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Sample records for binding transition metals

  1. A general scheme for the estimation of oxygen binding energies on binary transition metal surface alloys

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

    2005-01-01

    A simple scheme for the estimation of oxygen binding energies on transition metal surface alloys is presented. It is shown that a d-band center model of the alloy surfaces is a convenient and appropriate basis for this scheme; variations in chemical composition, strain effects, and ligand effects...... are all incorporated into the binding energy analysis through this parameter. With few exceptions, the agreement of the results from the simple model with full DFT calculations on hundreds of binary surface alloys is remarkable. The scheme should therefore provide a fast and effective method...... for the estimation of oxygen binding energies on a wide variety of transition metal alloys. (c) 2005 Elsevier B.V. All rights reserved....

  2. Extraction and Binding Efficiency of Calix[8]arene Derivative Toward Selected Transition Metals

    Directory of Open Access Journals (Sweden)

    Imdadullah Qureshi

    2008-12-01

    Full Text Available In this article we have explored the extraction efficiency as well as binding ability of calix[8]arene derivative (3 for selected transition metal ions (Co2+, Cd2+, Ni2+, Pb2+ and Cu2+. Picrate salt solutions of these metals were used in the liquid-liquid extraction experiments. It is apparent from the results that ligand 3 shows appreciable high extraction of transition metal cations, with the relative order Pb2+>Cu2+>Ni2+>Co2+>Cd2+ being observed. Highest extraction efficiency has been observed for Pb2+ and Cu2+ i.e. 95 and 91% respectively. The significant extraction and complexation ability for these metal ions may be attributed to the nature, size, structure and geometry of both ligand and metal ions.

  3. An efficient magnetic tight-binding method for transition metals and alloys

    DEFF Research Database (Denmark)

    Barreteau, Cyrille; Spanjaard, Daniel; Desjonquères, Marie-Catherine

    2016-01-01

    An efficient parameterized self-consistent tight-binding model for transition metals using s, p and d valence atomic orbitals as a basis set is presented. The parameters of our tight-binding model for pure elements are determined from a fit to bulk ab-initio calculations. A very simple procedure...... that does not necessitate any further fitting is proposed to deal with systems made of several chemical elements. This model is extended to spin (and orbital) polarized materials by adding Stoner-like and spin–orbit interactions. Collinear and non-collinear magnetism as well as spin-spirals are considered...

  4. Effective DNA binding and cleaving tendencies of malonic acid coupled transition metal complexes

    Science.gov (United States)

    Pravin, Narayanaperumal; Utthra, Ponnukalai Ponya; Kumaravel, Ganesan; Raman, Natarajan

    2016-11-01

    Eight transition metal complexes were designed to achieve maximum biological efficacy. They were characterized by elemental analysis and various other spectroscopic techniques. The monomeric complexes were found to espouse octahedral geometry and non-electrolytic nature. The DNA interaction propensity of the complexes with calf thymus DNA (CT-DNA), studied at physiological pH by spectrophotometric, spectrofluorometric, cyclic voltammetry, and viscometric techniques revealed intercalation as the possible binding mode. Fascinatingly, the complexes were found to exhibit greater binding strength than that of the free ligands. A strong hypochromism and a slight red shift were exhibited by complex 5 among the other complexes. The intrinsic binding constant values of all the complexes compared to cisplatin reveal that they are excellent metallonucleases than that of cisplatin. The complexes were also shown to reveal displacement of the ethidium bromide, a strong intercalator using fluorescence titrations. Gel electrophoresis was used to divulge the competence of the complexes in cleaving the supercoiled pBR322 plasmid DNA. From the results, it is concluded that the complexes, especially 5, are excellent chemical nucleases in the presence of H2O2. Furthermore, the in vitro antimicrobial screening of the complexes exposes that these complexes are excellent antimicrobial agents. Overall the effect of coligands is evident from the results of all the investigations.

  5. Calculation of elastic constants of BCC transition metals: tight-binding recursion method

    International Nuclear Information System (INIS)

    Masuda, K.; Hamada, N.; Terakura, K.

    1984-01-01

    The elastic constants of BCC transition metals (Fe, Nb, Mo and W) are calculated by using the tight-binding d band and the Born-Mayer repulsive potential. Introducing a small distortion characteristic to C 44 (or C') elastic deformation and calculating the energy change up to second order in the atomic displacement, the shear elastic constants C 44 and C' are determined. The elastic constants C 11 and C 12 are then calculated by using the relations B=1/3(C 11 + 2C 12 ) and C'=1/2(C 11 -C 12 ), where B is the bulk modulus. In general, the agreement between the present results and the experimental values is satisfactory. The characteristic elasticity behaviour, i.e. the strong Nsub(d) (number of d electrons) dependence of the observed anisotropy factor A=C 44 /C', will also be discussed. (author)

  6. A Transition Metal-Binding, Trimeric βγ-Crystallin from Methane-Producing Thermophilic Archaea, Methanosaeta thermophila.

    Science.gov (United States)

    Srivastava, Shanti Swaroop; Jamkhindikar, Aditya Anand; Raman, Rajeev; Jobby, Maroor K; Chadalawada, Swathi; Sankaranarayanan, Rajan; Sharma, Yogendra

    2017-03-07

    βγ-Crystallins are important constituents of the vertebrate eye lens, whereas in microbes, they are prevalent as Ca 2+ -binding proteins. In archaea, βγ-crystallins are conspicuously confined to two methanogens, viz., Methanosaeta and Methanosarcina. One of these, i.e., M-crystallin from Methanosarcina acetivorans, has been shown to be a typical Ca 2+ -binding βγ-crystallin. Here, with the aid of a high-resolution crystal structure and isothermal titration calorimetry, we report that "Methallin", a βγ-crystallin from Methanosaeta thermophila, is a trimeric, transition metal-binding protein. It binds Fe, Ni, Co, or Zn ion with nanomolar affinity, which is consistent even at 55 °C, the optimal temperature for the methanogen's growth. At the center of the protein trimer, the metal ion is coordinated by six histidines, two from each protomer, leading to an octahedral geometry. Small-angle X-ray scattering analysis confirms that the trimer seen in the crystal lattice is a biological assembly; this assembly dissociates to monomers upon removal of the metal ion. The introduction of two histidines (S17H/S19H) into a homologous βγ-crystallin, Clostrillin, allows it to bind nickel at the introduced site, though with micromolar affinity. However, because of the lack of a compatible interface, nickel binding could not induce trimerization, affirming that Methallin is a naturally occurring trimer for high-affinity transition metal binding. While βγ-crystallins are known to bind Ca 2+ and form homodimers and oligomers, the transition metal-binding, trimeric Methallin is a new paradigm for βγ-crystallins. The distinct features of Methallin, such as nickel or iron binding, are also possible imprints of biogeochemical changes during the period of its origin.

  7. Perspectives from ab-initio and tight-binding: Applications to transition metal compounds and superlattices

    Science.gov (United States)

    Venkataraman, Vijay Shankar

    The experimental and theoretical study of transition metal compounds have occupied condensed matter physicists for the best part of the last century. The rich variety of physical behaviour exhibited by these compounds owes its origin to the subtle balance of the energy scales at play for the d orbitals. In this thesis, we study three different systems comprised of transition metal atoms from the third, the fourth, and the fifth group of the periodic table using a combination of ab-initio density functional theory (DFT) computations and effective tight-binding models for the electronic properties. We first consider the electronic properties of artificially fabricated perovskite superlattices of the form [(SrIrO3)m / SrTiO3] with integer m denoting the number of layers of SrIrO3. After discussing the results of experiments undertaken by our collaborators, we present the results of our DFT calculations and build tight-binding models for the m = 1 and m = 2 superlattices. The active ingredient is found to be the 5d orbitals with significant spin-orbit coupling. We then study the energies of magnetic ground states within DFT and compare and contrast our results with those obtained for the bulk Ruddlesden-Popper iridates. Together with experimental measurements, our results suggest that these superlattices are an exciting venue to probe the magnetism and metal-insulator transitions that occur from the intricate balance of the spin-orbit coupling and electron interactions, as has been reported for their bulk counterparts. Next, we consider alpha-RuCl3, a honeycomb lattice compound. We first show using DFT calculations in conjunction with experiments performed by our collaborators, how spin-orbit coupling in the 4d orbitals of Ru is essential to understand the insulating state realized in this compound. Then, in the latter half of the chapter, we study the magnetic ground states of a two-dimensional analogue of alpha-RuCl3 in weak and strong-coupling regimes obtained from

  8. DNA binding, photo-induced DNA cleavage and cytotoxicity studies of lomefloxacin and its transition metal complexes

    Science.gov (United States)

    Ragheb, Mohamed A.; Eldesouki, Mohamed A.; Mohamed, Mervat S.

    2015-03-01

    This work was focused on a study of the DNA binding and cleavage properties of lomefloxacin (LMF) and its ternary transition metal complexes with glycine. The nature of the binding interactions between compounds and calf thymus DNA (CT-DNA) was studied by electronic absorption spectra, fluorescence spectra and thermal denaturation experiments. The obtained results revealed that LMF and its complexes could interact with CT-DNA via partial/moderate intercalative mode. Furthermore, the DNA cleavage activities of the compounds were investigated by gel electrophoresis. Mechanistic studies of DNA cleavage suggest that singlet oxygen (1O2) is likely to be the cleaving agent via an oxidative pathway, except for Cu(II) complex which proceeds via both oxidative and hydrolytic pathways. Antimicrobial and antitumor activities of the compounds were also studied against some kinds of bacteria, fungi and human cell lines.

  9. Application of equilibrium binding model for analysis of conformational transitions in poly(rA)poly(rU) complexes with metal ions

    OpenAIRE

    Sorokin V. A.; Gladchenko G. O.; Usenko E. L.; Egupov S. A.; Blagoi Yu. P.

    2010-01-01

    Aim. The study is aimed at generalization of the previous experimental results on the metal ion (Mg2+, Ni2+, Cd2+) effects on conformation transitions in poly(rA)·poly(rU). The objective was to find out how the type of a metal ion-polynucleotide complex influences the phase transitions and to estimate the constants (K) of ions binding to polymers of different structures. Methods. The K values were obtained upon theoretical and experimental transition temperature fitting by the least-square me...

  10. Occupancy of the Zinc-binding Site by Transition Metals Decreases the Substrate Affinity of the Human Dopamine Transporter by an Allosteric Mechanism.

    Science.gov (United States)

    Li, Yang; Mayer, Felix P; Hasenhuetl, Peter S; Burtscher, Verena; Schicker, Klaus; Sitte, Harald H; Freissmuth, Michael; Sandtner, Walter

    2017-03-10

    The human dopamine transporter (DAT) has a tetrahedral Zn 2+ -binding site. Zn 2+ -binding sites are also recognized by other first-row transition metals. Excessive accumulation of manganese or of copper can lead to parkinsonism because of dopamine deficiency. Accordingly, we examined the effect of Mn 2+ , Co 2+ , Ni 2+ , and Cu 2+ on transport-associated currents through DAT and DAT-H193K, a mutant with a disrupted Zn 2+ -binding site. All transition metals except Mn 2+ modulated the transport cycle of wild-type DAT with affinities in the low micromolar range. In this concentration range, they were devoid of any action on DAT-H193K. The active transition metals reduced the affinity of DAT for dopamine. The affinity shift was most pronounced for Cu 2+ , followed by Ni 2+ and Zn 2+ (= Co 2+ ). The extent of the affinity shift and the reciprocal effect of substrate on metal affinity accounted for the different modes of action: Ni 2+ and Cu 2+ uniformly stimulated and inhibited, respectively, the substrate-induced steady-state currents through DAT. In contrast, Zn 2+ elicited biphasic effects on transport, i.e. stimulation at 1 μm and inhibition at 10 μm A kinetic model that posited preferential binding of transition metal ions to the outward-facing apo state of DAT and a reciprocal interaction of dopamine and transition metals recapitulated all experimental findings. Allosteric activation of DAT via the Zn 2+ -binding site may be of interest to restore transport in loss-of-function mutants. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  11. Occupancy of the Zinc-binding Site by Transition Metals Decreases the Substrate Affinity of the Human Dopamine Transporter by an Allosteric Mechanism*

    Science.gov (United States)

    Li, Yang; Mayer, Felix P.; Hasenhuetl, Peter S.; Burtscher, Verena; Schicker, Klaus; Sitte, Harald H.; Freissmuth, Michael; Sandtner, Walter

    2017-01-01

    The human dopamine transporter (DAT) has a tetrahedral Zn2+-binding site. Zn2+-binding sites are also recognized by other first-row transition metals. Excessive accumulation of manganese or of copper can lead to parkinsonism because of dopamine deficiency. Accordingly, we examined the effect of Mn2+, Co2+, Ni2+, and Cu2+ on transport-associated currents through DAT and DAT-H193K, a mutant with a disrupted Zn2+-binding site. All transition metals except Mn2+ modulated the transport cycle of wild-type DAT with affinities in the low micromolar range. In this concentration range, they were devoid of any action on DAT-H193K. The active transition metals reduced the affinity of DAT for dopamine. The affinity shift was most pronounced for Cu2+, followed by Ni2+ and Zn2+ (= Co2+). The extent of the affinity shift and the reciprocal effect of substrate on metal affinity accounted for the different modes of action: Ni2+ and Cu2+ uniformly stimulated and inhibited, respectively, the substrate-induced steady-state currents through DAT. In contrast, Zn2+ elicited biphasic effects on transport, i.e. stimulation at 1 μm and inhibition at 10 μm. A kinetic model that posited preferential binding of transition metal ions to the outward-facing apo state of DAT and a reciprocal interaction of dopamine and transition metals recapitulated all experimental findings. Allosteric activation of DAT via the Zn2+-binding site may be of interest to restore transport in loss-of-function mutants. PMID:28096460

  12. Vacancies in transition metals

    International Nuclear Information System (INIS)

    Allan, G.; Lannoo, M.

    1976-01-01

    A calculation of the formation energy and volume for a vacancy in transition metals is described. A tight-binding scheme is used for the d band and a Born-Mayer type potential to account for the repulsive part of the energy at small distances. The results show that the relaxation energy is small in all cases, less than 0.1 eV. This seems to be coherent with the good agreement obtained for the theoretical and experimental values of the formation energy Esub(F)sup(V) of the vacancy, without including relaxation. The center of the transitional series is found to give a contraction (Formation volume of order -0.4 at.vol.) whereas the edges are found to produce dilations. (author)

  13. Electronic and Magnetic Properties of Transition-Metal Oxide Nanocomposites: A Tight-Binding Modeling at Mesoscale

    Science.gov (United States)

    Tai, Yuan-Yen; Zhu, Jian-Xin

    Transition metal oxides (TMOs) exhibit many emergent phenomena ranging from high-temperature superconductivity and giant magnetoresistance to magnetism and ferroelectricity. In addition, when TMOs are interfaced with each other, new functionalities can arise, which are absent in individual components. In this talk, I will present an overview on our recent efforts in theoretical understanding of the electronic and magnetic properties TMO nanocomposites. In particular, I will introduce our recently developed tight-binding modeling of these properties arising from the interplay of competing interactions at the interfaces of planar and pillar nanocomposites. Our theoretical tool package will provide a unique capability to address the emergent phenomena in TMO nanocomposites and their mesoscale response to such effects like strain and microstructures at the interfaces, and ultimately help establish design principles of new multifunctionality with TMOs. This work was carried out under the auspices of the National Nuclear Security Administration of the U.S. Department of Energy at LANL under Contract No. DE-AC52-06NA25396, and was supported by the LANL LDRD Program.

  14. Application of equilibrium binding model for analysis of conformational transitions in poly(rApoly(rU complexes with metal ions

    Directory of Open Access Journals (Sweden)

    Sorokin V. A.

    2010-09-01

    Full Text Available Aim. The study is aimed at generalization of the previous experimental results on the metal ion (Mg2+, Ni2+, Cd2+ effects on conformation transitions in poly(rA·poly(rU. The objective was to find out how the type of a metal ion-polynucleotide complex influences the phase transitions and to estimate the constants (K of ions binding to polymers of different structures. Methods. The K values were obtained upon theoretical and experimental transition temperature fitting by the least-square method with the root mean square deviation minimized through the procedure of the gradient descent in the multidimensional space. Results. Calcula- tions of diagrams with Mg2+ are shown to permit obtaining satisfactory results if concentration-independent, mean values of constants are used. For Ni2+ and Cd2+ the concentration dependence of K must be taken into account, especially for high ion contents at which compaction of single-stranded poly(rA emerges. It was revealed that the main factor responsible for the differences in diagrams with Ni2+ and Cd2+ is a significant distinction of their constants of binding to poly(rA and poly(rU. Conclusions. The model theory of equilibrium binding is capable to describe adequately conformation transitions in polynucleotides in the presence of metal ions.

  15. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    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. Quantifying the binding strength of salicylaldoxime-uranyl complexes relative to competing salicylaldoxime-transition metal ion complexes in aqueous solution: a combined experimental and computational study.

    Science.gov (United States)

    Mehio, Nada; Ivanov, Alexander S; Williams, Neil J; Mayes, Richard T; Bryantsev, Vyacheslav S; Hancock, Robert D; Dai, Sheng

    2016-05-31

    The design of new ligands and investigation of UO2(2+) complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime-UO2(2+) complexes were quantified for the first time and compared with the binding strengths of salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes. We found that the binding strengths of salicylaldoxime-UO2(2+) complexes are ∼2-4 log β2 units greater in magnitude than their corresponding salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes; moreover, the selectivity of salicylaldoxime towards the UO2(2+) cation over competing Cu(2+) and Fe(3+) cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO2(2+) selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime-UO2(2+) and salicylaldoxime-transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO2(2+) as a dianion species formed by η(2) coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO2(2+) cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives.

  17. Tight-binding calculations of structural energetics of transition metal-carbides. [TiC; ZrC; HfC; VC; NbC; TaC

    Energy Technology Data Exchange (ETDEWEB)

    Le, D.H.; Colinet, C.; Pasturel, A. (Lab. de Thermodynamique et Physico-Chimie Metallurgiques, ENSEEG, 38 - Saint-Martin-d' Heres (France))

    1991-05-01

    A tight-binding recursion method is used to study the electronic and cohesive properties of stoichiometric and substoichiometric transition metal-carbides crystallizing with the NaCl structure. The electronic structure is analyzed in terms of a p-d interaction between the p orbitals of C and the d orbitals of the transition metal. Concerning the cohesive properties of these compounds, we have calculated the energies of formation of stoichiometric (Ti, Zr, Hf, V, Nb, Ta)-C compounds and compared with the experimental values. We have also studied the stability of vacancy-ordered compounds with a vacancy concentration of 50% on the carbon sublattice, i.e. M{sub 2}C compounds. (orig.).

  18. Synthesis and thermal studies of tetraaza macrocylic ligand and its transition metal complexes. DNA binding affinity of copper complex.

    Science.gov (United States)

    Saif, M; Mashaly, Mahmoud M; Eid, Mohamed F; Fouad, R

    2011-09-01

    A Tetraaza Macrocylic Ligand (H2L) and its complexes, [Cd(H2L)(OH2)2](NO3)(2)·1/2OH2 (I), [Co(H2L)(OH2)](NO3)(2)·1/2OH2 (II), [Cu(H2L)(NO3)2]·3/2OH2 (III) and [Ni(H2L)(NO3)(OH2)]NO3·OH2 (IV), have been synthesized and characterized on the basis of elemental analysis, molar conductivity, 1H NMR, UV-vis, FT-IR and mass spectroscopy. All results confirm that the prepared compounds have 1:1 metal-to-ligand stoichiometry, octahedral configuration and the ligand behaves as a neutral tetradendate towards the metal ions. [CdL(OH2)2] (V), [CoL(OH2)2] (VI), [CuL(OH2)2] (VII) and [Ni(H2L)(NO3)2] (VIII) were synthesized pyrolytically in solid state from corresponding compounds (I-IV). Analytical results of complexes (V-VIII) show that the ligand behaves either as a neutral tetradendate or dianionic tetradentate ligand towards the metal ions. The binding of H2L and its copper complex (III) to DNA has been investigated by ultraviolet absorption spectroscopy. The experiments indicate that H2L and its copper complex (III) can bind to DNA through an intercalative mode. The H2L and its copper complex (III) exhibited anti-tumor activity against Ehrlich Acites Carcinoma (E.A.C) at the concentration of 100 μg/ml. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Band nesting, massive Dirac fermions, and valley Landé and Zeeman effects in transition metal dichalcogenides: A tight-binding model

    Science.gov (United States)

    Bieniek, Maciej; Korkusiński, Marek; Szulakowska, Ludmiła; Potasz, Paweł; Ozfidan, Isil; Hawrylak, Paweł

    2018-02-01

    We present here the minimal tight-binding model for a single layer of transition metal dichalcogenides (TMDCs) MX 2(M , metal; X , chalcogen) which illuminates the physics and captures band nesting, massive Dirac fermions, and valley Landé and Zeeman magnetic field effects. TMDCs share the hexagonal lattice with graphene but their electronic bands require much more complex atomic orbitals. Using symmetry arguments, a minimal basis consisting of three metal d orbitals and three chalcogen dimer p orbitals is constructed. The tunneling matrix elements between nearest-neighbor metal and chalcogen orbitals are explicitly derived at K ,-K , and Γ points of the Brillouin zone. The nearest-neighbor tunneling matrix elements connect specific metal and sulfur orbitals yielding an effective 6 ×6 Hamiltonian giving correct composition of metal and chalcogen orbitals but not the direct gap at K points. The direct gap at K , correct masses, and conduction band minima at Q points responsible for band nesting are obtained by inclusion of next-neighbor Mo-Mo tunneling. The parameters of the next-nearest-neighbor model are successfully fitted to MX 2(M =Mo ; X =S ) density functional ab initio calculations of the highest valence and lowest conduction band dispersion along K -Γ line in the Brillouin zone. The effective two-band massive Dirac Hamiltonian for MoS2, Landé g factors, and valley Zeeman splitting are obtained.

  20. Superconductivity in transition metals.

    Science.gov (United States)

    Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

    2015-03-13

    A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  1. Reference binding energies of transition metal carbides by core-level x-ray photoelectron spectroscopy free from Ar+ etching artefacts

    Science.gov (United States)

    Greczynski, G.; Primetzhofer, D.; Hultman, L.

    2018-04-01

    We report x-ray photoelectron spectroscopy (XPS) core level binding energies (BE's) for the widely-applicable groups IVb-VIb transition metal carbides (TMCs) TiC, VC, CrC, ZrC, NbC, MoC, HfC, TaC, and WC. Thin film samples are grown in the same deposition system, by dc magnetron co-sputtering from graphite and respective elemental metal targets in Ar atmosphere. To remove surface contaminations resulting from exposure to air during sample transfer from the growth chamber into the XPS system, layers are either (i) Ar+ ion-etched or (ii) UHV-annealed in situ prior to XPS analyses. High resolution XPS spectra reveal that even gentle etching affects the shape of core level signals, as well as BE values, which are systematically offset by 0.2-0.5 eV towards lower BE. These destructive effects of Ar+ ion etch become more pronounced with increasing the metal atom mass due to an increasing carbon-to-metal sputter yield ratio. Systematic analysis reveals that for each row in the periodic table (3d, 4d, and 5d) C 1s BE increases from left to right indicative of a decreased charge transfer from TM to C atoms, hence bond weakening. Moreover, C 1s BE decreases linearly with increasing carbide/metal melting point ratio. Spectra reported here, acquired from a consistent set of samples in the same instrument, should serve as a reference for true deconvolution of complex XPS cases, including multinary carbides, nitrides, and carbonitrides.

  2. Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

    Energy Technology Data Exchange (ETDEWEB)

    Greczynski, G., E-mail: grzgr@ifm.liu.se [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden); Primetzhofer, D. [Department of Physics and Astronomy, The Ångström Laboratory, Uppsala University, P.O. Box 516, SE-751 20 Uppsala (Sweden); Lu, J.; Hultman, L. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden)

    2017-02-28

    Highlights: • First non-destructive measurements of XPS core level binding energies for group IVb-VIb transition metal nitrides are presented. • All films are grown under the same conditions and analyzed in the same instrument, providing a useful reference for future XPS studies. • Extracted core level BE values are more reliable than those obtained from sputter-cleaned N-deficient surfaces. • Comparison to Ar+-etched surfaces reveals that even mild etching conditions result in the formation of a nitrogen-deficient surface layer. • The N/metal concentration ratios from capped samples are found to be 25-90% higher than those from the corresponding ion-etched surfaces. - Abstract: We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN’s) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N{sub 2} atmosphere. For XPS measurements, layers are either (i) Ar{sup +} ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy

  3. Transition metals in carbohydrate chemistry

    DEFF Research Database (Denmark)

    Madsen, Robert

    1997-01-01

    This review describes the application of transition metal mediated reactions in carbohydrate synthesis. The different metal mediated transformations are divided into reaction types and illustrated by various examples on monosaccharide derivatives. Carbon-carbon bond forming reactions are further ...

  4. Transition Metal Compounds Towards Holography

    Directory of Open Access Journals (Sweden)

    Volker Dieckmann

    2012-06-01

    Full Text Available We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications.

  5. Electrical Conductivity in Transition Metals

    Science.gov (United States)

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  6. Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

    Science.gov (United States)

    Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

    2017-02-01

    We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from

  7. 2,6-Diiminopiperidin-1-ol: an overlooked motif relevant to uranyl and transition metal binding on poly(amidoxime) adsorbents.

    Science.gov (United States)

    Kennedy, Zachary C; Cardenas, Allan Jay P; Corbey, Jordan F; Warner, Marvin G

    2016-07-07

    Glutardiamidoxime, a structural motif on sorbents used in uranium extraction from seawater, was discovered to cyclize in situ at room temperature to 2,6-diimino-piperidin-1-ol in the presence of uranyl nitrate. The new diimino motif was also generated when exposed to competing transition metals Cu(ii) and Ni(ii). Multinuclear μ-O bridged U(vi), Cu(ii), and Ni(ii) complexes featuring bound diimino ligands were isolated.

  8. Transition Metal Complexes and Catalysis

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 4; Issue 9. Transition Metal Complexes and Catalysis. Balaji R Jagirdar. General Article Volume 4 Issue 9 ... Author Affiliations. Balaji R Jagirdar1. Department of Inorganic & Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India.

  9. Evolution of Metal(Loid) Binding Sites in Transcriptional Regulators

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez, E.; Thiyagarajan, S.; Cook, J.D.; Stemmler, T.L.; Gil, J.A.; Mateos, L.M.; Rosen, B.P.

    2009-05-22

    Expression of the genes for resistance to heavy metals and metalloids is transcriptionally regulated by the toxic ions themselves. Members of the ArsR/SmtB family of small metalloregulatory proteins respond to transition metals, heavy metals, and metalloids, including As(III), Sb(III), Cd(II), Pb(II), Zn(II), Co(II), and Ni(II). These homodimeric repressors bind to DNA in the absence of inducing metal(loid) ion and dissociate from the DNA when inducer is bound. The regulatory sites are often three- or four-coordinate metal binding sites composed of cysteine thiolates. Surprisingly, in two different As(III)-responsive regulators, the metalloid binding sites were in different locations in the repressor, and the Cd(II) binding sites were in two different locations in two Cd(II)-responsive regulators. We hypothesize that ArsR/SmtB repressors have a common backbone structure, that of a winged helix DNA-binding protein, but have considerable plasticity in the location of inducer binding sites. Here we show that an As(III)-responsive member of the family, CgArsR1 from Corynebacterium glutamicum, binds As(III) to a cysteine triad composed of Cys{sup 15}, Cys{sup 16}, and Cys{sup 55}. This binding site is clearly unrelated to the binding sites of other characterized ArsR/SmtB family members. This is consistent with our hypothesis that metal(loid) binding sites in DNA binding proteins evolve convergently in response to persistent environmental pressures.

  10. Homogeneous catalysis by transition metals

    International Nuclear Information System (INIS)

    Masters, K.

    1983-01-01

    Fundamentals of homogeneous catalysis by metal complex aAe presented in the monograph along with the mechanisms of practically all types of catalytic reactions proceeding in the presence of transition metal complexes. In particular, considered are: catalytic cycles for olefin hydrogenation in the presence of Ru(2) complex; for alkene epoxidation catalyzed by Mo(6); for alkene metathesis reaction catalyzed by Ta and W compounds. Catalytic systems on the basis of Zr, Mo, W, Ru complexes being in the stage of development of the processes of nitrogen fixation reductive oligomerization alkene activation are described. Bibliography contains more than 400 references

  11. Immunoglobulin classes, metal binding proteins, and trace metals in ...

    African Journals Online (AJOL)

    , IgA and IgM), metal binding proteins (Transferrin, Caeruloplasmin, Alpha-2- Macroglobulin and Haptoglobin) and nutritionally essential trace metals/heavy metals (Zn, Fe, Se, Cu, Mg, Cd and Pb) in Nigerian cassava processors using single ...

  12. Metal binding by food components

    DEFF Research Database (Denmark)

    Tang, Ning

    For calcium binding: Electrochemical method (calcium ion selective electrode) combined with quantum mechanical calculations (density functional theory) were used to investigate the calcium binding affinity of the amino acids and small glycine peptides. The effects of the ionic strength and p......, synergistic effect in calcium binding was found for the small glycine peptide rather than amino acids mixtures with the enhanced driving force up to -6 kJ/mol. Such study provides useful information for the future development of calcium supplements. For zinc binding: Isothermal titration calorimetry...... titration calorimetry and quantum mechanical calculations. This is due to the zinc binding affinity of the relatively softer ligands (investigated food components) will become much stronger than citrate or phytate when they present together in aqueous solution. This mechanism indicates these food components...

  13. Metal-to-nonmetal transitions

    CERN Document Server

    Hensel, Friedrich; Holst, Bastian

    2010-01-01

    This book is devoted to nonmetal-to-metal transitions. The original ideas of Mott for such a transition in solids have been adapted to describe a broad variety of phenomena in condensed matter physics (solids, liquids, and fluids), in plasma and cluster physics, as well as in nuclear physics (nuclear matter and quark-gluon systems). The book gives a comprehensive overview of theoretical methods and experimental results of the current research on the Mott effect for this wide spectrum of topics. The fundamental problem is the transition from localized to delocalized states which describes the nonmetal-to-metal transition in these diverse systems. Based on the ideas of Mott, Hubbard, Anderson as well as Landau and Zeldovich, internationally respected scientists present the scientific challenges and highlight the enormous progress which has been achieved over the last years. The level of description is aimed to specialists in these fields as well as to young scientists who will get an overview for their own work...

  14. Enantioselective, transition metal catalyzed cycloisomerizations.

    Science.gov (United States)

    Marinetti, Angela; Jullien, Hélène; Voituriez, Arnaud

    2012-07-21

    This review illustrates enantioselective transition-metal promoted skeletal rearrangements of polyunsaturated substrates possessing olefin, alkyne or allene functions. These processes are classified according to the number of carbon atoms involved in the cyclization, from (1C+1C) to (2C+2C+2C) or (2C+5C) cyclizations. Thus, for instance, (1C+1C) processes are typified notably by Alder-ene type reactions taking place mainly under palladium and rhodium catalysis, in the presence of chiral phosphorus ligands. Also, rhodium, platinum, and gold promoted insertions of unsaturated carbon-carbon bonds into C-H bonds belong to this class. For each class of reactions or substrate type the best ligand-metal pairs are highlighted. Unfortunately, unlike other transition metal promoted reactions, the mechanisms of chiral induction and stereochemical pathways have not been established so far in any of these reactions. In only a few instances, qualitative heuristic models have been tentatively proposed. Although the available stereochemical information is systematically given here, the paper focuses mainly on synthetic aspects of enantioselective cycloisomerizations.

