouse gas emissions scenarios can be examined, including exploring thresholds of dangerous climate change and geo-engineering schemes. In response to requests from users for more information on regional climate change under both more optimistic and more pessimistic emissions scenarios than the range provided by SRES, EMICs are able to produce additional climate change projections relatively rapidly. However, as a result of their parameterizations and reduced complexity, EMICs have been generally avoided when examining sub-global spatial scales in favour of GCMs or RCMs. To investigate these concerns, we compare responses to changes in radiative forcing from both the University of Victoria Earth system climate model and an ensemble of CMIP3 global climate models at a variety of sub-global spatial scales. Temperature trends and anomalies from commonly used intervals in the 20th and 21st centuries (e.g. 1961-1990, 2046-2065) are evaluated for both model types under standard emissions scenarios. Results indicate that the UVIC model produces statistically similar regional temperature responses as those of the ensemble average of the IPCC AR4 global climate models. Precipitation anomalies display fewer statistical matches with rainfall increases underestimated and snowfall decreases overestimated by the UVIC model. The results suggest regional consequences of more varied emissions scenarios could be examined in certain cases using the UVIC model (and potentially other EMICs) instead of GCMs or RCMs. A selection of regional climate change responses comparing the UVIC model to the AR4 ensemble average will be presented for a variety of areas.

  20. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    DOEpatents

    Wong, Stanislaus; Zhang, Fen

    2014-05-13

    The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

  1. Squeezing and Heating Rock to Scope Out How Metallic Iron Dribbled to the Center of the Earth

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2005-07-01

    Formation of Earth's metallic core was one of the most important events in the history of the planet. Metallic iron is much denser than rock, so it sank to the middle, taking other elements that concentrate in metal rather than silicate (rock) with it. However, we do not understand everything about core formation. One particularly niggling puzzle is why cobalt (Co) and nickel (Ni) have the same concentration (relative to primitive carbonaceous chondrites) as one another in Earth's mantle. At low pressure these elements concentrate in metallic iron to different extents. Calculations show that if metal segregated from silicate at low pressure, nickel ought to be 100 times less abundant (normalized to chondrites) than cobalt, not equal. Cosmochemists have tackled this problem by doing experiments at high pressure and temperature to map out how cobalt and nickel partitioning between metal and silicate differs compared to low pressure. However, the studies differ in their predictions of the behavior because of differences in the assumed pressure, temperature, and oxidation state during core formation. Nancy Chabot (Case Western Reserve University, now at the Johns Hopkins Applied Physics Laboratory), and David Draper and Carl Agee from the University of New Mexico addressed the discrepancies by designing a series of experiments over a wide range in temperature. Their results plot out the conditions under which metal can sink to the core while leading to the observed cobalt and nickel concentrations in the mantle. While the results do not lead to a unique solution, they point the way for further studies of other elements that tend to concentrate in metallic iron, and they show clearly that the equal nickel and cobalt concentrations in the mantle can be the product of core formation in the early Earth.

  2. Proposing late transition metal complexes as frustrated Lewis pairs--a computational investigation.

    PubMed

    Pal, Amrita; Vanka, Kumar

    2013-10-14

    There has been considerable interest in recent times to develop transition metal complex systems that can demonstrate metal-ligand cooperativity. It has recently been shown (Wass et al., J. Am. Chem. Soc., 2011, 133, 18463) that early transition metals can cooperate with ligands carrying phosphines as pendant groups, working as metal analogues to frustrated Lewis pairs (FLPs) to mediate in a variety of important reactions. What the current work attempts to do is to show how this concept of metal containing FLPs can be expanded to include late transition metal complexes as well: complexes that have been modified from existing systems that serve as efficient catalysts for homogeneous polymerization. A modified palladium complex has been considered in this regard as an example of a potential late transition metal FLP and studied with full quantum mechanical calculations. The calculations indicate that this complex would be effective at catalyzing ammonia borane dehydrogenation. The possibility of competing side reactions such as reductive elimination have also been considered, and it has been found that such processes would also yield stable products which could act as an FLP in catalyzing reactions such as the dehydrogenation of ammonia borane. The current work therefore expands the scope of metal containing FLPs to include late transition metals and demonstrates computationally the potential of such complexes for exhibiting metal-ligand cooperativity. PMID:23912196

  3. A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State

    PubMed Central

    Chapman, Michael R.; Henkelis, Susan E.; Kapur, Nikil

    2016-01-01

    Abstract Synthetic methods to prepare organometallic and coordination compounds such as Schiff‐base complexes are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (MII/III/IV where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol‐switch is described which allows access to analytically pure FeII/III–salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers MnII/IV–salen complexes in high yield. PMID:27547645

  4. Metallophore mapping in complex matrices by metal isotope coded profiling of organic ligands.

    PubMed

    Deicke, Michael; Mohr, Jan Frieder; Bellenger, Jean-Philippe; Wichard, Thomas

    2014-12-01

    Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals. PMID:25298978

  5. Silicate-metal reaction-induced snow atop the Earth's core

    NASA Astrophysics Data System (ADS)

    Hernlund, J. W.; Labrosse, S.; Houser, C. T.; Hirose, K.; Caracas, R.

    2012-12-01

    Recent experiments and thermodynamical models indicate that typical iron-bearing rocks at the Earth's core-mantle boundary (CMB) should readily react with outer core fluid to produce a layer more enriched in light elements (primarily oxygen, and possibly silicon) than the freely convecting fluid at depth which comprises the bulk of Earth's outer core. If the metallic reaction products are fluid, the resultant density anomaly atop the core is expected to be many orders of magnitude larger (on the order of a percent) than the density fluctuations driving core convection at depth (order 10 ppb), thus a gravitational stratification atop the core is inevitable if these experimental inferences are robust. On the other hand, early work by Knittle and Jeanloz on CMB reactions suggested that such reaction products could instead be solid, giving rise to an accumulation of FeO and FeSi sediments at the CMB. Buffett et al. (Science, 2000) offered a model in which FeO and/or FeSi sediments crystallize from the ambient outer core to form an electrically conducting layer at the CMB, which could help explain decadal variations in length of day. However, new constraints on the phase diagram in systems like Fe-FeO indicate that the average outer core is on the Fe-side of the eutectic, with a eutectic temperature much smaller than plausible at the CMB, which implies that such a model is impossible. Assuming that the basic experimental constraints are robust, I will argue that: 1) CMB reactions in the hotter early Earth led to the formation of a buoyant fluid layer atop the core enriched in oxygen, and 2) this enrichment in oxygen allows for crystallization on the FeO side of the eutectic at later times in Earth's evolution following sufficient secular cooling. The "snow" that crystallizes in the stratified layer can either rise and compact onto the CMB or sink and melt at depth depending upon the degree of light alloy enrichment induced by CMB reactions, and in either case will

  6. Geomorphological experiments for understanding cross-scale complexity of earth surface processes

    NASA Astrophysics Data System (ADS)

    Seeger, Manuel

    2016-04-01

    The shape of the earth's surface is the result of a complex interaction of different processes at different spatial and temporal scales. The challenging problem is, that process observation is rarely possible due to this different scales. In addition, the resulting landform often does not match the scale of process observation. But it is indispensable for the development of concepts of formation of landforms to identify and understand the involved processes and their interaction. To develop models it is even necessary to quantify them and their relevant parameters. Experiments are able to bridge the constraints of process observation mentioned above: it is possible to observe and quantify individual processes as well as complex process combinations up to the development of geomorphological units. The contribution aims at showing, based on soil erosion research, the possibilities of experimental methods for contributing to th understanding of geomorphological processes. A special emphasis is put on the linkage of conceptual understanding of processes, their measurement and the following development of models. The development of experiments to quantify relevant parameters will be shown, as well as the steps undertaken to bring them into the field taking into account the resulting increase of uncertainty in system parameters and results. It will be shown that experiments are even so able to produce precise measurements on individual processes as well as of complex combinations of parameters and processes and to identify their influence on the overall geomorphological dynamics. Experiments are therefore a methodological package able to check complex soil erosion processes at different levels of conceptualization and to generate data for their quantification. And thus, also a methodological concept to take more into account and to further develop in geomorphological science.

  7. Student Cognitive Difficulties and Mental Model Development of Complex Earth and Environmental Systems

    NASA Astrophysics Data System (ADS)

    Sell, K.; Herbert, B.; Schielack, J.

    2004-05-01

    Students organize scientific knowledge and reason about environmental issues through manipulation of mental models. The nature of the environmental sciences, which are focused on the study of complex, dynamic systems, may present cognitive difficulties to students in their development of authentic, accurate mental models of environmental systems. The inquiry project seeks to develop and assess the coupling of information technology (IT)-based learning with physical models in order to foster rich mental model development of environmental systems in geoscience undergraduate students. The manipulation of multiple representations, the development and testing of conceptual models based on available evidence, and exposure to authentic, complex and ill-constrained problems were the components of investigation utilized to reach the learning goals. Upper-level undergraduate students enrolled in an environmental geology course at Texas A&M University participated in this research which served as a pilot study. Data based on rubric evaluations interpreted by principal component analyses suggest students' understanding of the nature of scientific inquiry is limited and the ability to cross scales and link systems proved problematic. Results categorized into content knowledge and cognition processes where reasoning, critical thinking and cognitive load were driving factors behind difficulties in student learning. Student mental model development revealed multiple misconceptions and lacked complexity and completeness to represent the studied systems. Further, the positive learning impacts of the implemented modules favored the physical model over the IT-based learning projects, likely due to cognitive load issues. This study illustrates the need to better understand student difficulties in solving complex problems when using IT, where the appropriate scaffolding can then be implemented to enhance student learning of the earth system sciences.

  8. Superconductors and Complex Transition Metal Oxides for Tunable THz Plasmonic Metamaterials

    SciTech Connect

    Singh, Ranjan; Xiong, Jie; Azad, Md A.; Yang, Hao; Trugman, Stuart A.; Jia, Quanxi; Taylor, Antoinette; Chen, Houtong

    2012-07-13

    The outline of this presentation are: (1) Motivation - Non-tunability of metal metamaterials; (2) Superconductors for temperature tunable metamaterials; (3) Ultrafast optical switching in superconductor metamaterials; (4) Controlling the conductivity with infrared pump beam; (5) Complex metal oxides as active substrates - Strontium Titanate; and (6) Conclusion. Conclusions are: (1) High Tc superconductors good for tunable and ultrafast metamaterials; (2) Large frequency and amplitude tunability in ultrathin superconductor films; (3) Such tunable properties cannot be accessed using metals; (4) Complex metal oxides can be used as active substrates - large tunability; (5) Complex oxides fail to address the issue of radiation losses in THz metamaterials.