  15. Heterostructures of transition metal dichalcogenides

    KAUST Repository

    Amin, Bin

    2015-08-24

    The structural, electronic, optical, and photocatalytic properties of out-of-plane and in-plane heterostructures of transition metal dichalcogenides are investigated by (hybrid) first principles calculations. The out-of-plane heterostructures are found to be indirect band gap semiconductors with type-II band alignment. Direct band gaps can be achieved by moderate tensile strain in specific cases. The excitonic peaks show blueshifts as compared to the parent monolayer systems, whereas redshifts occur when the chalcogen atoms are exchanged along the series S-Se-Te. Strong absorption from infrared to visible light as well as excellent photocatalytic properties can be achieved.

  16. 2D transition metal dichalcogenides

    Science.gov (United States)

    Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego; Yazyev, Oleg V.; Kis, Andras

    2017-08-01

    Graphene is very popular because of its many fascinating properties, but its lack of an electronic bandgap has stimulated the search for 2D materials with semiconducting character. Transition metal dichalcogenides (TMDCs), which are semiconductors of the type MX2, where M is a transition metal atom (such as Mo or W) and X is a chalcogen atom (such as S, Se or Te), provide a promising alternative. Because of its robustness, MoS2 is the most studied material in this family. TMDCs exhibit a unique combination of atomic-scale thickness, direct bandgap, strong spin-orbit coupling and favourable electronic and mechanical properties, which make them interesting for fundamental studies and for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. In this Review, the methods used to synthesize TMDCs are examined and their properties are discussed, with particular attention to their charge density wave, superconductive and topological phases. The use of TMCDs in nanoelectronic devices is also explored, along with strategies to improve charge carrier mobility, high frequency operation and the use of strain engineering to tailor their properties.

  17. ANIONS FUNCTIONS IN TRANSITION METALS COORDINATION COMPOUNDS

    Directory of Open Access Journals (Sweden)

    T. V. Koksharova

    2016-04-01

    Full Text Available The effect of anions on the structure and properties of coordination compounds of transition metals has been discussed. The examples of changes in the composition of the formed complexes by replacement of the anion are given: metal ratio to a neutral ligand, the composition of the inner sphere, the direction of template synthesis. Anions can determine the presence of isomers in complexes with different ligands. Examples of conformational, ionization isomerism, inner sphere bond isomerization are given. The nature of the coordination polyhedron is highly sensitive to the replacement of the anion too. Examples of coordination compounds where the anion change causes a change in coordination capacity of neutral ligands and the strength of their bonds with the metal, coordination number and geometry of the inner sphere, the organization of molecular structures (the structure of the hydrogen bond networks and the degree of polymerization, crystal packing. The anions significantly affect the binding of the solvent molecules, complexes magnetic and luminescent properties, they can change the compound color, the mechanisms of thermolysis. Anions make a very noticeable influence on possible redox processes following the complexation in some cases. Anions in the coordination sphere can change catalytic and biochemical processes as well as the ways of interaction of metal ions with drugs.

  18. Dark excitations in monolayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Deilmann, Thorsten; Thygesen, Kristian Sommer

    2017-01-01

    Monolayers of transition metal dichalcogenides (TMDCs) possess unique optoelectronic properties, including strongly bound excitons and trions. To date, most studies have focused on optically active excitations, but recent experiments have highlighted the existence of dark states, which are equally...... important in many respects. Here, we use ab initio many-body calculations to unravel the nature of the dark excitations in monolayer MoSe2, MoS2, WSe2, andWS(2). Our results show that all these monolayer TMDCs host dark states as their lowest neutral and charged excitations. We further show that dark...... excitons possess larger binding energies than their bright counterparts while the opposite holds for trions....

  19. Heavy metals binding properties of esterified lemon

    International Nuclear Information System (INIS)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

    2009-01-01

    Sorption of Cd 2+ , Cr 3+ , Cu 2+ , Ni 2+ , Pb 2+ and Zn 2+ onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni 2+ > Cd 2+ > Cu 2+ > Pb 2+ > Zn 2+ > Cr 3+ . The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb 2+ > Cu 2+ > Ni 2+ > Cd 2+ > Zn 2+ > Cr 3+ . The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol -1 for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The ΔG o and ΔH o values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low ΔH o values revealed that physical adsorption significantly contributed to the mechanism.

  20. Heavy metals binding properties of esterified lemon.

    Science.gov (United States)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

    2009-05-30

    Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.

  1. Heavy metals binding properties of esterified lemon

    Energy Technology Data Exchange (ETDEWEB)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey); Tumen, Fikret, E-mail: ftumen@firat.edu.tr [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey)

    2009-05-30

    Sorption of Cd{sup 2+}, Cr{sup 3+}, Cu{sup 2+}, Ni{sup 2+}, Pb{sup 2+} and Zn{sup 2+} onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni{sup 2+} > Cd{sup 2+} > Cu{sup 2+} > Pb{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb{sup 2+} > Cu{sup 2+} > Ni{sup 2+} > Cd{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol{sup -1} for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The {Delta}G{sup o} and {Delta}H{sup o} values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low {Delta}H{sup o} values revealed that physical adsorption significantly contributed to the mechanism.

  2. Superconducting Metallic Glass Transition-Edge-Sensors

    Science.gov (United States)

    Hays, Charles C. (Inventor)

    2013-01-01

    A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

  3. Electronic doping of transition metal oxide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz [Department of Control Engineering, Czech Technical University in Prague, Technicka 2, 16627 Prague 6 (Czech Republic); Rondinelli, James M. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States)

    2016-05-23

    CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  4. QM/MM Molecular Dynamics Studies of Metal Binding Proteins

    Directory of Open Access Journals (Sweden)

    Pietro Vidossich

    2014-07-01

    Full Text Available Mixed quantum-classical (quantum mechanical/molecular mechanical (QM/MM simulations have strongly contributed to providing insights into the understanding of several structural and mechanistic aspects of biological molecules. They played a particularly important role in metal binding proteins, where the electronic effects of transition metals have to be explicitly taken into account for the correct representation of the underlying biochemical process. In this review, after a brief description of the basic concepts of the QM/MM method, we provide an overview of its capabilities using selected examples taken from our work. Specifically, we will focus on heme peroxidases, metallo-β-lactamases, α-synuclein and ligase ribozymes to show how this approach is capable of describing the catalytic and/or structural role played by transition (Fe, Zn or Cu and main group (Mg metals. Applications will reveal how metal ions influence the formation and reduction of high redox intermediates in catalytic cycles and enhance drug metabolism, amyloidogenic aggregate formation and nucleic acid synthesis. In turn, it will become manifest that the protein frame directs and modulates the properties and reactivity of the metal ions.

  5. Design, synthesis and DNA binding activities of late first row transition metal(II) complexes of bi- functional tri - and tetratopic imines

    Science.gov (United States)

    Netalkar, Priya P.; Kamath, Anupama; Netalkar, Sandeep P.; Revankar, Vidyanand K.

    2012-11-01

    A series of novel Co(II), Ni(II), Cu(II) and Zn(II) complexes of tri and tetratopic hydrazones have been prepared. Ligands L1H2 and L2H2 were synthesized by the condensation of 2-formylphenoxyacetic acid with 2-hydrazinobenzothiazole and 2-hydroxy-3-hydrazinebenzopyrazine, respectively. The prepared complexes were characterized by the analytical and spectral techniques. All the complexes were found to be monomeric in nature with octahedral geometry. Both ligands were found to be electrochemically active in the working potential range showing single electron transfer process attributed to the deprotonation of carboxylic group of the 2-formylphenoxyacetic acid. The potency of the ligand and its complexes as antimicrobial agents has been investigated and made to interact with Escherichia coli DNA to investigate the binding/cleaving ability by absorption, hydrodynamic and electrophoresis studies.

  6. Polyoxometalate coordinated transition metal complexes as ...

    Indian Academy of Sciences (India)

    Keywords. Heptamolybdate type polyoxometalate cluster anion; transition metal coordination complexes; ... industrial chemistry. This oxidation can be divided into three categories: (i) the cleavage of the C=C bond by using the surface of the metal oxide, e.g., osmium or .... supported cobalt complexes (catalysts 1 and 2) pro-.

  7. Transition metal catalysis in confined spaces

    NARCIS (Netherlands)

    Leenders, S.H.A.M.; Gramage-Doria, R.; de Bruin, B.; Reek, J.N.H.

    2015-01-01

    Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has

  8. New transition metal complexes of 2,4-dihydroxybenzaldehyde benzoylhydrazone Schiff base (H2dhbh): Synthesis, spectroscopic characterization, DNA binding/cleavage and antioxidant activity

    Science.gov (United States)

    Aboafia, Seyada A.; Elsayed, Shadia A.; El-Sayed, Ahmed K. A.; El-Hendawy, Ahmed M.

    2018-04-01

    New complexes [VO2(Hdhbh)] (1), [VO(phen)(dhbh)].1.5H2O (2), [Zn(Hdhbh)2] (3), [MoO2(dhbh)(D)] (D = H2O (4) or MeOH (5)), [Ru(PPh3)(dhbh)Cl(H2O)] (6), and [Pd(Hdhbh)Cl]·H2O (7) (H2dhbh = Schiff base derived from 2,4-dihydroxybenzaldehyde and benzoylhydrazone) have been isolated and characterized by IR, 1H NMR, Mass, UV-Visible and ESR spectroscopy. They were also investigated by cyclic voltammetry, thermal and magnetic measurements and the structure of complex cis-[MoO2(dhbh)(H2O)] (4) was solved by X-ray crystallography. Analytical data showed that H2dhbh behaves as monobasic/or dibasic tridentate ligand via phenolate O, azomethine N and amide O/or deprotonated amide O atoms. Antioxidant activity of the complexes has been evaluated against DPPH (2,2-diphenyl-1-picrylhydrazyl) radical and it has been found that oxovandium (IV) complex (2) displays the highest radical scavenging potency comparable to ascorbic acid as a standard antioxidant. The DNA binding properties of the ligand and its complexes have been investigated by electronic spectroscopy together with DNA cleavage by gel electrophoresis whose results showed also that vanadium (IV) complex (2) has a significant oxidative cleavage among other complexes.

  9. Capturing the photo-signaling state of a photoreceptor in a steady-state fashion by binding a transition metal complex.

    Science.gov (United States)

    Yu, Pengyun; Song, Lei; Qin, Jun; Wang, Jianping

    2017-11-01

    Binding a small molecule to proteins causes conformational changes, but often to a limited extent. Here, we demonstrate that the interaction of a CO-releasing molecule (CORM3) with a photoreceptor photoactive yellow protein (PYP) drives large structural changes in the latter. The interaction of CORM3 and a mutant of PYP, Met100Ala, not only trigger the isomerization of its chromophore, p-coumaric acid, from its anionic trans configuration to a protonated cis configuration, but also increases the content of β-sheet at the cost of α-helix and random coil in the secondary structure of the protein. The CORM3 derived Met100Ala is found to highly resemble the signaling state, which is one of the key photo-intermediates of this photoactive protein, in both protein local conformation and chromophore configuration. The organometallic reagents hold promise as protein engineering tools. This work highlights a novel approach to structurally accessing short lived intermediates of proteins in a steady-state fashion. © 2017 The Protein Society.

  10. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

    We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

  11. LCAO-Xα calculations of transition metal clusters

    International Nuclear Information System (INIS)

    Seifert, G.; Eschrig, H.

    1985-01-01

    The electronic structure of some transition metal clusters (V 6 , Cr 6 , Cu 6 , Ag 6 ) is studied by an approximate LCAO-Xα scheme. Energy level spectra are discussed with respect to other theoretical investigations. The density-of-states curves are represented and compared with those from band-structure calculations. The correlation between binding energies of clusters and the corresponding cohesive energies of the bulk material is shown. Furthermore, the binding energies in copper clusters versus cluster size are discussed. Finally, some experimental results according beams of copper clusters and ESR studies of matrix isolated copper clusters are explained briefly. (author)

  12. Transition metal catalysis in confined spaces.

    Science.gov (United States)

    Leenders, Stefan H A M; Gramage-Doria, Rafael; de Bruin, Bas; Reek, Joost N H

    2015-01-21

    Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has recently been shown to be a viable method to induce new selectivity and activity in transition metal catalysis. In this review we focus on supramolecular strategies to encapsulate transition metal complexes with the aim of controlling the selectivity via the second coordination sphere. As we will discuss, catalyst confinement can result in selective processes that are impossible or difficult to achieve by traditional methods. We will describe the template-ligand approach as well as the host-guest approach to arrive at such supramolecular systems and discuss how the performance of the catalyst is enhanced by confining it in a molecular container.

  13. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  14. Strong-Superstrong Transition in Glass Transition of Metallic Glass

    International Nuclear Information System (INIS)

    Dan, Wang; Hong-Yan, Peng; Xiao-Yu, Xu; Bao-Ling, Chen; Chun-Lei, Wu; Min-Hua, Sun

    2010-01-01

    Dynamic fragility of bulk metallic glass (BMG) of Zr 64 Cu 16 Ni 10 Al 10 alloy is studied by three-point beam bending methods. The fragility parameter mfor Zr 64 Cu 16 Ni 10 Al 10 BMG is calculated to be 24.5 at high temperature, which means that the liquid is a 'strong' liquid, while to be 13.4 at low temperature which means that the liquid is a 'super-strong' liquid. The dynamical behavior of Zr 64 Cu 16 Ni 10 Al 10 BMG in the supercooled region undergoes a strong to super-strong transition. To our knowledge, it is the first time that a strong-to-superstrong transition is found in the metallic glass. Using small angle x-ray scattering experiments, we find that this transition is assumed to be related to a phase separation process in supercooled liquid. (condensed matter: structure, mechanical and thermal properties)

  15. Solubility of hydrogen in transition metals

    International Nuclear Information System (INIS)

    Lee, H.M.

    1976-01-01

    Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

  16. Metals and Neuronal Metal Binding Proteins Implicated in Alzheimer's Disease

    Science.gov (United States)

    2016-01-01

    Alzheimer's disease (AD) is the most prevalent age-related dementia affecting millions of people worldwide. Its main pathological hallmark feature is the formation of insoluble protein deposits of amyloid-β and hyperphosphorylated tau protein into extracellular plaques and intracellular neurofibrillary tangles, respectively. Many of the mechanistic details of this process remain unknown, but a well-established consequence of protein aggregation is synapse dysfunction and neuronal loss in the AD brain. Different pathways including mitochondrial dysfunction, oxidative stress, inflammation, and metal metabolism have been suggested to be implicated in this process. In particular, a body of evidence suggests that neuronal metal ions such as copper, zinc, and iron play important roles in brain function in health and disease states and altered homeostasis and distribution as a common feature across different neurodegenerative diseases and aging. In this focused review, we overview neuronal proteins that are involved in AD and whose metal binding properties may underlie important biochemical and regulatory processes occurring in the brain during the AD pathophysiological process. PMID:26881049

  17. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina

    2016-01-01

    -principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...... shallow defect levels and are thus predicted to be defect-tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with a very similar orbital composition. This indicates a bonding/antibonding nature of the gap, which in turn suggests that dangling bonds will fall inside...

  18. Phase stability of transition metals and alloys

    International Nuclear Information System (INIS)

    Hixson, R.S.; Schiferl, D.; Wills, J.M.; Hill, M.A.

    1997-01-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloy systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results

  19. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  20. Metal ion binding with dehydroannulenes – Plausible two ...

    Indian Academy of Sciences (India)

    WINTEC

    Abstract. Theoretical investigations have been carried out at B3LYP/6-311++G** level of theory to study the binding interaction of various metal ions, Li+, Na+ and K+ with dehydroannulene systems. The present study reveals that alkali metal ions bind strongly to dehydroannulenes and the passage through the central.

  1. Binding properties of oxacalix[4]arenes derivatives toward metal cations

    International Nuclear Information System (INIS)

    Mellah, B.

    2006-11-01

    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) 1 H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na + , K + , Ca 2+ , Pb 2+ and Mn 2+ of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li + , Ba 2+ , Zn 2+ and Hg 2+ . A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs + , Ba 2+ , Cu 2+ and Hg 2+ were noted. (author)

  2. A comparison in activity between transition-metal oxides and transition metals

    Science.gov (United States)

    Vojvodic, Aleksandra; Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Nørskov, Jens

    2012-02-01

    Transition-metal oxides are widely used materials in catalysis as substrates and promoters, but also as the active catalyst materials themselves. We compare the reactivity of transition-metal oxides with the one of transition metals. The comparison is exemplified for the ammonia synthesis reaction. First we show that there exist characteristic Brønsted-Evans Polanyi (BEP) relations (linear relations between transition state and dissociation energies) for dissociation of molecules on transition-metal oxides in the rutile and perovskite structure. It is well-known that the (211) metal surface is several orders of magnitude more reactive than the (111) metal surface due to the lower BEP line for the 211 facet. We find that both rutiles and perovskites follow BEP relations that are lower than the one of the 211 facet. Second we utilize the established BEP relations together with calculated adsorption energetics in a micro-kinetic model to obtain a volcano plot for the catalytic activity. We find that oxides have a higher turn over frequency as compared with metals. Hence, oxides intrinsically have a great advantage in terms of catalytic activity which opens up for catalyst design.

  3. First-row transition metal hydrogenation and hydrosilylation catalysts

    Science.gov (United States)

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

  4. Conformational Transitions and Convergence of Absolute Binding Free Energy Calculations

    Science.gov (United States)

    Lapelosa, Mauro; Gallicchio, Emilio; Levy, Ronald M.

    2011-01-01

    The Binding Energy Distribution Analysis Method (BEDAM) is employed to compute the standard binding free energies of a series of ligands to a FK506 binding protein (FKBP12) with implicit solvation. Binding free energy estimates are in reasonably good agreement with experimental affinities. The conformations of the complexes identified by the simulations are in good agreement with crystallographic data, which was not used to restrain ligand orientations. The BEDAM method is based on λ -hopping Hamiltonian parallel Replica Exchange (HREM) molecular dynamics conformational sampling, the OPLS-AA/AGBNP2 effective potential, and multi-state free energy estimators (MBAR). Achieving converged and accurate results depends on all of these elements of the calculation. Convergence of the binding free energy is tied to the level of convergence of binding energy distributions at critical intermediate states where bound and unbound states are at equilibrium, and where the rate of binding/unbinding conformational transitions is maximal. This finding mirrors similar observations in the context of order/disorder transitions as for example in protein folding. Insights concerning the physical mechanism of ligand binding and unbinding are obtained. Convergence for the largest FK506 ligand is achieved only after imposing strict conformational restraints, which however require accurate prior structural knowledge of the structure of the complex. The analytical AGBNP2 model is found to underestimate the magnitude of the hydrophobic driving force towards binding in these systems characterized by loosely packed protein-ligand binding interfaces. Rescoring of the binding energies using a numerical surface area model corrects this deficiency. This study illustrates the complex interplay between energy models, exploration of conformational space, and free energy estimators needed to obtain robust estimates from binding free energy calculations. PMID:22368530

  5. Metal-insulator transition in vanadium dioxide

    International Nuclear Information System (INIS)

    Zylbersztejn, A.; Mott, N.F.

    1975-01-01

    The basic physical parameters which govern the metal-insulator transition in vanadium dioxide are determined through a review of the properties of this material. The major importance of the Hubbard intra-atomic correlation energy in determining the insulating phase, which was already evidence by studies of the magnetic properties of V 1 -/subx/Cr/subx/O 2 alloys, is further demonstrated from an analysis of their electrical properties. An analysis of the magnetic susceptibility of niobium-doped VO 2 yields a picture for the current carrier in the low-temperature phase in which it is accompanied by a spin cloud (owing to Hund's-rule coupling), and has therefore an enhanced mass (m approx. = 60m 0 ). Semiconducting vanadium dioxide turns out to be a borderline case for a classical band-transport description; in the alloys at high doping levels, Anderson localization with hopping transport can take place. Whereas it is shown that the insulating phase cannot be described correctly without taking into account the Hubbard correlation energy, we find that the properties of the metallic phase are mainly determined by the band structure. Metallic VO 2 is, in our view, similar to transition metals like Pt or Pd: electrons in a comparatively wide band screening out the interaction between the electrons in a narrow overlapping band. The magnetic susceptibility is described as exchange enhanced. The large density of states at the Fermi level yields a substantial contribution of the entropy of the metallic electrons to the latent heat. The crystalline distortion removes the band degeneracy so that the correlation energy becomes comparable with the band width and a metal-insulator transition takes place

  6. (Electronic structure and reactivities of transition metal clusters)

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  7. Spin-Orbitronics at Transition Metal Interfaces

    KAUST Repository

    Manchon, Aurelien

    2017-11-09

    The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

  8. The phosphorus and the transition metals chemistry

    International Nuclear Information System (INIS)

    Mathey, F.

    1988-01-01

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown [fr

  9. Lattice Location of Transition Metals in Semiconductors

    CERN Multimedia

    2002-01-01

    %IS366 %title\\\\ \\\\Transition metals (TMs) in semiconductors have been the subject of considerable research for nearly 40 years. This is due both to their role as important model impurities for deep centers in semiconductors, and to their technological impact as widespread contaminants in Si processing, where the miniaturization of devices requires to keep their sheet concentration below 10$^{10}$ cm$^{-2}$. As a consequence of the low TM solubility, conventional ion beam methods for direct lattice location have failed completely in identifying the lattice sites of isolated transition metals. Although electron paramagnetic resonance (EPR) has yielded valuable information on a variety of TM centers, it has been unable to detect certain defects considered by theory, e.g., isolated interstitial or substitutional Cu in Si. The proposed identity of other EPR centers such as substitutional Fe in Si, still needs confirmation by additional experimental methods. As a consequence, the knowledge on the structural propert...

  10. Transformation paths in transition-metal disilicides

    Czech Academy of Sciences Publication Activity Database

    Káňa, Tomáš; Šob, Mojmír; Vitek, V.

    2011-01-01

    Roč. 465, - (2011), s. 61-64 ISSN 1662-9795. [MSMF /6./ Materials Structure and Micromechanics of Fracture. Brno, 28.06.2010-30.06.2010] R&D Projects: GA AV ČR IAA100100920; GA MŠk(CZ) OC10008 Institutional research plan: CEZ:AV0Z20410507 Keywords : transition-metal disilicides * transformation path * structural stability * electronic structure Subject RIV: BM - Solid Matter Physics ; Magnetism

  11. Single-layer transition metal sulfide catalysts

    Science.gov (United States)

    Thoma, Steven G [Albuquerque, NM

    2011-05-31

    Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

  12. Magnetic Interactions in Transition-Metal Oxides

    OpenAIRE

    Solovyev, I. V.

    2003-01-01

    This a review article, which presents a general framework for the analysis of interatomic magnetic interactions in the spin-density-functional theory, which is based on the magnetic force theorem, make a link with the models for transition-metal oxides, and gives several examples of how this strategy can be used for the analysis of magnetic properties of colossal-magnetoresistive perovskite manganites, double perovskite and pyrochlore compounds.

  13. Transition Metal Intercalators as Anticancer Agents—Recent Advances

    Directory of Open Access Journals (Sweden)

    Krishant M. Deo

    2016-10-01

    Full Text Available The diverse anticancer utility of cisplatin has stimulated significant interest in the development of additional platinum-based therapies, resulting in several analogues receiving clinical approval worldwide. However, due to structural and mechanistic similarities, the effectiveness of platinum-based therapies is countered by severe side-effects, narrow spectrum of activity and the development of resistance. Nonetheless, metal complexes offer unique characteristics and exceptional versatility, with the ability to alter their pharmacology through facile modifications of geometry and coordination number. This has prompted the search for metal-based complexes with distinctly different structural motifs and non-covalent modes of binding with a primary aim of circumventing current clinical limitations. This review discusses recent advances in platinum and other transition metal-based complexes with mechanisms of action involving intercalation. This mode of DNA binding is distinct from cisplatin and its derivatives. The metals focused on in this review include Pt, Ru and Cu along with examples of Au, Ni, Zn and Fe complexes; these complexes are capable of DNA intercalation and are highly biologically active.

  14. Transition Metal Intercalators as Anticancer Agents—Recent Advances

    Science.gov (United States)

    Deo, Krishant M.; Pages, Benjamin J.; Ang, Dale L.; Gordon, Christopher P.; Aldrich-Wright, Janice R.

    2016-01-01

    The diverse anticancer utility of cisplatin has stimulated significant interest in the development of additional platinum-based therapies, resulting in several analogues receiving clinical approval worldwide. However, due to structural and mechanistic similarities, the effectiveness of platinum-based therapies is countered by severe side-effects, narrow spectrum of activity and the development of resistance. Nonetheless, metal complexes offer unique characteristics and exceptional versatility, with the ability to alter their pharmacology through facile modifications of geometry and coordination number. This has prompted the search for metal-based complexes with distinctly different structural motifs and non-covalent modes of binding with a primary aim of circumventing current clinical limitations. This review discusses recent advances in platinum and other transition metal-based complexes with mechanisms of action involving intercalation. This mode of DNA binding is distinct from cisplatin and its derivatives. The metals focused on in this review include Pt, Ru and Cu along with examples of Au, Ni, Zn and Fe complexes; these complexes are capable of DNA intercalation and are highly biologically active. PMID:27809241

  15. An approximate method for calculating electron-phonon matrix element of a disordered transition metal and relevant comments on superconductivity

    International Nuclear Information System (INIS)

    Zhang, L.

    1981-08-01

    A method based on the tight-binding approximation is developed to calculate the electron-phonon matrix element for the disordered transition metals. With the method as a basis the experimental Tsub(c) data of the amorphous transition metal superconductors are re-analysed. Some comments on the superconductivity of the disordered materials are given

  16. Electronic structure of hcp transition metals

    DEFF Research Database (Denmark)

    Jepsen, O.; Andersen, O. Krogh; Mackintosh, A. R.

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects...... of hybridization, relativistic band shifts, and spin-orbit coupling by the example of Os. By making use of parameters derived from the muffin-tin potential, we discuss trends in the positions and widths of the energy bands, especially the d bands, as a function of the location in the periodic table. The densities...... of states of the four metals are presented, and the calculated heat capacities compared with experiment. The Fermi surfaces of both Ru and Os are found to be in excellent quantitative agreement with de Haas-van Alphen measurements, indicating that the calculated d-band position is misplaced by less than 10...

  17. Synthesis of arsenic transition metal sulfides and metal arsenides

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, G.H.; Brown, L.D.; Ryan, D.F. [Exxon Research & Development Labs, Baton Rouge, LA (United States)

    1993-12-31

    One of the chief problems in upgrading shale oil is the presence of inherent arsenic which is known to poison downstream catalysts. Highly dispersed transition metal sulfides formed in situ from the decomposition of dithiocarbamate (DTC) complexes of transition metals show excellent potential as dearsenation agents. The authors have studied the reaction of these sulfides with various arsenic compositions and characterized the metal arsenides and arsenic metal sulfides formed as well as the ease of their formation. Thus, the reaction of bis(butyldithiocarbamato)Ni, (NiBuDTC) with model compounds was very facile and gave NiAs, NiAsS, and NiAs2=xSx. In general the effectiveness of the sulfides for dearsenation followed the sequence Ni>Mo{much_gt}Co, while iron sulfides were totally ineffective. Based upon these results, tests were run in autoclaves (as well as a fixed-bed flow-through unit) with NiBuDTC and shale oil having 73 ppm inherent As. Under optimum conditions, dearsenation down to les than 1 ppm was obtained.

  18. Synthesis, spectroscopic, molecular orbital calculation, cytotoxic, molecular docking of DNA binding and DNA cleavage studies of transition metal complexes with N-benzylidene-N'-salicylidene-1,1-diaminopropane

    Science.gov (United States)

    Al-Mogren, Muneerah M.; Alaghaz, Abdel-Nasser M. A.; Elbohy, Salwa A. H.

    2013-10-01

    Eight mononuclear chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of Schiff's base ligand were synthesized and determined by different physical techniques. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the eight metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff base is found to act as tridentate ligand using N2O donor set of atoms leading to an octahedral geometry for the complexes around all the metal ions. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of the ligand and its complexes. Additionally in silico, the docking studies and the calculated pharmacokinetic parameters show promising futures for application of the ligand and complexes as high potency agents for DNA binding activity. The interaction of the complexes with calf thymus DNA (CT-DNA) has been investigated by UV absorption method, and the mode of CT-DNA binding to the complexes has been explored. Furthermore, the DNA cleavage activity by the complexes was performed. The Schiff base and their complexes have been screened for their antibacterial activity against bacterial strains [Staphylococcus aureus (RCMB010027), Staphylococcus epidermidis (RCMB010024), Bacillis subtilis (RCMB010063), Proteous vulgaris (RCMB 010085), Klebsiella pneumonia (RCMB 010093) and Shigella flexneri (RCMB 0100542)] and fungi [(Aspergillus fumigates (RCMB 02564), Aspergillus clavatus (RCMB 02593) and Candida albicans (RCMB05035)] by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligand.

  19. Metal binding proteins, recombinant host cells and methods

    Science.gov (United States)

    Summers, Anne O.; Caguiat, Jonathan J.

    2004-06-15

    The present disclosure provides artificial heavy metal binding proteins termed chelons by the inventors. These chelons bind cadmium and/or mercuric ions with relatively high affinity. Also disclosed are coding sequences, recombinant DNA molecules and recombinant host cells comprising those recombinant DNA molecules for expression of the chelon proteins. In the recombinant host cells or transgenic plants, the chelons can be used to bind heavy metals taken up from contaminated soil, groundwater or irrigation water and to concentrate and sequester those ions. Recombinant enteric bacteria can be used within the gastrointestinal tracts of animals or humans exposed to toxic metal ions such as mercury and/or cadmium, where the chelon recombinantly expressed in chosen in accordance with the ion to be rededicated. Alternatively, the chelons can be immobilized to solid supports to bind and concentrate heavy metals from a contaminated aqueous medium including biological fluids.

  20. First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Mann, Gregory W., E-mail: gmann@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Mesosphere, Inc., San Francisco, California 94105 (United States); Lee, Kyuho, E-mail: kyuholee@lbl.gov [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Synopsys, Inc., Mountain View, California 94043 (United States); Cococcioni, Matteo, E-mail: matteo.cococcioni@epfl.ch [Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Smit, Berend, E-mail: Berend-Smit@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion (Switzerland); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2016-05-07

    We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

  1. Validating metal binding sites in macromolecule structures using the CheckMyMetal web server

    Science.gov (United States)

    Zheng, Heping; Chordia, Mahendra D.; Cooper, David R.; Chruszcz, Maksymilian; Müller, Peter; Sheldrick, George M.

    2015-01-01

    Metals play vital roles in both the mechanism and architecture of biological macromolecules. Yet structures of metal-containing macromolecules where metals are misidentified and/or suboptimally modeled are abundant in the Protein Data Bank (PDB). This shows the need for a diagnostic tool to identify and correct such modeling problems with metal binding environments. The "CheckMyMetal" (CMM) web server (http://csgid.org/csgid/metal_sites/) is a sophisticated, user-friendly web-based method to evaluate metal binding sites in macromolecular structures in respect to 7350 metal binding sites observed in a benchmark dataset of 2304 high resolution crystal structures. The protocol outlines how the CMM server can be used to detect geometric and other irregularities in the structures of metal binding sites and alert researchers to potential errors in metal assignment. The protocol also gives practical guidelines for correcting problematic sites by modifying the metal binding environment and/or redefining metal identity in the PDB file. Several examples where this has led to meaningful results are described in the anticipated results section. CMM was designed for a broad audience—biomedical researchers studying metal-containing proteins and nucleic acids—but is equally well suited for structural biologists to validate new structures during modeling or refinement. The CMM server takes the coordinates of a metal-containing macromolecule structure in the PDB format as input and responds within a few seconds for a typical protein structure modeled with a few hundred amino acids. PMID:24356774

  2. Magnetic excitations in transition-metal ferromagnets

    International Nuclear Information System (INIS)

    Uemura, Y.J.