  9. Assigning Oxidation States to Some Metal Dioxygen Complexes of Biological Interest.

    ERIC Educational Resources Information Center

    Summerville, David A.; And Others

    1979-01-01

    The bonding of dioxygen in metal-dioxygen complexes is discussed, paying particular attention to the problems encountered in assigning conventional oxidation numbers to both the metal center and coordinated dioxygen. Complexes of iron, cobalt, chromium, and manganese are considered. (BB)

  10. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Pt. 414, App. B Appendix B to Part 414—Complexed Metal-Bearing...

  11. 40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 30 2012-07-01 2012-07-01 false Complexed Metal-Bearing Waste Streams B Appendix B to Part 414 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS Pt. 414, App. B Appendix B to Part 414—Complexed Metal-Bearing...

  12. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    ERIC Educational Resources Information Center

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  13. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    PubMed

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides. PMID:26077621

  14. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  15. Toxicity of chlortetracycline and its metal complexes to model microorganisms in wastewater sludge.

    PubMed

    Pulicharla, Rama; Das, Ratul Kumar; Brar, Satinder Kaur; Drogui, Patrick; Sarma, Saurabh Jyoti; Verma, Mausam; Surampalli, Rao Y; Valero, Jose R

    2015-11-01

    Complexation of antibiotics with metals is a well-known phenomenon. Wastewater treatment plants contain metals and antibiotics, thus it is essential to know the effect of these complexes on toxicity towards microorganisms, typically present in secondary treatment processes. In this study, stability constants and toxicity of chlortetracycline (CTC) and metal (Ca, Mg, Cu and Cr) complexes were investigated. The calculated stability constants of CTC-metal complexes followed the order: Mg-CTC>Ca-CTC>Cu-CTC>Cr-CTC. Gram positive Bacillus thuringiensis (Bt) and Gram negative Enterobacter aerogenes (Ea) bacteria were used as model microorganisms to evaluate the toxicity of CTC and its metal complexes. CTC-metal complexes were more toxic than the CTC itself for Bt whereas for Ea, CTC and its metal complexes showed similar toxicity. In contrast, CTC spiked wastewater sludge (WWS) did not show any toxic effect compared to synthetic sewage. This study provides evidence that CTC and its metal complexes are toxic to bacteria when they are biologically available. As for WWS, CTC was adsorbed to solid part and was not biologically available to show measurable toxic effects. PMID:26119381

  16. Solid State Pathways to Complex Shape Evolution and Tunable Porosity during Metallic Crystal Growth

    PubMed Central

    Valenzuela, Carlos Díaz; Carriedo, Gabino A.; Valenzuela, María L.; Zúñiga, Luis; O'Dwyer, Colm

    2013-01-01

    Growing complex metallic crystals, supported high index facet nanocrystal composites and tunable porosity metals, and exploiting factors that influence shape and morphology is crucial in many exciting developments in chemistry, catalysis, biotechnology and nanoscience. Assembly, organization and ordered crystallization of nanostructures into complex shapes requires understanding of the building blocks and their association, and this relationship can define the many physical properties of crystals and their assemblies. Understanding crystal evolution pathways is required for controlled deposition onto surfaces. Here, complex metallic crystals on the nano- and microscale, carbon supported nanoparticles, and spinodal porous noble metals with defined inter-feature distances in 3D, are accomplished in the solid-state for Au, Ag, Pd, and Re. Bottom-up growth and positioning is possible through competitive coarsening of mobile nanoparticles and their site-specific crystallization in a nucleation-dewetted matrix. Shape evolution, density and growth mechanism of complex metallic crystals and porous metals can be imaged during growth. PMID:24026532

  17. Novel Route to Transition Metal Isothiocyanate Complexes Using Metal Powders and Thiourea

    NASA Technical Reports Server (NTRS)

    Harris, Jerry D.; Eckles, William E.; Hepp, Aloysius F.; Duraj, Stan A.; Hehemann, David G.; Fanwick, Phillip E.; Richardson, John

    2003-01-01

    A new synthetic route to isothiocyanate-containing materials is presented. Eight isothiocyanate- 4-methylpyridine (y-picoline) compounds were prepared by refluxing metal powders (Mn, Fe, Co, Ni, and Cu) with thiourea in y-picoline. With the exception of compound 5,prepared with Co, the isothiocyanate ligand was generated in situ by the isomerization of thiourea to NH4+SCN- at reflux temperatures. The complexes were characterized by x-ray crystallography. Compounds 1,2, and 8 are the first isothiocyanate- 4-methylpyridine anionic compounds ever prepared and structurally characterized. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound y-picoline molecules. Compound 8 is a five-coordinate copper(II) molecule with a distorted square-pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. Structural data are presented for all compounds.

  18. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    SciTech Connect

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  19. Strongly luminescent rare-earth-ion-doped DNA-CTMA complex film and fiber materials

    NASA Astrophysics Data System (ADS)

    Wang, Lili; Ishihara, Koki; Izumi, H.; Wada, M.; Zhang, Gongjian; Ishikawa, T.; Watanabe, A.; Horinouchi, Suguru; Ogata, Naoya

    2002-08-01

    A rare-earth chelate, Europium 6,6.7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5,-octanedionate, (Eu3+-FOD) doped DNACTMA complex as fiber and film materials was prepared by casting solution method and gel-spinning method. The Eu-FOD-DNA-CTMA complex was luminescent and has 750 μs of fluorescence lifetime, sharply-spiked emission spectra, excellent film and fiber formability, moderate absorption (40000M-1cm-1) at 327 nm and high quantum yield forlanthanide emission. By comparison of fluorescence lifetime of Eu-FOD doped DNA-CTMA solid matrix with that of Eu-FOD doped in PMMA, it was clear that energy transfer from DNA to FOD leads to enhancement of fluorescence emission at 613 nm. Analysis results for fluorescence spectra and fluorescence relaxation time of Eu3+ doped in the materials indicated that Eu3+-FOD is chemically bond within the DNA-CTMA matrix. Amplified spontaneous emission (ASE) at 612 nm by pumping with UV laser (355 nm) was observed in the materials. Fluorescence lifetime of the Eu-FOD doped in the DNA-CTMA solid matrix was evaluated to be 750 μs, which is ca. 230μs longer than that of Eu-FOD doped in PMMA solid matrix. Efficient Energy transfer from base of DNA to FOD, then to Eu, occurred when irradiated by UV light or 355 laser beams.

  20. Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

    PubMed

    Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

    2015-12-14

    We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very

  1. DFT study of metal-complex structural variation on tensile force profiles

    NASA Astrophysics Data System (ADS)

    Rinderspacher, B. Christopher; Andzelm, Jan W.; Lambeth, Robert H.

    2012-12-01

    We present calculations on metal-ligand complexes for the evaluation of mechanical properties as they pertain to the inclusion in polymer-linked supramolecular complexes. To this end, we investigate the energy profiles of stretching various complexes according to external forces exerted on each complex via the attached polymer strands. Zn2+ and Fe2+ complexated by 2,6-bisbenzimidazolyl-pyridine (BP) were considered in the presence of tetrafluoro borate. We find that the yield characteristics are subject to a complex interplay of steric and electronic effects of the ligands and metal center.

  2. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    ERIC Educational Resources Information Center

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  3. Solvation-Driven Charge Transfer and Localization in Metal Complexes

    PubMed Central

    2016-01-01

    stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent–solute interactions to describe the dynamical changes of the solute excited states during the solvent response. PMID:25902015

  4. Antimalarial and antimicrobial activities of 8-Aminoquinoline-Uracils metal complexes

    PubMed Central

    Phopin, Kamonrat; Sinthupoom, Nujarin; Treeratanapiboon, Lertyot; Kunwittaya, Sarun; Prachayasittikul, Supaluk; Ruchirawat, Somsak; Prachayasittikul, Virapong

    2016-01-01

    8-Aminoquinoline (8AQ) derivatives have been reported to have antimalarial, anticancer, and antioxidant activities. This study investigated the potency of 8AQ-5-substituted (iodo and nitro) uracils metal (Mn, Cu, Ni) complexes (1-6) as antimalarial and antimicrobial agents. Interestingly, all of these metal complexes (1-6) showed fair antimalarial activities. Moreover, Cu complexes 2 (8AQ-Cu-5Iu) and 5 (8AQ-Cu-5Nu) exerted antimicrobial activities against Gram-negative bacteria including P. shigelloides and S. dysenteriae. The results reveal application of 8AQ and its metal complexes as potential compounds to be further developed as novel antimalarial and antibacterial agents. PMID:27103894

  5. Filament wound metal lined propellant tanks for future Earth-to-orbit transports

    NASA Technical Reports Server (NTRS)

    Macconochie, Ian O.; Davis, Robert B.; Freeman, William T., Jr.

    1988-01-01

    For future Earth-to-orbit transport vehicles, reusability and lighter weights are sought for the main propellant tanks. To achieve this, a filament wound tank with a metal liner and an intermediate layer of foam-filled honeycomb is proposed. A hydrogen tank is used as an example. To accommodate mismatches in the expansion of liner and overwrap a design is proposed wherin the liner is configured so that the extension of the liner under pressure matches the expected contraction of the same liner due to the presence of a cryogen. In operation, the liner is pressurized at a rate such that the pressure strain matches the contraction due to decrease in temperature. As an alternate approach, compressive pre-stress is placed in the liner such that it will not separate from the overwrap. A finite element program is used to show stresses in the liner and overwrap for various tank pressures for the pre-stressed liner concept. A fracture mechanics analysis is made of the liners to determine tank life. The tank concept shown has a similar weight to the Shuttle external hydrogen tank, but the filament wound tank is expected to be reusable. Integration of the propellant tanks into a future transport vehicle is discussed.

  6. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    SciTech Connect

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-03

    Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

  7. Effect of patch borders on coercivity in amorphous rare earth-transition metal thin films

    NASA Technical Reports Server (NTRS)

    Patterson, G.; Fu, H.; Giles, R. C.; Mansuripur, M.

    1991-01-01

    The coercivity at the micron scale is a very important property of magneto-optical media. It is a key factor that determines the magnetic domain wall movement and domain reversal. How the coercivity is influenced by a special type of patch borders is discussed. Patch formation is a general phenomenon in growth processes of amorphous rare earth transition metal thin films. Different patches may stem from different seeds and the patch borders are formed when they merge. Though little is known about the exact properties of the borders, we may expect that the exchange interaction at the patch border is weaker than that within a patch, since there is usually a spatial gap between two patches. Computer simulations were performed on a 2-D hexagonal lattice consisting of 37 complete patches with random shape and size. From the series of simulations we may conclude that the domain in the patch with borders of 30 percent exchange strength can expand most easily to the whole lattice, because the exchange strength can expand most easily to the whole lattice, because the exchange strength of the border is not too high to prevent the domain from growing within the patch and it is not too low to prevent the domain from expanding beyond the patch.