    1984-01-01

    A review is given on current neutron scattering experiments at Brookhaven National Laboratory on transition-metal ferromagnets Ni, Fe, Pd 2 MnSn and MnSi. The scattering intensity in constant-energy scans, observed above T/sub c/ in all of these materials, exhibited a clear peak at finite momentum transfers. Using a simple scattering function with double-Lorentzian shape, we demonstrate that this peak is a manifestation of simple diffusive spin fluctuations. Experimental results of several parameters are compared in the context of localized-moment and itinerant-electron pictures. The ratio of spin wave stiffness constant D and transition temperature kT/sub c/ is shown to be a good yardstick for the degree of itinerancy of d-electrons

  3. Versatile two-dimensional transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Canulescu, Stela; Affannoukoué, Kévin; Döbeli, Max

    Two-dimensional transition metal dichalcogenides (2D-TMDCs), such as MoS2, have emerged as a new class of semiconducting materials with distinct optical and electrical properties. The availability of 2D-TMDCs with distinct band gaps allows for unlimited combinations of TMDC monolayers (MLs...... vacancies. We have found that the absorption spectra of the MoS2 films exhibit distinct excitonic peaks at ~1.8 and ~2 eV when grown in the presence of a sulfur evaporation beam as compared to those deposited in vacuum. The structure of the PLD-grown MoS2 films will be further discussed based Raman...

  4. Magnetic correlations in doped transition metal oxides

    International Nuclear Information System (INIS)

    The authors review recent reactor- and spallation-source-based neutron scattering experiments on the magnetic fluctuations and order in a variety of doped transition metal oxides. In particular, data are shown for the NiO chain compound, Y 2-x Ca x BaNiO 5 , the two-dimensional cuprate superconductors La 2-x Sr x CuO 4 and YBa 2 Cu 3 O 6+x , and the classical three-dimensional ''Mott-Hubbard'' system V 2-y O 3

  5. Magnetic Ground State Properties of Transition Metals

    DEFF Research Database (Denmark)

    Andersen, O. K.; Madsen, J.; Poulsen, U. K.

    1977-01-01

    We review a simple one-electron theory of the magnetic and cohesive properties of ferro- and nearly ferromagnetic transition metals at 0 K. The theory is based on the density functional formalism, it makes use of the local spin density and atomic sphere approximations and it may, with further...... approximations, be reduced to the Stoner model. Results for the volume dependence of the ferromagnetic moment and the electronic pressure of bcc, fcc and hcp Fe are presented, together with theoretical values for the equilibrium atomic volume, the bulk modulus, the ferromagnetic moment, the spin susceptibility...

  6. Alkali metal and alkali metal hydroxide intercalates of the layered transition metal disulfides

    International Nuclear Information System (INIS)

    Kanzaki, Y.; Konuma, M.; Matsumoto, O.

    1981-01-01

    The intercalation reaction of some layered transition metal disulfides with alkali metals, alkali metal hydroxides, and tetraalkylammonium hydroxides were investigated. The alkali metal intercalates were prepared in the respective metal-hexamethylphosphoric triamide solutions in vaccuo, and the hydroxide intercalates in aqueous hydroxide solutions. According to the intercalation reaction, the c-lattice parameter was increased, and the increase indicated the expansion of the interlayer distance. In the case of alkali metal intercalates, the expansion of the interlayer distance increased continuously, corresponding to the atomic radius of the alkali metal. On the other hand, the hydroxide intercalates showed discrete expansion corresponding to the effective ionic radius of the intercalated cation. All intercalates of TaS 2 amd NbS 2 were superconductors. The expansion of the interlayer distance tended to increase the superconducting transition temperature in the intercalates of TaS 2 and vice versa in those of NbS 2 . (orig.)

  7. Metal ion binding with dehydroannulenes – Plausible two ...

    Indian Academy of Sciences (India)

    WINTEC

    has highest interaction energy of –50∙6 kcal/mol at. B3LYP/6-311++G** level and is 128∙0 kcal/mol more than 1′-K+ complex. Understandably, the binding energy of metal complexes decreases with increase in the size of the metal ion, in accordance with ear- lier results.16,21. Placement of the metal ions at the centroid of ...

  8. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    International Nuclear Information System (INIS)

    Richard T. Scalettar; Warren E. Pickett

    2005-01-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals

  9. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Scalettar, Richard T.; Pickett, Warren E.

    2004-07-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals.

  10. High-Pressure Thermodynamic Properties of f-electron Metals, Transition Metal Oxides, and Half-Metallic Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Richard T. Scalettar; Warren E. Pickett

    2005-08-02

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (i) Mott transitions in transition metal oxides, (ii) magnetism in half-metallic compounds, and (iii) large volume-collapse transitions in f-band metals.

  11. Local Oxidation Nanolithography on Metallic Transition Metal Dichalcogenides Surfaces

    Directory of Open Access Journals (Sweden)

    Elena Pinilla-Cienfuegos

    2016-09-01

    Full Text Available The integration of atomically-thin layers of two dimensional (2D materials in nanodevices demands for precise techniques at the nanoscale permitting their local modification, structuration or resettlement. Here, we present the use of Local Oxidation Nanolithography (LON performed with an Atomic Force Microscope (AFM for the patterning of nanometric motifs on different metallic Transition Metal Dichalcogenides (TMDCs. We show the results of a systematic study of the parameters that affect the LON process as well as the use of two different modes of lithographic operation: dynamic and static. The application of this kind of lithography in different types of TMDCs demonstrates the versatility of the LON for the creation of accurate and reproducible nanopatterns in exfoliated 2D-crystals and reveals the influence of the chemical composition and crystalline structure of the systems on the morphology of the resultant oxide motifs.

  12. Metal non-metal transitions in doped semiconductors

    International Nuclear Information System (INIS)

    Brezini, A.

    1989-12-01

    A disordered Hubbard model with diagonal disorder is used to examine the electron localization effects associated with both disorder and electron-electron interaction. Extensive results are reported on the ground state properties and compared with other theories. In particular two regimes are observed; when the electron-electron interaction U is greater than the disorder parameter and when is smaller. Furthermore the effect of including conduction-band minima into the calculation of metal-insulator transitions in doped Si and Ge is investigated with use of Berggren approach. Good agreement with experiments are found when both disorder and interactions are included. (author). 37 refs, 7 figs, 3 tabs

  13. Computation of the Structure Factor of Some Transition Liquid Metals

    African Journals Online (AJOL)

    Applying the solution of the Percus-Yevic equation to a one component hard sphere system and using the recently developed potential for liquid transition liquid metals, the structure factor of transition liquid metals were computed. The peak height and peak position of the structure factor of the liquid metals were studied.

  14. Metal Insulator transition in Vanadium Dioxide

    Science.gov (United States)

    Jovaini, Azita; Fujita, Shigeji; Suzuki, Akira; Godoy, Salvador

    2012-02-01

    MAR12-2011-000262 Abstract Submitted for the MAR12 Meeting of The American Physical Society Sorting Category: 03.9 (T) On the metal-insulator-transition in vanadium dioxide AZITA JOVAINI, SHIGEJI FUJITA, University at Buffalo, SALVADOR GODOY, UNAM, AKIRA SUZUKI, Tokyo University of Science --- Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity _/ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop. Prefer Oral Session X Prefer .

  15. Janus monolayers of transition metal dichalcogenides

    KAUST Repository

    Lu, Ang-Yu

    2017-05-15

    Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

  16. Study of concentrated metal-ammonia solutions: magnetic properties and non metal-metal transition

    International Nuclear Information System (INIS)

    Lelieur, Jean-Pierre

    1972-01-01

    The magnetic susceptibility of alkali metal-liquid ammonia solutions has been measured in the concentration range where the solutions show a progressive passage toward the metallic state. The Knight shift of the metal nuclei and the nitrogen nucleus have been determined as a function of concentration and temperature, in Na-NH 3 and Cs-NH 3 solutions. A phenomenological analysis of the transport properties of metal-ammonia solutions is also presented. This analysis permits the presentation of a model for the mechanism of the transition to the metallic state. (author) [fr

  17. Fluorescence signalling of the transition metal ions: Design strategy ...

    Indian Academy of Sciences (India)

    on fluorescence signalling systems for the transition metal ions. It is shown that even simple fluorophore-spacer-receptor systems can display excellent off-on fluorescence signalling towards the quenching metal ions when the fluorophore ...

  18. Molecular recognition in homogeneous transition metal catalysis: a biomimetic strategy for high selectivity.

    Science.gov (United States)

    Das, Siddartha; Brudvig, Gary W; Crabtree, Robert H

    2008-01-28

    Traditional methods for selectivity control in homogeneous transition metal catalysis either employ steric effects in a binding pocket or chelate control. In a supramolecular strategy, encapsulation of the substrate can provide useful shape and size selectivity. A fully developed molecular recognition strategy involving hydrogen bonding or solvophobic forces has given almost completely regioselective functionalization of remote, unactivated C-H bonds.

  19. Metal ion binding to iron oxides

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.; Benedetti, M.F.; Ponthieu, M.

    2006-01-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to

  20. Neutron irradiation damage in transition metal carbides

    International Nuclear Information System (INIS)

    Matsui, Hisayuki; Nesaki, Kouji; Kiritani, Michio

    1991-01-01

    Effects of neutron irradiation on the physical properties of light transition metal carbides, TiC x , VC x and NbC x , were examined, emphasizing the characterization of irradiation induced defects in the nonstoichiometric composition. TiC x irradiated with 14 MeV (fusion) neutrons showed higher damage rates with increasing C/Ti (x) ratio. A brief discussion is made on 'cascade damage' in TiC x irradiated with fusion neutrons. Two other carbides (VC x and NbC x ) were irradiated with fission reactor neutrons. The irradiation effects on VC x were not so simple, because of the complex irradiation behavior of 'ordered' phases. For instance, complete disordering was revealed in an ordered phase, 'V 8 C 7 ', after an irradiation dose of 10 25 n/m 2 . (orig.)

  1. Dark excitons in transition metal dichalcogenides

    Science.gov (United States)

    Malic, Ermin; Selig, Malte; Feierabend, Maja; Brem, Samuel; Christiansen, Dominik; Wendler, Florian; Knorr, Andreas; Berghäuser, Gunnar

    2018-01-01

    Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a nondirect gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

  2. Mesoporous diphosphine-transition metal complex catalyst for hydroformylation

    NARCIS (Netherlands)

    Reek, J.N.H.; Coppens, M.O.

    2012-01-01

    The invention pertains to a diphosphine-transition metal complex comprising a diphosphine-transition metal ligand that is covalently bonded to an insoluble mesoporous support having an average pore diameter of from 4.5 nm to 50 nm, characterized in that the ligand as attached to the support has the

  3. Surface segregation energies in transition-metal alloys

    DEFF Research Database (Denmark)

    Ruban, Andrei; Skriver, Hans Lomholt; Nørskov, Jens Kehlet

    1999-01-01

    We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...

  4. Nanostructured transition metal oxides useful for water oxidation catalysis

    Science.gov (United States)

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  5. Vibrational properties of vacancy in bcc transition metals using ...

    Indian Academy of Sciences (India)

    By introducing a few modifications in the Johnson and. Oh model, Guellil and Adams [5] have applied the EAM model for studying phonon dis- persion, thermal and surface properties of alkali and transition metals and their alloys. An empirical many-body interaction potential for the bcc transition metals Nb, Fe and Cr was.

  6. Fluorescence signalling of the transition metal ions: Design strategy ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. Transition metal ions are notorious for their fluorescence quenching abilities. In this paper, we discuss the design strategies for the development of efficient off-on fluorescence signalling systems for the transition metal ions. It is shown that even simple fluorophore-spacer-receptor systems can display excellent.

  7. Reentrant Metal-Insulator Transitions in Silicon -

    Science.gov (United States)

    Campbell, John William M.

    This thesis describes a study of reentrant metal -insulator transitions observed in the inversion layer of extremely high mobility Si-MOSFETs. Magneto-transport measurements were carried out in the temperature range 20mK-4.2 K in a ^3He/^4 He dilution refrigerator which was surrounded by a 15 Tesla superconducting magnet. Below a melting temperature (T_{M}~500 mK) and a critical electron density (n_{s }~9times10^{10} cm^{-2}), the Shubnikov -de Haas oscillations in the diagonal resistivity enormous maximum values at the half filled Landau levels while maintaining deep minima corresponding to the quantum Hall effect at filled Landau levels. At even lower electron densities the insulating regions began to spread and eventually a metal-insulator transition could be induced at zero magnetic field. The measurement of extremely large resistances in the milliKelvin temperature range required the use of very low currents (typically in the 10^ {-12} A range) and in certain measurements minimizing the noise was also a consideration. The improvements achieved in these areas through the use of shielding, optical decouplers and battery operated instruments are described. The transport signatures of the insulating state are considered in terms of two basic mechanisms: single particle localization with transport by variable range hopping and the formation of a collective state such as a pinned Wigner crystal or electron solid with transport through the motion of bound dislocation pairs. The experimental data is best described by the latter model. Thus the two dimensional electron system in these high mobility Si-MOSFETs provides the first and only experimental demonstration to date of the formation of an electron solid at zero and low magnetic fields in the quantum limit where the Coulomb interaction energy dominates over the zero point oscillation energy. The role of disorder in favouring either single particle localization or the formation of a Wigner crystal is explored by

  8. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    International Nuclear Information System (INIS)

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  9. Stable carbides in transition metal alloys

    International Nuclear Information System (INIS)

    Piotrkowski, R.

    1991-01-01

    In the present work different techniques were employed for the identification of stable carbides in two sets of transition metal alloys of wide technological application: a set of three high alloy M2 type steels in which W and/or Mo were total or partially replaced by Nb, and a Zr-2.5 Nb alloy. The M2 steel is a high speed steel worldwide used and the Zr-2.5 Nb alloy is the base material for the pressure tubes in the CANDU type nuclear reactors. The stability of carbide was studied in the frame of Goldschmidt's theory of interstitial alloys. The identification of stable carbides in steels was performed by determining their metallic composition with an energy analyzer attached to the scanning electron microscope (SEM). By these means typical carbides of the M2 steel, MC and M 6 C, were found. Moreover, the spatial and size distribution of carbide particles were determined after different heat treatments, and both microstructure and microhardness were correlated with the appearance of the secondary hardening phenomenon. In the Zr-Nb alloy a study of the α and β phases present after different heat treatments was performed with optical and SEM metallographic techniques, with the guide of Abriata and Bolcich phase diagram. The α-β interphase boundaries were characterized as short circuits for diffusion with radiotracer techniques and applying Fisher-Bondy-Martin model. The precipitation of carbides was promoted by heat treatments that produced first the C diffusion into the samples at high temperatures (β phase), and then the precipitation of carbide particles at lower temperature (α phase or (α+β)) two phase field. The precipitated carbides were identified as (Zr, Nb)C 1-x with SEM, electron microprobe and X-ray diffraction techniques. (Author) [es

  10. Computational study of 5d transition metal mononitrides and ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 33; Issue 3. Computational study of 5 transition metal mononitrides and monoborides using ... affinity and ionization potential is wider for mononitrides than that for monoborides. The properties of 5-metal mononitrides and 3-metal mononitrides are also compared.

  11. Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

    Science.gov (United States)

    Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

    2017-03-15

    In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Electronic specific heat of transition metal carbides

    International Nuclear Information System (INIS)

    Conte, R.

    1964-07-01

    The experimental results that make it possible to define the band structure of transition metal carbides having an NaCI structure are still very few. We have measured the electronic specific heat of some of these carbides of varying electronic concentration (TiC, either stoichiometric or non-stoichiometric, TaC and mixed (Ti, Ta) - C). We give the main characteristics (metallography, resistivity, X-rays) of our samples and we describe the low temperature specific heat apparatus which has been built. In one of these we use helium as the exchange gas. The other is set up with a mechanical contact. The two use a germanium probe for thermometer. The measurement of the temperature using this probe is described, as well as the various measurement devices. The results are presented in the form of a rigid band model and show that the density of the states at the Fermi level has a minimum in the neighbourhood of the group IV carbides. (author) [fr

  13. Photocatalysis of Modified Transition Metal Oxide Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Batzill, Matthias

    2018-02-28

    The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anataseTiO2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

  14. Preparation and characterization of several transition metal oxides

    International Nuclear Information System (INIS)

    Wold, A.; Dwight, K.

    1989-01-01

    The structure-property relationships of several conducting transition metal oxides, as well as their preparative methods, are presented in this paper. The importance of preparing homogeneous phases with precisely known stoichiometry is emphasized. A comparison is also made of the various techniques used to prepare both polycrystalline and single crystal samples. For transition metal oxides, the metallic properties are discussed either in terms of metal-metal distances which are short enough to result in metallic behavior, or in terms of the formation of a π* conduction band resulting from covalent metal-oxygen interactions. Metallic behavior is observed when the conduction bands are populated with either electrons or holes. The concentration of these carriers can be affected by either cation or anion substitutions. The discussion in this presentation will be limited to the elements Re, Ti, V, Cr, Mo, and Cu

  15. Endonuclease active site plasticity allows DNA cleavage with diverse alkaline Earth and transition metal ions.

    Science.gov (United States)

    Vasu, Kommireddy; Saravanan, Matheshwaran; Nagaraja, Valakunja

    2011-09-16

    A majority of enzymes show a high degree of specificity toward a particular metal ion in their catalytic reaction. However, Type II restriction endonuclease (REase) R.KpnI, which is the first member of the HNH superfamily of REases, exhibits extraordinary diversity in metal ion dependent DNA cleavage. Several alkaline earth and transition group metal ions induce high fidelity and promiscuous cleavage or inhibition depending upon their concentration. The metal ions having different ionic radii and co-ordination geometries readily replace each other from the enzyme's active site, revealing its plasticity. Ability of R.KpnI to cleave DNA with both alkaline earth and transition group metal ions having varied ionic radii could imply utilization of different catalytic site(s). However, mutation of the invariant His residue of the HNH motif caused abolition of the enzyme activity with all of the cofactors, indicating that the enzyme follows a single metal ion catalytic mechanism for DNA cleavage. Indispensability of His in nucleophile activation together with broad cofactor tolerance of the enzyme indicates electrostatic stabilization function of metal ions during catalysis. Nevertheless, a second metal ion is recruited at higher concentrations to either induce promiscuity or inhibit the DNA cleavage. Regulation of the endonuclease activity and fidelity by a second metal ion binding is a unique feature of R.KpnI among REases and HNH nucleases. The active site plasticity of R.KpnI opens up avenues for redesigning cofactor specificities and generation of mutants specific to a particular metal ion.

  16. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  17. Electronic structure of disordered transition metals within scattering theory

    International Nuclear Information System (INIS)

    Yakyibchuk, P.M.; Volkov, O.V.; Vakarchuk, S.O.

    2005-01-01

    Here we present a new approach to the calculation of density of states of disordered transition metals based on the T-matrix framework presented by Lloyd within generalized Ziman's theory of transport properties and energy structure of disordered metals. This approach makes it possible to avoid such difficulties of familiar calculations as renormalized perturbation theory. We have achieved double hill energy resonance for transition metals at Fe and Co groups caused by hybridization potential. So the results are in good correlation with model presentation of energy structure of these metals conduction band for explaining magnetic and transport properties

  18. SYNTHESIS AND CHARACTERIZATION OF TRANSITION METAL ...

    African Journals Online (AJOL)

    a

    The metal complexes separated out were filtered through the sintered glass crucible ... All the metal complexes (Table 2) are colored, stable to air at room temperature ... Table 2. Physical characteristics and conductivity data of metal complexes and ligands. Ligand/complex. Color. Melting/decomposition temperature, 0C.

  19. The metallicities of stars with and without transiting planets

    DEFF Research Database (Denmark)

    Buchhave, Lars A.; Latham, David W.

    2015-01-01

    terrestrial-sized planets. Here, we report metallicities for a sample of 518 stars in the Kepler field that have no detected transiting planets and compare their metallicity distribution to a sample of stars that hosts small planets (). Importantly, both samples have been analyzed in a homogeneous manner...... using the same set of tools (Stellar Parameters Classification tool). We find the average metallicity of the sample of stars without detected transiting planets to be and the sample of stars hosting small planets to be . The average metallicities of the two samples are indistinguishable within......Host star metallicities have been used to infer observational constraints on planet formation throughout the history of the exoplanet field. The giant planet metallicity correlation has now been widely accepted, but questions remain as to whether the metallicity correlation extends to the small...

  20. On metal-insulator transition in cubic fullerides

    Science.gov (United States)

    Iwahara, Naoya; Chibotaru, Liviu

    The interplay between degenerate orbital and electron correlation is a key to characterize the electronic phases in, for example, transition metal compounds and alkali-doped fullerides. Besides, the degenerate orbital couples to spin and lattice degrees of freedom ,giving rise to exotic phenomena. Here, we develop the self-consistent Gutzwiller approach for the simultaneous treatment of the Jahn-Teller effect and electron correlation, and apply the methodology to reveal the nature of the ground electronic state of fullerides. For small Coulomb repulsion on site U, the fulleride is quasi degenerate correlated metal. With increase of U, we found the quantum phase transition from the metallic phase to JT split phase. In the latter, the Mott transition (MT) mainly develops in the half-filled subband, whereas the empty and the completely filled subbands are almost uninvolved. Therefore, we can qualify the metal-insulator transition in fullerides as an orbital selective MT induced by JT effect.

  1. Spectrum of ferromagnetic transition metal magnetic excitations and neutron scattering

    International Nuclear Information System (INIS)

    Kuzemskij, A.L.

    1979-01-01

    Quantum statistical models of ferromagnetic transition metals as well as methods of their solutions are reviewed. The correspondence of results on solving these models and the data on scattering thermal neutrons in ferromagnetic is discussed

  2. New approaches in organometallic and transition metal assemblies

    Indian Academy of Sciences (India)

    Stannoxanes and phosphonates: New approaches in organometallic and transition metal assemblies. VADAPALLI CHANDRASEKHAR*, KANDASAMY GOPAL,. LOGANATHAN NAGARAJAN, PALANI SASIKUMAR and PAKKIRISAMY THILAGAR. Department of Chemistry, Indian Institute of Technology, Kanpur 208 016.

  3. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe

    2007-01-01

    The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

  4. Early Transition Metal Alkyl and Tetrahydroborate Complexes.

    Science.gov (United States)

    Jensen, James Allen

    1988-06-01

    An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX _2 (dmpe)_2, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH_4, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH_4^{-} groups in Ti(BH_4)_2(dmpe) _2 bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH_4)_2 (dmpe)_2, which displays two unidentate BH_4^{-} groups. Alkylation of Ti(BH_4)_2 (dmpe)_2 with LiMe results in the complex TiMe_2(dmpe) _2 which is diamagnetic in both solution and solid state. Single crystal X-ray and neutron diffraction studies show that there may be strong Ti-C pi -bonding. A tetragonal compression along the C -Ti-C bond vector accounts for the observed diamegnetism. A series of complexes of the formula Ti(BH _4)_3(PR_3)_2 has been prepared where PR_3 = PMe_3, PEt_3, PMe_3Ph, and P(OMe)_3 . The X-ray crystal structure of Ti(BH _4)_3(PMe_3)_2 reveals a pseudo trigonal bipyramidal geometry in which two BH_4^{-} groups display an unusual "side-on" bonding mode. The "side-on" ligation mode has been attributed to a Jahn-Teller distortion of the orbitally degenerate d^1 ground state. In contrast, the non-Jahn-Teller susceptible vanadium analogue, V(BH_4)_3 (PMe_3)_2, possesses a nearly ideal D_{rm 3h} >=ometry with three bidentate tetrahydroborate groups. Addition of excess PMe_3 to V(BH_4)_3(PMe _3)_2water forms the vanadium(III) oxo dimer (V(BH_4)_2 (PMe_3)_2]_2 [mu-O) which has been structurally characterized. The compound Ti(CH_2CMe _3)_4 can be prepared by addition of Ti(OEt)_4 to LiCH_2 CMe_3. Sublimation of Ti(CH _2CMe_3)_4 over a substrate heated to 250^ circC results in the chemical vapor deposition of amorphous TiC thin films. This CVD approach has been extended to the Group 4 borides: Ti

  5. A spin transition mechanism for cooperative adsorption in metal-organic frameworks

    Science.gov (United States)

    Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

    2017-10-01

    Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

  6. Transition metal mediated transformations of small molecules

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-08

    Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.

  7. High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

    Science.gov (United States)

    Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

    2017-06-01

    A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

  8. [Non-empirical interatomic potentials for transition metals

    International Nuclear Information System (INIS)

    1993-01-01

    The report is divided into the following sections: potential-energy functions for d-band metals, potential-energy functions for aluminides and quasicrystals, electronic structure of complex structures and quasicrystals, potential-energy functions in transition-metal oxides, applications to defect structure and mechanical properties, and basic theory of interatomic potentials

  9. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  10. Nonmetal-metal transition in metal–molten-salt solutions

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1996-01-01

    The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to study the nonmetal-metal transition in two different metal–molten-salt solutions, Kx(KCl)1-x and Nax(NaBr)1-x. As the excess metal concentration is increased the electronic density becomes

  11. Robust tunable excitonic features in monolayer transition metal dichalcogenide quantum dots

    Science.gov (United States)

    Fouladi-Oskouei, J.; Shojaei, S.; Liu, Z.

    2018-04-01

    The effects of quantum confinement on excitons in parabolic quantum dots of monolayer transition metal dichalcogenides (TMDC QDs) are investigated within a massive Dirac fermion model. A giant spin-valley coupling of the TMDC QDs is obtained, larger than that of monolayer TMDC sheets and consistent with recent experimental measurements. The exciton transition energy and the binding energy are calculated, and it is found that the strong quantum confinement results in extremely high exciton binding energies. The enormously large exciton binding energy in TMDC QDs (({{E}{{B2D}}}∼ 500 meV)quantum confinements, leading to tunable quantum dots in monolayer TMDCs. This finding offers new functionality in engineering the interaction of a 2D material with light and creates promise for the quantum manipulation of spin and valley degrees of freedom in TMDC nanostructures, enabling versatile novel 2D quantum photonic and optoelectronic nanodevices.

  12. Synthesis, structure, DNA/BSA binding and antibacterial studies of NNO tridentate Schiff base metal complexes

    Science.gov (United States)

    Sakthi, Marimuthu; Ramu, Andy

    2017-12-01

    A new salicylaldehyde derived 2,4-diiodo-6-((2-phenylaminoethylimino)methyl)phenol Schiff base(L) and its transition metal complexes of the type MLCl where, M = Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been synthesized. The coordination mode of Schiff base holding NNO donor atoms with metal ions was well investigated by elemental analysis, ESI-mass as well as IR, UV-vis, CV and NMR spectral studies. The binding efficiency and mode of these complexes with biological macromolecules viz., herring sperm DNA (HS- DNA) and bovine serum albumin (BSA) have been explored through various spectroscopic techniques. The characteristic changes in absorption, emission and, circular dichroism spectra of the complexes with DNA indicate the noticeable interaction between them. From the all spectral information complexes could interact with DNA via non-intercalation mode of binding. The hyperchromisim in absorption band and hypochromisim in emission intensity of BSA with different complex concentrations shown significant information, and the binding affinity value has been predicted from Stern-Volmer plots. Further, all the complexes could cleave the circular plasmid pUC19 DNA efficiently by using an activator H2O2. The ligand and all metal(II) complexes showed good antibacterial activities. The molecular docking studies of the complexes with DNA were performed in order to make a comparison and conclusion with spectral technic results.

  13. Coherent quantum dynamics of excitons in monolayer transition metal dichalcogenides

    KAUST Repository

    Moody, Galan

    2016-03-14

    Transition metal dichalcogenides (TMDs) have garnered considerable interest in recent years owing to their layer thickness-dependent optoelectronic properties. In monolayer TMDs, the large carrier effective masses, strong quantum confinement, and reduced dielectric screening lead to pronounced exciton resonances with remarkably large binding energies and coupled spin and valley degrees of freedom (valley excitons). Coherent control of valley excitons for atomically thin optoelectronics and valleytronics requires understanding and quantifying sources of exciton decoherence. In this work, we reveal how exciton-exciton and exciton-phonon scattering influence the coherent quantum dynamics of valley excitons in monolayer TMDs, specifically tungsten diselenide (WSe2), using two-dimensional coherent spectroscopy. Excitation-density and temperature dependent measurements of the homogeneous linewidth (inversely proportional to the optical coherence time) reveal that exciton-exciton and exciton-phonon interactions are significantly stronger compared to quasi-2D quantum wells and 3D bulk materials. The residual homogeneous linewidth extrapolated to zero excitation density and temperature is ~1:6 meV (equivalent to a coherence time of 0.4 ps), which is limited only by the population recombination lifetime in this sample. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  14. The metal binding potential of a dairy isolate

    Directory of Open Access Journals (Sweden)

    K. Ramyakrishna

    2017-12-01

    Full Text Available Excess iron in water resources can lead to health hazards and problems. The ability of lactic acid bacteria to bind iron has not yet been widely studied. In the present study, sorption of iron ions from aqueous solutions onto lactic acid bacterium was determined. Elemental analyses were carried out by inductively coupled plasma optical emission spectrometry. The kinetics of Fe(III biosorption was investigated at different initial concentrations of metal ion. The highest uptake capacity was found to be 16 mg of Fe(III per gram of adsorbent with a contact time of 24 hr and at initial metal ion concentration of 34 mg/L. The uptake capacity of Fe(III ion varied from 83.2 to 46.7% across the range of initial metal ion concentrations. The equilibrium data were evaluated by Langmuir and Freundlich isotherms, and were found to fit better with the latter (R2 = 0.9999. The surface morphology of the biomass and percentage of metal was characterized by using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy. The functional groups on the cell wall surface of biomass involved in biosorption of heavy metals were studied by Fourier transform infrared spectroscopy spectrum.

  15. Special about transition metals in alloy phase formation

    Energy Technology Data Exchange (ETDEWEB)

    Watson, R E; Bennett, L H

    1979-01-01

    The d-electrons are special, though their bonding properties remain to be completely understood. It is recognized that d band broadening is the dominant term contributing to transition metal cohesion. It is also generally recognized that in compound formation between transition-metals and polyvalent metals, hybridization between d-bands and polyvalent atom p bands provides a significant contribution to the energy (for example there is such a term in Miedema's scheme). Less generally realized is that d-band hybridization leads to changes in d-electron counts at a transition metal site which are opposite in sign to the net charge transfer on or off the site. The renormalized atom picture of cohesion of the pure transition metals and consider the experimental evidence and the theoretical understanding of d charge transfer going the wrong way are reviewed. A picture of the electronegativity of transition metals based on this trend is developed. Charge transfer associated with equalizing the local chemical potentials in alloys is estimated. Friedel type model alloy calculations are reviewed. The implications of the experimental charge transfer information from Moessbauer isomer shifts to such model alloy calculations and to the strength of the Coulomb enery associated with charge transfer is considered.

  16. Reactivity of monoolefin ligand in transition metal complexes

    International Nuclear Information System (INIS)

    Rybinskaya, M.I.

    1978-01-01

    The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

  17. Electrocatalytic reduction of carbon dioxide on post-transition metal and metal oxide nanoparticles

    Science.gov (United States)

    White, James L.

    The electroreduction of carbon dioxide to liquid products is an important component in the utilization of CO2 and in the high-density storage of intermittent renewable energy in the form of chemical bonds. Materials based on indium and tin, which yield predominantly formic acid, have been investigated in order to gain a greater understanding of the electrochemically active species and the mechanism of CO2 reduction on these heavy post-transition metals, since prior studies on the bulk metals did not provide thermodynamically sensible reaction pathways. Nanoparticles of the oxides and hydroxides of tin and indium have been prepared and characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and various electrochemical methods in order to obtain structural information and analyze the role of various surface species on the CO2 reduction pathway. On both indium and tin, metastable surface-bound hydroxides bound CO2 and formed metal carbonates, which can then be reduced electrochemically. The relevant oxidation state of tin was suggested to be SnII rather than SnIV, necessitating a pre reduction to generate the CO2-binding species. Metallic indium nanoparticles partially oxidized in air and became highly efficient CO2 reduction electrocatalysts. Unit Faradaic efficiencies for formate, much higher than on bulk indium, were achieved with only 300 mV of overpotential on these particles, which possessed an oxyhydroxide shell surrounding a conductive metallic core. Alloys and mixed-metal oxide and hydroxide particles of tin and indium have also been studied for their carbon dioxide electrocatalytic capabilities, especially in comparison to the pure metal species. Additionally, a solar-driven indium-based CO2 electrolyzer was developed to investigate the overall efficiency for intermittent energy storage. The three flow cells were powered by a commercial photovoltaic array and had a maximum conversion efficiency of incident

  18. Metal-insulator transition in one-dimensional lattices with chaotic energy sequences

    International Nuclear Information System (INIS)

    Pinto, R.A.; Rodriguez, M.; Gonzalez, J.A.; Medina, E.

    2005-01-01

    We study electronic transport through a one-dimensional array of sites by using a tight binding Hamiltonian, whose site-energies are drawn from a chaotic sequence. The correlation degree between these energies is controlled by a parameter regulating the dynamic Lyapunov exponent measuring the degree of chaos. We observe the effect of chaotic sequences on the localization length, conductance, conductance distribution and wave function, finding evidence of a metal-insulator transition (MIT) at a critical degree of chaos. The one-dimensional metallic phase is characterized by a Gaussian conductance distribution and exhibits a peculiar non-selfaveraging

  19. Flexible metallic seal for transition duct in turbine system

    Science.gov (United States)

    Flanagan, James Scott; LeBegue, Jeffrey Scott; McMahan, Kevin Weston; Dillard, Daniel Jackson; Pentecost, Ronnie Ray

    2014-04-22

    A turbine system is disclosed. In one embodiment, the turbine system includes a transition duct. The transition duct includes an inlet, an outlet, and a passage extending between the inlet and the outlet and defining a longitudinal axis, a radial axis, and a tangential axis. The outlet of the transition duct is offset from the inlet along the longitudinal axis and the tangential axis. The transition duct further includes an interface member for interfacing with a turbine section. The turbine system further includes a flexible metallic seal contacting the interface member to provide a seal between the interface member and the turbine section.

  20. [Transition metal mediated transformations of small molecules

    Energy Technology Data Exchange (ETDEWEB)

    Sen, A.

    1992-01-01

    Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of [alpha]-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors when doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.

  1. Engineered Bacterial Metal-binding Proteins for Nanoscale Self-assembly and heavy Metal Tolerance

    Science.gov (United States)

    Hall Sedlak, Ruth Amanda

    Implementing biological principles in material synthesis and assembly is one way to expand our abilities to efficiently assemble nanoscale materials and devices. Specifically, recent advances in identifying peptides that bind inorganic materials with high affinity and specificity has spurred investigation of protein models for nanoscale inorganic assembly. This dissertation presents the results of my studies of several E. coli proteins engineered to bind inorganic materials through simple peptide motifs. I demonstrate that these proteins modulate the self-assembly of DNA-based nanostructures and can introduce heavy metal tolerance into metal-sensitive bacteria. Chapter 2 explores use of the engineered F plasmid DNA relaxase/helicase TraI for the self-assembly of complex DNA-protein-gold nanostructures. The full-length protein is engineered with a gold binding motif at an internal permissive site (TraI369GBP1-7x), while a truncated version of TraI is engineered with the same gold binding motif at the C-terminus (TraI361GBP1-7x). Both constructs bind gold nanoparticles while maintaining their DNA binding activity, and transmission electron microscopy reveals TraI369GBP1-7x utilizes its non-specific DNA binding activity to decorate single-stranded and double-stranded DNA with gold nanoparticles. The self assembly principles demonstrated in this work will be fundamental to constructing higher ordered hybrid nanostructures through DNA-protein-nanoparticle interactions. Chapter 3 studies the effects of expressing inorganic binding peptides within cells. I identified a silver binding peptide that, when fused to the periplasmic maltose binding protein, protects E. coli from silver toxicity in batch culture and reduces silver ions to silver nanoparticles within the bacterial periplasm. Engineered metal-ion tolerant microorganisms such as this E. coli could potentially be used in applications ranging from remediation to interrogation of biomolecule-metal interactions in vivo

  2. Transition-metal-free chemo- and regioselective vinylation of azaallyls

    Science.gov (United States)

    Li, Minyan; Gutierrez, Osvaldo; Berritt, Simon; Pascual-Escudero, Ana; Yeşilçimen, Ahmet; Yang, Xiaodong; Adrio, Javier; Huang, Georgia; Nakamaru-Ogiso, Eiko; Kozlowski, Marisa C.; Walsh, Patrick J.

    2017-10-01

    Direct C(sp3)-C(sp2) bond formation under transition-metal-free conditions offers an atom-economical, inexpensive and environmentally benign alternative to traditional transition-metal-catalysed cross-coupling reactions. A new chemo- and regioselective coupling protocol between 3-aryl-substituted-1,1-diphenyl-2-azaallyl derivatives and vinyl bromides has been developed. This is the first transition-metal-free cross-coupling of azaallyls with vinyl bromide electrophiles and delivers allylic amines in excellent yields (up to 99%). This relatively simple and mild protocol offers a direct and practical strategy for the synthesis of high-value allylic amine building blocks that does not require the use of transition metals, special initiators or photoredox catalysts. Radical clock experiments, electron paramagnetic resonance studies and density functional theory calculations point to an unprecedented substrate-dependent coupling mechanism. Furthermore, an electron paramagnetic resonance signal was observed when the N-benzyl benzophenone ketimine was subjected to silylamide base, supporting the formation of radical species upon deprotonation. The unique mechanisms outlined herein could pave the way for new approaches to transition-metal-free C-C bond formations.

  3. Harnessing the metal-insulator transition for tunable metamaterials

    Science.gov (United States)

    Charipar, Nicholas A.; Charipar, Kristin M.; Kim, Heungsoo; Bingham, Nicholas S.; Suess, Ryan J.; Mathews, Scott A.; Auyeung, Raymond C. Y.; Piqué, Alberto

    2017-08-01

    The control of light-matter interaction through the use of subwavelength structures known as metamaterials has facilitated the ability to control electromagnetic radiation in ways not previously achievable. A plethora of passive metamaterials as well as examples of active or tunable metamaterials have been realized in recent years. However, the development of tunable metamaterials is still met with challenges due to lack of materials choices. To this end, materials that exhibit a metal-insulator transition are being explored as the active element for future metamaterials because of their characteristic abrupt change in electrical conductivity across their phase transition. The fast switching times (▵t properties associated with thin film metal-insulator transition materials are strongly dependent on the growth conditions. For this work, we have studied how growth conditions (such as gas partial pressure) influence the metalinsulator transition in VO2 thin films made by pulsed laser deposition. In addition, strain engineering during the growth process has been investigated as a method to tune the metal-insulator transition temperature. Examples of both the optical and electrical transient dynamics facilitating the metal-insulator transition will be presented together with specific examples of thin film metamaterial devices.

  4. Stable isotopes of transition and post-transition metals as tracers in environmental studies

    Science.gov (United States)

    Bullen, Tomas D.; Baskaran, Mark

    2011-01-01

    The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

  5. The Thermodynamics of Proteins Interactions with Essential First Raw Transition Metals

    Science.gov (United States)

    Bou-Abdallah, Fadi; Giffune, Thomas

    2015-01-01

    Background The binding of metal ions to proteins is a crucial process required for their catalytic activity, structural stability and/or functional regulation. Isothermal titration calorimetry provides a wealth of fundamental information which when combined with structural data allow for a much deeper understanding of the underlying molecular mechanism. Scope of review A rigorous understanding of any molecular interaction requires in part an in-depth quantification of its thermodynamic properties. Here, we provide an overview of recent studies that have used ITC to quantify the interaction of essential first raw transition metals with relevant proteins and highlight major findings from these thermodynamic studies. General significance The thermodynamic characterization of metal ions-proteins interactions is one important step to understanding the role that metal ions play in living systems. Such characterization has important implications not only to elucidating proteins’ structure-function relationships and biological properties but also in the biotechnology sector, medicine and drug design particularly since a number of metal ions are involved in several neurodegenerative diseases. Major conclusions Isothermal titration calorimetry measurements can provide complete thermodynamic profiles of any molecular interaction through the simultaneous determination of the reaction binding stoichiometry, binding affinity as well as the enthalpic and entropic contributions to the free energy change thus enabling a more in-depth understanding of the nature of these interactions. PMID:26569121

  6. The thermodynamics of protein interactions with essential first row transition metals.

    Science.gov (United States)

    Bou-Abdallah, Fadi; Giffune, Thomas R

    2016-05-01

    The binding of metal ions to proteins is a crucial process required for their catalytic activity, structural stability and/or functional regulation. Isothermal titration calorimetry provides a wealth of fundamental information which when combined with structural data allow for a much deeper understanding of the underlying molecular mechanism. A rigorous understanding of any molecular interaction requires in part an in-depth quantification of its thermodynamic properties. Here, we provide an overview of recent studies that have used ITC to quantify the interaction of essential first row transition metals with relevant proteins and highlight major findings from these thermodynamic studies. The thermodynamic characterization of metal ion-protein interactions is one important step to understanding the role that metal ions play in living systems. Such characterization has important implications not only to elucidating proteins' structure-function relationships and biological properties but also in the biotechnology sector, medicine and drug design particularly since a number of metal ions are involved in several neurodegenerative diseases. Isothermal titration calorimetry measurements can provide complete thermodynamic profiles of any molecular interaction through the simultaneous determination of the reaction binding stoichiometry, binding affinity as well as the enthalpic and entropic contributions to the free energy change thus enabling a more in-depth understanding of the nature of these interactions. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

    Science.gov (United States)

    Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

    2017-05-01

    Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Nanodisperse transition metal electrodes (NTME) for electrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Striebel, Kathryn A.; Wen, Shi-Jie

    1998-12-01

    Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

  9. Unusual metal-insulator transition in disordered ferromagnetic films

    International Nuclear Information System (INIS)

    Muttalib, K.A.; Wölfle, P.; Misra, R.; Hebard, A.F.

    2012-01-01

    We present a theoretical interpretation of recent data on the conductance near and farther away from the metal-insulator transition in thin ferromagnetic Gd films of thickness b≈2-10 nm. For increasing sheet resistances a dimensional crossover takes place from d=2 to d=3 dimensions, since the large phase relaxation rate caused by scattering of quasiparticles off spin wave excitations renders the dephasing length L φ ≲b at strong disorder. The conductivity data in the various regimes obey fractional power-law or logarithmic temperature dependence. One observes weak localization and interaction induced corrections at weaker disorder. At strong disorder, near the metal-insulator transition, the data show scaling and collapse onto two scaling curves for the metallic and insulating regimes. We interpret this unusual behavior as proof of two distinctly different correlation length exponents on both sides of the transition.

  10. Covalency, Excitons, Double Counting and the Metal-Insulator Transition in Transition Metal Oxides

    Science.gov (United States)

    Wang, Xin

    2012-02-01

    We present single-site dynamical mean-field studies of realistic models of transition metal oxides, including the cuprate superconductors and rare earth nickelates (in bulk and superlattice form). We include orbital multiplet effects and hybridization to ligands. We explicitly calculate the d-d exciton spectra for cuprates, finding sharp exciton lines in both metallic and insulating phases, which should be visible in experiments. We also find that the additional d3z^2-r^2 orbital does not contribute to an additional Fermi surface at any reasonable doping, in contradiction to previous slave-boson studies. The hybridization to ligands is shown to have crucial effects, for example suppressing the ferro-orbital order previously found in Hubbard model studies of nickelates. Hybridization to ligands is shown to be most naturally parametrized by the d-orbital occupancy. For cuprates and nickelates, insulating behavior is found to be present only for a very narrow range of d-occupancy, irrespective of the Coulomb repulsion. The d-occupancy predicted by standard band calculations is found to be very far from the values required to obtain an insulating phase, calling into question the interpretation of these materials as charge transfer insulators. [4pt] This work is done in collaboration with A.J. Millis, M.J. Han, C.A. Marianetti, L. de' Medici, and H.T. Dang, and is supported by NSF-DMR-1006282, the Army Office of Scientific Research, and the Condensed Matter Theory Center and CNAM at University of Maryland. [4pt] [1] X. Wang, H. T. Dang, and A. J. Millis, Phys. Rev. B 84, 014530 (2011).[0pt] [2] X. Wang, M. J. Han, L. de' Medici, C. A. Marianetti, and A. J. Millis, arXiv:1110.2782.[0pt] [3] M. J. Han, X. Wang, C. A. Marianetti, and A. J. Millis, Phys. Rev. Lett. 107, 206804 (2011).

  11. Phase stabilisation of hexagonal barium titanate doped with transition metals: A computational study

    Science.gov (United States)

    Dawson, J. A.; Freeman, C. L.; Harding, J. H.; Sinclair, D. C.

    2013-04-01

    Interatomic potentials recently developed for the modelling of BaTiO3 have been used to explore the stabilisation of the hexagonal polymorph of BaTiO3 by doping with transition metals (namely Mn, Co, Fe and Ni) at the Ti-site. Classical simulations have been completed on both the cubic and hexagonal polymorphs to investigate the energetic consequences of transition metal doping on each polymorph. Ti-site charge compensation mechanisms have been used for the multi-valent transition metal ions and cluster binding energies have been considered. Simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. This energetic difference between the two polymorphs is true for all transition metals tested and all charge states and in the case of tri- and tetra-valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions as observed experimentally. Oxidation during incorporation of Ni2+ and Fe3+ ions has also been considered.

  12. The nonmetal-metal transition in solutions of metals in molten salts

    International Nuclear Information System (INIS)

    Tosi, M.P.

    1997-04-01

    Solutions of metals in molten salts present a rich phenomenology: localization of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal - molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides. (author). 51 refs, 2 figs

  13. Differential plasma protein binding to metal oxide nanoparticles

    International Nuclear Information System (INIS)

    Deng, Zhou J; Mortimer, Gysell; Minchin, Rodney F; Schiller, Tara; Musumeci, Anthony; Martin, Darren

    2009-01-01

    Nanoparticles rapidly interact with the proteins present in biological fluids, such as blood. The proteins that are adsorbed onto the surface potentially dictate the biokinetics of the nanomaterials and their fate in vivo. Using nanoparticles with different sizes and surface characteristics, studies have reported the effects of physicochemical properties on the composition of adsorbed plasma proteins. However, to date, few studies have been conducted focusing on the nanoparticles that are commonly exposed to the general public, such as the metal oxides. Using previously established ultracentrifugation approaches, two-dimensional gel electrophoresis and mass spectrometry, the current study investigated the binding of human plasma proteins to commercially available titanium dioxide, silicon dioxide and zinc oxide nanoparticles. We found that, despite these particles having similar surface charges in buffer, they bound different plasma proteins. For TiO 2 , the shape of the nanoparticles was also an important determinant of protein binding. Agglomeration in water was observed for all of the nanoparticles and both TiO 2 and ZnO further agglomerated in biological media. This led to an increase in the amount and number of different proteins bound to these nanoparticles. Proteins with important biological functions were identified, including immunoglobulins, lipoproteins, acute-phase proteins and proteins involved in complement pathways and coagulation. These results provide important insights into which human plasma proteins bind to particular metal oxide nanoparticles. Because protein absorption to nanoparticles may determine their interaction with cells and tissues in vivo, understanding how and why plasma proteins are adsorbed to these particles may be important for understanding their biological responses.

  14. Development of dissimilar metal transition joint by hot bond rolling

    International Nuclear Information System (INIS)

    Kurokawa, Hiroyuki; Nakasuji, Kazuyuki; Kajimura, Haruhiko; Nagai, Takayuki; Takeda, Seiichiro.

    1997-01-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) to stainless steel piping are required for nuclear fuel reprocessing plants. The authors have developed dissimilar transition joints made of stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot bond rolling process of clad bars and clad pipes, using a newly developed mill called 'rotary reduction mill'. This report presents the manufacturing process of dissimilar transition joints produced from the clad pipe with three layers by the hot bond rolling. First, the method of hot bond rolling of clad pipe is proposed. Then, the mechanical and corrosion properties of the dissimilar transition joints are evaluated in detail by carrying out various tests. Finally, the rolling properties in the clad pipe method are discussed. (author)

  15. The study of structural phase transitions and static properties using transition metal model pseudopotential (TMMP) for Ca and Sr

    Energy Technology Data Exchange (ETDEWEB)

    Rakhecha, Shalu, E-mail: shalurakhecha@yahoo.com; Vyas, P. R.; Gohel, V. B. [Department of Physics, School of Sciences, Gujarat University, Ahmedabad - 380009, Gujarat (India); Bhatt, N. K. [Department of Physics, Sardar Patel University, Vallabh Vidyanagar - 388120, Gujarat (India)

    2016-05-06

    In the present communication, we have computed static and dynamic properties (binding energy-E, bulk modulus-B and second moment- <ω{sup 2}>) as well as first order pressure induced phase transition (FCC-BCC) using local form of pseudopotential for Calcium and Strontium. The form of pseudopotential used for the computation is directly extracted from Generalized Pseudopotential Theory (GPT) which contains three parameters (r{sub c}, r{sub d} and β). We have suggested a simple method using which pseudopotential is determined by single parameter (β). Our computed results for binding energy and bulk modulii are in excellent agreement with experimental findings and are better than other theoretical results. The present study confirms that s-d hybridization is accounted properly in the presently used pseudopotential and can be extended for the study of lattice mechanical properties of these metals.

  16. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...... of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of a Sabatier-Gibbs-type analysis, and we...... demonstrate that this type of analysis yields results that to within a surprisingly small margin of error are directly proportional to the measured direct NO decomposition over Ru, Rh, Pt, Pd, Ag, and An. We suggest that Pd, which is a better catalyst than Pt under the employed reaction conditions...

  17. THE INFLUENCE OF TRANSITION METALS ON THE ...

    African Journals Online (AJOL)

    Experimental results show that the addition of Zr, Mn, Co, and Cu promoters improved the activity of Pt Rh Pd/γ-Al2O3 catalyst remarkably for CO, CH and NOx conversion, respectively. The effective order of the promoters is CuO > ZrO2 > Co3O4 > MnO2. The addition of CuO improved the dispersion of the noble metal on ...

  18. Bias-induced insulator-metal transition in organic electronics

    Science.gov (United States)

    Wei, J. H.; Xie, S. J.; Mei, L. M.; Yan, YiJing

    2007-07-01

    The authors investigate the bias-induced insulator-metal transition in organic electronics devices on the basis of the Su-Schrieffer-Heeger model [W. P. Su et al., Phys. Rev. B 22, 2099 (1980)] combined with the nonequilibrium Green's function formalism. The insulator-metal transition is explained with the energy level crossover that eliminates the Peierls phase [R. Peierls, Quantum Theory of Solids (Oxford University Press, Oxford, 1955)] and delocalizes the electron states near the threshold voltage. This may account for the experimental observations on the devices that exhibit intrinsic bistable conductance switching with large on-off ratio.

  19. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    KAUST Repository

    Fhayli, Karim

    2016-04-14

    Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

  20. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

  1. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

    The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

  2. Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Nørskov, Jens Kehlet

    2010-01-01

    Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced...... and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbate-adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small...... influence on the position of the top of the volcano, that is, on which metal is the best catalyst....

  3. Study of the Interactions Between Transition Metal Ions and Peptides by CALIFORNIUM-252 Plasma Desorption Mass Spectrometry

    Science.gov (United States)

    Hu, Zhaohong

    This dissertation focuses on the study of interactions between transition metal ions (Cu(II), Zn(II), Pd(II), Pt(II)) and peptides (bradykinins and angiotensins). Chapter I provides an overview on the fundamental issues related to and techniques used for studying transition metal ion -peptide/protein complexes. It also reviews different mass spectroscopic techniques used for metal ion-peptide studies. Chapter II delineates the principle of ^{252 }Cf-PDMS instrumentation and the sample preparation methods utilized for this dissertation research. In order to study metal ion-peptide complexes with PDMS, it is essential to define the relationship between complex structures identified from PD mass spectra and complexes formed in solution phase. Chapter III includes the studies of the effects of solution conditions on the detection of metal ion-peptide complexes in PDMS. Solution pH is the most important factor for determining the formation of a complex. Reaction time, reactant concentration, and reaction temperature all display distinct influences on PDMS results. It demonstrates that the PDMS results are closely correlated with the complexes pre-formed in aqueous solution. Chapter IV provides ample spectroscopic data on peptides and their metal ion complexes. The metal ion -containing molecular ions observed provide information on numbers of metal ion-binding sites in a peptide and metal ion-affinity of the peptide. By analyzing fragmentation patterns, amino acid residues and functional groups involved in metal ion binding in a peptide can be identified.

  4. Ternary scandium and transition metals germanides

    International Nuclear Information System (INIS)

    Kotur, B.Ya.

    1992-01-01

    Brief review of data on phase diagram of ternary Sc-Me-Ge systems (Me-d - , f-transition element) is given. Isothermal sections at 870 and 1070 K of 17 ternary systems are plotted. Compositions and their structural characteristics are presented. Variability of crystal structure is typical for ternary scandium germanides: 70 compounds with the studied structure belong to 23 structural types. Ternary germanides isostructural to types of Sm 4 Ge 4 , ZrCrSi 2 , ZrNiAl, ScCeSi, TiNiSi U 4 Re 7 Si 6 145 compounds from 70 under investigation are mostly formed in studied systems

  5. Noncollinear magnetism in surfaces and interfaces of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Huahai

    2009-09-15

    Noncollinear (NC) magnetism is common in nature, especially when there exist geometrical frustration and chemical imparity in the system. In this work we studied the NC magnetism and the response to external magnetic fields in surfaces and interfaces of transition metals by using an semi-empirical tight-binding (TB) method that parameterized to the ab initio TB-LMTO calculations. We implemented this method to study two systems. The first one is the system of 6 Mn monolayers on Fe(001) substrate. Due to the complex structure and magnetic properties of Mn, we found 23 collinear magnetic configurations but only one NC configuration. The collinear ground state has a layered antiferromagnetic (AFM) coupling which agrees with previous experiments and calculations. In the NC configuration the local AFM coupling in the Mn layers is preserved, but the surface is 90 degree coupled to the substrate. Similar to the experiment in CdCr{sub 2}O{sub 4}, we obtained a collinear plateau in the NC evolution of the average magnetic moment in Mn slab under external magnetic fields. Another is the system of a Cr monolayer on a stepped Fe(001) substrate. As expected, the local AFM coupling in the interface of Cr and Fe are preserved. However, the edge Cr atoms is about 90 coupled to their nearest Fe neighbors. We also simulated the procedure of adding more Cr coverages gradually to a Cr bilayer coverage. As coverages increase, the magnetic moments in the Cr interface reduce, and the collinear plateau becomes wider as coverages increase. However, the saturation fields in both the two systems are extremely high, around 10 kT.We expect that when the effect of temperature is taken into account, and in some proper systems, the saturation fields could be largely reduced to the scale that can be implemented in experiment, and our study may shed light on information storage devices with ultrahigh storage density. (orig.)

  6. Electronic and thermodynamic properties of transition metal elements and compounds

    International Nuclear Information System (INIS)

    Haeglund, J.

    1993-01-01

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC 1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  7. Metal-insulator transition in epitaxial vanadium sesquioxide thin films

    Science.gov (United States)

    Allimi, Bamidele S.

    Of all the transition metal oxides which exhibit metal-insulator transitions (MIT), one of the most extensively studied in recent years is the vanadium sesquioxide (V2O3), both from experimental and theoretical point of view. At a transition temperature of about 160 K at an ambient pressure of 1 atm, pure V2O3 transforms from a rhombohedral paramagnetic metallic (PM) to a monoclinic antiferromagnetic insulating (AFI) phase upon cooling, with a jump in the resistivity of about seven orders of magnitude. Experimental studies have focused more on bulk V2O3 and recently there have been significant interest in thin film fabrication of this material due to potential applications as thermal sensors, current limiters, Positive Temperature Coefficient (PTC) thermistors, and optical switches. This study addresses the deposition, characterization, and properties of high-quality epitaxial V2O3 thin films grown on a-, c-Al2O3 and c-LiTaO 3 substrates by a straightforward method of pulsed laser deposition (PLD). Various characterization techniques including X-ray diffraction, atomic force microscopy, scanning electron microscopy, and X-ray photoemission spectroscopy were used to examine the structural, crystallographic, and surface properties, while four point probe resistivity measurements were used to examine the electrical properties of the films. V2O3 thin films of different thicknesses ranging from 10-450 nm were deposited on c-Al 2O3 and c-LiTaO3 substrates by PLD to understand also the role of epitaxial strains. Resistivity measurements showed that depending on the thicknesses of films, different electrical transitions were exhibited by the samples. While some of the samples displayed the expected metal-insulator transition typical of bulk V2O3, some showed insulating behavior only and others exhibited metallic characteristics only over the whole temperature range. For example, for films on c-LiTaO3 with increasing film thickness, first an insulator-insulator, then a

  8. Synthesis and enantiopreferential DNA-binding profile of late 3d transition metal R- and S-enantiomeric complexes derived from N,N-bis-(1-benzyl-2-ethoxyethane): Validation of R-enantiomer of copper(II) complex as a human topoisomerase II inhibitor.

    Science.gov (United States)

    Arjmand, Farukh; Sharma, Girish Chandra; Muddassir, Mohd; Tabassum, Sartaj

    2011-08-01

    To evaluate the biological preference of chiral drug candidates for molecular target DNA, new potential metal-based chemotherapeutic agents 1-3 (a and b) of late 3d transition metals Ni(II), Cu(II), and Zn(II), respectively, derived from (R)- and (S)-2-amino-2-phenylethanol with CH(2) CH(2)  linker were synthesized and thoroughly characterized. Interaction studies of 1-3 (a and b) with calf thymus DNA in Tris buffer were studied by electronic absorption titrations, luminescence titrations, cyclic voltammetry, and circular dichroism. The results reveal that the extent of DNA binding of R-enantiomer of copper 1a was highest in comparison to rest of the complexes via electrostatic interaction mode. The nuclease activity of 1(a and b) with supercoiled pBR322 DNA was further examined by gel electrophoresis, which reveals that complex 1a exhibits a remarkable DNA cleavage activity (concentration dependent) with pBR322DNA, and the cleavage activity of both enantiomers of complex 1 was significantly enhanced in the presence of activators. The activating efficiency follows the order Asc > H(2) O(2) > MPA for 1a, and reverse order was observed for 1b, because of the differences in enantioselectivity and conformation. Further, it was observed that cleavage reaction involves singlet oxygen species and superoxide radicals via oxidative cleavage mechanism. In addition, complex 1a exhibits significant inhibitory effects on the topoisomerase II (topo II) activity at a very low concentration ∼24 μM, which suggest that complex 1a is indeed catalytic inhibitor or (poison) of human topo II. Copyright © 2011 Wiley-Liss, Inc.

  9. Exploiting Cancer Metal Metabolism using Anti-Cancer Metal-Binding Agents.

    Science.gov (United States)

    Merlot, Angelica M; Kalinowski, Danuta S; Kovacevic, Zaklina; Jansson, Patric J; Sahni, Sumit; Huang, Michael L; Lane, Darius L; Lok, Hiu; Richardson, Des R

    2017-07-05

    Metals are vital cellular elements necessary for multiple indispensable biological processes of living organisms, including energy transduction and cell proliferation. Interestingly, alterations in metal levels and also changes in the expression of proteins involved in metal metabolism have been demonstrated in a variety of cancers. Considering this and the important role of metals for cell growth, the development of drugs that sequester metals have become an attractive target for the development of novel anti-cancer agents. Interest in this field has surged with the design and development of new generations of chelators of the thiosemicarbazone class. These ligands have shown potent anti-cancer and anti-metastatic activity in vitro and in vivo. Due to their efficacy and safe toxicological assessment, some of these agents have recently entered multi-center clinical trials as therapeutics for advanced and resistant tumors. This review highlights the role, and changes in homeostasis, of metals in cancer and emphasizes the pre-clinical development and clinical assessment of metal ion-binding agents, namely, thiosemicarbazones, as anti-tumor agents. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  10. Adlayer Core-Level Shifts of Random Metal Overlayers on Transition-Metal Substrates

    DEFF Research Database (Denmark)

    Ganduglia-Pirovano, M. V.; Kudrnovský, J.; Scheffler, M.

    1997-01-01

    and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from...

  11. Metal binding is critical for the folding and function of laminin binding protein, Lmb of Streptococcus agalactiae.

    Directory of Open Access Journals (Sweden)

    Preethi Ragunathan

    Full Text Available Lmb is a 34 kDa laminin binding surface adhesin of Streptococcus agalactiae. The structure of Lmb reported by us recently has shown that it consists of a metal binding crevice, in which a zinc ion is coordinated to three highly conserved histidines. To elucidate the structural and functional significance of the metal ion in Lmb, these histidines have been mutated to alanine and single, double and triple mutants were generated. These mutations resulted in insolubility of the protein and revealed altered secondary and tertiary structures, as evidenced by circular dichroism and fluorescence spectroscopy studies. The mutations also significantly decreased the binding affinity of Lmb to laminin, implicating the role played by the metal binding residues in maintaining the correct conformation of the protein for its binding to laminin. A highly disordered loop, proposed to be crucial for metal acquisition in homologous structures, was deleted in Lmb by mutation (ΔLmb and its crystal structure was solved at 2.6 Å. The ΔLmb structure was identical to the native Lmb structure with a bound zinc ion and exhibited laminin binding activity similar to wild type protein, suggesting that the loop might not have an important role in metal acquisition or adhesion in Lmb. Targeted mutations of histidine residues confirmed the importance of the zinc binding crevice for the structure and function of the Lmb adhesin.

  12. Chiral structures and tunable magnetic moments in 3d transition metal doped Pt6 clusters

    International Nuclear Information System (INIS)

    Zhang Xiu-Rong; Yang Xing; Ding Xun-Lei

    2012-01-01

    The structural, electronic, and magnetic properties of transition metal doped platinum clusters MPt 6 (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) are systematically studied by using the relativistic all-electron density functional theory with the generalized gradient approximation. Most of the doped clusters show larger binding energies than the pure Pt 7 cluster, which indicates that the doping of the transition metal atom can stabilize the pure platinum cluster. The results of the highest occupied molecular orbital (HOMO)—lowest unoccupied molecular orbital (LUMO) gaps suggest that the doped clusters can have higher chemical activities than the pure Pt 7 cluster. The magnetism calculations demonstrate that the variation range of the magnetic moments of the MPt 6 clusters is from 0 μ B to 7 μ B , revealing that the MPt 6 clusters have potential utility in designing new spintronic nanomaterials with tunable magnetic properties

  13. How absorbed hydrogen affects the catalytic activity of transition metals.

    Science.gov (United States)

    Aleksandrov, Hristiyan A; Kozlov, Sergey M; Schauermann, Swetlana; Vayssilov, Georgi N; Neyman, Konstantin M

    2014-12-01

    Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H(sub) , may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H(ad) , depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H(sub) , especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Parkinson disease protein DJ-1 binds metals and protects against metal-induced cytotoxicity.

    Science.gov (United States)

    Björkblom, Benny; Adilbayeva, Altynai; Maple-Grødem, Jodi; Piston, Dominik; Ökvist, Mats; Xu, Xiang Ming; Brede, Cato; Larsen, Jan Petter; Møller, Simon Geir

    2013-08-02

    The progressive loss of motor control due to reduction of dopamine-producing neurons in the substantia nigra pars compacta and decreased striatal dopamine levels are the classically described features of Parkinson disease (PD). Neuronal damage also progresses to other regions of the brain, and additional non-motor dysfunctions are common. Accumulation of environmental toxins, such as pesticides and metals, are suggested risk factors for the development of typical late onset PD, although genetic factors seem to be substantial in early onset cases. Mutations of DJ-1 are known to cause a form of recessive early onset Parkinson disease, highlighting an important functional role for DJ-1 in early disease prevention. This study identifies human DJ-1 as a metal-binding protein able to evidently bind copper as well as toxic mercury ions in vitro. The study further characterizes the cytoprotective function of DJ-1 and PD-mutated variants of DJ-1 with respect to induced metal cytotoxicity. The results show that expression of DJ-1 enhances the cells' protective mechanisms against induced metal toxicity and that this protection is lost for DJ-1 PD mutations A104T and D149A. The study also shows that oxidation site-mutated DJ-1 C106A retains its ability to protect cells. We also show that concomitant addition of dopamine exposure sensitizes cells to metal-induced cytotoxicity. We also confirm that redox-active dopamine adducts enhance metal-catalyzed oxidation of intracellular proteins in vivo by use of live cell imaging of redox-sensitive S3roGFP. The study indicates that even a small genetic alteration can sensitize cells to metal-induced cell death, a finding that may revive the interest in exogenous factors in the etiology of PD.