  8. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    DOE PAGESBeta

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-03

    Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This ismore » followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

  9. Rare-earth vs. heavy metal pigments and their colors from first principles

    PubMed Central

    Tomczak, Jan M.; Pourovskii, Leonid V.; Vaugier, Loig; Georges, Antoine; Biermann, Silke

    2013-01-01

    Many inorganic pigments contain heavy metals hazardous to health and environment. Much attention has been devoted to the quest for nontoxic alternatives based on rare-earth elements. However, the computation of colors from first principles is a challenge to electronic structure methods, especially for materials with localized f-orbitals. Here, starting from atomic positions only, we compute the colors of the red pigment cerium fluorosulfide as well as mercury sulfide (classic vermilion). Our methodology uses many-body theories to compute the optical absorption combined with an intermediate length-scale modelization to assess how coloration depends on film thickness, pigment concentration, and granularity. We introduce a quantitative criterion for the performance of a pigment. While for mercury sulfide, this criterion is satisfied because of large transition matrix elements between wide bands, cerium fluorosulfide presents an alternative paradigm: the bright red color is shown to stem from the combined effect of the quasi-2D and the localized nature of states. Our work shows the power of modern computational methods, with implications for the theoretical design of materials with specific optical properties. PMID:23302689

  10. Sol-gel-derived hybrid materials multi-doped with rare-earth metal ions

    NASA Astrophysics Data System (ADS)

    Zelazowska, E.; Rysiakiewicz-Pasek, E.; Borczuch-Laczka, M.; Cholewa-Kowalska, K.

    2012-06-01

    Four different hybrid organic-inorganic materials based on TiO2-SiO2 matrices with organic additives and doped with rare-earth metal ions (III) from the group of europium, cerium, terbium, neodymium, dysprosium and samarium, were synthesized by sol-gel method. Tetraethyl orthosilicate, titanium (IV) isopropoxide and organic compounds, such as butyl acrylate, butyl methacrylate, ethyl acetoacetate, ethylene glycol dimethacrylate, ethyl acetate, propylene carbonate, organic solvents and certain inorganic salts were used in the synthesis. The inorganic part of the sols, which were used in the synthesis of all the hybrid materials, was prepared separately and then the organic parts were added. The materials obtained were aged for three weeks at room temperature and then heated in an electric oven for three hours at temperatures of 80 °C-150 °C. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX); X-ray diffraction (XRD); Fourier transform infrared spectroscopy (KBr technique); 29Si magic-angle spinning nuclear magnetic resonance; and fluorescence spectroscopy were used for the examination of morphology, microstructure and luminescence properties, respectively. Photoluminescence properties with relatively intense narrow emission lines of Tb, Eu, Dy, Nd, Sm respectively to the RE-ions doping, were observed for all the hybrid materials.

  11. Sol-gel derived hybrid materials doped with rare earth metal ions

    NASA Astrophysics Data System (ADS)

    Zelazowska, E.; Rysiakiewicz-Pasek, E.; Borczuch-Laczka, M.; Cholewa-Kowalska, K.

    2011-10-01

    Sol-gel derived organic-inorganic hybrid materials doped with rare earth metal ions (Pr 3+) and small amounts of lithium ions (˜0.1-0.2 wt.%) were produced from the tetraethyl orthosilicate (TEOS), AlCl 3·6H 2O (about 10 mol%), ethyl methacrylate, butyl methacrylate and some other organic additions (ca. 35-40 wt.% of organics in the fresh gels) to obtain hybrid organic-inorganic hosts. The gel and hybrid materials obtained were aged at room temperature for three weeks, then heated in an electric drier for 3 h at temperature of 125 °C and investigated for morphology, structure and luminescence properties by X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), 29Si and 27Al MAS nuclear magnetic resonance and fluorescence spectroscopy. An influence of the organic additions and inorganic dopants on microstructure of the materials obtained and their luminescence properties has been examined. Under excitation with UV radiation in a range of ˜210-350 nm, the sharp and relatively intense luminescence emission lines due to 3P 0 → 3H 4 (blue) and 3P 0 → 3F 3 (red) transitions of Pr 3+ ions were observed in the luminescence spectra of gel and hybrid materials of SA-series.

  12. Modified electronic population analysis for transition-metal complexes

    SciTech Connect

    Noell, J.O.

    1982-01-01

    A modification to the Mulliken electronic population analysis designed primarily for use on transition-metal systems is presented. All terms arising from the metal basis functions including diagonal terms are repartioned between the metal and the ligands. This reapportionment is an attempt to reflect more accurately the actual electron density in well-defined areas of space, which characterize the metal and the ligand. This modified analysis appears to yield more reasonable charge assignments than a conventional Mulliken analysis. The cost of the analysis is negligible in comparison with that of calculating the wave function.

  13. Double-decker bis(tetradiazepinoporphyrazinato) rare earth complexes: crucial role of intramolecular hydrogen bonding.

    PubMed

    Tarakanova, Ekaterina N; Trashin, Stanislav A; Simakov, Anton O; Furuyama, Taniyuki; Dzuban, Alexander V; Inasaridze, Liana N; Tarakanov, Pavel A; Troshin, Pavel A; Pushkarev, Victor E; Kobayashi, Nagao; Tomilova, Larisa G

    2016-07-26

    A series of homoleptic bis{tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazinato}lanthanide sandwich complexes [(tBuPh)DzPz]2Ln (Ln = Lu, Er, Dy, Eu, Nd, Ce, La) were prepared and their physicochemical properties were studied to gain insight into the nature of specific interactions in diazepinoporphyrazines. The effect of annulated diazepine moieties and the Ln ionic radius on the properties of the complexes was investigated in comparison with double-decker phthalocyanines. A combination of experimental and theoretical studies revealed the presence of two types of hydrogen bonding interactions in the metal-free porphyrazine and the corresponding sandwich complexes, namely, interligand C-H(ax)N(meso) hydrogen bonding and O-HN(Dz) ligand-water interaction. The interligand hydrogen bonding imparts high stability of the ligand dimer and the double-decker compounds in a reduced state. This work is the first comprehensive investigation into the fundamental understanding of the unusual properties of diazepine-containing macroheterocycles. PMID:27396712

  14. Water-free rare-earth-metal ionic liquids/ionic liquid crystals based on hexanitratolanthanate(III) anion.

    PubMed

    Ji, Shun-Ping; Tang, Meng; He, Ling; Tao, Guo-Hong

    2013-04-01

    The hexanitratolanthanate anion (La(NO(3))(6)(3-)) is an interesting symmetric anion suitable to construct the component of water-free rare-earth-metal ionic liquids. The syntheses and structural characterization of eleven lanthanum nitrate complexes, [C(n)mim](3)[La(NO(3))(6)] (n=1, 2, 4, 6, 8, 12, 14, 16, 18), including 1,3-dimethylimidazolium hexanitratolanthanate ([C(1)mim](3)[La(NO(3))(6)], 1), 1-ethyl-3-methylimidazolium hexanitratolanthanate ([C(2)mim](3)[La(NO(3))(6)], 2), 1-butyl-3-methylimidazolium hexanitratolanthanate ([C(4)mim](3)[La(NO(3))(6)], 3), 1-isobutyl-3-methylimidazolium hexanetratolanthanate ([isoC(4)mim](3)[La(NO(3))(6)], 4), 1-methyl-3-(3'-methylbutyl)imidazolium hexanitratolanthanate ([MC(4)mim](3)[La(NO(3))(6)], 5), 1-hexyl-3-methylimidazolium hexanitratolanthanate ([C(6)mim](3)[La(NO(3))(6)], 6), 1-methyl-3-octylimidazolium hexanitratolanthanate ([C(8)mim](3)[La(NO(3))(6)], 7), 1-dodecyl-3-methylimidazolium hexanitratolanthanate ([C(12)mim](3)[La(NO(3))(6)], 8), 1-methyl-3-tetradecylimidazolium hexanitratolanthanate ([C(14)mim](3)[La-(NO(3))(6)], 9), 1-hexadecyl-3-methylimid-azolium hexanitratolanthanum ([C(16)dmim](3)[La(NO(3))(6)], 10), and 1-methyl-3-octadecylimidazolium hexanitratolanthanate ([C(18)mim](3)[La(NO(3))(6)], 11) are reported. All new compounds were characterized by (1)H and (13)C NMR, and IR spectroscopy as well as elemental analysis. The crystal structure of compound 1 was determined by using single-crystal X-ray diffraction, giving the following crystallographic information: monoclinic; P2(1)/c; a=15.3170 (3), b=14.2340 (2), c=13.8954(2) Å; β=94.3453(15)°, V=3020.80(9) Å(3), Z=4, ρ=1.764 g cm(-3). The coordination polyhedron around the lanthanum ion is rationalized by six nitrate anions with twelve oxygen atoms. No hydrogen-bonding network or water molecule was found in 1. The thermodynamic stability of the new complexes was investigated by using thermogravimetric analysis (TGA). The water

  15. The mechanism of alkene addition to a nickel bis(dithiolene) complex: the role of the reduced metal complex.

    PubMed

    Dang, Li; Shibl, Mohamed F; Yang, Xinzheng; Alak, Aiman; Harrison, Daniel J; Fekl, Ulrich; Brothers, Edward N; Hall, Michael B

    2012-03-14

    The binding of an alkene by Ni(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] is one of the most intriguing ligand-based reactions. In the presence of the anionic, reduced metal complex, the primary product is an interligand adduct, while in the absence of the anion, dihydrodithiins and metal complex decomposition products are preferred. New kinetic (global analysis) and computational (DFT) data explain the crucial role of the anion in suppressing decomposition and catalyzing the formation of the interligand product through a dimetallic complex that appears to catalyze alkene addition across the Ni-S bond, leading to a lower barrier for the interligand adduct. PMID:22364208

  16. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    PubMed

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. PMID:26945123

  17. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    NASA Astrophysics Data System (ADS)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  18. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    NASA Astrophysics Data System (ADS)

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  19. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

    SciTech Connect

    Sadikin, Yolanda; Stare, Katarina; Schouwink, Pascal; Brix Ley, Morten; Jensen, Torben R.; Meden, Anton; Černý, Radovan

    2015-05-15

    The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with

  20. Advanced analysis of complex seismic waveforms to characterize the subsurface Earth structure

    NASA Astrophysics Data System (ADS)

    Jia, Tianxia

    2011-12-01

    This thesis includes three major parts, (1) Body wave analysis of mantle structure under the Calabria slab, (2) Spatial Average Coherency (SPAC) analysis of microtremor to characterize the subsurface structure in urban areas, and (3) Surface wave dispersion inversion for shear wave velocity structure. Although these three projects apply different techniques and investigate different parts of the Earth, their aims are the same, which is to better understand and characterize the subsurface Earth structure by analyzing complex seismic waveforms that are recorded on the Earth surface. My first project is body wave analysis of mantle structure under the Calabria slab. Its aim is to better understand the subduction structure of the Calabria slab by analyzing seismograms generated by natural earthquakes. The rollback and subduction of the Calabrian Arc beneath the southern Tyrrhenian Sea is a case study of slab morphology and slab-mantle interactions at short spatial scale. I analyzed the seismograms traversing the Calabrian slab and upper mantle wedge under the southern Tyrrhenian Sea through body wave dispersion, scattering and attenuation, which are recorded during the PASSCAL CAT/SCAN experiment. Compressional body waves exhibit dispersion correlating with slab paths, which is high-frequency components arrivals being delayed relative to low-frequency components. Body wave scattering and attenuation are also spatially correlated with slab paths. I used this correlation to estimate the positions of slab boundaries, and further suggested that the observed spatial variation in near-slab attenuation could be ascribed to mantle flow patterns around the slab. My second project is Spatial Average Coherency (SPAC) analysis of microtremors for subsurface structure characterization. Shear-wave velocity (Vs) information in soil and rock has been recognized as a critical parameter for site-specific ground motion prediction study, which is highly necessary for urban areas located

  1. (Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis.