  15. Parkinson Disease Protein DJ-1 Binds Metals and Protects against Metal-induced Cytotoxicity*

    Science.gov (United States)

    Björkblom, Benny; Adilbayeva, Altynai; Maple-Grødem, Jodi; Piston, Dominik; Ökvist, Mats; Xu, Xiang Ming; Brede, Cato; Larsen, Jan Petter; Møller, Simon Geir

    2013-01-01

    The progressive loss of motor control due to reduction of dopamine-producing neurons in the substantia nigra pars compacta and decreased striatal dopamine levels are the classically described features of Parkinson disease (PD). Neuronal damage also progresses to other regions of the brain, and additional non-motor dysfunctions are common. Accumulation of environmental toxins, such as pesticides and metals, are suggested risk factors for the development of typical late onset PD, although genetic factors seem to be substantial in early onset cases. Mutations of DJ-1 are known to cause a form of recessive early onset Parkinson disease, highlighting an important functional role for DJ-1 in early disease prevention. This study identifies human DJ-1 as a metal-binding protein able to evidently bind copper as well as toxic mercury ions in vitro. The study further characterizes the cytoprotective function of DJ-1 and PD-mutated variants of DJ-1 with respect to induced metal cytotoxicity. The results show that expression of DJ-1 enhances the cells' protective mechanisms against induced metal toxicity and that this protection is lost for DJ-1 PD mutations A104T and D149A. The study also shows that oxidation site-mutated DJ-1 C106A retains its ability to protect cells. We also show that concomitant addition of dopamine exposure sensitizes cells to metal-induced cytotoxicity. We also confirm that redox-active dopamine adducts enhance metal-catalyzed oxidation of intracellular proteins in vivo by use of live cell imaging of redox-sensitive S3roGFP. The study indicates that even a small genetic alteration can sensitize cells to metal-induced cell death, a finding that may revive the interest in exogenous factors in the etiology of PD. PMID:23792957

  16. The metal-rich sulfides and phosphides of the early transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Franzen, H.F. [Ames Lab., IA (United States)]|[Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

    1996-06-01

    Early work on the preparation of refractory metal-rich compounds of the early transition metals resulted in the understanding that metal-metal bonding results in a structural variety that plays an important role in the high-temperature chemistry of these systems. The binary metal-rich systems have been thoroughly studied at high temperatures, and the structures of most, if not all, of the refractory sulfides and phosphides are known. More recently new ternary phases have been discovered, and these have been shown to result from distributed fractional site occupation of metal atom sites in complex structures. The extent of metal-metal bonding has been quantified by Extended-Hueckel Tight-Bonding calculations using Mullikan Overlap Populations. Correlations of site occupancy with MOP based upon the DFSO model have been observed. 44 refs.

  17. Electrocatalysis of Hydrogen Evolution by Transition Metal Complexes

    Czech Academy of Sciences Publication Activity Database

    Heyrovský, Michael

    2001-01-01

    Roč. 66, č. 1 (2001), s. 67-80 ISSN 0010-0765 R&D Projects: GA ČR GV204/97/K084 Institutional research plan: CEZ:AV0Z4040901 Keywords : transition metals * thiocyanate complexes * electroreduction Subject RIV: CG - Electrochemistry Impact factor: 0.778, year: 2001

  18. Synthesis, spectral characterization of Schiff base transition metal ...

    Indian Academy of Sciences (India)

    TECS

    Synthesis, spectral characterization of Schiff base transition metal complexes: DNA cleavage and antimicrobial activity studies. N RAMAN,* J DHAVEETHU RAJA and A SAKTHIVEL. Department of Chemistry, VHNSN College, Virudhunagar 626 001 e-mail: drn_ raman@yahoo.co.in. MS received 1 May 2007; revised 7 July ...

  19. Transition metal chemistry of hydroxy(–OH)-rich molecules ...

    Indian Academy of Sciences (India)

    Administrator

    Transition metal chemistry of hydroxy(–OH)-rich molecules: Syntheses, crystal structures and solution reactivity studies. MISHTU DEY 1, P K SAARENKETO 2, E KOLEHMAINEN 2,. K RISSANEN 2 and CHEBROLU P RAO 1. 1Bioinorganic Laboratory, Department of Chemistry, Indian Institute of. Technology Bombay, Powai ...

  20. Mechanical failure and glass transition in metallic glasses

    International Nuclear Information System (INIS)

    Egami, T.

    2011-01-01

    Research highlights: → We review the recent results of molecular dynamics simulations on metallic glasses. → They show the equivalence of mechanical failure and glass transition. → We discuss the microscopic mechanism behind this equivalence. → We show that the density of defects in metallic glasses is as high as a quarter. → Our concepts about the defect state in glasses need to be changed. - Abstract: The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

  1. Reactions of transition metal complexes with cyclic ethers

    International Nuclear Information System (INIS)

    Milstein, D.

    1977-02-01

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  2. Effect of transition metal elements on the structural and optical ...

    Indian Academy of Sciences (India)

    Effect of transition metal elements on the structural and optical properties of ZnO nanoparticles. I KAZEMINEZHAD1, S SAADATMAND1 and RAMIN YOUSEFI2,∗. 1Nanotechnology Laboratory, Physics Department, Shahid Chamran University of Ahvaz, Ahvaz, Iran. 2Department of Physics, Islamic Azad University (IAU), ...

  3. Transport properties of transition metal impurities on gold nanowires

    Science.gov (United States)

    Pontes, Renato B.; da Silva, Edison Z.; Fazzio, Adalberto; da Silva, Antônio J. R.

    2009-03-01

    Performing first principles density functional theory (DFT) we calculated the electronic and transport properties of a Au thin nanowire with transition metal atoms (Mn, Fe, Ni or Co) bridging the two sides of the Au nanowire. We will show that these systems have strong spin dependent transport properties and that the local symmetry can dramatically change them, leading to a significant spin polarized conductance. This spin dependent transport is also associated with the transition metal in the nanowire, in particular with the d-level positioning. Using Co, for example [1], when the symmetry permits the mixing between the wire s-orbitals with the transition metal d-states, there are interference effects that resemble Fano-like resonances with an anisotropy of 0.07 at the Fermi level. On the other hand, if this symmetry decouples such states, we simply have a sum of independent transmission channels and the calculated anisotropy was 0.23. The anisotropies for the other transition metals, as well as calculated transmittances for two Co impurities will also be presented [1] R. B. Pontes, E. Z. da Silva, A. Fazzio and Antônio J. R. da Silva, J. Am. Chem. Soc. 130 (30), 9897-903, 2008

  4. Vibrational properties of vacancy in bcc transition metals using ...

    Indian Academy of Sciences (India)

    The embedded atom method (EAM) potentials, with the universal form of the embedding function along with the Morse form of pair potential, have been employed to determine the potential parameters for three bcc transition metals: Fe, Mo, and W, by fitting to Cauchy pressure (C12−C44)/2, shear constants ...

  5. Exciton ionization in multilayer transition-metal dichalcogenides

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Latini, Simone; Thygesen, Kristian Sommer

    2016-01-01

    Photodetectors and solar cells based on materials with strongly bound excitons rely crucially on field-assisted exciton ionization. We study the ionization process in multilayer transition-metal dichalcogenides (TMDs) within the Mott-Wannier model incorporating fully the pronounced anisotropy...

  6. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  7. Transition metal-free, base-promoted hydroalkoxylation: Synthesis ...

    Indian Academy of Sciences (India)

    Abstract. An efficient,transition metal-free method to synthesize substituted imidazo[2,1-c][1,4]oxazine derivatives via hydroalkoxylation of 1,5-alkynyl alcohol has been described. The reaction ... Muthusubramanian1. Department of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India ...

  8. Phenalenyl-based ligand for transition metal chemistry: Application ...

    Indian Academy of Sciences (India)

    mandal@iiserkol.ac.in. Abstract. We report the synthesis and characterization of the first transition metal complex of a phenalenyl- based ligand. The reaction of Cu(OAc)2.H2O with 9-N-methylamino-1-N -methylimino-phenalene (LH) in 1:1.

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

    Science.gov (United States)

    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.

  10. Tridentate Schiff base (ONO) transition metal complexes: Synthesis ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 7. Tridentate Schiff base (ONO) transition metal complexes: Synthesis, crystal structure, spectroscopic and larvicidal studies. SUNDARAMURTHY SANTHA LAKSHMI KANNAPPAN GEETHA P MAHADEVI. Regular Article Volume 128 Issue 7 July 2016 pp ...

  11. Volume variation of Gruneisen parameters of fcc transition metals

    Indian Academy of Sciences (India)

    Unknown

    ultrasonic measurements and melting of solids (Mulargia and Boschi 1978 .... Several studies in the past based on model pseudo- potential suggest ... Volume variation of fcc transition metals. 65. The present value for Cu is in good agreement with the experimental values. Also, the presently obtained value agrees well with ...

  12. Spin, Charge, and Bonding in Transition Metal Mono Silicides

    NARCIS (Netherlands)

    Marel, D. van der; Damascelli, A.; Schulte, K.; Menovsky, A. A.

    1997-01-01

    Published in: Physica B 244 (1998) 138-147 citations recorded in [Science Citation Index] Abstract: We review some of the relevant physical properties of the transition metal mono-silicides with the FeSi structure (CrSi, MnSi, FeSi, CoSi, NiSi, etc) and explore the relation between their structural

  13. Effect of transition metal dopants on the optical and magnetic ...

    Indian Academy of Sciences (India)

    2015-06-02

    Jun 2, 2015 ... This review discusses the recent developments in doped semiconductor nanocrystals with a special emphasis on the effect of dopant on the electronic structure of the host nanocrystals. The review focusses on 3 transition metal dopants with unique electronic structure making them receptive for dramatic ...

  14. Comparison of metal-binding strength between methionine and cysteine residues: Implications for the design of metal-binding motifs in proteins.

    Science.gov (United States)

    Krishna Deepak, R N V; Chandrakar, Brijesh; Sankararamakrishnan, Ramasubbu

    2017-05-01

    Metals play vital role in various physiological processes and are bound to biomolecules. Although cysteine sulfur is more frequently found as metal-binding ligand, methionine prefers to occur in copper-binding motifs of some proteins. To address methionine's lower preference in copper-binding sites in comparison to cysteine, we have considered copper-binding motifs (His-Cys-His-Met) from seven different high-resolution protein structures. We performed quantum chemical calculations to find out the strength of interactions between sulfur and metal ion in both Met and Cys residues. In the case of Cys, both neutral (CysH) and the deprotonated form (Cys - ) were considered. We used two different levels of theory (B3LYP and M06-2X) and the model compounds methyl propyl sulfide, ethanethiol and ethanethiolate were used to represent Met, CysH and Cys - respectively. To compare the metal-binding strength, we mutated Met in silico to CysH/Cys - and performed the calculations. We also carried out calculations with wild-type Cys present in the same metal-binding motif. On average, interactions of Met with copper ion are stronger by 13-35kcal/mol compared to CysH. However, Cys - interactions with copper is stronger than that of Met by ~250kcal/mol. We then considered the entire metal-binding motif with four residues and calculated the interaction energies with the copper ion. We also considered Met→Cys - mutation in the motif and repeated the calculations. Interaction of the wild-type motif with the copper ion is ~160kcal/mol weaker than that of mutated motif. Our studies suggest the factors that could explain why Met is not as frequently observed as Cys in the metal-binding motifs. Results of these studies will help in designing metal-binding motifs in proteins with varying interaction strengths. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    di Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  16. Covalent bonds against magnetism in transition metal compounds.

    Science.gov (United States)

    Streltsov, Sergey V; Khomskii, Daniel I

    2016-09-20

    Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect-an orbital-selective formation of covalent metal-metal bonds that leads to an "exclusion" of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d-5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin-orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior.

  17. Empirical prediction of optical transitions in metallic armchair SWCNTs

    Directory of Open Access Journals (Sweden)

    G. R. Ahmed Jamal

    2015-12-01

    Full Text Available In this work, a quick and effective method to calculate the second and third optical transition energies of metallic armchair single-wall carbon nanotubes (SWCNT is presented. In this proposed method, the transition energy of any armchair SWCNT can be predicted directly by knowing its one chiral index as both of its chiral indices are same. The predicted results are compared with recent experimental data and found to be accurate over a wide diameter range from 2 to 4.8 nm. The empirical equation proposed here is also compared with that proposed in earlier works. The proposed way may help the research works or applications where information of optical transitions of armchair metallic nanotubes is needed.

  18. Disorder-Driven Metal-Insulator Transitions in Deformable Lattices.

    Science.gov (United States)

    Di Sante, Domenico; Fratini, Simone; Dobrosavljević, Vladimir; Ciuchi, Sergio

    2017-01-20

    We show that, in the presence of a deformable lattice potential, the nature of the disorder-driven metal-insulator transition is fundamentally changed with respect to the noninteracting (Anderson) scenario. For strong disorder, even a modest electron-phonon interaction is found to dramatically renormalize the random potential, opening a mobility gap at the Fermi energy. This process, which reflects disorder-enhanced polaron formation, is here given a microscopic basis by treating the lattice deformations and Anderson localization effects on the same footing. We identify an intermediate "bad insulator" transport regime which displays resistivity values exceeding the Mott-Ioffe-Regel limit and with a negative temperature coefficient, as often observed in strongly disordered metals. Our calculations reveal that this behavior originates from significant temperature-induced rearrangements of electronic states due to enhanced interaction effects close to the disorder-driven metal-insulator transition.

  19. Biophysical and Bioinformatic Analyses Implicate the Treponema pallidum Tp34 Lipoprotein (Tp0971) in Transition Metal Homeostasis

    Science.gov (United States)

    Brautigam, Chad A.; Deka, Ranjit K.; Ouyang, Zhiming; Machius, Mischa; Knutsen, Gregory; Tomchick, Diana R.

    2012-01-01

    Metal ion homeostasis is a critical function of many integral and peripheral membrane proteins. The genome of the etiologic agent of syphilis, Treponema pallidum, is compact and devoid of many metabolic enzyme genes. Nevertheless, it harbors genes coding for homologs of several enzymes that typically require either iron or zinc. The product of the tp0971 gene of T. pallidum, designated Tp34, is a periplasmic lipoprotein that is thought to be tethered to the inner membrane of this organism. Previous work on a water-soluble (nonacylated) recombinant version of Tp34 established that this protein binds to Zn2+, which, like other transition metal ions, stabilizes the dimeric form of the protein. In this study, we employed analytical ultracentrifugation to establish that four transition metal ions (Ni2+, Co2+, Cu2+, and Zn2+) readily induce the dimerization of Tp34; Cu2+ (50% effective concentration [EC50] = 1.7 μM) and Zn2+ (EC50 = 6.2 μM) were the most efficacious of these ions. Mutations of the crystallographically identified metal-binding residues hindered the ability of Tp34 to dimerize. X-ray crystallography performed on crystals of Tp34 that had been incubated with metal ions indicated that the binding site could accommodate the metals examined. The findings presented herein, coupled with bioinformatic analyses of related proteins, point to Tp34's likely role in metal ion homeostasis in T. pallidum. PMID:23042995

  20. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

    Science.gov (United States)

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Vudamala, Krushna; Sarkar, Arindam; Nath, B Nagender

    2016-02-01

    Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

  1. Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

    Science.gov (United States)

    Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

    2018-03-01

    Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

  2. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    Science.gov (United States)

    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. The allosteric transition of GroEL induced by metal fluoride-ADP complexes.

    Science.gov (United States)

    Inobe, Tomonao; Kikushima, Kenji; Makio, Tadashi; Arai, Munehito; Kuwajima, Kunihiro

    2003-05-23

    To understand the mechanism of a functionally important ATP-induced allosteric transition of GroEL, we have studied the effect of a series of metal fluoride-ADP complexes and vanadate-ADP on GroEL by kinetic fluorescence measurement of pyrene-labeled GroEL and by small-angle X-ray scattering measurement of wild-type GroEL. The metal fluorides and vanadate, complexed with ADP, are known to mimic the gamma-phosphate group of ATP, but they differ in geometry and size; it is expected that these compounds will be useful for investigating the strikingly high specificity of GroEL for ATP that enables the induction of the allosteric transition. The kinetic fluorescence measurement revealed that aluminium, beryllium, and gallium ions, when complexed with the fluoride ion and ADP, induced a biphasic fluorescence change of pyrenyl GroEL, while scandium and vanadate ions did not induce any kinetically observed change in fluorescence. The burst phase and the first phase of the fluorescence kinetics were reversible, while the second phase and subsequent changes were irreversible. The dependence of the burst-phase and the first-phase fluorescence changes on the ADP concentration indicated that the burst phase represents non-cooperative nucleotide binding to GroEL, and that the first phase represents the allosteric transition of GroEL. Both the amplitude and the rate constant of the first phase of the fluorescence kinetics were well understood in terms of a kinetic allosteric model, which is a combination of transition state theory and the Monod-Wyman-Changeux allosteric model. From the kinetic allosteric model analysis, the relative free energy of the transition state in the metal fluoride-ADP-induced allosteric transition of GroEL was found to be larger than the corresponding free energy of the ATP-induced allosteric transition by more than 5.5kcal/mol. However, the X-ray scattering measurements indicated that the allosteric state induced by these metal fluoride-ADP complexes is

  4. Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces.

    Science.gov (United States)

    Kuhl, Kendra P; Hatsukade, Toru; Cave, Etosha R; Abram, David N; Kibsgaard, Jakob; Jaramillo, Thomas F

    2014-10-08

    Fuels and industrial chemicals that are conventionally derived from fossil resources could potentially be produced in a renewable, sustainable manner by an electrochemical process that operates at room temperature and atmospheric pressure, using only water, CO2, and electricity as inputs. To enable this technology, improved catalysts must be developed. Herein, we report trends in the electrocatalytic conversion of CO2 on a broad group of seven transition metal surfaces: Au, Ag, Zn, Cu, Ni, Pt, and Fe. Contrary to conventional knowledge in the field, all metals studied are capable of producing methane or methanol. We quantify reaction rates for these two products and describe catalyst activity and selectivity in the framework of CO binding energies for the different metals. While selectivity toward methane or methanol is low for most of these metals, the fact that they are all capable of producing these products, even at a low rate, is important new knowledge. This study reveals a richer surface chemistry for transition metals than previously known and provides new insights to guide the development of improved CO2 conversion catalysts.

  5. Alkali metal ion templated transition metal formate framework materials: synthesis, crystal structures, ion migration, and magnetism.

    Science.gov (United States)

    Eikeland, Espen; Lock, Nina; Filsø, Mette; Stingaciu, Marian; Shen, Yanbin; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-10-06

    Four transition metal formate coordination polymers with anionic frameworks, namely, Na[Mn(HCOO)3], K[Mn(HCOO)3], Na2[Cu3(HCOO)8], and K2[Cu5(HCOO)12], were synthesized using a mild solution chemistry approach. Multitemperature single-crystal (100-300 K) and powder X-ray diffraction studies of the compounds reveal structures of large diversity ranging from cubic chiral Na-Mn formate to triclinic Na-Cu formate. The structural variety is caused by the nature of the transition metals, the alkali metal ion templation, and the versatility of the formate group, which offers metal-metal coordination through three different O-C-O bridging modes (syn-syn, syn-anti, anti-anti) in addition to metal-metal bridging via a single oxygen atom. The two manganese(II) compounds contain mononuclear, octahedrally coordinated moieties, but the three-dimensional connectivity between the manganese octahedra is very different in the two structures. The two copper frameworks, in contrast, consist of binuclear and mononuclear moieties (Na-Cu formate) and trinuclear and mononuclear moieties (K-Cu formate), respectively. Procrystal electron density analysis of the compounds indicates one-dimensional K(+)-ion conductivity in K-Mn and K-Cu, and the nature of the proposed potassium ion migration is compared with results from similar analysis on known Na(+) and K(+) ion conductors. K-Mn and Na-Mn were tested as cathode materials, but this resulted in poor reversibility due to low conductivity or structural collapse. The magnetic properties of the compounds were studied by vibrating sample magnetometric measurements, and their thermal stabilities were determined by thermogravimetric analysis and differential thermal analysis. Despite structural differences, the metal formates that contain the same transition metal have similar magnetic properties and thermal decomposition pathways, that is, the nature of the transition metal controls the compound properties.

  6. Slow- and fast-binding inhibitors of thermolysin display different modes of binding: crystallographic analysis of extended phosphonamidate transition-state analogues.

    Science.gov (United States)

    Holden, H M; Tronrud, D E; Monzingo, A F; Weaver, L H; Matthews, B W

    1987-12-29

    The modes of binding to thermolysin of two phosphonamidate peptide inhibitors, carbobenzoxy-GlyP-L-Leu-L-Leu (ZGPLL) and carbobenzoxy-L-PheP-L-Leu-L-Ala (ZFPLA), have been determined by X-ray crystallography and refined at high resolution to crystallographic R-values of 17.7% and 17.0%, respectively. (GlyP is used to indicate that the trigonal carbon of the peptide linkage is replaced by the tetrahedral phosphorus of a phosphonamidate group.). These inhibitors were designed to be structural analogues of the presumed catalytic transition state and are potent inhibitors of thermolysin (ZGPLL, Ki = 9.1 nM; ZFPLA, Ki = 0.068 nM) [Bartlett, P. A., & Marlowe, C. K. (1987) Biochemistry (following paper in this issue)]. ZFPLA binds to thermolysin in the manner expected for the transition state and, for the first time, provides direct support for the presumed mode of binding of extended substrates in the S2 subsite. The mode of binding of ZFPLA displays all the interactions that are presumed to stabilize the transition state and supports the postulated mechanism of catalysis [Hangauer, D. G., Monzingo, A. F., & Matthews, B. W. (1984) Biochemistry 23, 5730-5741]. The two oxygens of the phosphonamidate moiety are liganded to the zinc to give overall pentacoordination of the metal. For the second inhibitor the situation is different. Although both ZFPLA and ZGPLL have similar modes of binding in the S1' and S2' subsites, the configurations of the carbobenzoxy-Phe and carbobenzoxy-Gly moieties are different. For ZFPLA the carbonyl group of the carbobenzoxy group is hydrogen bonded directly to the enzyme, whereas in ZGPLL the carbonyl group is rotated 117 degrees, and there is a water molecule interposed between the inhibitor and the enzyme. For ZGPLL only one of the phosphonamidate oxygens is liganded to the zinc. Correlated with the change in inhibitor-zinc ligation from monodentate in ZGPLL to bidentate in ZFPLA there is an increase in the phosphorus-nitrogen bond length of

  7. Ab initio modelling of transition metals in diamond

    International Nuclear Information System (INIS)

    Watkins, M; Mainwood, A

    2003-01-01

    Transition metals (TM) from the first transition series are commonly used as solvent catalysts in the synthesis of diamond by high pressure, high temperature processes. Ab initio calculations on these metals, in finite clusters of tetrahedrally coordinated carbon, enable us to investigate trends in their stability and properties. By carrying out systematic studies of interstitial, substitutional and semi-vacancy TM defects, we show that the electronic structure of the TMs is complicated by the presence of 'dangling bonds' when the TM disrupts the crystal lattice: interstitial defects conform to the Ludwig-Woodbury (LW) model, whilst substitutional and semi-vacancy defects move from approximating the LW model early in the transition series to approaching the vacancy model for the heavier metals. Multi-configurational self-consistent field methods allow genuine many-electron states to be modelled; for neutral interstitial, and all substitutional TMs, the crystal fields are found to exceed the exchange energies in strength. Consequently, low spin states are found for these defects. We find substitutional defects to be the most stable, but that semi-vacancy TMs are very similar in energy to the substitutional defects late in the transition series; interstitial defects are only metastable in diamond. Given appropriate charge compensators neutral and positively charged interstitial TM defects were stable, while negatively charged species appeared to be strongly disfavoured

  8. Validation of metal-binding sites in macromolecular structures with the CheckMyMetal web server.

    Science.gov (United States)

    Zheng, Heping; Chordia, Mahendra D; Cooper, David R; Chruszcz, Maksymilian; Müller, Peter; Sheldrick, George M; Minor, Wladek

    2014-01-01

    Metals have vital roles in both the mechanism and architecture of biological macromolecules. Yet structures of metal-containing macromolecules in which metals are misidentified and/or suboptimally modeled are abundant in the Protein Data Bank (PDB). This shows the need for a diagnostic tool to identify and correct such modeling problems with metal-binding environments. The CheckMyMetal (CMM) web server (http://csgid.org/csgid/metal_sites/) is a sophisticated, user-friendly web-based method to evaluate metal-binding sites in macromolecular structures using parameters derived from 7,350 metal-binding sites observed in a benchmark data set of 2,304 high-resolution crystal structures. The protocol outlines how the CMM server can be used to detect geometric and other irregularities in the structures of metal-binding sites, as well as how it can alert researchers to potential errors in metal assignment. The protocol also gives practical guidelines for correcting problematic sites by modifying the metal-binding environment and/or redefining metal identity in the PDB file. Several examples where this has led to meaningful results are described in the ANTICIPATED RESULTS section. CMM was designed for a broad audience--biomedical researchers studying metal-containing proteins and nucleic acids--but it is equally well suited for structural biologists validating new structures during modeling or refinement. The CMM server takes the coordinates of a metal-containing macromolecule structure in the PDB format as input and responds within a few seconds for a typical protein structure with 2-5 metal sites and a few hundred amino acids.

  9. Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

    Science.gov (United States)

    Kostic, N.M.; Chen, J.

    1991-03-05

    Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme. No Drawings

  10. Chirality-induced conformational preferences in peptide-metal ion binding revealed by IR spectroscopy

    NARCIS (Netherlands)

    Dunbar, R.C.; Steill, J.D.; Oomens, J.

    2011-01-01

    Chirality reversal of a residue in a peptide can change its mode of binding to a metal ion, as shown here experimentally by gas-phase IR spectroscopy of peptide−metal ion complexes. The binding conformations of Li+, Na+, and H+ with the ll and dl stereoisomers of PhePhe were compared through IR ion

  11. Chirality-Induced Conformational Preferences in Peptide-Metal Ion Binding Revealed by IR Spectroscopy

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Oomens, J.

    2011-01-01

    Chirality reversal of a residue in a peptide can change its mode of binding to a metal ion, as shown here experimentally by gas-phase IR spectroscopy of peptide metal ion complexes. The binding conformations of Li+, Na+, and H+ with the LL and DL stereoisomers of PhePhe were compared through IR ion

  12. Generic NICA-Donnan model parameters for metal-ion binding by humic substances

    NARCIS (Netherlands)

    Milne, C.J.; Kinniburgh, D.G.; Riemsdijk, van W.H.; Tipping, E.

    2003-01-01

    A total of 171 datasets of literature and experimental data for metal-ion binding by fulvic and humic acids have been digitized and re-analyzed using the NICA-Donnan model. Generic parameter values have been derived that can be used for modeling in the absence of specific metal-ion binding

  13. Optical properties of monolayer transition metal dichalcogenides probed by spectroscopic ellipsometry

    KAUST Repository

    Liu, Hsiang-Lin

    2014-11-17

    Spectroscopic ellipsometry was used to characterize the complex refractive index of chemical-vapor-deposited monolayer transition metal dichalcogenides (TMDs). The extraordinary large value of the refractive index in the visible frequency range is obtained. The absorption response shows a strong correlation between the magnitude of the exciton binding energy and band gap energy. Together with the observed giant spin-orbit splitting, these findings advance the fundamental understanding of their novel electronic structures and the development of monolayer TMDs-based optoelectronic and spintronic devices.

  14. Magnetic anisotropy of two-dimensional nanostructures: Transition-metal triangular stripes

    International Nuclear Information System (INIS)

    Dorantes-Davila, J.; Villasenor-Gonzalez, P.; Pastor, G.M.

    2005-01-01

    The magnetic anisotropy energy (MAE) of one-dimensional stripes having infinite length and triangular lateral structure are investigated in the framework of a self-consistent tight-binding method. One observes discontinuous changes in the easy magnetization direction along the crossover from one to two dimensions. The MAE oscillates as a function of stripe width and depends strongly on the considered transition metal (TM). The MAE of the two-leg ladder is strongly reduced as compared to that of the monoatomic chain and the convergence to the two-dimensional limit is rather slow

  15. Magnetic anisotropy of two-dimensional nanostructures: Transition-metal triangular stripes

    Energy Technology Data Exchange (ETDEWEB)

    Dorantes-Davila, J. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, San Luis Potosi (Mexico)]. E-mail: jdd@ifisica.uaslp.mx; Villasenor-Gonzalez, P. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, San Luis Potosi (Mexico); Pastor, G.M. [Laboratoire de Physique Quantique, Centre National de la Recherche Scientifique, Universite Paul Sabatier, Toulouse (France)

    2005-07-15

    The magnetic anisotropy energy (MAE) of one-dimensional stripes having infinite length and triangular lateral structure are investigated in the framework of a self-consistent tight-binding method. One observes discontinuous changes in the easy magnetization direction along the crossover from one to two dimensions. The MAE oscillates as a function of stripe width and depends strongly on the considered transition metal (TM). The MAE of the two-leg ladder is strongly reduced as compared to that of the monoatomic chain and the convergence to the two-dimensional limit is rather slow.

  16. Heterostructures of phosphorene and transition metal dichalcogenides for excitonic solar cells: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ganesan, Vellayappan Dheivanayagam; Shen, Lei, E-mail: shenlei@nus.edu.sg [Engineering Science Programme, National University of Singapore, 9 Engineering Drive 1, Singapore 117575 (Singapore); Linghu, Jiajun; Zhang, Chun; Feng, Yuan Ping [Department of Physics, National University of Singapore, Singapore 117542 (Singapore)

    2016-03-21

    Using the many-body perturbation GW theory, we study the quasiparticle conduction-band offsets of phosphorene, a two-dimensional atomic layer of black phosphorus, and transition-metal dichalcogenides (TMDs). The calculated large exciton binding energies of phosphorene and TMDs indicate that their type-II heterostructures are suitable for excitonic thin-film solar cell applications. Our results show that these heterojunctions have a potential maximum power conversion efficiency of up to 12%, which can be further enhanced up to 20% by strain engineering.

  17. Electropholic Transition Metal Complexes: Catalysis of Isotope Exchange. April 1, 1992 - December 3, 1996. Final Report

    International Nuclear Information System (INIS)

    Heinekey, D. Michael

    1997-01-01

    The central aim of this project is to exploit transition metal dihydrogen complexes to develop catalysts for isotope exchange reactions between hydrogen and substrates such as water. The authors have partially met this goal by the synthesis of novel cationic rhenium complexes of the form [Re(CO) 3 (PR 3 ) 2 (H 2 )] + . These complexes bind hydrogen somehwat more strongly than the neutral tungsten analogs but also activate the bound H 2 to heterolytic cleavage. Thus rapid proton (deuteron) exchange between hydrogen and water can be achieved. An example of this reaction is the rapid formation of bound HD from the complex [Re(CO) 3 (PR 3 ) 2 (H 2 )] + and deuterium gas. Rapid incorporation of deuterium from D 2 O has also been observed. In these systems, the competitive binding of water to the metal center is a drawback. The affinity of the Re center for water depends upon the nature of the phosphine ligands, with the presumably more electrophilic PPh 3 complex binding water strongly and irreversibly, while the PCy 3 complex binds water reversibly. These results have been published in J.Am.Chem.Soc 1994, 116, 4515 and J.Am.Chem.Soc 1997, 119, 4172

  18. Crystal structure of Yersinia pestis virulence factor YfeA reveals two polyspecific metal-binding sites.

    Science.gov (United States)

    Radka, Christopher D; DeLucas, Lawrence J; Wilson, Landon S; Lawrenz, Matthew B; Perry, Robert D; Aller, Stephen G

    2017-07-01

    Gram-negative bacteria use siderophores, outer membrane receptors, inner membrane transporters and substrate-binding proteins (SBPs) to transport transition metals through the periplasm. The SBPs share a similar protein fold that has undergone significant structural evolution to communicate with a variety of differentially regulated transporters in the cell. In Yersinia pestis, the causative agent of plague, YfeA (YPO2439, y1897), an SBP, is important for full virulence during mammalian infection. To better understand the role of YfeA in infection, crystal structures were determined under several environmental conditions with respect to transition-metal levels. Energy-dispersive X-ray spectroscopy and anomalous X-ray scattering data show that YfeA is polyspecific and can alter its substrate specificity. In minimal-media experiments, YfeA crystals grown after iron supplementation showed a threefold increase in iron fluorescence emission over the iron fluorescence emission from YfeA crystals grown from nutrient-rich conditions, and YfeA crystals grown after manganese supplementation during overexpression showed a fivefold increase in manganese fluorescence emission over the manganese fluorescence emission from YfeA crystals grown from nutrient-rich conditions. In all experiments, the YfeA crystals produced the strongest fluorescence emission from zinc and could not be manipulated otherwise. Additionally, this report documents the discovery of a novel surface metal-binding site that prefers to chelate zinc but can also bind manganese. Flexibility across YfeA crystal forms in three loops and a helix near the buried metal-binding site suggest that a structural rearrangement is required for metal loading and unloading.

  19. Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

    Energy Technology Data Exchange (ETDEWEB)

    Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo; Milliron, Delia J.; Trizio, Luca De; Dahlman, Clayton

    2017-10-10

    An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

  20. The 1s x-ray absorption pre-edge structures in transition metal oxides

    NARCIS (Netherlands)

    de Groot, Frank|info:eu-repo/dai/nl/08747610X; Vanko, Gyoergy; Glatzel, Pieter

    2009-01-01

    We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are

  1. Transition Metal-Promoted V2CO2 (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution Reaction.

    Science.gov (United States)

    Ling, Chongyi; Shi, Li; Ouyang, Yixin; Chen, Qian; Wang, Jinlan

    2016-11-01

    Developing alternatives to precious Pt for hydrogen production from water splitting is central to the area of renewable energy. This work predicts extremely high catalytic activity of transition metal (Fe, Co, and Ni) promoted two-dimensional MXenes, fully oxidized vanadium carbides (V 2 CO 2 ), for hydrogen evolution reaction (HER). The first-principle calculations show that the introduction of transition metal can greatly weaken the strong binding between hydrogen and oxygen and engineer the hydrogen adsorption free energy to the optimal value ≈0 eV by choosing the suitable type and coverage of the promoters as well as the active sites. Strain engineering on the performance of transition metal promoted V 2 CO 2 further reveals that the excellent HER activities can maintain well while those poor ones can be modulated to be highly active. This study provides new possibilities for cost-effective alternatives to Pt in HER and for the application of 2D MXenes.

  2. Marrying Excitons and Plasmons in Monolayer Transition-Metal Dichalcogenides

    Science.gov (United States)

    Van Tuan, Dinh; Scharf, Benedikt; Žutić, Igor; Dery, Hanan

    2017-10-01

    Just as photons are the quanta of light, plasmons are the quanta of orchestrated charge-density oscillations in conducting media. Plasmon phenomena in normal metals, superconductors, and doped semiconductors are often driven by long-wavelength Coulomb interactions. However, in crystals whose Fermi surface is comprised of disconnected pockets in the Brillouin zone, collective electron excitations can also attain a shortwave component when electrons transition between these pockets. In this work, we show that the band structure of monolayer transition-metal dichalcogenides gives rise to an intriguing mechanism through which shortwave plasmons are paired up with excitons. The coupling elucidates the origin for the optical sideband that is observed repeatedly in monolayers of WSe2 and WS2 but not understood. The theory makes it clear why exciton-plasmon coupling has the right conditions to manifest itself distinctly only in the optical spectra of electron-doped tungsten-based monolayers.

  3. COMPARATIVE ANALYSIS FOR METAL BINDING CAPACITY OF CYSTEINE BY USING UV-VIS SPECTROPHOTOMETER

    OpenAIRE

    Shivendu Ranjan; Nandita Dasgupta; Gyanendra Gour; Rashmi Dubey; Kumari Amrita

    2012-01-01

    The metal binding capacity of cysteine with three different metals Nickel, Copper and Lead was studied using UV-Vis spectrophotometer for which absorbance values were taken after interaction of cysteine with metal salt solutions (10ppm and 100ppm). Before taking above absorbance dilution factor was set using cysteine stock. The increase in peak intensity was observed when metal salt solution and metal saltcysteine solution were compared. Based on peak shift and peak intensity finally it can b...

  4. Metal binding spectrum and model structure of the Bacillus anthracis virulence determinant MntA.

    Science.gov (United States)

    Vigonsky, Elena; Fish, Inbar; Livnat-Levanon, Nurit; Ovcharenko, Elena; Ben-Tal, Nir; Lewinson, Oded

    2015-10-01

    The potentially lethal human pathogen Bacillus anthracis expresses a putative metal import system, MntBCA, which belongs to the large family of ABC transporters. MntBCA is essential for virulence of Bacillus anthracis: deletion of MntA, the system's substrate binding protein, yields a completely non-virulent strain. Here we determined the metal binding spectrum of MntA. In contrast to what can be inferred from growth complementation studies we find no evidence that MntA binds Fe(2+) or Fe(3+). Rather, MntA binds a variety of other metal ions, including Mn(2+), Zn(2+), Cd(2+), Co(2+), and Ni(2+) with affinities ranging from 10(-6) to 10(-8) M. Binding of Zn(2+) and Co(2+) have a pronounced thermo-stabilizing effect on MntA, with Mn(2+) having a milder effect. The thermodynamic stability of MntA, competition experiments, and metal binding and release experiments all suggest that Mn(2+) is the metal that is likely transported by MntBCA and is therefore the limiting factor for virulence of Bacillus anthracis. A homology-model of MntA shows a single, highly conserved metal binding site, with four residues that participate in metal coordination: two histidines, a glutamate, and an aspartate. The metals bind to this site in a mutually exclusive manner, yet surprisingly, mutational analysis shows that for proper coordination each metal requires a different subset of these four residues. ConSurf evolutionary analysis and structural comparison of MntA and its homologues suggest that substrate binding proteins (SBPs) of metal ions use a pair of highly conserved prolines to interact with their cognate ABC transporters. This proline pair is found exclusively in ABC import systems of metal ions.

  5. Complex band structures of transition metal dichalcogenide monolayers with spin–orbit coupling effects

    International Nuclear Information System (INIS)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-01-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2 , where M   =  Mo, W; X   =  S, Se, Te) while including spin–orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed. (paper)

  6. Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects

    Science.gov (United States)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

  7. Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

    Science.gov (United States)

    Maksoed, Wh-

    2016-11-01

    Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

  8. Structure and properties of transition metal-metalloid glasses based on refractory metals

    International Nuclear Information System (INIS)

    Johnson, W.L.; Williams, A.R.

    1979-01-01

    The structure and properties of several new transition metal-metalloid (TM/sub 1-x/M/sub x/) metallic glasses based on refractory transition metals (e.g. Mo, W, Ru etc.) have been systemically investigated as a function of composition. The structure of the alloys has been investigated by x-ray diffraction methods and measurements of superconducting properties, electrical resistivity, density, hardness, and mechanical behavior were made. These data are used in developing a novel description of the structure of TM/sub 1-x/M/sub x/ glasses. The experimental evidence suggests that an ideal amorphous phase forms at a specific composition x/sub c/ and that this phase has a well defined atomic short range order. For metallic glasses having x x/sub c/. This novel picture can explain the variation of many properties of these glasses with metalloid concentration

  9. Examination of Solubility Models for the Determination of Transition Metals within Liquid Alkali Metals

    Directory of Open Access Journals (Sweden)

    Jeremy Isler

    2016-06-01

    Full Text Available The experimental solubility of transition metals in liquid alkali metal was compared to the modeled solubility calculated using various equations for solubility. These equations were modeled using the enthalpy calculations of the semi-empirical Miedema model and various entropy calculations. The accuracy of the predicted solubility compared to the experimental data is more dependent on which liquid alkali metal is being examined rather than the transition metal solute examined. For liquid lithium the calculated solubility by the model was generally larger than experimental values, while for liquid cesium the modeling solubility was significantly smaller than the experimental values. For liquid sodium, potassium, and rubidium the experimental solubilities were within the range calculated by this study. Few data approached the predicted temperature dependence of solubility and instead most data exhibited a less pronounced temperature dependence.

  10. Transition Metal Oxides: Many Body Physics Meets Solid State ...

    Indian Academy of Sciences (India)

    New two-fluid (localized + band electron) model for manganites · Slide 19 · Picturizing the ferro-insulator to ferro-metal transition and the 2-fluid model · Material Systematics (varying Do) ( For fixed EJT = 0.5 eV , U = 5 eV, JF ~ (Do)2 ) · Real space structure in the presence of long range Coulomb interactions · Slide 23.

  11. The dynamic behavior of the exohedral transition metal complexes ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 7. The dynamic behavior of the exohedral transition metal complexes of B₄₀ : η⁶- and η⁷-B₄₀Cr(CO) ₃ and Cr(CO) ₃η⁷-B₄η₀-Cr(CO) ₃. NAIWRIT KARMODAK ELUVATHINGAL D JEMMIS. REGULAR ARTICLE Volume 129 Issue 7 July 2017 pp ...

  12. Liquid state properties of certain noble and transition metals

    International Nuclear Information System (INIS)

    Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

    1998-07-01

    Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

  13. Thermomagnetic marking of rare-earth-transition-metal thin films

    Science.gov (United States)

    Bartholomeusz, Brian Josef

    1989-01-01

    Analytical derivation of temperature profiles in laser-irradiated thin-film structures is hindered by the nature of the heat source terms and by the geometrical complexity that often exists. This study utilizes a combined Laplace-transform-Fourier-integral method to obtain approximate solutions for a number of simple cases. The results are used to study the thermomagnetic marking process in rare-earth-transition-metal (RE-TM) thin films, and the predictions are compared with experimental observations.

  14. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  15. Magnetic properties of fcc Ni-based transition metal alloy

    Czech Academy of Sciences Publication Activity Database

    Kudrnovský, Josef; Drchal, Václav

    2009-01-01

    Roč. 100, č. 9 (2009), s. 1193-1196 ISSN 1862-5282 R&D Projects: GA MŠk OC 150; GA AV ČR IAA100100616 Institutional research plan: CEZ:AV0Z10100520 Keywords : transition metal alloys * Ni-based * pair exchange interactions * Curie temperatures * renormalized RPA Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.862, year: 2009

  16. Metal-insulator transition: the Mott criterion and coherence length

    CERN Document Server

    Pergament, A

    2003-01-01

    On the basis of the Mott criterion for metal-insulator transition (MIT), an expression for the correlation length, identical to that for the coherence length in the theory of superconductivity, is obtained. This correlation length characterizes the size of an electron-hole pair (in an excitonic insulator) or the effective Bohr radius (as, e.g., in doped semiconductors). The relation obtained is used for calculation of the coherence length in vanadium dioxide. The presence of two characteristic coherence lengths (xi sub 1 approx 20 A and xi sub 2 approx 2 A) is found. This is associated with the specific features of the transition mechanism in VO sub 2 : this mechanism represents a combination of the purely electronic Mott-Hubbard contribution and the structural (Peierls-like) one. It is shown, however, that the driving force of the MIT in VO sub 2 is the electron-correlation Mott-Hubbard transition.

  17. Spatiotemporal Analysis of Heavy Metal Water Pollution in Transitional China

    Directory of Open Access Journals (Sweden)

    Huixuan Li

    2015-07-01

    Full Text Available China’s socioeconomic transitions have dramatically accelerated its economic growth in last three decades, but also companioned with continuous environmental degradation. This study will advance the knowledge of heavy metal water pollution in China from a spatial–temporal perspective. Specifically, this study addressed the following: (1 spatial patterns of heavy metal water pollution levels were analyzed using data of prefecture-level cities from 2004 to 2011; and (2 spatial statistical methods were used to examine the underlying socioeconomic and physical factors behind water pollution including socioeconomic transitions (industrialization, urbanization, globalization and economic development, and environmental characteristic (natural resources, hydrology and vegetation coverage. The results show that only Cr pollution levels increased over the years. The individual pollution levels of the other four heavy metals, As, Cd, Hg, and Pb, declined. High heavy metal water pollution levels are closely associated with both anthropogenic activities and physical environments, in particular abundant mineral resources and industrialization prosperity. On the other hand, economic development and urbanization play important roles in controlling water pollution problems. The analytical findings will provide valuable information for policy-makers to initiate and adjust protocols and strategies for protecting water sources and controlling water pollution; thus improving the quality of living environments.

  18. Insulator-metal transition of fluid molecular hydrogen

    International Nuclear Information System (INIS)

    Ross, M.

    1996-01-01

    Dynamically compressed fluid hydrogen shows evidence for metallization at the relatively low pressure of 140 GPa (1.4 Mbar) while experiments on solid hydrogen made in a diamond-anvil cell have failed to detect any evidence for gap closure up to a pressure of 230 GPa (2.3 Mbar). Two possible mechanisms for metal- liclike resistivity are put forward. The first is that as a consequence of the large thermal disorder in the fluid (kT∼0.2 endash 0.3 eV) short-range molecular interactions lead to band tailing that extends the band edge into the gap, resulting in closure at a lower pressure than in the solid. The second mechanism argues that molecular dissociation creates H atoms that behave similar to n-type donors in a heavily doped semiconductor and undergo a nonmetal-metal Mott-type transition. copyright 1996 The American Physical Society

  19. Quantum-based Atomistic Simulation of Transition Metals

    International Nuclear Information System (INIS)

    Moriarty, J A; Benedict, L X; Glosli, J N; Hood, R Q; Orlikowski, D A; Patel, M V; Soderlind, P; Streitz, F H; Tang, M; Yang, L H

    2005-01-01

    First-principles generalized pseudopotential theory (GPT) provides a fundamental basis for transferable multi-ion interatomic potentials in d-electron transition metals within density-functional quantum mechanics. In mid-period bcc metals, where multi-ion angular forces are important to structural properties, simplified model GPT or MGPT potentials have been developed based on canonical d bands to allow analytic forms and large-scale atomistic simulations. Robust, advanced-generation MGPT potentials have now been obtained for Ta and Mo and successfully applied to a wide range of structural, thermodynamic, defect and mechanical properties at both ambient and extreme conditions of pressure and temperature. Recent algorithm improvements have also led to a more general matrix representation of MGPT beyond canonical bands allowing increased accuracy and extension to f-electron actinide metals, an order of magnitude increase in computational speed, and the current development of temperature-dependent potentials

  20. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

  1. Determination of Surface Properties of Liquid Transition Metals

    International Nuclear Information System (INIS)

    Korkmaz, S. D.

    2008-01-01

    Certain surface properties of liquid simple metals are reported. Using the expression derived by Gosh and coworkers we investigated the surface entropy of liquid transition metals namely Fe, Co and Ni. We have also computed surface tensions of the metals concerned. The pair distribution functions are calculated from the solution of Ornstein-Zernike integral equation with Rogers-Young closure using the individual version of the electron-ion potential proposed by Fioalhais and coworkers which was originally developed for solid state. The predicted values of surface tension and surface entropy are in very good agreement with available experimental data. The present study results show that the expression derived by Gosh and coworkers is very useful for the surface entropy by using Fioalhais pseudopotential and Rogers-Young closure

  2. Thermophysical Property Measurements of Silicon-Transition Metal Alloys

    Science.gov (United States)

    Banish, R. Michael; Erwin, William R.; Sansoucie, Michael P.; Lee, Jonghyun; Gave, Matthew A.

    2014-01-01

    Metals and metallic alloys often have high melting temperatures and highly reactive liquids. Processing reactive liquids in containers can result in significant contamination and limited undercooling. This is particularly true for molten silicon and it alloys. Silicon is commonly termed "the universal solvent". The viscosity, surface tension, and density of several silicon-transition metal alloys were determined using the Electrostatic Levitator system at the Marshall Space Flight Center. The temperature dependence of the viscosity followed an Arrhenius dependence, and the surface tension followed a linear temperature dependence. The density of the melts, including the undercooled region, showed a linear behavior as well. Viscosity and surface tension values were obtain for several of the alloys in the undercooled region.

  3. Metal ion interaction of an oligopeptide fragment representing the regulatory metal binding site of a CueR protein

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szokolai, Hajnalka; Roszahegyi, Livia

    2013-01-01

    Metalloregulatory proteins of the MerR family are transcriptional activators that sense/control the concentration of various metal ions inside bacteria.1 The Cu+ efflux regulator CueR, similarly to other MerR proteins, possesses a short multiple Cys-containing metal binding loop close to the C......-terminus. CueR has a high selectivity for Cu+, Ag+ and Au+, but exhibits no transcriptional activity for the divalent ions Hg2+ and Zn2+.2 The two Cys- residues of the metal binding loop were shown to settle M+ ions into a linear coordination environment but other factors may also play a role in the recognition...... of cognate metal ions.2 Nevertheless, it is an interesting question whether the same sequence, when removed from the protein, shows a flexibility to adopt different coordination environments and may efficiently bind metal ions having preferences for larger coordination numbers....

  4. Exposing "Bright" Metals: Promising Advances in Photoactivated Anticancer Transition Metal Complexes.

    Science.gov (United States)

    Bjelosevic, Aleksandra; Pages, Benjamin J; Spare, Lawson K; Deo, Krishant M; Ang, Dale L; Aldrich-Wright, Janice R

    2018-02-12

    Photodynamic therapy (PDT) is an increasingly prominent field in anticancer research. PDT agents are typically nontoxic in the absence of light and can be stimulated with nonionising irradiation to "activate" their cytotoxic effect. Photosensitzers are not classified as chemotherapy drugs although it is advantageous to control the toxicity of a drug through localised irradiation allowing for selective treatment. Transition metals are an extremely versatile class of compounds with various unique properties such as oxidation state, coordination number, redox potential and molecular geometry that can be tailored for specific uses. This makes them excellent PDT candidates as their properties can be manipulated to absorb a specific range of light wavelengths, cross cellular membranes or target specific sites in vitro. This article reviews recent advances in transition metal PDT agents, with a focus on structural scaffolds from which several metal complexes in a series are synthesised, as well as their in vitro cytotoxicity in the presence or absence of irradiation. The success of clinical photoactive agents such as Photofrin® has inspired the development of thousands of potential PDT agents. Transition metal complexes in particular have demonstrated excellent versatility and diversity when it comes to PDT for treatment of invasive cancers. This review has highlighted some of the many recent advances of transition metal PDT agents with high in vitro and in vivo phototoxic activity. Photoactive transition metal complexes have proven their potential due to their inherent physicochemical variety, allowing them to fill a niche in the PDT world. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  5. Synthesis of Mg2FeH6 containing as additives transition metal and transition metal fluorides or carbon

    International Nuclear Information System (INIS)

    Zepon, G.; Leiva, D.R.; Botta, W.J.

    2010-01-01

    The Mg 2 FeH 6 is a promising way of storing hydrogen in solid form, composed by elements that have low cost and, at the same time, high volumetric storage density: 150 kg H 2 /m 3 . However, this complex hydride is not easily synthesized as a single phase material. The hydrogen sorption high temperature and slow kinetics are the major limitations for the practical application of the Mg 2 FeH 6 as a hydrogen storage material. Little is known about the effects of additives in Mg 2 FeH 6 based nanocomposites in this work were synthesized by MAE under hydrogen atmosphere nanocomposites based on Mg 2 FeH 6 containing additives as transition metals, transition metals fluorides of transition metals or carbon, in order to obtain information on the effects of the selected additives. To this end, we used characterization techniques such as XRD, SEM and TEM, thermal analysis by DSC and curves made in apparatus PCT.(author)

  6. On the Mott transition and the new metal-insulator transitions in doped covalent and polar crystals

    International Nuclear Information System (INIS)

    Dzhumanov, S.; Begimkulov, U.; Kurbanov, U.T.; Yavidov, B.Y.

    2001-10-01

    The Mott transition and new metal-insulator transitions (MIT's) and their distinctive features in doped covalent semiconductors and polar compounds are studied within the continuum model of extrinsic carrier self-trapping, the Hubbard impurity band model (with on-site Coulomb repulsion and screening effects) and the extrinsic (bi)polaronic band model (with short- and long-range carrier-impurity, impurity-phonon and carrier-phonon interactions and intercarrier correlation) using the appropriate tight-binding approximations and variational methods. We have shown the formation possibility of large-radius localized one- and two-carrier impurity (or defect) states and narrow impurity bands in the band gap and charge transfer gap of these carrier-doped systems. The extrinsic Mott-Hubbard and (bi)polaronic insulating gaps are calculated exactly. The proper criterions for Mott transition, extrinsic excitonic and (bi)polaronic MIT's are obtained. We have demonstrated that the Mott transition occurs in doped covalent semiconductors (i.e. Si and Ge) and some insulators with weak carrier-phonon coupling near the large-radius dopants. While, in doped polar compounds (e.g. oxide high-T c superconductors (HTSC) and related materials) the MIT's are new extrinsic (or intrinsic) (bi)polaronic MIT's. We have found that the anisotropy of the dielectric (or (bi)polaronic) properties of doped cuprate HTSC is responsible for smooth (or continuous) MIT's, stripe formation and suppression of high-T c superconductivity. Various experimental results on in-gap states, bands and MIT's in doped covalent semiconductors, oxide HTSC and related materials are in good agreement with the developed theory of Mott transition and new (bi)polaronic MIT's. (author)

  7. The nature of transition-metal-oxide surfaces

    Science.gov (United States)

    Henrich, V. E.

    The surfaces of the 3d-transition-metal oxides form a rich and important system in which to study the effects of atomic geometry, ligand coordination and d-orbital population on surface electronic structure and chemisorption. This article considers the properties of those surfaces in terms of the types of surface structures that can exist, including steps and point defects, and their relation to the experimental data that is available for well characterized, single-crystal surfaces. The electronic structure of nearly perfect surfaces is very similar to that of the bulk for many of the oxides that have been studied; atoms at step sites also appear to have properties similar to those of atoms on terraces. Point defects are often associated with surfaces 0 vacancies and attendant transfer of electrons to adjacent metal cations. Those cations are poorly screened from each other, and the excess charge is presumably shared between two or more cations having reduced ligand coordination. Point defects are generally more active for chemisorption than are perfect surfaces, however for Ti 2O 3 and V 2O 3, whose cations have 3d 1 and 3d 2 electronic configurations respectively, the cleaved (047) surface is more active than are surfaces having a high density of defects. The chemisorption behavior of both nearly perfect and defect surfaces of 3d-transition-metal oxides varies widely from one material to another, and it is suggestive to correlate this with cation d-orbital population. However, too few oxides have yet been studied to draw any firm conclusions. Additional theoretical work on perfect surfaces, defects and chemisorption is also necessary in order to gain a more complete understanding of transition-metal-oxide surfaces.

  8. Isolation and characterization of iron chelators from turmeric (Curcuma longa): selective metal binding by curcuminoids.

    Science.gov (United States)

    Messner, Donald J; Surrago, Christine; Fiordalisi, Celia; Chung, Wing Yin; Kowdley, Kris V

    2017-10-01

    Iron overload disorders may be treated by chelation therapy. This study describes a novel method for isolating iron chelators from complex mixtures including plant extracts. We demonstrate the one-step isolation of curcuminoids from turmeric, the medicinal food spice derived from Curcuma longa. The method uses iron-nitrilotriacetic acid (NTA)-agarose, to which curcumin binds rapidly, specifically, and reversibly. Curcumin, demethoxycurcumin, and bisdemethoxycurcumin each bound iron-NTA-agarose with comparable affinities and a stoichiometry near 1. Analyses of binding efficiencies and purity demonstrated that curcuminoids comprise the primary iron binding compounds recovered from a crude turmeric extract. Competition of curcuminoid binding to the iron resin was used to characterize the metal binding site on curcumin and to detect iron binding by added chelators. Curcumin-Iron-NTA-agarose binding was inhibited by other metals with relative potency: (>90% inhibition) Cu 2+  ~ Al 3+  > Zn 2+  ≥ Ca 2+  ~ Mg 2+  ~ Mn 2+ (80% by addition of iron to the media; uptake was completely restored by desferoxamine. Ranking of metals by relative potencies for blocking curcumin uptake agreed with their relative potencies in blocking curcumin binding to iron-NTA-agarose. We conclude that curcumin can selectively bind toxic metals including iron in a physiological setting, and propose inhibition of curcumin binding to iron-NTA-agarose for iron chelator screening.

  9. Controlled formation of emissive silver nanoclusters using rationally designed metal-binding proteins.

    Science.gov (United States)

    Morozov, Vasily A; Ogawa, Michael Y

    2013-08-19

    The metal-binding properties of rationally designed, synthetic proteins were used to prepare a series of emissive silver nanoclusters having predictable sizes and emission energies. Metal-binding α-helical coiled coils were designed to exist as peptide trimers, tetramers, and hexamers and found to uniquely bind 6, 8, and 12 Ag(+) ions, respectively. Subsequent treatment with a chemical reducing agent produced a series of peptide-bound Ag(0) nanoclusters that display a strong visible fluorescence whose emission energies depend on the number of bound metal ions in excellent agreement with theory.

  10. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    Science.gov (United States)

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  11. MeRNA: a Database of Metal Ion Binding Sites in RNAStructures

    Energy Technology Data Exchange (ETDEWEB)

    Stefan, Liliana R.; Zhang, Rui; Levitan, Aaron G.; Hendrix, DonnaF.; Brenner, Steven E.; Holbrook, Stephen R.

    2005-10-05

    Metal ions are essential for the folding of RNA into stable tertiary structures and for the catalytic activity of some RNA enzymes. To aid in the study of the roles of metal ions in RNA structural biology, we have created MeRNA (Metals in RNA), a comprehensive compilation of all metal binding sites identified in RNA three-dimensional structures available from the Protein Data Bank (PDB) and Nucleic Acid Database (NDB). Currently, our database contains information relating to binding of 9764 metal ions corresponding to 23 distinct elements; in 256 RNA structures. The metal ion locations were confirmed and ligands characterized using original literature references. MeRNA includes eight manually identified metal-ion binding motifs, which are described in the literature. MeRNA is searchable by PDB identifier, metal ion, method of structure determination, resolution and R-values for X-ray structure, and distance from metal to any RNA atom or to water. New structures with their respective binding motifs will be added to the database as they become available. The MeRNA database will further our understanding of the roles of metal ions in RNA folding and catalysis and have applications in structural and functional analysis, RNA design and engineering.

  12. Transition metal complexes of an isatinic quinolyl hydrazone

    Directory of Open Access Journals (Sweden)

    Seleem Hussein S

    2011-06-01

    Full Text Available Abstract 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-ylhydrazono] 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. (NNO2-, (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

  13. Roles of transition metals interchanging with lithium in electrode materials.

    Science.gov (United States)

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Tokuda, Kazuya; Sakaida, Masashi; Ichitsubo, Tetsu; Oishi, Masatsugu; Mizuki, Jun'ichiro; Matsubara, Eiichiro

    2015-06-07

    Roles of antisite transition metals interchanging with Li atoms in electrode materials of Li transition-metal complex oxides were clarified using a newly developed direct labeling method, termed powder diffraction anomalous fine structure (P-DAFS) near the Ni K-edge. We site-selectively investigated the valence states and local structures of Ni in Li0.89Ni1.11O2, where Ni atoms occupy mainly the NiO2 host-layer sites and partially the interlayer Li sites in-between the host layers, during electrochemical Li insertion/extraction in a lithium-ion battery (LIB). The site-selective X-ray near edge structure evaluated via the P-DAFS method revealed that the interlayer Ni atoms exhibited much lower electrochemical activity as compared to those at the host-layer site. Furthermore, the present analyses of site-selective extended X-ray absorption fine structure performed using the P-DAFS method indicates local structural changes around the residual Ni atoms at the interlayer space during the initial charge; it tends to gather to form rock-salt NiO-like domains around the interlayer Ni. The presence of the NiO-like domains in the interlayer space locally diminishes the interlayer distance and would yield strain energy because of the lattice mismatch, which retards the subsequent Li insertion both thermodynamically and kinetically. Such restrictions on the Li insertion inevitably make the NiO-like domains electrochemically inactive, resulting in an appreciable irreversible capacity after the initial charge but an achievement of robust linkage of neighboring NiO2 layers that tend to be dissociated without the Li occupation. The P-DAFS characterization of antisite transition metals interchanging with Li atoms complements the understanding of the detailed charge-compensation and degradation mechanisms in the electrode materials.

  14. Kondo Lattices and the Mott Metal-Insulator Transition

    Science.gov (United States)

    Nozières, Ph.

    2005-01-01

    In Kondo lattices with one magnetic impurity at every lattice site, few electrons must quench many spins. This old “exhaustion” issue has been pending for years: it now appears it does not arise: the coherence temperature at which a singlet ground state emerges is the Kondo temperature itself. We survey the evolution of that problem. We then argue that such a lattice Kondo effect governs the Mott transition from a paramagnetic metal to an incoherent spin disordered insulator. It explains the appearance of a narrow resonance in the middle of a large preformed gap. Our naive arguments can be extended to an orbitally degenerate situation: they provide a qualitative understanding of the effect discovered numerically by Capone et al. [Science 296 (2002) 2364], namely the appearance of s-wave superconductivity near the Mott transition when the atomic ground state is a singlet with no residual degeneracy.

  15. Holographic metal-insulator transition in higher derivative gravity

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Yi, E-mail: lingy@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai, 200444 (China); Liu, Peng, E-mail: liup51@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu, Jian-Pin, E-mail: jianpinwu@mail.bnu.edu.cn [Institute of Gravitation and Cosmology, Department of Physics, School of Mathematics and Physics, Bohai University, Jinzhou 121013 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai, 200444 (China); Zhou, Zhenhua, E-mail: zhouzh@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2017-03-10

    We introduce a Weyl term into the Einstein–Maxwell-Axion theory in four dimensional spacetime. Up to the first order of the Weyl coupling parameter γ, we construct charged black brane solutions without translational invariance in a perturbative manner. Among all the holographic frameworks involving higher derivative gravity, we are the first to obtain metal-insulator transitions (MIT) when varying the system parameters at zero temperature. Furthermore, we study the holographic entanglement entropy (HEE) of strip geometry in this model and find that the second order derivative of HEE with respect to the axion parameter exhibits maximization behavior near quantum critical points (QCPs) of MIT. It testifies the conjecture in that HEE itself or its derivatives can be used to diagnose quantum phase transition (QPT).

  16. Efficient photocarrier injection in a transition metal oxide heterostructure

    CERN Document Server

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

    An efficient method for doping a transition metal oxide (TMO) with hole carriers is presented: photocarrier injection (PCI) in an oxide heterostructure. It is shown that an insulating vanadium dioxide (VO sub 2) film is rendered metallic under light irradiation by PCI from an n-type titanium dioxide (TiO sub 2) substrate doped with Nb. Consequently, a large photoconductivity, which is exceptional for TMOs, is found in the VO sub 2 /TiO sub 2 :Nb heterostructure. We propose an electronic band structure where photoinduced holes created in TiO sub 2 :Nb can be transferred into the filled V 3d band via the low-lying O 2p band of VO sub 2. (letter to the editor)

  17. Dinuclear transition metal complexes in carbon nanostructured materials synthesis

    Science.gov (United States)

    Ayuso, J. I.; Hernández, E.; Delgado, E.