    PubMed

    Schmid, Matthias; Oña-Burgos, Pascual; Guillaume, Sophie M; Roesky, Peter W

    2015-07-21

    The (iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh2=NSiMe3)(PPh2=S)}(-) ligand has been used for the synthesis of divalent and trivalent rare-earth borohydride complexes. The salt metathesis of the potassium reagent [K{CH(PPh2=NSiMe3)(PPh2=S)}]2 with [Yb(BH4)2(THF)2] resulted in the divalent monoborohydride ytterbium complex [{CH(PPh2=NSiMe3)(PPh2=S)}Yb(BH4)(THF)2]. The 2D (31)P/(171)Yb HMQC-NMR spectrum clearly showed the coupling between both nuclei. The trivalent bisborohydrides [{CH(PPh2=NSiMe3)(PPh2=S)}Ln(BH4)2(THF)] (Ln = Y, Sm, Tb, Dy, Er, Yb and Lu) were obtained by reaction of [K{CH(PPh2=NSiMe3)(PPh2=S)}]2 with [Ln(BH4)3(THF)3]. All new compounds were characterized by single X-ray diffraction. The divalent and trivalent compounds were next used as initiators in the ring-opening polymerization (ROP) of ε-caprolactone (CL) and trimethylene carbonate (TMC). All complexes afforded a generally well-controlled ROP of both of these cyclic esters. High molar mass poly(ε-caprolactone) diols (Mn,NMR < 101,300 g mol(-1), ĐM = 1.44), and α,ω-dihydroxy and α-hydroxy,ω-formate telechelic poly(trimethylene carbonate)s (Mn,NMR < 20,000 g mol(-1), ĐM = 1.61) were thus synthesized under mild operating conditions. PMID:25683468

  2. Behavior and Distribution of Heavy Metals Including Rare Earth Elements, Thorium, and Uranium in Sludge from Industry Water Treatment Plant and Recovery Method of Metals by Biosurfactants Application

    PubMed Central

    Gao, Lidi; Kano, Naoki; Sato, Yuichi; Li, Chong; Zhang, Shuang; Imaizumi, Hiroshi

    2012-01-01

    In order to investigate the behavior, distribution, and characteristics of heavy metals including rare earth elements (REEs), thorium (Th), and uranium (U) in sludge, the total and fractional concentrations of these elements in sludge collected from an industry water treatment plant were determined and compared with those in natural soil. In addition, the removal/recovery process of heavy metals (Pb, Cr, and Ni) from the polluted sludge was studied with biosurfactant (saponin and sophorolipid) elution by batch and column experiments to evaluate the efficiency of biosurfactant for the removal of heavy metals. Consequently, the following matters have been largely clarified. (1) Heavy metallic elements in sludge have generally larger concentrations and exist as more unstable fraction than those in natural soil. (2) Nonionic saponin including carboxyl group is more efficient than sophorolipid for the removal of heavy metals in polluted sludge. Saponin has selectivity for the mobilization of heavy metals and mainly reacts with heavy metals in F3 (the fraction bound to carbonates) and F5 (the fraction bound to Fe-Mn oxides). (3) The recovery efficiency of heavy metals (Pb, Ni, and Cr) reached about 90–100% using a precipitation method with alkaline solution. PMID:22693485

  3. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  4. Tuning carrier density at complex oxide interface with metallic overlayer

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Shi, Y. J.; Jiang, S. W.; Yue, F. J.; Wang, P.; Ding, H. F.; Wu, D.

    2016-06-01

    We have systematically investigated the electronic transport properties of the LaAlO3/SrTiO3 interfaces with several different metal capping layers. The sheet carrier density can be tuned in a wide range by the metallic overlayer without changing the carrier mobility. The sheet carrier density variation is found to be linearly dependent on the size of metal work function. This behavior is explained by the mechanism of the charge transfer between the oxide interface and the metal overlayer across the LaAlO3 layer. Our results confirm the existence of a built-in electric field in LaAlO3 film with an estimated value of 67.7 eV/Å. Since the metallic overlayer is essential for devices, the present phenomena must be considered for future applications.

  5. Identification of metal species by ESI-MS/MS through release of free metals from the corresponding metal-ligand complexes

    PubMed Central

    Tsednee, Munkhtsetseg; Huang, Yu-Chen; Chen, Yet-Ran; Yeh, Kuo-Chen

    2016-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is used to analyze metal species in a variety of samples. Here, we describe an application for identifying metal species by tandem mass spectrometry (ESI-MS/MS) with the release of free metals from the corresponding metal–ligand complexes. The MS/MS data were used to elucidate the possible fragmentation pathways of different metal–deoxymugineic acid (–DMA) and metal–nicotianamine (–NA) complexes and select the product ions with highest abundance that may be useful for quantitative multiple reaction monitoring. This method can be used for identifying different metal–ligand complexes, especially for metal species whose mass spectra peaks are clustered close together. Different metal–DMA/NA complexes were simultaneously identified under different physiological pH conditions with this method. We further demonstrated the application of the technique for different plant samples and with different MS instruments. PMID:27240899

  6. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1990-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

  7. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1991-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

  8. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1990-08-28

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

  9. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1991-10-15

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

  10. Process for the displacement of cyanide ions from metal-cyanide complexes

    DOEpatents

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  11. Modelling of trace metal uptake by roots taking into account complexation by exogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Jean-Marc, Custos; Christian, Moyne; Sterckeman, Thibault

    2010-05-01

    The context of this study is phytoextraction of soil trace metals such as Cd, Pb or Zn. Trace metal transfer from soil to plant depends on physical and chemical processes such as minerals alteration, transport, adsorption/desorption, reactions in solution and biological processes including the action of plant roots and of associated micro-flora. Complexation of metal ions by organic ligands is considered to play a role on the availability of trace metals for roots in particular in the event that synthetic ligands (EDTA, NTA, etc.) are added to the soil to increase the solubility of the contaminants. As this role is not clearly understood, we wanted to simulate it in order to quantify the effect of organic ligands on root uptake of trace metals and produce a tool which could help in optimizing the conditions of phytoextraction.We studied the effect of an aminocarboxilate ligand on the absorption of the metal ion by roots, both in hydroponic solution and in soil solution, for which we had to formalize the buffer power for the metal. We assumed that the hydrated metal ion is the only form which can be absorbed by the plants. Transport and reaction processes were modelled for a system made up of the metal M, a ligand L and the metal complex ML. The Tinker-Nye-Barber model was adapted to describe the transport of solutes M, L and ML in the soil and absorption of M by the roots. This allowed to represent the interactions between transport, chelating reactions, absorption of the solutes at the root surface, root growth with time, in order to simulate metal uptake by a whole root system.Several assumptions were tested such as i) absorption of the metal by an infinite sink and according to a Michaelis-Menten kinetics, solutes transport by diffusion with and without ii) mass flow and iii) soil buffer power for the ligand L. In hydroponic solution (without soil buffer power), ligands decreased the trace metal flux towards roots, as they reduced the concentration of hydrated

  12. The Electromagnetically Equivalent Complex Network Modeling of Compact Seismo-Climatic Processes for the Complete Earth

    NASA Astrophysics Data System (ADS)

    Sengor, T.

    2009-04-01

    the natural iterations of the geo-data at future on both the region under the observation and some locations non-related to the observation region either geologically or seismically or climatically or phenomenologically relating to the earth. The inversion processes from the electromagnetically equivalent complex system models, which are called EECSMs in short, will be discussed in this paper [1] - [5]. The fine model of 13D-hypersurface is generated by using the geophysical EQ data set. The coarse model of 10D-hypersurface is generated by using the data set of waveforms of electromagnetic quantities. The method is applied to both seismic and climatic phenomena at the Marmara Sea region and useful extractions for the prediction of both whether and seismicity are given. 2 References [1] T. Sengor, "The electromagnetic device optimization modeling of seismo-electromagnetic processes," IUGG Perugia 2007. [2] T. Sengor, "The electromagnetic device optimization modeling of seismo-electromagnetic processes for Marmara Sea earthquakes," EGU 2008. [3] T. Sengor, "On the exact interaction mechanism of electromagnetically generated phenomena with significant earthquakes and the observations related the exact predictions before the significant earthquakes at July 1999-May 2000 period," Helsinki Univ. Tech. Electrom. Lab. Rept. 368, May 2001. [4] T. Sengor, "The Observational Findings Before The Great Earthquakes Of December 2004 And The Mechanism Extraction From Associated Electromagnetic Phenomena," Book of XXVIIIth URSI GA 2005, pp. 191, EGH.9 (01443) and Proceedings 2005 CD, New Delhi, India, Oct. 23-29, 2005. [5] T. Sengor, "The interaction mechanism among electromagnetic phenomena and geophysical-seismic-ionospheric phenomena with extraction for exact earthquake prediction genetics," 10th SA of the IAGA 2005, Abst. CD,. GAI, C109, No.: IAGA2005-A-0134, Toulouse, France, July18-29, 2005.

  13. Heavy-metal complexation by de novo peptide design.

    PubMed

    Farrer, Brian T; Pecoraro, Vincent L

    2002-11-01

    From poisoning caused by lead-based paint on domestic buildings to groundwater contamination by naturally occurring arsenic deposits in India, heavy-metal toxicity is a global health problem. Contaminated ground water and acute cases of heavy-metal poisoning are treated with chelators to remove the heavy metals from the contaminated site or person. This review discusses the effort to generate heavy-metal chelators through peptide de novo design. De novo design entails the design of a primary sequence that will precisely fold into a predetermined secondary and tertiary protein structure. The first-generation peptide chelator used to initiate this investigation is the three-stranded coild coil containing Cys. Cys provides a potential trigonal binding site with soft thiolate ligands, which has been proposed to provide specific interactions with heavy metals. This hypothesis derives from the observation that similar sites on natural proteins show selectivity for heavy metals over other essential metals, such as Zn or Mg. A description of two systems, the TRI series and the IZ-AC peptide, is given, highlighting the interaction of these peptides with Hg, Cd, As and Pb. Arguments are also presented for the potential use of three-helix bundles as a second-generation design. PMID:12478724

  14. Metal-isonitrile adducts for preparing radionuclide complexes for labelling and imaging agents

    DOEpatents

    Jones, Alun G.; Davison, Alan; Abrams, Michael J.