    2013-06-01

    Carbon nanomaterials (CNMs) were prepared with two similar techniques using organometallic complexes as catalysts precursors. Chemical vapour deposition (CVD) and pyrolysis with chlorine gas approaches were employed in order to explore the effect of dinuclear transition metal compounds [Fe2(CO)6(μ-S2C6H2X2), (X=OH, Cl)] in synthesis of CNMs. Our to-date results have shown these complexes generate different carbonaceous materials when they are used in bulk, it was also observed that their performances in synthesis differ even though these compounds are analogous. With X=OH complex used in CVD process, metal nanoparticles of ca. 20-50 nm in size and embedded in carbon matrix were obtained. X=C1 complex has been used in pyrolysis experiments and showed an entire volatilisation or no reaction, depending on selected temperature. Furthermore, obtaining of a new tetranuclear iron cluster is presented in this work.

  18. Electronic and optical properties of vacancy defects in single-layer transition metal dichalcogenides

    Science.gov (United States)

    Khan, M. A.; Erementchouk, Mikhail; Hendrickson, Joshua; Leuenberger, Michael N.

    2017-06-01

    A detailed first-principles study has been performed to evaluate the electronic and optical properties of single-layer (SL) transition metal dichalcogenides (TMDCs) (M X 2 ; M = transition metal such as Mo, W, and X = S, Se, Te), in the presence of vacancy defects (VDs). Defects usually play an important role in tailoring electronic, optical, and magnetic properties of semiconductors. We consider three types of VDs in SL TMDCs: (i) X vacancy, (ii) X2 vacancy, and (iii) M vacancy. We show that VDs lead to localized defect states (LDS) in the band structure, which in turn gives rise to sharp transitions in in-plane and out-of-plane optical susceptibilities, χ∥ and χ⊥. The effects of spin-orbit coupling (SOC) are also considered. We find that SOC splitting in LDS is directly related to the atomic number of the transition metal atoms. Apart from electronic and optical properties we also find magnetic signatures (local magnetic moment of ˜μB ) in MoSe2 in the presence of the Mo vacancy, which breaks the time-reversal symmetry and therefore lifts the Kramers degeneracy. We show that a simple qualitative tight-binding model (TBM), involving only the hopping between atoms surrounding the vacancy with an on-site SOC term, is sufficient to capture the essential features of LDS. In addition, the existence of the LDS can be understood from the solution of the two-dimensional Dirac Hamiltonian by employing infinite mass boundary conditions. In order to provide a clear description of the optical absorption spectra, we use group theory to derive the optical selection rules between LDS for both χ∥ and χ⊥.

  19. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  20. Ferromagnetic semiconductor-metal transition in europium monoxide

    International Nuclear Information System (INIS)

    Arnold, M.

    2007-10-01

    We present a microscopical model to describe the simultaneous para-to-ferromagnetic and semiconductor-to-metal transition in electron-doped EuO. The physical properties of the model are systematically studied, whereas the main remark is on the interplay between magnetic order and the transport properties. The theory correctly describes detailed experimental features of the conductivity and of the magnetization, obtained for EuO 1-x or Gd-doped Gd x Eu 1-x 0. In particular the doping dependence of the Curie temperature is reproduced The existence of correlation-induced local moments on the impurity sites is essential for this description. (orig.)

  1. Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

    International Nuclear Information System (INIS)

    Guo, Yuzheng; Robertson, John

    2016-01-01

    We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

  2. Magnetism in 3d transition metal doped SnO

    KAUST Repository

    Albar, Arwa

    2016-09-12

    Using first principles calculations, we investigate the structural and electronic properties of 3d transition metal doped SnO. We examine the stability of different doping sites using formation energy calculations. The magnetic behavior of the dopant atoms is found to be complex because of interplay between strong structural relaxation, spin-lattice coupling, and crystal field splitting. The interaction between dopant atoms is analyzed as a function of their separation, showing that clustering typically counteracts spin polarization. An exception is found for V doping, which thus turns out to be a promising candidate for realizing a magnetic p-type oxide.

  3. Synthesis and metal binding properties of salicylate-, catecholate-, and hydroxypyridinonate-functionalized dendrimers.

    Science.gov (United States)

    Cohen, S M; Petoud, S; Raymond, K N

    2001-01-05

    The synthesis, characterization, and metal-binding studies of chelate-functionalized dendrimers is reported. Salicylate, catecholate, and hydroxypyridinonate bidentate chelators have been coupled to the surface of both poly(propyleneimine) (Astramol) and poly(amidoamine) (Starburst, PAMAM) dendrimers up to the fifth generation (64 endgroups). A general method has been developed for the facile and high quality chromatographic purification of poly(propyleneimine) and poly(amidoamine) dendrimer derivatives. One- and two-dimensional (TOCSY) 1H NMR experiments and electrospray ionization mass spectrometry (ESI-MS) have confirmed the exhaustive coupling of these chelators to the primary amine functionalities of the dendrimers. Spectrophotometric titrations were used to investigate the metal binding ability of these macrochelates. Spectral analysis shows that ferric iron binding to these ligands is localized to the chelating endgroups. The ability of these dendritic polymers to bind large numbers of metal ions may lead to applications as metal sequestering agents for waste remediation technologies.

  4. Redefining the metal/charge-transfer insulator paradigm in transition metal oxides

    Science.gov (United States)

    Dang, Hung; Ai, Xinyuan; Marianetti, Chris; Millis, Andrew

    2012-02-01

    The universality of the phase diagram in the variables of interaction strength and d-occupancy, shown for late transition metal oxides in Ref.[1], is examined for two series of early transition metal oxides: (SrVO3, SrCrO3, SrMnO3) and (LaTiO3, LaVO3, LaCrO3) using density functional theory (DFT), DFT+U and DFT+dynamical mean field theory methods. The interaction required to drive the metal-insulator transition is found to depend sensitively on the d-occupancy Nd, and beyond a threshold value of the d-occupancy an insulating state cannot be achieved for any practical value of the interaction. The critical Nd values are determined and compared to ab initio and experimental estimates where available. Additionally, the minimal model for the transition is determined and the crucial role played by the Hunds coupling is demonstrated. [4pt] [1] Xin Wang, M. J. Han, Luca de' Medici, C. A. Marianetti, and Andrew J. Millis (2011). arXiv:1110.2782

  5. Transition metal borides. Synthesis, characterization and superconducting properties

    International Nuclear Information System (INIS)

    Kayhan, Mehmet

    2013-01-01

    A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M 2 B, MB, M 3 B 2 , MB 2 , and M 2 B 4 . The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W 2 B 4 to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W 2 B 4 was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB 2 (T C = 3.5 K), β-MoB (T C = 2.4 K), β-WB (T C = 2.0 K), α-WB (T C = 4.3 K), W 2 B 4 (T C = 5.4 K), Re 7 B 3 (T C = 2.4 K). A relationship between the superconducting properties and the compositional and structural features was discussed for metal diborides. Also it was

  6. Binding of heavy metals to derivatives of cholesterol and sodium dodecyl sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Ahmadi, S.; Batchelor, B.; Koseoglu, S.S. [Texas A and M Univ., College Station, TX (United States); Huang, Y.C.

    1995-09-01

    The binding behaviors of five metals (cadmium, copper, nickel, lead, and zinc), individually at pH 6 and collectively at pHs 6 and 3, to deoxycholic acid (DCA) and taurocholic acid (TCA) were compared with those of sodium dodecyl sulfate (SDS) using a continuous diafiltration method. DCA and SDS have been successfully applied in micellar-enhanced ultrafiltration (MEUF) for metal removal from water. In this study, SDS exhibits the strongest binding in the single-component experiments while DCA binds the most in the multicomponent trials. TCA does not show any significant biding compared with DCA and SDS. Overall the molar binding ratios of the mixture at pH 3 were well below those of the other two solutions. This diafiltration technique quantifies the binding characteristics of a surfactant by generating sorption isotherms and determining the intrinsic association constraints with corresponding number of binding sites. These parameters can be useful in designing an efficient MEUF system.

  7. Hydrogen collisions with transition metal surfaces: Universal electronically nonadiabatic adsorption

    Science.gov (United States)

    Dorenkamp, Yvonne; Jiang, Hongyan; Köckert, Hansjochen; Hertl, Nils; Kammler, Marvin; Janke, Svenja M.; Kandratsenka, Alexander; Wodtke, Alec M.; Bünermann, Oliver

    2018-01-01

    Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence—consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, Ein, metal atom mass, M, and incidence angle, 𝜗i n. S =(S0+a ṡEi n+b ṡM ) *(1 -h (𝜗i n-c ) (1 -cos(𝜗 i n-c ) d ṡh (Ei n-e ) (Ei n-e ) ) ) , where h is the Heaviside step function and for H, S0 = 1.081, a = -0.125 eV-1, b =-8.40 ṡ1 0-4 u-1, c = 28.88°, d = 1.166 eV-1, and e = 0.442 eV; whereas for D, S0 = 1.120, a = -0.124 eV-1, b =-1.20 ṡ1 0-3 u-1, c = 28.62°, d = 1.196 eV-1, and e = 0.474 eV.

  8. Transition-metal interactions in aluminum-rich intermetallics

    International Nuclear Information System (INIS)

    Al-Lehyani, Ibrahim; Widom, Mike; Wang, Yang; Moghadam, Nassrin; Stocks, G. Malcolm; Moriarty, John A.

    2001-01-01

    The extension of the first-principles generalized pseudopotential theory (GPT) to transition-metal (TM) aluminides produces pair and many-body interactions that allow efficient calculations of total energies. In aluminum-rich systems treated at the pair-potential level, one practical limitation is a transition-metal overbinding that creates an unrealistic TM-TM attraction at short separations in the absence of balancing many-body contributions. Even with this limitation, the GPT pair potentials have been used effectively in total-energy calculations for Al-TM systems with TM atoms at separations greater than 4 Aa. An additional potential term may be added for systems with shorter TM atom separations, formally folding repulsive contributions of the three- and higher-body interactions into the pair potentials, resulting in structure-dependent TM-TM potentials. Towards this end, we have performed numerical ab initio total-energy calculations using the Vienna ab initio simulation package for an Al-Co-Ni compound in a particular quasicrystalline approximant structure. The results allow us to fit a short-ranged, many-body correction of the form a(r 0 /r) b to the GPT pair potentials for Co-Co, Co-Ni, and Ni-Ni interactions

  9. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  10. Colloquium: Excitons in atomically thin transition metal dichalcogenides

    Science.gov (United States)

    Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.; Heinz, Tony F.; Marie, Xavier; Amand, Thierry; Urbaszek, Bernhard

    2018-04-01

    Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weak dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. Here recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.

  11. Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

    2015-01-01

    The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

  12. Novel doping alternatives for single-layer transition metal dichalcogenides

    Science.gov (United States)

    Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

    2017-11-01

    Successful doping of single-layer transition metal dichalcogenides (TMDs) remains a formidable barrier to their incorporation into a range of technologies. We use density functional theory to study doping of molybdenum and tungsten dichalcogenides with a large fraction of the periodic table. An automated analysis of the energetics, atomic and electronic structure of thousands of calculations results in insightful trends across the periodic table and points out promising dopants to be pursued experimentally. Beyond previously studied cases, our predictions suggest promising substitutional dopants that result in p-type transport and reveal interesting physics behind the substitution of the metal site. Doping with early transition metals (TMs) leads to tensile strain and a significant reduction in the bandgap. The bandgap increases and strain is reduced as the d-states are filled into the mid TMs; these trends reverse as we move into the late TMs. Additionally, the Fermi energy increases monotonously as the d-shell is filled from the early to mid TMs and we observe few to no gap states, indicating the possibility of both p- (early TMs) and n- (mid TMs) type doping. Quite surprisingly, the simulations indicate the possibility of interstitial doping of TMDs; the energetics reveal that a significant number of dopants, increasing in number from molybdenum disulfide to diselenide and to ditelluride, favor the interstitial sites over adsorbed ones. Furthermore, calculations of the activation energy associated with capturing the dopants into the interstitial site indicate that the process is kinetically possible. This suggests that interstitial impurities in TMDs are more common than thought to date and we propose a series of potential interstitial dopants for TMDs relevant for application in nanoelectronics based on a detailed analysis of the predicted electronic structures.

  13. Investigation of the metal binding site in methionine aminopeptidase by density functional theory

    DEFF Research Database (Denmark)

    Jørgensen, Anne Techau; Norrby, Per-Ola; Liljefors, Tommy

    2002-01-01

    All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ ions or Zn2+ ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions...

  14. Controls on Transition Metal Concentrations in Crustal Brines

    Science.gov (United States)

    Yardley, B. W.

    2004-12-01

    as the major controls on transition metal contents of crustal fluids, with little evidence for significant changes in chloride complexing over the range of compositions and conditions encountered in the crust. Preliminary results on low salinity, gas-rich fluid inclusions suggest that their transition metal contents fit on the same trends as those of brines.

  15. Selective and low temperature transition metal intercalation in layered tellurides

    Science.gov (United States)

    Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

    2016-12-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid.

  16. Insertion compounds of transition-metal and uranium oxides

    International Nuclear Information System (INIS)

    Chippindale, A.M.; Dickens, P.G.; Powell, A.V.

    1991-01-01

    Several transition-metal and actinide oxides, in which the metal occurs in a high oxidation state, have open covalent structures and are capable of incorporating alkali and other electropositive metals under mild conditions to form insertion compounds A x MO n . These are solids which have several features in common: Over a range of compositions, A x MO n exists as one or more stable or metastable phases in which the structure of the parent oxide MO n is largely retained and the insertion element A is accommodated interstitially. Insertion is accompanied by a redox process A=A i . + e - M in which M is reduced and the electronic properties of the parent oxide change to those typical of a mixed-valence compound. The insertion process xA + MO n = A x MO n can be reversed, at least to some extent, by chemical or electrochemical reaction, with retention of structure (topotactic reaction). This review concentrates on methods of synthesis, characterisation, crystal structure and thermochemistry of these insertion compounds. It updates and extends previous work. (author)

  17. Two-dimensional transition metal dichalcogenides: interface and defect engineering.

    Science.gov (United States)

    Hu, Zehua; Wu, Zhangting; Han, Cheng; He, Jun; Ni, Zhenhua; Chen, Wei

    2018-03-06

    Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been considered as promising candidates for next generation nanoelectronics. Because of their atomically-thin structure and high surface to volume ratio, the interfaces involved in TMDC-based devices play a predominant role in determining the device performance, such as charge injection/collection at the metal/TMDC interface, and charge carrier trapping at the dielectric/TMDC interface. On the other hand, the crystalline structures of TMDCs are enriched by a variety of intrinsic defects, including vacancies, adatoms, grain boundaries, and substitutional impurities. Customized design and engineering of the interfaces and defects provides an effective way to modulate the properties of TMDCs and finally enhance the device performance. Herein, we summarize and highlight recent advances and state-of-the-art investigations on the interface and defect engineering of TMDCs and their corresponding applications in electronic and optoelectronic devices. Various interface engineering approaches for TMDCs are overviewed, including surface charge transfer doping, TMDC/metal contact engineering, and TMDC/dielectric interface engineering. Subsequently, different types of structural defects in TMDCs are introduced. Defect engineering strategies utilized to modulate the optical and electronic properties of TMDCs, as well as the developed high-performance and functional devices are summarized. Finally, we highlight the challenges and opportunities for interface and defect engineering in TMDC materials for electronics and optoelectronics.

  18. Selective and low temperature transition metal intercalation in layered tellurides

    Science.gov (United States)

    Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

    2016-01-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid. PMID:27966540

  19. Estimation of stacking fault and twin energies in transition metals

    International Nuclear Information System (INIS)

    Papon, Anne-Marie

    1979-01-01

    As twins and stacking faults play an important role in the plastic deformation of metals, the objective of this research thesis is, by using an as correct as possible description of band d state density, to assess the internal energy of twins and stacking faults in metals with a CFC, HC or CC crystal structure. If, in transition metals, cohesion mainly results from d electron attraction, other terms intervening in crystal equilibrium must also be taken into account. Thus, the author proposes a decomposition of cohesion energy. The geometry of twins and stacking faults in compact phases is defined, and energy calculations are presented and discussed. Alloying effects are then addressed, as well as a general comparison with available experimental results. After a geometric description of twins and stacking faults in CC structures, their energies are calculated for a Gaussian distribution of state density. For higher order moments, defect energy due to d orbital anisotropy is assessed, and then applied to energy and stability calculations in twins and stacking faults for various relaxed atomic configurations

  20. Electronic and magnetic properties of transition metal doped graphyne

    Science.gov (United States)

    Gangan, Abhijeet Sadashiv; Yadav, Asha S.; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2017-05-01

    We have theoretically investigated the interaction of few 3d (V,Mn) and 4d (Y,Zr) transition metals with the γ-graphyne structure using the spin-polarized density functional theory for its potentials application in Hydrogen storage, spintronics and nano-electronics. By doping different TMs we have observed that the system can be either metallic(Y), semi-conducting or half metallic. The system for Y and Zr doped graphyne becomes non-magnetic while V and Mn doped graphyne have a magnetic moments of l μB and 3 μB respectively From bader charge analysis it is seen that there is a charge transfer from the TM atom to the graphyne. Zr and Y have a net charge transfer of 2.15e and 1.73e respectively. Charge density analysis also shows the polarization on the carbon skeleton which becomes larger as the charge transfer for the TM atom increases. Thus we see Y and Zr are better candidates for hydrogen storage devices since they are non-magnetic and have less d electrons which is ideal for kubas-type interactions between hydrogen molecule and TM.

  1. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  2. Magic pairs and structural transitions in binary metallic clusters.

    Science.gov (United States)

    Cune, Liviu-Cristian

    2012-06-04

    Structures and binding energies for bimetallic clusters consisting of a large variety of atomic species are obtained for all atomic sizes N≤40 and all concentrations, using an interatomic potential derived within a quasi-classical description. It is found that increasing the difference between the two types of atoms leads to a gradual disappearance of the well-known homo-atomic geometric magic numbers and the appearance of magic pairs corresponding to the number of atoms of each atomic species in binary nanostructures with higher stability. This change is accompanied by structural transitions and ground-state↔isomer inversions, induced by changes in composition or concentration. There is a clear tendency towards phase separation, the core-shell radial segregation being predominant (energetically favored) in this model. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Distinct effect of xenobiotics on the metal-binding properties of protein molecules.

    Science.gov (United States)

    Novikova, Natalia; Kovalchuk, Mikhail; Stepina, Nina; Gaynutdinov, Radmir; Chukhrai, Elena; Yurieva, Eleonora

    2015-07-01

    The X-ray standing-wave method was applied to study the elemental composition and molecular organization of ordered protein films of alkaline phosphatase exposed to different xenobiotics (drug compounds, lead). Binding of metal ions from triply distilled water to protein molecules has been experimentally observed. Definite differences in the arrangement of impurity metal ions in the films have been established. The considerable enhancement of protein-metal interactions is attributed to partial rearrangement of the protein native structure, induced by xenobiotics.

  4. How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

    Science.gov (United States)

    Dudev, Todor; Grauffel, Cédric; Lim, Carmay

    2017-02-01

    Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

  5. Structure and properties of transition metal-metalloid glasses based on refractory metals

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, W.L.; Williams, A.R.

    1979-01-01

    The structure and properties of several new transition metal-metalloid (TM/sub 1-x/M/sub x/) metallic glasses based on refractory transition metals (e.g. Mo, W, Ru etc.) have been systemically investigated as a function of composition. The structure of the alloys has been investigated by x-ray diffraction methods and measurements of superconducting properties, electrical resistivity, density, hardness, and mechanical behavior were made. These data are used in developing a novel description of the structure of TM/sub 1-x/M/sub x/ glasses. The experimental evidence suggests that an ideal amorphous phase forms at a specific composition x/sub c/ and that this phase has a well defined atomic short range order. For metallic glasses having x < x/sub c/ (metalloid poor glasses) vacancy-like defects form, which are characterized by the excess volume which they contribute to the glass. Another, as yet unspecified defect appears to form in glasses with x > x/sub c/. This novel picture can explain the variation of many properties of these glasses with metalloid concentration.

  6. Calculated distortions induced by metal-ion binding to simple oligonucleotide systems: Implications for toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Turner, J.E.; Hingerty, B.E.; England, M.W.; Jacobson, K.B.

    1990-01-01

    We have previously published detailed results of calculations of the binding of the metal ions, Cd{sup 2+} and Ca{sup 2+}, to the dinucleoside monophosphate GpC in water. These ions, which have the same charge and radius, differ enormously in their toxicity to man and other biological systems. Our calculations showed contrasting behavior in the binding of these two metal ions to GpC. We suggest the hypothesis that structural distortions calculated for metal ions binding to simple nucleic-acid systems might serve as a indicator of an ion's potential ability to alter molecular activity and hence to be toxic to an organism. Furthermore, the degree of distortion might be correlated with the degree of toxicity as measured by some suitable criteria. The present paper reports the results of binding calculations for a number of other metal ions, of different valence states, with several dinucleoside monophosphates in water. A general trend of distortion with the type of binding of the metal ions is found. We are seeking quantitative measures of distortion to correlate with indicators of acute toxicity that we have measured for 24 metal ions using mice, Drosophila, and CHO cells. 3 refs., 3 figs.

  7. Electronic Relaxation Processes of Transition Metal Atoms in Helium Nanodroplets

    Science.gov (United States)

    Kautsch, Andreas; Lindebner, Friedrich; Koch, Markus; Ernst, Wolfgang E.

    2014-06-01

    Spectroscopy of doped superfluid helium nanodroplets (He_N) gives information about the influence of this cold, chemically inert, and least interacting matrix environment on the excitation and relaxation dynamics of dopant atoms and molecules. We present the results from laser induced fluorescence (LIF), photoionization (PI), and mass spectroscopy of Cr and Cu doped He_N. From these results, we can draw a comprehensive picture of the complex behavior of such transition metal atoms in He_N upon photo-excitation. The strong Cr and Cu ground state transitions show an excitation blueshift and broadening with respect to the bare atom transitions which can be taken as indication for the solvation inside the droplet. From the originally excited states the atoms relax to energetically lower states and are ejected from the He_N. The relaxation processes include bare atom spin-forbidden transitions, which clearly bears the signature of the He_N influence. Two-color resonant two-photon ionization (2CR2PI) also shows the formation of bare atoms and small Cr-He_n and Cu-He_n clusters in their ground and metastable states ^c. Currently, Cr dimer excitation studies are in progress and a brief outlook on the available results will be given. C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, 2011. A. Kautsch, M. Koch, and W. E. Ernst, J. Phys. Chem. A, 117 (2013) 9621-9625, DOI: 10.1021/jp312336m F. Lindebner, A. Kautsch, M. Koch, and W. E. Ernst, Int. J. Mass Spectrom. (2014) in press, DOI: 10.1016/j.ijms.2013.12.022 M. Koch, A. Kautsch, F. Lackner, and W. E. Ernst, submitted to J. Phys. Chem. A

  8. Regulation of the heavy metal pump AtHMA4 by a metal-binding autoinhibitory domain

    DEFF Research Database (Denmark)

    Bækgaard, Lone; Roed, Maria Dalgaard; Zhang, Yang

    Heavy metal pumps, or P1B ATPases, are important for heavy metal homeostasis in most cells. In general, these pumps contain extended N- and/or C-termini with one or more metal-binding domains (MBDs), but the role of the extended termini is still not clear. The Arabidopsis thaliana Zn2+-ATPase At......HMA4 contains a very long C-terminus with 13 cysteine pairs and an 11 amino acid residue long histidine stretch at the end. To ascertain the role of the potentially metal-binding domains in the C-terminus of AtHMA4, the C-terminal region alone was expressed in yeast. This resulted in increased Zn...

  9. Metal centre effects on HNO binding in porphyrins and the electronic origin: metal's electronic configuration, position in the periodic table, and oxidation state.

    Science.gov (United States)

    Yang, Liu; Fang, Weihai; Zhang, Yong

    2012-04-21

    HNO binds to many different metals in organometallic and bioinorganic chemistry. To help understand experimentally observed metal centre effects, a quantum chemical investigation was performed, revealing clear general binding trends with respect to metal centre characteristics and the electronic origin for the first time. This journal is © The Royal Society of Chemistry 2012

  10. Correlated effective field theory in transition metal compounds

    International Nuclear Information System (INIS)

    Mukhopadhyay, Subhasis; Chatterjee, Ibha

    2004-01-01

    Mean field theory is good enough to study the physical properties at higher temperatures and in higher dimensions. It explains the critical phenomena in a restricted sense. Near the critical temperatures, when fluctuations become important, it may not give the correct results. Similarly in low dimensions, the correlations become important and the mean field theory seems to be inadequate to explain the physical phenomena. At low-temperatures too, the quantum correlations become important and these effects are to be treated in an appropriate way. In 1974, Prof. M.E. Lines of Bell Laboratories, developed a theory which goes beyond the mean field theory and is known as the correlated effective field (CEF) theory. It takes into account the fluctuations in a semiempirical way. Lines and his collaborators used this theory to explain the short-range correlations and their anisotropy in the paramagnetic phase. Later Suzuki et al., Chatterjee and Desai, Mukhopadhyay and Chatterjee applied this theory to the magnetically ordered phase and a tremendous success of the theory has been found in real systems. The success of the CEF theory is discussed in this review. In order to highlight the success of this theory, earlier effective field theories and their improvements over mean field theories e.g., Bethe-Peierls-Weiss method, reaction field approximation, etc., are also discussed in this review for completeness. The beauty of the CEF theory is that it is mean field-like, but captures the essential physics of real systems to a great extent. However, this is a weak correlated theory and as a result is inappropriate for the metallic phase when strong correlations become important. In recent times, transition metal oxides become important due to the discovery of the high-temperature superconductivity and the colossal magnetoresistance phenomena. These oxides seem to be Mott insulators and undergo an insulator to metal transition by applying magnetic field, pressure and by changing

  11. Tuning the electronic and magnetic properties of borophene by 3d transition-metal atom adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Li, J.Y. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); University of Science and Technology of China, Hefei, 230026 (China); Lv, H.Y. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Lu, W.J., E-mail: wjlu@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Shao, D.F. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Xiao, R.C. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); University of Science and Technology of China, Hefei, 230026 (China); Sun, Y.P. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei, 230031 (China)

    2016-12-01

    Highlights: • Electronic and magnetic properties of borophene can be effectively tuned by the adsorption of 3d transition metal atoms. • The borophene tends to be ferromagnetic when Ti, V, Cr, Mn, and Fe atoms are adsorbed. • The origin of the ferromagnetism is analyzed based on the Stoner itinerant ferromagnetic model. - Abstract: The electronic and magnetic properties of borophene functionalized by 3d transition metal (TM) atom adsorption are investigated by using first-principles calculations. The results show that the 3d TM atoms can be adsorbed on borophene with high binding energies ranging between 5.9 and 8.3 eV. Interestingly, the originally nonmagnetic borophene tends to be ferromagnetic when Ti, V, Cr, Mn, and Fe atoms are adsorbed, and the magnetic moments are dominated by the TM atoms. The origin of the ferromagnetism is discussed based on the Stoner criterion. Our results indicate that the magnetic properties of borophene can be effectively tuned through the adsorption of 3d TM atoms, which could have promising applications in spintronics and nanoelectronics.

  12. Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

    Science.gov (United States)

    Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

    2015-02-10

    Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

  13. Molecular dynamics simulations of Pd-Ni transition metal alloys

    International Nuclear Information System (INIS)

    Kart, S. O.; Kart, H. H.; Uludogan, M.; Tomak, M.; Cagin, T.

    2002-01-01

    Molecular Dynamics simulations are performed to study bulk properties of fcc metals and metal alloys by using the quantum Sutton-Chen many-body potentials within the context of the tight-binding approach. The Molecular Dynamics algorithms we used in the simulations of Pd-Ni alloys are based on an extended Hamiltonian formalism arising from the works of Andersen (1980), Parinello and Rahman (1980), Nose (1984), Hoover (1985) and Cagin (1988). In these simulations, the effect of temperature and concentration on the solid and liquid properties are studied. Elastic constants and phonon dispersion relation are the solid properties we simulated in this work. Dynamic and static properties of liquid Pd-Ni are also computed by examining the behavior of density, enthalpy, pair distribution function and structure factor. The melting temperatures of Pd-Ni alloys are investigated. The diffusion coefficients are calculated from the mean square displacement using Einstein relation and from velocity auto-correlation function using Green-Kubo relations. The simulation results are in good agreement with the experiments

  14. Laser surface alloying of aluminium-transition metal alloys

    International Nuclear Information System (INIS)

    Almeida, A.; Vilar, R.

    1998-01-01

    Laser surface alloying has been used as a tool to produce hard and corrosion resistant Al-transition metal (TM) alloys. Cr and Mo are particularly interesting alloying elements to produce stable high-strength alloys because they present low diffusion coefficients and solid solubility in Al. To produce Al-TM surface alloys a two-step laser process was developed: firstly, the material is alloyed using low scanning speed and secondly, the microstructure is modified by a refinement step. This process was used in the production of Al-Cr, Al-Mo and Al-Mo and Al-Nb surface alloys by alloying Cr, Mo or Nb powder into an Al and 7175 Al alloy substrate using a CO 2 laser . This paper presents a review of the work that has been developed at Instituto Superior Tecnico on laser alloying of Al-TM alloy, over the last years. (Author) 16 refs

  15. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.

    2010-01-01

    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  16. Heterogeneous Catalytic Oxidation of Simple Alcohols by Transition Metals.

    Science.gov (United States)

    Jacobse, Leon; Vink, Sebastiaan O; Wijngaarden, Sven; Juurlink, Ludo B F

    2017-09-12

    The "exploding" flask demonstration presents a well-known illustration of heterogeneous catalyzed methanol oxidation. We find that for the same vapor pressure, the demonstration also works for all primary and secondary alcohols up to butanol but not for a tertiary alcohol. Also, we show that the demonstration works for a large range of transition metal catalysts. Hence, this demonstration, which is often applied for the repetitive explosions when methanol is used, may also be used to argue the requirement of initial dehydrogenation of the alcohol to an aldehyde in the catalytic reaction mechanism to support the general insensitivity to reactant molecules in heterogeneous catalysis in contrast to biological catalysis and to provide proof for activity trends as often depicted by volcano plots.

  17. Molecule signatures in photoluminescence spectra of transition metal dichalcogenides

    Science.gov (United States)

    Feierabend, Maja; Berghäuser, Gunnar; Selig, Malte; Brem, Samuel; Shegai, Timur; Eigler, Siegfried; Malic, Ermin

    2018-01-01

    Monolayer transition metal dichalcogenides (TMDs) show an optimal surface-to-volume ratio and are thus promising candidates for novel molecule sensor devices. It was recently predicted that a certain class of molecules exhibiting a large dipole moment can be detected through the activation of optically inaccessible (dark) excitonic states in absorption spectra of tungsten-based TMDs. In this paper, we investigate the molecule signatures in photoluminescence spectra in dependence of a number of different experimentally accessible quantities, such as excitation density, temperature, as well as molecular characteristics including the dipole moment and its orientation, molecule-TMD distance, molecular coverage, and distribution. We show that under certain optimal conditions even room-temperature detection of molecules can be achieved.

  18. On holographic disorder-driven metal-insulator transitions

    International Nuclear Information System (INIS)

    Baggioli, Matteo; Pujolàs, Oriol

    2017-01-01

    We give a minimal holographic model of a disorder-driven metal-insulator transition. It consists in a CFT with a charge sector and a translation-breaking sector that interact in the most generic way allowed by the symmetries and by dynamical consistency. In the gravity dual, it reduces to a Massive Gravity-Maxwell model with a new direct coupling between the gauge field and the metric that is allowed when gravity is massive. We show that the effect of this coupling is to decrease the DC electrical conductivity generically. This gives a nontrivial check that holographic massive gravity can be consistently interpreted as disorder from the CFT perspective. The suppression of the conductivity happens to such an extent that it does not obey any lower bound and it can be very small in the insulating phase. In some cases, the large disorder limit produces gradient instabilities that hint at the formation of modulated phases.