    1987-01-01

    A method for preparing a coordination complex of an isonitrile ligand and radionuclide such as Tc, Ru, Co, Pt, Fe, Os, Ir, W, Re, Cr, Mo, Mn, Ni, Rh, Pd, Nb and Ta is disclosed. The method comprises preparing a soluble metal adduct of said isonitrile ligand by admixing said ligand with a salt of a displaceable metal having a complete d-electron shell selected from the group consisting of Zn, Ga, Cd, In, Sn, Hg, Tl, Pb and Bi to form a soluble metal-isonitrile salt, and admixing said metal isonitrile salt with a salt comprising said radioactive metal in a suitable solvent to displace said displaceable metal with the radioactive metal thereby forming said coordination. The complex is useful as a diagnostic agent for labelling liposomes or vesicles, and selected living cells containing lipid membranes, such as blood clots, myocardial tissue, gall bladder tissue, etc.

  15. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices--CCSD(T) calculations and atomic site occupancies.

    PubMed

    Davis, Barry M; McCaffrey, John G

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y(1)P ← a(1)S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm(-1)). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr2 while this transition is quenched in Ba2. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba2 indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications. PMID:26827218

  16. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices—CCSD(T) calculations and atomic site occupancies

    NASA Astrophysics Data System (ADS)

    Davis, Barry M.; McCaffrey, John G.

    2016-01-01

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ṡ RG ground state interaction potentials. The y1P←a1S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ṡ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm-1). All of the M ṡ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr2 while this transition is quenched in Ba2. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba2 indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.

  17. Super earth interiors and validity of Birch's Law for ultra-high pressure metals and ionic solids

    NASA Astrophysics Data System (ADS)

    Ware, Lucas Andrew

    2015-01-01

    Super Earths, recently detected by the Kepler Mission, expand the ensemble of known terrestrial planets beyond our Solar System's limited group. Birch's Law and velocity-density systematics have been crucial in constraining our knowledge of the composition of Earth's mantle and core. Recently published static diamond anvil cell experimental measurements of sound velocities in iron, a key deep element in most super Earth models, are inconsistent with each other with regard to the validity of Birch's Law. We examine the range of validity of Birch's Law for several metallic elements, including iron, and ionic solids shocked with a two-stage light gas gun into the ultra-high pressure, temperature fluid state and make comparisons to the recent static data.

  18. Effect of entropy-packing fraction relation on the formation of complex metallic materials

    NASA Astrophysics Data System (ADS)

    Tourki Samaei, Arash; Mohammadi, Ehsan

    2015-09-01

    By combining a number of elements to form complex metallic materials without a base element, it was recently shown that one can obtain rather complex structures, including random solute solutions, multi-phased mixtures and amorphous structures with/without nano-precipitations. Compared to conventional metallic materials, these complex ones could show excellent mechanical and physical properties across a wide range of temperatures, therefore being a promising advanced material for high-temperature applications; however, designing these complex materials, at present, still lacks a unified physical approach but relies on the choice of a few metallurgical parameters, such as atomic size mismatch, heat of mixing and valence electron concentration. Here, we identify a physical mechanism through the optimization of the excess configurational entropy of mixing in the control of phase formation in these metallic materials. The theoretical framework herein established is expected to provide a new paradigm in pursuit of complex metallic materials with superior properties.

  19. Determination of stability constants of aminoglycoside antibiotics with their metal complexes

    NASA Astrophysics Data System (ADS)

    Tiwow, Vanny M. A.

    2014-03-01

    One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

  20. DETERMINATION OF METALS IN SOLID SAMPLES BY COMPLEXATION-SFE AND GC-ATOMIC EMISSION DETECTION

    EPA Science Inventory

    Complexation followed by SFE has been investigated for the extraction of Cu2+, Co2+, Cd2+, and Zn2+ ions from solid samples. ithium bis(trifluoroethyl)dithiocarbamate (FDDC) was used as the complexing agent in this study. he metal-FDDC complexes in the SFE extracts were determine...

  1. Optimization of film synthesized rare earth transition metal permanent magnet systems. Progress report, August 1, 1991--July 31, 1992

    SciTech Connect

    Cadieu, F.J.

    1992-08-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  2. Optimization of film synthesized rare earth transition metal permanent magnet systems. Progress report, August 1, 1989--July 1990

    SciTech Connect

    Cadieu, F.J.

    1990-12-31

    This report reviews work on the optimization of film synthesized rare earth transition metal permanent magnet systems. Topics include: high coercivity in Sm-Fe-Ti-V, Sm-Fe-V, and two element systems; ThMn{sub 12} type pseudobinary SmFe{sub 12 {minus} X}T{sub X}; and sputter process control for the synthesis of precisely textured RE-TM magnetic films. (JL)

  3. Heavy metals and rare earth elements source-sink in some Egyptian cigarettes as determined by neutron activation analysis.

    PubMed

    Nada, A; Abdel-Wahab, M; Sroor, A; Abdel-Haleem, A S; Abdel-Sabour, M F

    1999-07-01

    Heavy metals and rare earth elements in two types of cigarettes were studied. The contents of trace elements were determined by using delayed neutron activation analysis. In the present study 11 elements have been detected in popular and fine brand cigarettes marketed in Egypt. Evaluation of these elements with their potential hazards for smokers is briefly discussed. The material balance (source and sink) for each element was determined. Also the ratio of element recovery to the total amount was assessed. PMID:10376325

  4. Influence of doping with alkaline earth metals on the optical properties of thermochromic VO2

    NASA Astrophysics Data System (ADS)

    Dietrich, Marc K.; Kramm, Benedikt G.; Becker, Martin; Meyer, Bruno K.; Polity, Angelika; Klar, Peter J.

    2015-05-01

    Thin films of doped VO2 were deposited, analyzed, and optimized with regard to their solar energy transmittance (Tsol) and visible/luminous light transmittance (Tlum) which are important parameters in the context of smart window applications in buildings. The doping with alkaline earth metals (AEM) like Mg, Ca, Sr, or Ba increased both Tsol and Tlum due to a bandgap widening and an associated absorption edge blue-shift. Thereby, the brown-yellowish color impression of pure VO2 thin films, which is one major hindrance limiting the usage of VO2 as thermochromic window coating, was overcome. Transparent thin films with excellent switching behavior were prepared by sputtering. Highly doped V1-xMexO2 (Me = Ca, Sr, Ba) kept its excellent thermochromic switching behavior up to x(Me) = Me/(Me + V) = 10 at. % doping level, while the optical bandgap energy was increased from 1.64 eV for undoped VO2 to 2.38 eV for x(Mg) = 7.7 at. %, 1.85 eV for x(Ca) = 7.4 at. %, 1.84 eV for x(Sr) = 6.4 at. % and 1.70 eV for x(Ba) = 6.8 at. %, as well as the absorption edge is blue shifted by increasing AEM contents. Also, the critical temperature ϑc, at which the semiconductor-to-metal transition (SMT) occurs, was decreased by AEM doping, which amounted to about -0.5 K/at. % for all AEM on average. The critical temperature was determined by transmittance-temperature hysteresis measurements. Furthermore, Tsol and Tlum were calculated and were found to be significantly enhanced by AEM doping. Tlum increased from 32.0% in undoped VO2 to 43.4% in VO2 doped with 6.4 at. % Sr. Similar improvements were found for other AEM. The modulation of the solar energy transmittance ΔTsol, which is the difference of the Tsol values in the low and high temperature phase, was almost constant or even slightly increased when the doping level was increased up to about 10 at. % Ca, Sr, or Ba.

  5. Surface structure of the Ag-In-(rare earth) complex intermetallics

    NASA Astrophysics Data System (ADS)

    Hars, S. S.; Sharma, H. R.; Smerdon, J. A.; Yadav, T. P.; Al-Mahboob, A.; Ledieu, J.; Fournée, V.; Tamura, R.; McGrath, R.

    2016-05-01

    We present a study of the surface structure of the Ag-In-RE (RE: rare-earth elements Gd, Tb, and Yb) complex intermetallics using scanning tunneling microscopy and low-energy electron diffraction. The surface of the Ag-In-Yb approximant prepared by sputter-annealing methods under ultrahigh-vacuum conditions produces a flat (100) surface with no facets. However, the Ag-In-Gd and Ag-In-Tb 1/1 approximants, which have a surface miscut of about 12∘ relative to the (100) plane, develop surface facets along various crystallographic directions. The structure of each facet can be explained as a truncation of the rhombic triacontahedral clusters, i.e., the main building blocks of these systems. Despite their differences in atomic structure, symmetry, and density, the facets show common features. The facet planes are In rich. The analysis of the nearest-neighbor atom distances suggests that In atoms form bonds with the RE atoms, which we suggest is a key factor that stabilizes even low-density facet planes.

  6. The occurrence of heavy metals in the vicinity of industrial complexes in Nigeria

    SciTech Connect

    Ndiokwere, C.L.; Ezihe, C.A. )

    1990-01-01

    The accumulation of Cd, Cr, Cu, Ni, Pb, and Zn in soils, crops, and plants as a result of industrial activities has been examined at various locations in the vicinities of steel and refinery complexes. High concentrations of the metals were recorded in all the samples from the sites close to the emission sources and the levels decreased with distance away from the sources. Considerable amounts of the metals found in the crops and plants were mainly due to aerial deposition. Soil and crop contamination by the metals was generally higher in the steel complex than the refinery. Cadmium and lead levels were particularly high in all the samples from both complexes.

  7. Ln₃FeGaQ₇: A new series of transition-metal rare-earth chalcogenides

    SciTech Connect

    Yin, Wenlong; Wang, Wendong; Kang, Lei; Lin, Zheshuai; Feng, Kai; Shi, Youguo; and others

    2013-06-01

    A new series of transition-metal rare-earth chalcogenides, Ln₃FeGaQ₇ (Ln=Nd, Sm, Gd, Dy, Q=S; Ln=Nd, Gd, Dy, Q=Se), have been synthesized by solid state reactions. They are isostructural and crystallize in the space group P6₃. They adopt a three-dimensional framework composed of LnQ₇ monocapped trigonal prisms with the interesting 1[FeS₃]⁴⁻ chains and isolated GaQ₄ tetrahedra lying in two sets of channels in the framework. Magnetic susceptibility measurements on Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) indicate that they are paramagnetic and obey the Curie–Weiss law. Based on the diffuse reflectance spectra, Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) should have band gaps smaller than 0.5 eV. Electronic conductivity measurement on Dy₃FeGaSe₇ demonstrates semiconducting behavior with σ₃₀₀=0.124 S/cm. The first-principles calculations were also performed to study the electronic structures of these compounds. - Graphical abstract: Ln₃FeGaQ₇ adopt a three-dimensional framework composed of LnQ₇ monocapped trigonal prisms with interesting 1[FeS₃]⁴⁻ chains and isolated GaQ₄ tetrahedra lying in two sets of channels in the framework. Highlights: • New compounds, Ln₃FeGaQ₇ (Ln=Nd, Sm, Gd, Dy, Q=S, Se), were synthesized. • They are isostructural and crystallize in the noncentrosymmetric space group P6₃. • They adopt a three-dimensional framework built by LnQ₇ monocapped trigonal prisms. • Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) are paramagnetic and obey the Curie–Weiss law. • Electronic conductivity of Dy₃FeGaSe₇ shows semiconducting behavior.

  8. Materials flow analysis of neodymium, status of rare earth metal in the Republic of Korea.

    PubMed

    Swain, Basudev; Kang, Leeseung; Mishra, Chinmayee; Ahn, JoongWoo; Hong, Hyun Seon

    2015-11-01

    Materials flow analysis of neodymium, status of rare earth elements (REEs) in the Republic of Korea has been investigated. Information from various resources like the Korean Ministry of Environment, Korea international trade association, United Nations Commodity Trade Statistics Database and from individual industry were collected and analyzed for materials flow analysis of neodymium. Demand of neodymium in the Republic of Korea for the year 2010 was 409.5 tons out of which the majority of neodymium, i.e., 68.41% was consumed by domestic electronics industry followed by medical appliances manufacturing (13.36%). The Republic Korea is one of the biggest consumer and leading exporter of these industrial products, absolutely depends on import of neodymium, as the country is lacking natural resources. The Republic of Korea has imported 325.9 tons of neodymium permanent magnet and 79.5 tons of neodymium containing equipment parts mainly for electronics, medical appliances, and heavy/light vehicles manufacturing industry. Out of which 95.4 tons of neodymium permanent magnet get exported as an intermediate product and 140.6 tons of neodymium in the form of consumable products get exported. Worldwide the neodymium is at the high end of supply chain critical metal because of increasing demand, scarcity and irreplaceable for technological application. To bring back the neodymium to supply stream the recycling of end of life neodymium-bearing waste can be a feasible option. Out of total domestic consumption, only 21.9 tons of neodymium have been collected and subsequently recycled. From material flow analysis, the requirement for an efficient recycling system and element-wise material flow management for these REEs in the Republic of Korea were realized and recommended. PMID:26210233

  9. Accumulation of alkaline earth metals by the green macroalga Bryopsis maxima.

    PubMed

    Takahashi, Shigekazu; Aizawa, Kyoko; Nakamura, Saki; Nakayama, Katsumi; Fujisaki, Shingo; Watanabe, Soichiro; Satoh, Hiroyuki

    2015-04-01

    Twenty-five days after the disaster at the Fukushima Daiichi nuclear power plant in 2011, we collected samples of the green macroalga Bryopsis maxima from the Pacific coast of Japan. Bryopsis maxima is a unicellular, multinuclear, siphonous green macroalga. Radiation analysis revealed that B. maxima emitted remarkably high gamma radiation of (131)I, (134)Cs, (137)Cs, and (140)Ba as fission products of (235)U. Interestingly, B. maxima contained naturally occurring radionuclides derived from (226)Ra and (228)Ra. Analysis of element content revealed that B. maxima accumulates many ocean elements, especially high quantities of the alkaline earth metals Sr (15.9 g per dry-kg) and Ba (3.79 g per dry-kg), whereas Ca content (12.5 g per dry-kg) was lower than that of Sr and only 61 % of the mean content of 70 Japanese seaweed species. Time-course analysis determined the rate of radioactive (85)Sr incorporation into thalli to be approximately 0.13 g Sr per dry-kg of thallus per day. Subcellular fractionation of B. maxima cells showed that most of the (85)Sr was localized in the soluble fraction, predominantly in the vacuole or cytosol. Given that (85)Sr radioactivity was permeable through a dialysis membrane, the (85)Sr was considered to be a form of inorganic ion and/or bound with a small molecule. Precipitation analysis with sodium sulfate showed that more than 70% of the Sr did not precipitate as SrSO4, indicating that a proportion of the Sr may bind with small molecules in B. maxima. PMID:25744028

  10. OBSERVATIONAL EVIDENCE FOR A METAL-RICH ATMOSPHERE ON THE SUPER-EARTH GJ1214b

    SciTech Connect

    Desert, Jean-Michel; Jacob Bean; Berta, Zachory K.; Charbonneau, David; Irwin, Jonathan; Burke, Christopher J.; Kempton, Eliza Miller-Ricci; Fortney, Jonathan; Nutzman, Philip

    2011-04-20

    We report observations of two consecutive transits of the warm super-Earth exoplanet GJ 1214b at 3.6 and 4.5 {mu}m with the Infrared Array Camera instrument on board the Spitzer Space Telescope. The two transit light curves allow for the determination of the transit parameters for this system. We find these parameters to be consistent with the previously determined values and no evidence for transit timing variations. The main investigation consists of measuring the transit depths in each bandpass to constrain the planet's transmission spectrum. Fixing the system scale and impact parameters, we measure R{sub p} /R{sub *} = 0.1176{sup +0.0008}{sub -0.0009} and 0.1163{sup +0.0010}{sub -0.0008} at 3.6 and 4.5 {mu}m, respectively. Combining these data with the previously reported MEarth Observatory measurements in the red optical allows us to rule out a cloud-free, solar composition (i.e., hydrogen-dominated) atmosphere at 4.5{sigma} confidence. This independently confirms a recent finding that was based on a measurement of the planet's transmission spectrum using the Very Large Telescope (VLT). The Spitzer, MEarth, and VLT observations together yield a remarkably flat transmission spectrum over the large wavelength domain spanned by the data. Consequently, cloud-free atmospheric models require more than 30% metals (assumed to be in the form of H{sub 2}O) by volume to be consistent with all the observations.

  11. Cadmium sorption onto Natural Red Earth - An assessment using batch experiments and surface complexation modeling

    NASA Astrophysics Data System (ADS)

    Mahatantila, K.; Minoru, O.; Seike, Y.; Vithanage, M. S.

    2010-12-01

    Natural red earth (NRE), an iron coated sand found in north western part of Sri Lanka was used to examine its retention behavior of cadmium, a heavy metal postulated as a factor of chronic kidney disease in Sri Lanka. Adsorption studies were examined in batch experiments as a function of pH, ionic strength and initial cadmium loading. Proton binding sites on NRE were characterized by potentiometric titration yielding a pHzpc around 6.6. The cadmium adsorption increased from 6% to 99% along with a pH increase from 4 to 8.5. In addition, the maximum adsorption was observed when pH is greater than 7.5. Ionic strength dependency of cadmium adsorption for 100 fold variation of NaNO3 evidences the dominance of an inner-sphere bonding mechanism for 10 fold variation of initial cadmium loadings (4.44 and 44.4 µmol/L). Adsorption edges were quantified with a 2pK generalized diffuse double layer model considering two site types, >FeOH and >AlOH, for Cd2+ binding. From modeling, we introduced a monodentate chemical bonding mechanism for cadmium binding on to NRE and this finding was further verified with FTIR spectroscopy. Intrinsic constants determined were log KFeOCd = 8.543 and log KAlOCd = 13.917. Isotherm data implies the heterogeneity of NRE surface and the sorption maximum of 9.418 x10-6 mol/g and 1.3x10-4 mol/g for Langmuir and Freundlich isotherm models. The study suggested the potential of NRE as a material in decontaminating environmental water polluted with cadmium.

  12. A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

    PubMed

    Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

    2016-08-01

    Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst. PMID:27335012

  13. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  14. Characterization of metal-peptide complexes in feed supplements of essential trace elements.

    PubMed

    Yiannikouris, Alexandros; Connolly, Cathal; Power, Ronan; Lobinski, Ryszard

    2009-01-01

    Metal chelates with biomolecules are increasingly used in animal supplementation to increase the bioavailability of essential trace elements. However, the transfer of the chelates is not well understood and speciation studies may bring a comprehensive insight to further investigate the biological uptake mechanism(s) implicated. An analytical method was developed for the characterization of the water-soluble metal complexes in animal feed supplements obtained by reaction of a metal salt with a non-GMO soybean enzymatic digest. The method was based on fractionation of the extract by size-exclusion chromatography followed by the analysis of the metal-containing fraction by reversed-phase nanoHPLC with parallel ICP MS and electrospray MS/MS detection. The metal complexes were identified in the mass spectra owing to the Cu characteristic isotopic pattern; the complexation was corroborated by the presence of a peak corresponding to the non-metallated peptide. The study demonstrated the feasibility of SEC-ICP MS to produce characteristic metal (Cu, Zn, Mn, Fe) distribution patterns, which can be of interest to test batch-to-batch reproducibility and to determine the origin of the supplement. The use of the method could be extended to animal feeds prepared using the metal-chelated complexes. Electrospray MS/MS allowed the identification of a number of Cu complexes with peptides. Four different structure conformations were modeled by means of molecular mechanics investigations to assess the chelation stability. PMID:21305120

  15. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    PubMed Central

    Kuroiwa, Keita; Masaki, Yoshitaka; Koga, Yuko; Deming, Timothy J.

    2013-01-01

    The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN)2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN)2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM) showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals). This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water. PMID:23337202

  16. Rare earth element mineralogy, geochemistry, and preliminary resource assessment of the Khanneshin carbonatite complex, Helmand Province, Afghanistan

    USGS Publications Warehouse

    Tucker, Robert D.; Belkin, Harvey E.; Schulz, Klaus J.; Peters, Stephen G.; Buttleman, Kim P.

    2011-01-01

    There is increased concern about the future availability of rare earth elements (REE) because of China's dominance as the supplier of more than 95 percent of world REE output, their decision to restrict exports of rare earth products, and the rapid increase in world-wide consumption of rare earth product. As a result, countries such as the United States, Japan, and member nations of the European Union face a future of tight supplies and high prices for rare earth products unless other sources of REE are found and developed (Long and others, 2010; U.S. Geological Survey, 2011, p. 128-129, 184-185). We report and describe a significant new deposit of light rare earth elements (LREE), estimated at 1 Mt, within the Khanneshin carbonatite complex of south Afghanistan. The potential resource is located in a remote and rugged part of the igneous complex in a region previously identified by Soviet geologists in the 1970s. This report reviews the geologic setting of LREE deposit, presents new geochemical data documenting the grade of LREE mineralization, briefly describes the mineralogy and mineralogical associations of the deposit, and presents a preliminary estimate of LREE resources based on our current understanding of the geology.

  17. Alkali metal, alkaline earth metal, and ammonium ion selectivities of dibenzo-16-crown-5 compounds with functional side arms in ion-selective electrodes

    SciTech Connect

    Ohki, Akira; Lu, J.P.; Huang, X.; Bartsch, R.A. )

    1994-12-01

    Potentiometric selectivities of 11 dibenzo-16-crown-5 compounds for alkali metal, alkaline earth metal, and ammonium ions have been determined in solvent polymeric membrane electrodes. The ionophores bear one or two pendent groups on the central carbon of the three-carbon bridge in the polyether ring. Side-arm variation includes OCH[sub 3], OCH[sub 2]CH[sub 2]OCH[sub 3], OCH[sub 2]CO[sub 2]C[sub 2]H[sub 5], OCH[sub 2]C(O)N(C[sub 2]H[sub 5])[sub 2], and OCH[sub 2]C(O)N(C[sub 5]H[sub 11])[sub 2] units. Attachment of a propyl group to the ring carbon that bears an extended, oxygen-containing side arm increases the selectivity for Na[sup +] relative to larger alkali metal and alkaline earth metal cations. For a given side arm, a linear relationship is obtained when the enhancement in Na[sup +] selectivity produced by attachment of a geminal propyl group is plotted against the diameter of the interference ion. Potentiometric responses of the dibenzo-16-crown-5 compounds are rationalized in terms of the crown ether ring size and the oxygen basicity, conformational positioning, and rigidity of the side arm. 22 refs., 3 figs., 2 tabs.

  18. Binding of dihydromyricetin and its metal ion complexes with bovine serum albumin

    PubMed Central

    Guo, Qingquan; Yuan, Juan; Zeng, Jinhua

    2014-01-01

    The binding mechanisms of the interaction of three dihydromyricetin (DMY)–metal complexes (DMY–Cu (II) complex, DMY–Mn (II) complex, DMY–Zn (II) complex) and DMY with bovine serum albumin (BSA) were investigated using fluorescence and ultraviolet spectroscopy at different temperatures. The results indicated some differences in the binding process between different DMY–metal complexes and BSA compared with that of free DMY. All of the complexes and DMY quenched the fluorescence of BSA based on static mode combined with radiationless energy transfer, yet having different binding distance based on the Förster theory. Different DMY–metal complexes can change the binding constants. The binding constants increase for DMY–Cu (II) and DMY–Mn (II) complexes, whereas the opposite is true for the DMY–Zn (II) complex compared to the one with free DMY. The DMY–metal complexes can also affect the types of the interaction. The van der Waals forces and hydrogen bonding may play a major role in the interaction of free DMY with BSA, while for the three complexes, the nature of the binding forces lies in hydrophobic forces and hydrogen bonding based on the thermodynamic parameters. PMID:26019518

  19. 1H-NMR studies on the ternary complexes of rare-earth ions with thenoyltrifluoroacetone and polyethers in dichloromethane.

    PubMed

    Gagabe, Gene Frederick; Satoh, Keiichi; Sawada, Kiyoshi

    2009-07-28

    The structures of the ternary complexes of lanthanoid and yttrium (Ln3+)-thenoyltrifluoroacetonates (tta-) with polyether (POE) in organic phase were investigated by 1H-NMR spectroscopy, where the POEs are crown ethers (18-crown-6 and benzo-18-crown-6) and monodispersed linear polyethers (DEOn: HO-(CH2CH2O-)nC12H25, where n=4, 6, 8). The changes in chemical shift of methylene protons of POE by addition of the adduct complex [Ln(tta)3(POE)] were measured at various Ln3+-to-POE concentration ratios. Chemical shift changes for each proton of POE by the formation of [Ln(tta)3(POE)] were determined. Results revealed that oxygen atoms at the hydroxyl terminal of linear POE have higher tendency to coordinate to the metal ion in [Ln(tta)3] complex. Three (for La3+) or two (for Lu3+ or Y3+) oxygen atoms of the POE coordinate to the metal ion without substitution of tta- ligands to satisfy the metal ion's coordination number of nine or eight, respectively. In the case of 18-membered crown ether complexes, La3+ is incorporated inside the cavity of the POE, displacing one of the three tta- from the inner coordination sphere while the other two remain coordinated to the metal ion. On the other hand, for the adduct of Y3+ complex with crown ether, all three tta- ligands are directly coordinating to the metal ion. PMID:19587993

  20. Complex inner core of the Earth: The last frontier of global seismology

    NASA Astrophysics Data System (ADS)

    Tkalčić, Hrvoje

    2015-03-01

    The days when the Earth's inner core (IC) was viewed as a homogeneous solid sphere surrounded by the liquid outer core (OC) are now behind us. Due to a limited number of data sampling the IC and a lack of experimentally controlled conditions in the deep Earth studies, it has been difficult to scrutinize competitive hypotheses in this active area of research. However, a number of new concepts linking IC structure and dynamics has been proposed lately to explain different types of seismological observations. A common denominator of recent observational work on the IC is increased complexity seen in IC physical properties such as its isotropic and anisotropic structure, attenuation, inner core boundary (ICB) topography, and its rotational dynamics. For example, small-scale features have been observed to exist as a widespread phenomenon in the uppermost inner core, probably superimposed on much longer-scale features. The characterization of small-scale features sheds light on the nature of the solidification process and helps in understanding seismologically observed hemispherical dichotomy of the IC. The existence of variations in the rate and level of solidification is a plausible physical outcome in an environment where vigorous compositional convection in the OC and variations in heat exchange across the ICB may control the process of crystal growth. However, further progress is hindered by the fact that the current traveltime data of PKIKP waves traversing the IC do not allow discriminating between variations in isotropic P wave velocity and velocity anisotropy. Future studies of attenuation in the IC might provide crucial information about IC structure, although another trade-off exists—that of the relative contribution of scattering versus viscoelastic attenuation and the connection with the material properties. Future installations of dense arrays, cross paths of waves that sample the IC, and corresponding array studies will be a powerful tool to image and

  1. Historical and idealized climate model experiments: an intercomparison of Earth system models of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Eby, M.; Weaver, A. J.; Alexander, K.; Zickfeld, K.; Abe-Ouchi, A.; Cimatoribus, A. A.; Crespin, E.; Drijfhout, S. S.; Edwards, N. R.; Eliseev, A. V.; Feulner, G.; Fichefet, T.; Forest, C. E.; Goosse, H.; Holden, P. B.; Joos, F.; Kawamiya, M.; Kicklighter, D.; Kienert, H.; Matsumoto, K.; Mokhov, I. I.; Monier, E.; Olsen, S. M.; Pedersen, J. O. P.; Perrette, M.; Philippon-Berthier, G.; Ridgwell, A.; Schlosser, A.; Schneider von Deimling, T.; Shaffer, G.; Smith, R. S.; Spahni, R.; Sokolov, A. P.; Steinacher, M.; Tachiiri, K.; Tokos, K.; Yoshimori, M.; Zeng, N.; Zhao, F.

    2013-05-01

    Both historical and idealized climate model experiments are performed with a variety of Earth system models of intermediate complexity (EMICs) as part of a community contribution to the Intergovernmental Panel on Climate Change Fifth Assessment Report. Historical simulations start at 850 CE and continue through to 2005. The standard simulations include changes in forcing from solar luminosity, Earth's orbital configuration, CO2, additional greenhouse gases, land use, and sulphate and volcanic aerosols. In spite of very different modelled pre-industrial global surface air temperatures, overall 20th century trends in surface air temperature and carbon uptake are reasonably well simulated when compared to observed trends. Land carbon fluxes show much more variation between models than ocean carbon fluxes, and recent land fluxes appear to be slightly underestimated. It is possible that recent modelled climate trends or climate-carbon feedbacks are overestimated resulting in too much land carbon loss or that carbon uptake due to CO2 and/or nitrogen fertilization is underestimated. Several one thousand year long, idealized, 2 × and 4 × CO2 experiments are used to quantify standard model characteristics, including transient and equilibrium climate sensitivities, and climate-carbon feedbacks. The values from EMICs generally fall within the range given by general circulation models. Seven additional historical simulations, each including a single specified forcing, are used to assess the contributions of different climate forcings to the overall climate and carbon cycle response. The response of surface air temperature is the linear sum of the individual forcings, while the carbon cycle response shows a non-linear interaction between land-use change and CO2 forcings for some models. Finally, the preindustrial portions of the last millennium simulations are used to assess historical model carbon-climate feedbacks. Given the specified forcing, there is a tendency for the

  2. Coordination chemistry of the alkaline earth metal ions with Zwitterionic forms of the Schift bases. X-Ray studies and other spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Tajmir-Riahi, H. A.; Lotfipoor, M.

    The non-ionized forms of tetradentate Schiff bases NN'-ethylenebis(salicylideneimine), H 2L and NN'-propane-1,3-diylbis(salicylideneimine), H 2L' react with hydrated alkaline earth halide and nitrate to give complexes of the type: M(H 2L)Cl 2· nH 2O [M = Mg(II), Ca(II), Sr(II); n = 0-4], M(H 2L) 2Cl 2 [M = Ca(II), Sr(II), M(H 2L) nBr 2 [M = Ca(II), Sr(II); n = 2, 3 and Mg 2(H 2L) 3Br 4], M(H 2L) nI 2 [M = Mg(II), Ca(II), Sr(II), Ba(II); n = 2, 3)], M(H 2L) n(NO 3) 2 and M(H 2L') n(NO 1) 2[M = Mg(II), Ca(II); n = 1, 2)]. Because of distinct spectral similarities with structurally known Ca(H 2L')(NO 3) 2 compound, the Schiff bases are coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms of the azomethine groups, which carry the protons transferred from phenolic groups on complexation. Halide and nitrate are coordinated to the central metal ion except in 2:1 nitrato complexes where the presence of both ionic and coordinated nitrate groups are evident and also in 3:1 halide complexes where the presence of non-coordinated halide cannot be excluded. X-Ray powder photographs showed no marked similarities between Ca(H 2L')(NO 3) 2 and Mg(H 2L')(NO 3) 2 while there are some isomorphic features between the same types of halide complexes. Infrared spectra and other structural information revealed the polymeric nature of the complexes. Therefore the coordination numbers exhibited by the alkaline earth metal cations would be 4, 6 or 8 in these series of Schiff base complexes.

  3. Structure Characterization and Properties of Metal-Surfactant Complexes Dispersed in Organic Solvents.

    PubMed

    de la Iglesia, Pablo; Jaeger, Vance W; Xi, Yuyin; Pfaendtner, Jim; Pozzo, Lilo D

    2015-08-25

    This work describes the synthesis and characterization of metal-surfactant complexes. Dioctyl sulfosuccinate and dodecylbenzenesulfonate are associated with multivalent aluminum, iron, and vanadium ions using an ion exchange reaction. The metal complexes are dispersible in various organic solvents. In solvents with low polarity, the complexes form "inverse" macromolecular structures with multiple metal ions. In contrast, in alcohols, the complex size is reduced, showing a more disperse conformation. The metal and surfactant ions are still strongly bonded to each other in all the solvents probed. Small-angle X-ray and neutron scattering (SAXS and SANS) are used to characterize the structures. Simultaneous fitting of neutron and X-ray scattering spectra is performed in order to obtain an accurate description of the system. Scattering results are also validated by performing molecular dynamics (MD) simulations. The conductive and electrochemical properties of the complexes in solution are also evaluated. The dispersion of metal-organic complexes significantly increases electric conductivity, and some metal ions in the core of the complexes are shown to be electrochemically active in apolar solvents. PMID:26212253

  4. Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand.

    PubMed

    Davenport, T C; Tilley, T D

    2015-07-21

    A series of dinuclear and tetranuclear first-row transition metal complexes were synthesized with the dinucleating ligand 2,7-bis(di(2-pyridyl)fluoromethyl)-1,8-naphthyridine (DPFN). The coordination pocket and rigidity of the DPFN ligand enforces pseudo-octahedral geometries about the metal centers that contain chloro, hydroxo, and aqua bridging ligands forming a "diamond" shaped configuration with metal-metal distances varying from 2.7826(5) to 3.2410(11) Å. Each metal center in the dinuclear complexes has an additional open coordination site that accommodates terminal ligands in a syn geometry of particular interest in catalyst design. The complexes are characterized by electronic spectroscopy, electrochemistry and potentiometric titration methods. PMID:25420206

  5. Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

    PubMed

    Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

    2007-02-01

    Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction. PMID:17013632

  6. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre.

    PubMed

    Humbert, Nicolas; Mazet, Clément

    2016-08-23

    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated. PMID:27498763

  7. Reactivity of halide and pseudohalide ligands in transition-metal complexes

    SciTech Connect

    Kukushkin, Yu.N.; Kukushkin, V.Yu.

    1985-10-01

    The experimental material on the reactions of coordinated halide ligands, as well as cyanide, azido, thiocyanato, and cyanato ligands, in transition-metal complexes has been generalized in this review.

  8. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1998-06-23

    Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  9. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1998-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  10. Metal-metal interactions in weakly coupled mixed-valence E- and Z-diferrocenylethylene complexes.

    PubMed

    Chen, Y J; Pan, D S; Chiu, C F; Su, J X; Lin, S J; Kwan, K S

    2000-03-01

    To study metal-to-metal interactions in mixed-valence states of two weakly coupling ferrocenyl groups assembled in E or Z conformation on an ethylenic double bond, E-1,2-dimethyldiferrocenylethylene (1), Z-1,2-dimethyldi-ferrocenylethylene (2), and 1,2-diferrocenylcyclohexene (3) were synthesized and structurally characterized. Crystals of 1 are triclinic, P1, with a = 7.494(9) A, b = 10.801(3) A, c = 11.971(2) A, alpha = 102.17(2) degrees, beta = 106.12(9) degrees, gamma = 90.42(2) degrees, V = 907.8 A3, and Z = 2. Crystals of 2 are monoclinic, P2(1)/c, with a = 13.601(8) A, b = 11.104(4) A, c = 13.732(1) A, beta = 114.26(7) degrees, V = 1890.8(3) A3, and Z = 4. Crystals of 3 are orthorhombic, P2(1)2(1)2(1), with a = 5.766(2) A, b = 13.090(1) A, c = 26.695(2) A, V = 2014.9(3) A3, and Z = 4. Intervalence transition spectra (IT) and electrochemical data have been determined and compared with those of diferrocenyl-benzene (para, ortho, and meta). The comproportionation constants in nitrobenzene at 25 degrees C were found to be 490 and 813 for 1 and 3, respectively. That of 2 was not measured because of the fact that 2+ isomerizes rapidly in all solvents tested, yielding nearly a racemic mixture of E and Z conformers. This finding helps to clear the paradoxical phenomenon between experimental results of mixed-valence complexes of E- and Z-1,2-bis(1'-ethyl-1-ferrocenyl)-1,2-dimethylethylene and theories. The stability of the mixed-valence species was discussed in terms of resonance delocalization, Coulomb repulsion energy, inductive effect, magnetic interaction, structural factors, and statistical factor. According to our analysis based on the Hush formalism, the contribution due to Coulomb repulsion energy dominates the overall stability of the mixed-valence state in 1+, 2+, and 3+. Stabilization that arises from resonance delocalization is only minor and contributes less than 4% to the overall stability, even in 3+ where linked Cp rings and the ethylenic plane are

  11. Tunable magnetic and magnetocaloric properties in heavy rare-earth based metallic glasses through the substitution of similar elements

    NASA Astrophysics Data System (ADS)

    Zhang, Huiyan; Li, Ran; Zhang, Leilei; Zhang, Tao

    2014-04-01

    The influence of interchangeable substitution of similar heavy rare-earth-elements (HRE), i.e., Gd-Ho, Gd-Er, and Ho-Er, on the magnetic and magnetocaloric properties of HRE55Al27.5Co17.5 metallic glasses was evaluated. The magnetic transition temperature (TC) can be tuned in a wide temperature range from 8 K to 93 K by adjusting the substitutional concentration in the resulting metallic glasses. A roughly linear correlation between peak value of magnetic entropy change (|ΔSMpk|) and TC-2/3 was obtained in the three systems. This kind of substitutional adjustment provides a useful method for designing desirable candidates in metallic glasses with high magnetic entropy change, large magnetic cooling efficiency, and tunable TC for magnetic refrigerant in nitrogen and hydrogen liquefaction temperature ranges.

  12. Manipulation of a Schlenk Line: Preparation of Tetrahydrofuran Complexes of Transition-Metal Chlorides

    ERIC Educational Resources Information Center

    Davis, Craig M.; Curran, Kelly A.

    2007-01-01

    Before taking an inorganic laboratory course few students have experience handling air-sensitive materials using Schlenk techniques. This exercise introduces them to techniques they will employ in later syntheses. The procedure involves the formation of anhydrous tetrahydrofuran complexes of transition-metal chlorides from metal-chloride hydrates;…

  13. Light element partitioning between silicate and metallic melts: Insights into the formation and composition of Earth's core

    NASA Astrophysics Data System (ADS)

    Myhill, R.; Rubie, D. C.; Frost, D. J.

    2015-12-01

    The mass deficit of the Earth's core, and the increasing solubility of light elements into metallic iron with increasing pressure demonstrate that the Earth's core must contain several weight percent of light elements such as Si, O, C and S. These light elements place important constraints on the depth of the primordial magma ocean(s), the chemical potentials of many of these elements in coexisting phases during differentiation, the temperature of the inner core boundary, and the composition of the bulk Earth. The P-wave velocity, Earth's mass deficit, and depth of the inner core boundary place two important constraints on the chemical composition of the core, but there are multiple trade-offs which cannot be resolved using seismology alone. In this study, we use a large experimental partitioning dataset to build activity-composition models for light elements in metallic melts in equilibrium with oxide and silicate phases (both solid and liquid). We avoid the use of epsilon models, which commonly fail at solute concentrations above a few weight percent. Instead we employ a modified subregular solution model, using intermediate species to calculate excess free energies of mixing. Flexible models like these are required to fit the experimental data which spans 0 - 100 GPa and 1500 - 5500 K. Several heuristics are used to reduce the number of free parameters where they are not independently constrained. We use our models to investigate the conditions of core formation and the chemical composition of the Earth's core using the approach of Rubie et al. (2015; Icarus v.248; pp 89-108).

  14. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1985-01-01

    Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

  15. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1981-11-04

    Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  16. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1983-05-13

    Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  17. Recovery of nickel and cobalt from organic acid complexes: adsorption mechanisms of metal-organic complexes onto aminophosphonate chelating resin.

    PubMed

    Deepatana, A; Valix, M

    2006-09-21

    This study examined the recovery of nickel and cobalt from organic acid complexes using a chelating aminophosphonate Purolite S950 resin. These metal complexes are generated by bioleaching nickel laterite ores, a commercial nickel and cobalt mineral oxide, with heterotrophic organism and their metabolites or organic acid products. Equilibrium adsorption tests were conducted as a function of Ni and Co concentrations (15-2000 mg/L), solution pH (0.01 and 0.1 M acids) and three metabolic complexing agents (citrate, malate and lactate). It was shown that the adsorption of the various Ni- and Co-complexes on Purolite were quite low, 16-18 and 5.4-9 mg/g of resin, respectively, in comparison to the smaller nickel ions and nickel sulfate. This was attributed to the bulky organic ligands which promoted crowding effect or steric hindrance. The adsorption of these complexes was further hampered by the strong affinity of the resin to H+ ions under acidic conditions. Mechanisms of adsorption, as inferred from the fitted empirical Langmuir and Freundlich models, were correlated to the proposed steric hindrance and competitive adsorption effects. Nickel and cobalt elution from the resin were found be effective and were independent of the type of metal complexes and metal concentrations. This study demonstrated the relative challenges involved in recovering nickel and cobalt from bioleaching solutions. PMID:16698178

  18. Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare-earth nickelate thin films.

    PubMed

    Mikheev, Evgeny; Hauser, Adam J; Himmetoglu, Burak; Moreno, Nelson E; Janotti, Anderson; Van de Walle, Chris G; Stemmer, Susanne

    2015-11-01

    Resistances that exceed the Mott-Ioffe-Regel limit (known as bad metal behavior) and non-Fermi liquid behavior are ubiquitous features of the normal state of many strongly correlated materials. We establish the conditions that lead to bad metal and non-Fermi liquid phases in NdNiO3, which exhibits a prototype bandwidth-controlled metal-insulator transition. We show that resistance saturation is determined by the magnitude of Ni eg orbital splitting, which can be tuned by strain in epitaxial films, causing the appearance of bad metal behavior under certain conditions. The results shed light on the nature of a crossover to a non-Fermi liquid metal phase and provide a predictive criterion for Anderson localization. They elucidate a seemingly complex phase behavior as a function of film strain and confinement and provide guidelines for orbital engineering and novel devices. PMID:26601140

  19. Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare-earth nickelate thin films

    PubMed Central

    Mikheev, Evgeny; Hauser, Adam J.; Himmetoglu, Burak; Moreno, Nelson E.; Janotti, Anderson; Van de Walle, Chris G.; Stemmer, Susanne

    2015-01-01

    Resistances that exceed the Mott-Ioffe-Regel limit (known as bad metal behavior) and non-Fermi liquid behavior are ubiquitous features of the normal state of many strongly correlated materials. We establish the conditions that lead to bad metal and non-Fermi liquid phases in NdNiO3, which exhibits a prototype bandwidth-controlled metal-insulator transition. We show that resistance saturation is determined by the magnitude of Ni eg orbital splitting, which can be tuned by strain in epitaxial films, causing the appearance of bad metal behavior under certain conditions. The results shed light on the nature of a crossover to a non-Fermi liquid metal phase and provide a predictive criterion for Anderson localization. They elucidate a seemingly complex phase behavior as a function of film strain and confinement and provide guidelines for orbital engineering and novel devices. PMID:26601140

  20. Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

    NASA Astrophysics Data System (ADS)

    Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

    2009-02-01

    Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.