  19. Ferromagnetism in Fe-doped transition metal nitrides

    Science.gov (United States)

    Sharma, Ramesh; Sharma, Yamini

    2018-04-01

    Early transition metal mononitrides ScN and YN are refractory compounds with high hardness and melting points as well semiconducting properties. The presence of nitrogen vacancies in ScN/YN introduces asymmetric peaks in the density of states close to Fermi level, the same effects can be achieved by doping by Mn or Fe-atoms. Due to the substitution of TM atoms at Sc/Y sites, it was found that the p-d hybridization induces small magnetic moments at both Sc/Y and N sites giving rise to magnetic semiconductors (MS). From the calculated temperature dependent transport properties, the power factor and ZT is found to be lowered for doped ScN whereas it increases for doped YN. It is proposed that these materials have promising applications as spintronics and thermoelectric materials.

  20. Investigation of electronic transport properties of some liquid transition metals

    Science.gov (United States)

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

    2018-04-01

    We investigated electronic transport properties of some liquid transition metals (V, Cr, Mn, Fe, Co and Pt) using Ziman formalism. Our parameter free model potential which is realized on ionic and atomic radius has been incorporated with the Hard Sphere Yukawa (HSY) reference system to study the electronic transport properties like electrical resistivity (ρ), thermal conductivity (σ) and thermo electrical power (Q). The screening effect on aforesaid properties has been studied by using different screening functions. The correlations of our results and others data with in addition experimental values are profoundly promising to the researchers working in this field. Also, we conclude that our newly constructed parameter free model potential is capable to explain the aforesaid electronic transport properties.

  1. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting.

    Science.gov (United States)

    Ma, Liang; Wang, Jinlan; Yip, Joanne; Ding, Feng

    2014-04-03

    Catalytic cutting by transition-metal (TM) particles is a promising method for the synthesizing of high-quality graphene quantum dots and nanoribbons with smooth edges. Experimentally, it is observed that the cutting always results in channels with zigzag (ZZ) or armchair (AC) edges. However, the driving force that is responsible for such a cutting behavior remains a puzzle. Here, by calculating the interfacial formation energies of the TM-graphene edges with ab initio method, we show that the surface of a catalyst particle tends to be aligned along either AC or ZZ direction of the graphene lattice, and thus the cutting of graphene is guided as such. The different cutting behaviors of various catalysts are well-explained based on the competition between TM-passivated graphene edges and the etching-agent-terminated ones. Furthermore, the kinetics of graphene catalytic cutting along ZZ and AC directions, respectively, are explored at the atomic level.

  2. Metal-semiconductor transition of graphene nanoribbons with different addends

    Science.gov (United States)

    Zhang, X. W.; Dai, B.; Liu, J. S.; Yang, G. W.

    2012-02-01

    Using a LCAO method, which is based on spinless sp3 scheme, we have studied the electronic properties of graphene nanoribbons with zigzag edges (ZGNRs) terminated partially by methylene groups. Metal-semiconductor transition is proved when the H atoms at both sides of ZGNRs are partially substituted by methylene groups. Furthermore, when one-third of H atoms are substituted and the distribution of methylenes is symmetric, the band gap comes to about 0.59 eV, which is the widest energy gap in this work. Otherwise, when the addends at both sides are of asymmetric distribution, a band gap of only 0.21 eV is obtained. These results suggest that the addends at the edge of ZGNRs play an important role in modifying the electronic properties.

  3. Metal-semiconductor transition of graphene nanoribbons with different addends

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, X.W., E-mail: xiaoweizhang@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Dai, B; Liu, J.S. [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Yang, G.W. [State Key Laboratory of Optoelectronic Materials and Technologies, Institute of Optoelectronic and Functional Composite Materials, School of Physics Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2012-02-15

    Using a LCAO method, which is based on spinless sp{sup 3} scheme, we have studied the electronic properties of graphene nanoribbons with zigzag edges (ZGNRs) terminated partially by methylene groups. Metal-semiconductor transition is proved when the H atoms at both sides of ZGNRs are partially substituted by methylene groups. Furthermore, when one-third of H atoms are substituted and the distribution of methylenes is symmetric, the band gap comes to about 0.59 eV, which is the widest energy gap in this work. Otherwise, when the addends at both sides are of asymmetric distribution, a band gap of only 0.21 eV is obtained. These results suggest that the addends at the edge of ZGNRs play an important role in modifying the electronic properties.

  4. Electrically Induced Multiple Metal-Insulator Transitions in Oxide Nanodevices

    Science.gov (United States)

    del Valle, Javier; Kalcheim, Yoav; Trastoy, Juan; Charnukha, Aliaksei; Basov, Dimitri N.; Schuller, Ivan K.

    2017-11-01

    We show that electrical resistive switching can trigger the appearance of multiple metal-insulator transitions (MITs) in VO2 and V2O3 planar nanodevices. We have fabricated planar devices to electrically induce oxygen vacancy drift and filament formation. We show that oxygen migration can create ordered vanadium-oxide phases of varying stoichiometry with an intrinsic MIT, resulting in well-defined hysteresis loops in the R vs T characteristics of the device. We also show that oxygen migration induces oxide phases displaying correlated behaviors. Our results open up the possibility to electrically control the MIT, enabling alternative functionalities in memristive devices and allowing for alternative paradigms in neuromorphic computing or memory applications.

  5. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.

    2011-10-26

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  6. Intrinsic disorder in graphene on transition metal dichalcogenide heterostructures

    Science.gov (United States)

    Yankowitz, Matthew; Larentis, Stefano; Kim, Kyounghwam; Xue, Jiamin; McKenzie, Devin; Huang, Shengqiang; Paggen, Marina; Ali, Mazhar; Cava, Robert; Tutuc, Emanuel; Leroy, Brian J.

    2015-03-01

    Recently, semiconducting materials in the transition metal dichalcogenide (TMD) family have gained great popularity for use in novel graphene-based heterostructure devices such as tunneling transistors, highly efficient flexible photovoltaic devices, and nonvolatile memory cells. TMDs have also been explored as alternatives to hexagonal boron nitride (hBN) as substrates for pristine graphene devices. However, their quality has thus far been significantly worse than comparable hBN devices. We examine graphene on numerous TMD substrates (MoS2, WS2, WSe2, MoTe2) with scanning tunneling microscopy and spectroscopy and find that point and line defects intrinsic to all TMD crystals (both of natural and synthetic origin) result in scattering of electrons in graphene. Our findings suggest that the quality of graphene on TMD heterostructures is limited by the intrinsic crystalline quality of the TMDs.

  7. Magnetism of 3d transition metal atoms on W(001): submonolayer films

    International Nuclear Information System (INIS)

    Ondracek, M; Kudrnovsky, J; Turek, I; Maca, F

    2007-01-01

    We have investigated random submonolayer films of 3d transition metals on W(001). The tight-binding linear muffin-tin orbital method combined with the coherent potential approximation was employed to calculate the electronic structure of the films. We have estimated local magnetic moments and the stability of different magnetic structures, namely the ferromagnetic order, the disordered local moments and the non-magnetic state, by comparing the total energies of the corresponding systems. It has been found that the magnetic moments of V and Cr decrease and eventually disappear with decreasing coverage. On the other hand, Fe retains approximately the same magnetic moment throughout the whole concentration range from a single impurity to the monolayer coverage. Mn is an intermediate case between Cr and Fe since it is non-magnetic at very low coverages and (ferro)magnetic otherwise

  8. Magnetism of 3d transition metal atoms on W(001): submonolayer films

    Energy Technology Data Exchange (ETDEWEB)

    Ondracek, M [Institute of Physics, Academy of Sciences of the Czech Republic, Prague, CZ (Czech Republic); Kudrnovsky, J [Institute of Physics, Academy of Sciences of the Czech Republic, Prague, CZ (Czech Republic); Turek, I [Institute of Physics of Materials, Academy of Sciences of the Czech Republic, Brno, CZ (Czech Republic); Maca, F [Institute of Physics, Academy of Sciences of the Czech Republic, Prague, CZ (Czech Republic)

    2007-04-15

    We have investigated random submonolayer films of 3d transition metals on W(001). The tight-binding linear muffin-tin orbital method combined with the coherent potential approximation was employed to calculate the electronic structure of the films. We have estimated local magnetic moments and the stability of different magnetic structures, namely the ferromagnetic order, the disordered local moments and the non-magnetic state, by comparing the total energies of the corresponding systems. It has been found that the magnetic moments of V and Cr decrease and eventually disappear with decreasing coverage. On the other hand, Fe retains approximately the same magnetic moment throughout the whole concentration range from a single impurity to the monolayer coverage. Mn is an intermediate case between Cr and Fe since it is non-magnetic at very low coverages and (ferro)magnetic otherwise.

  9. First-principles studies on graphene-supported transition metal clusters

    International Nuclear Information System (INIS)

    Sahoo, Sanjubala; Khanna, Shiv N.; Gruner, Markus E.; Entel, Peter

    2014-01-01

    Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM 13 (TM = Fe, Co, Ni) clusters, deposited on pristine (defect free) and defective graphene sheet as well as graphene flakes, have been carried out within a gradient corrected density functional framework. The defects considered in our study include a carbon vacancy for the graphene sheet and a five-membered and a seven-membered ring structures for graphene flakes (finite graphene chunks). It is observed that the presence of defect in the substrate has a profound influence on the electronic structure and magnetic properties of graphene-transition metal complexes, thereby increasing the binding strength of the TM cluster on to the graphene substrate. Among TM 13 clusters, Co 13 is absorbed relatively more strongly on pristine and defective graphene as compared to Fe 13 and Ni 13 clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters

  10. Probing Magnetism in 2D Molecular Networks after in Situ Metalation by Transition Metal Atoms.

    Science.gov (United States)

    Schouteden, K; Ivanova, Ts; Li, Z; Iancu, V; Janssens, E; Van Haesendonck, C

    2015-03-19

    Metalated molecules are the ideal building blocks for the bottom-up fabrication of, e.g., two-dimensional arrays of magnetic particles for spintronics applications. Compared to chemical synthesis, metalation after network formation by an atom beam can yield a higher degree of control and flexibility and allows for mixing of different types of magnetic atoms. We report on successful metalation of tetrapyridyl-porphyrins (TPyP) by Co and Cr atoms, as demonstrated by scanning tunneling microscopy experiments. For the metalation, large periodic networks formed by the TPyP molecules on a Ag(111) substrate are exposed in situ to an atom beam. Voltage-induced dehydrogenation experiments support the conclusion that the porphyrin macrocycle of the TPyP molecule incorporates one transition metal atom. The newly synthesized Co-TPyP and Cr-TPyP complexes exhibit striking differences in their electronic behavior, leading to a magnetic character for Cr-TPyP only as evidenced by Kondo resonance measurements.

  11. NMR Structures and Dynamics in a Prohead RNA Loop that Binds Metal Ions.

    Science.gov (United States)

    Gu, Xiaobo; Park, Sun-Young; Tonelli, Marco; Cornilescu, Gabriel; Xia, Tianbing; Zhong, Dongping; Schroeder, Susan J

    2016-10-06

    Metal ions are critical for RNA structure and enzymatic activity. We present the structure of an asymmetric RNA loop that binds metal ions and has an essential function in a bacteriophage packaging motor. Prohead RNA is a noncoding RNA that is required for genome packaging activity in phi29-like bacteriophage. The loops in GA1 and phi29 bacteriophage share a conserved adenine that forms a base triple, although the structural context for the base triple differs. NMR relaxation studies and femtosecond time-resolved fluorescence spectroscopy reveal the dynamic behavior of the loop in the metal ion bound and unbound forms. The mechanism of metal ion binding appears to be an induced conformational change between two dynamic ensembles rather than a conformational capture mechanism. These results provide experimental benchmarks for computational models of RNA-metal ion interactions.

  12. Plasmonic percolation: Plasmon-manifested dielectric-to-metal transition

    KAUST Repository

    Chen, Huanjun

    2012-08-28

    Percolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures. When the Pd volume fraction in the shell consisting of palladium and water approaches the plasmonic percolation threshold, ∼70%, the plasmon of the nanostructure transits from red to blue shifts with respect to that of the unshelled Au nanorod. This plasmonic percolation behavior is also confirmed by the scattering measurements on the individual core-shell nanostructures. Quasistatic theory and numerical simulations show that the plasmonic percolation originates from a positive-to-negative transition in the real part of the dielectric function of the shell as the Pd volume fraction is increased. The observed plasmonic percolation is found to be independent of the metal type in the shell. Moreover, compared to the unshelled Au nanorods with similar plasmon wavelengths, the Au nanorod core-Pd shell nanostructures exhibit larger refractive index sensitivities, which is ascribed to the expulsion of the electric field intensity from the Au nanorod core by the adsorbed Pd nanoparticles. © 2012 American Chemical Society.

  13. Generic trend of work functions in transition-metal carbides and nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Yoshitake, Michiko, E-mail: yoshitake.michiko@nims.go.jp [MANA Nanoelectronics Materials Unit, National Institute for Materials Science, Tsukuba, Ibaraki 305-0003 (Japan)

    2014-11-15

    Transition-metal carbides and nitrides (TMCs and TMNs) are promising electrode materials for various electronic devices such as metal-oxide-semiconductor field-effect transistors and metal-insulator-metal capacitors. In this paper, the work functions of TMCs and TMNs are discussed systematically. Based upon the origin of the work function, the effect upon transition metal species by different periodic table groups is explained, carbides are compared with nitrides for the same transition metal, and the effect of carbon or nitrogen vacancies is discussed. In addition, a method to estimate the generic trend of the work function is proposed for TMC{sub x}, TMN{sub x}, TMC{sub 1−y}N{sub y} (transition metal carbonitrides), and TM{sub 1−z}TM′{sub z}C (alloy carbides)

  14. Mechanistic Inferences from the Binding of Ligands to LpxC, A Metal-Dependent Deacetylase

    Energy Technology Data Exchange (ETDEWEB)

    Gennadios,H.; Whittington, D.; Li, X.; Fierke, C.; Christianson, D.

    2006-01-01

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 Angstroms resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 Angstroms resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A.

  15. Mechanistic inferences from the binding of ligands to LpxC, a metal-dependent deacetylase.

    Science.gov (United States)

    Gennadios, Heather A; Whittington, Douglas A; Li, Xuechen; Fierke, Carol A; Christianson, David W

    2006-07-04

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 A resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 A resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A.

  16. Mechanistic Inferences from the Binding of Ligands to LpxC, A Metal-Dependent Deacetylase

    International Nuclear Information System (INIS)

    Gennadios, H.; Whittington, D.; Li, X.; Fierke, C.; Christianson, D.

    2006-01-01

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 Angstroms resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 Angstroms resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A

  17. Enzymatic hydrolysis by transition-metal-dependent nucleophilic aromatic substitution.

    Science.gov (United States)

    Kalyoncu, Sibel; Heaner, David P; Kurt, Zohre; Bethel, Casey M; Ukachukwu, Chiamaka U; Chakravarthy, Srinivas; Spain, Jim C; Lieberman, Raquel L

    2016-12-01

    Nitroaromatic compounds are typically toxic and resistant to degradation. Bradyrhizobium species strain JS329 metabolizes 5-nitroanthranilic acid (5NAA), which is a molecule secreted by Streptomyces scabies, the plant pathogen responsible for potato scab. The first biodegradation enzyme is 5NAA-aminohydrolase (5NAA-A), a metalloprotease family member that converts 5NAA to 5-nitrosalicylic acid. We characterized 5NAA-A biochemically and obtained snapshots of its mechanism. 5NAA-A, an octamer that can use several divalent transition metals for catalysis in vitro, employs a nucleophilic aromatic substitution mechanism. Unexpectedly, the metal in 5NAA-A is labile but is readily loaded in the presence of substrate. 5NAA-A is specific for 5NAA and cannot hydrolyze other tested derivatives, which are likewise poor inhibitors. The 5NAA-A structure and mechanism expand our understanding of the chemical ecology of an agriculturally important plant and pathogen, and will inform bioremediation and biocatalytic approaches to mitigate the environmental and ecological impact of nitroanilines and other challenging substrates.

  18. Kohn Anomaly and Phase Stability in Group VB Transition Metals

    Directory of Open Access Journals (Sweden)

    Alexander Landa

    2018-03-01

    Full Text Available In the periodic table, only a few pure metals exhibit lattice or magnetic instabilities associated with Fermi surface nesting, the classical examples being α-U and Cr. Whereas α-U displays a strong Kohn anomaly in the phonon spectrum that ultimately leads to the formation of charge density waves (CDWs, Cr is known for its nesting-induced spin density waves (SDWs. Recently, it has become clear that a pronounced Kohn anomaly and the corresponding softening in the elastic constants is also the key factor that controls structural transformations and mechanical properties in compressed group VB metals—materials with relatively high superconducting critical temperatures. This article reviews the current understanding of the structural and mechanical behavior of these metals under pressure with an introduction to the concept of the Kohn anomaly and how it is related to the important concept of Peierls instability. We review both experimental and theoretical results showing different manifestations of the Kohn anomaly in the transverse acoustic phonon mode TA (ξ00 in V, Nb, and Ta. Specifically, in V the anomaly triggers a structural transition to a rhombohedral phase, whereas in Nb and Ta it leads to an anomalous reduction in yield strength.

  19. The mechanism of anomalous hardening in transition-metal monoborides.

    Science.gov (United States)

    Liang, Yongcheng; Gao, Zhenbang; Qin, Ping; Gao, Li; Tang, Chun

    2017-07-06

    The quest for novel nanomaterials with unusual functionalities continues to be a central challenge to modern nanoscience. Here we report a surprisingly anomalous hardening behavior exhibited by a class of transition-metal monoborides (TMB). Most remarkable is the occurrence of the intrinsic hardness maximum at the valence-electron concentration (VEC) of about 8 electrons per formula unit (e per f.u.); both lower and higher VECs lead to the decrease of hardness, contrasting with the expected positive correlation between hardness and VEC. Such an unexpected phenomenon originates from the presence of two sorts of bands near the Fermi level that respond oppositely to the movement of dislocations within the metal bilayer. Furthermore, we demonstrate that the hardness is closely related to the formation energy for TMB, which justifies the importance of the thermodynamic stability in designing superhard materials. Our findings not only elucidate the unique mechanism responsible for unusual atom-scale hardening but also open a new avenue towards designing novel multifunctional nanomaterials with the coexistence of high hardness and excellent electrical conductivity.

  20. Ensemble and single-molecule studies on fluorescence quenching in transition metal bipyridine-complexes.

    Directory of Open Access Journals (Sweden)

    Dominik Brox

    Full Text Available Beyond their use in analytical chemistry fluorescent probes continuously gain importance because of recent applications of single-molecule fluorescence spectroscopy to monitor elementary reaction steps. In this context, we characterized quenching of a fluorescent probe by different metal ions with fluorescence spectroscopy in the bulk and at the single-molecule level. We apply a quantitative model to explain deviations from existing standard models for fluorescence quenching. The model is based on a reversible transition from a bright to a dim state upon binding of the metal ion. We use the model to estimate the stability constants of complexes with different metal ions and the change of the relative quantum yield of different reporter dye labels. We found ensemble data to agree widely with results from single-molecule experiments. Our data indicates a mechanism involving close molecular contact of dye and quenching moiety which we also found in molecular dynamics simulations. We close the manuscript with a discussion of possible mechanisms based on Förster distances and electrochemical potentials which renders photo-induced electron transfer to be more likely than Förster resonance energy transfer.

  1. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH3 and NH2NH2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH3- and NH2NH2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

  2. Realization of a half-metallic state on bilayer WSe2 using doping transition metals (Cr, Mn, Fe, Co, Ni) in its interlayer

    Science.gov (United States)

    Yang, Guang; Yang, Yanmin; Ma, Hongran; Mao, Xiujuan; Li, Congcong; Li, Jie; Zhang, Qiang; Zhang, Zhidong; Yin, Fuxing; Li, Jia

    2018-03-01

    The structural, electronic and magnetic properties of Cr, Mn, Fe, Co and Ni-doped bilayer WSe2 are predicted by using first principles calculations. The doped transition-metal (TM) atoms show a covalent-binding with the nearest Se atoms. The calculated electronic structures reveal that the TM Cr, Mn, Fe and Co-doped bilayer WSe2 exhibits a half-metallic character with a 100% spin polarization at the Fermi level, and the reason is ascribed to the strong hybridization peak between the transition metals and the parent W and Se atoms. The Ni-doped bilayer WSe2 is still a semiconductor with nonmagnetism. The Fe-doped system has a robust stability of half-metallicity because there are three connected states peak spanning the Fermi level. The doping of Cr, Mn, Fe and Co atoms leads to a prominent total magnetism (0.93–3.65 {μ }{{B}} moment per unit cell), and an induced ∼0.3 {μ }{{B}} moment in parent W atoms is found in addition to the main contribution of TM atomic magnetism (0.71–3.33 {μ }{{B}} moment per atom). The predicted Cr, Mn, Fe and Co-doped bilayer WSe2 should be the candidate materials for spintronic devices due to their magnetic and half-metallic nature.

  3. Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions

    Science.gov (United States)

    Patil, Amit; Lande, Dipali N.; Nalkar, Archana; Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tânia; Rangel, Maria; Pereira, Eulália; Salunke-Gawali, Sunita

    2017-09-01

    The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl)methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of Nsbnd H⋯O, Csbnd H⋯O, Csbnd H⋯π and π⋯π interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and 1H NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible.

  4. Calculation of the magnetic anisotropy energy and finite-temperature magnetic properties of transition-metal films

    International Nuclear Information System (INIS)

    Garibay-Alonso, R; Villasenor-Gonzalez, P; Dorantes-Davila, J; Pastor, G M

    2004-01-01

    The magnetic anisotropy energy at the interface (IMAE) of Co films deposited on the Pd(111) surface are determined in the framework of a self-consistent, real-space tight-binding method at zero temperature. Significant spin moments are induced at the Pd atoms at the interface which have an important influence on the observed reorientation transitions as a function of Co film thickness. Film-substrate hybridizations are therefore crucial for the magneto-anisotropic behaviour of thin transition-metal films deposited on metallic non-magnetic substrates. Furthermore, using a real-space recursive expansion of the local Green function and within the virtual-crystal approximation we calculate the magnetization curves and the Curie temperature T C for free-standing Fe films

  5. Calculation of the magnetic anisotropy energy and finite-temperature magnetic properties of transition-metal films

    Energy Technology Data Exchange (ETDEWEB)

    Garibay-Alonso, R [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, San Luis Potosi (Mexico); Villasenor-Gonzalez, P [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, San Luis Potosi (Mexico); Dorantes-Davila, J [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, San Luis Potosi (Mexico); Pastor, G M [Laboratoire de Physique Quantique, UMR 5626 du CNRS, Universite Paul Sabatier, Toulouse (France)

    2004-06-09

    The magnetic anisotropy energy at the interface (IMAE) of Co films deposited on the Pd(111) surface are determined in the framework of a self-consistent, real-space tight-binding method at zero temperature. Significant spin moments are induced at the Pd atoms at the interface which have an important influence on the observed reorientation transitions as a function of Co film thickness. Film-substrate hybridizations are therefore crucial for the magneto-anisotropic behaviour of thin transition-metal films deposited on metallic non-magnetic substrates. Furthermore, using a real-space recursive expansion of the local Green function and within the virtual-crystal approximation we calculate the magnetization curves and the Curie temperature T{sub C} for free-standing Fe films.

  6. Cooperative binding of copper(I) to the metal binding domains in Menkes disease protein

    DEFF Research Database (Denmark)

    Jensen, P Y; Bonander, N; Møller, L B

    1999-01-01

    spectroscopy, and their copper(I) binding properties have been determined. Structure prediction derived from far-UV CD indicates that the secondary structure is similar in the three proteins and dominated by beta-sheet. The tryptophan fluorescence maximum is blue-shifted in the constructs containing two...... and six MBDs relative to the monomer, suggesting more structurally buried tryptophan(s), compared to the single MBD construct. Copper(I) binding has been studied by equilibrium dialysis under anaerobic conditions. We show that the copper(I) binding to constructs containing two and six domains...... is cooperative, with Hill coefficients of 1.5 and 4, respectively. The apparent affinities are described by K(0.5), determined to be 65 microM and 19 microM for constructs containing two and six domains, respectively. Our data reveal a unique regulation of Menkes protein upon a change in copper(I) concentration...

  7. Influence of host matrices on krypton electron binding energies and KLL Auger transition energies

    Czech Academy of Sciences Publication Activity Database

    Inoyatov, A. K.; Perevoshchikov, L. L.; Kovalík, Alojz; Filosofov, D. V.; Yushkevich, Yu. V.; Ryšavý, Miloš; Lee, B. Q.; Kibédi, T.; Stuchbery, A. E.; Zhdanov, V. S.

    2014-01-01

    Roč. 197, DEC (2014), s. 64-71 ISSN 0368-2048 R&D Projects: GA ČR(CZ) GAP203/12/1896; GA MŠk LG14004 Institutional support: RVO:61389005 Keywords : Kr-83 * Rb-83 * Sr-83 * electron binding energy * KLL transitions * natural atomic level width * multiconfiguration Dirac-Fock calculations Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.436, year: 2014

  8. High-frequency EPR on high-spin transition-metal sites

    NARCIS (Netherlands)

    Mathies, Guinevere

    2012-01-01

    The electronic structure of transition-metal sites can be probed by electron-paramagnetic-resonance (EPR) spectroscopy. The study of high-spin transition-metal sites benefits from EPR spectroscopy at frequencies higher than the standard 9.5 GHz. However, high-frequency EPR is a developing field. In

  9. Predicted stability, structures, and magnetism of 3d transition metal nitrides: the M4N phases

    NARCIS (Netherlands)

    Fang, C.M.; Koster, R.S.; Li, W.F.; van Huis, M.A.

    2014-01-01

    The 3d transition metal nitrides M4N (Sc4N, Ti4N, V4N, Cr4N, Mn4N, Fe4N, Co4N, Ni4N, and Cu4N) have unique phase relationships, crystal structures, and electronic and magnetic properties. Here we present a systematic density functional theory (DFT) study on these transition metal nitrides, assessing

  10. Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

    Science.gov (United States)

    Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

    2018-03-01

    The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

  11. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    Energy Technology Data Exchange (ETDEWEB)

    Sharp, Paul [Univ. of Missouri, Columbia, MO (United States)

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  12. A comparative study of the metal binding behavior of alanine based bis-thiourea isomers

    OpenAIRE

    Fakhar, Imran; Yamin, Bohari M.; Hasbullah, Siti Aishah

    2017-01-01

    Two new symmetrical bis-thiourea, 2,2?-[{(terephthaloylbis(azanediyl)bis(carbonothioyl) bis(azanediyl)}dipropanoic acid] (1A) and 3,3?-[{(terephthaloylbis(azanediyl)bis (carbonothioyl)bis(azanediyl)} dipropanoic acid] (1B) were synthesized by the reaction of terephthaloyl chloride with ?- and ?-alanine in good yields. Their binding properties were investigated with various metal cations using UV?Vis titration experiments. Both isomers exhibited effective binding with Ag+, Cu2+, Hg2+, Pb2+, Fe...

  13. Discrepancy of structural and electronic transitions in the vicinity of the Metal-Insulator-transition in V2 O 3

    Science.gov (United States)

    Kim, Hyun-Tak; Shin, Jun-Hwan; Choi, Jung-Young; Kim, Bong-Jun

    2011-03-01

    Vanadium sesquioxide (V2 O3) , representative of strongly correlated electronic system, has been known as undergoing the MIT (Metal-Insulator-Transition) which is between rhombohedral paramagnetic metallic phase and monoclinic antiferromagnetic insulating phase near the transition temperature, (Tc) ~ }150 K. In order to reveal a relation between electronic and structural atomic transition, we has measured the temperature dependence of DC conductivity and structural crystallographic characterization with various temperatures from 90 K to 300 K by using low-temperature X-Ray diffraction (LTXRD). The obtained results show a discrepancy of structural and electronic transitions. This discrepancy can be explained by forming of the metallic puddles whose the size and number increased by nucleation and percolation[1,2] during the electronic transition progress from 120 K to 180 K. The puddles have an insulating monoclinic structure before the structural phase transition at ~ 185 K. These metallic puddles are induced by the MIT not related to the SPT (structure phase transition). (1. M. M. Qazilbash et al., Science 318, 1750 (2007); 2. B. J. Kim et al., Phys. Rev. B 77, 235401(2008))

  14. Converged G W quasiparticle energies for transition metal oxide perovskites

    Science.gov (United States)

    Ergönenc, Zeynep; Kim, Bongjae; Liu, Peitao; Kresse, Georg; Franchini, Cesare

    2018-02-01

    The ab initio calculation of quasiparticle (QP) energies is a technically and computationally challenging problem. In condensed matter physics, the most widely used approach to determine QP energies is the G W approximation. Although the G W method has been widely applied to many typical semiconductors and insulators, its application to more complex compounds such as transition metal oxide perovskites has been comparatively rare, and its proper use is not well established from a technical point of view. In this work, we have applied the single-shot G0W0 method to a representative set of transition metal oxide perovskites including 3 d (SrTiO3, LaScO3, SrMnO3, LaTiO3, LaVO3, LaCrO3, LaMnO3, and LaFeO3), 4 d (SrZrO3, SrTcO3, and Ca2RuO4 ), and 5 d (SrHfO3, KTaO3, and NaOsO3) compounds with different electronic configurations, magnetic orderings, structural characteristics, and band gaps ranging from 0.1 to 6.1 eV. We discuss the proper procedure to obtain well-converged QP energies and accurate band gaps within single-shot G0W0 by comparing the conventional approach based on an incremental variation of a specific set of parameters (number of bands, energy cutoff for the plane-wave expansion and number of k points) and the basis-set extrapolation scheme [J. Klimeš et al., Phys. Rev. B 90, 075125 (2014), 10.1103/PhysRevB.90.075125]. Although the conventional scheme is not supported by a formal proof of convergence, for most cases it delivers QP energies in reasonably good agreement with those obtained by the basis-set correction procedure and it is by construction more useful for calculating band structures. In addition, we have inspected the difference between the adoption of norm-conserving and ultrasoft potentials in G W calculations and found that the norm violation for the d shell can lead to less accurate results in particular for charge-transfer systems and late transition metals. A minimal statistical analysis indicates that the correlation of the G W data

  15. Ordering phenomena in transition-metal-oxide heterostructures

    International Nuclear Information System (INIS)

    Frano Pereira, Alex Manuel

    2014-01-01

    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L 3 -edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO 3 -RXO 3 (RXO 3 = LaAlO 3 , DyScO 3 ) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q SDW = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO 3 being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO 3 layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q SDW were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis will address the observation of charge density

  16. Identification of metal ion binding sites based on amino acid sequences

    Science.gov (United States)

    Cao, Xiaoyong; Zhang, Xiaojin; Gao, Sujuan; Ding, Changjiang; Feng, Yonge; Bao, Weihua

    2017-01-01

    The identification of metal ion binding sites is important for protein function annotation and the design of new drug molecules. This study presents an effective method of analyzing and identifying the binding residues of metal ions based solely on sequence information. Ten metal ions were extracted from the BioLip database: Zn2+, Cu2+, Fe2+, Fe3+, Ca2+, Mg2+, Mn2+, Na+, K+ and Co2+. The analysis showed that Zn2+, Cu2+, Fe2+, Fe3+, and Co2+ were sensitive to the conservation of amino acids at binding sites, and promising results can be achieved using the Position Weight Scoring Matrix algorithm, with an accuracy of over 79.9% and a Matthews correlation coefficient of over 0.6. The binding sites of other metals can also be accurately identified using the Support Vector Machine algorithm with multifeature parameters as input. In addition, we found that Ca2+ was insensitive to hydrophobicity and hydrophilicity information and Mn2+ was insensitive to polarization charge information. An online server was constructed based on the framework of the proposed method and is freely available at http://60.31.198.140:8081/metal/HomePage/HomePage.html. PMID:28854211

  17. Spectroscopic Signature of a Ubiquitous Metal Binding Site in the Metallo-beta-lactamase Superfamily

    Energy Technology Data Exchange (ETDEWEB)

    V Campos-Bermudez; J Gonzalez; D Tierney; A Vila

    2011-12-31

    The metallo-{beta}-lactamase (M{beta}L) superfamily is a functionally diverse group of metalloproteins sharing a distinctive {alpha}{beta}/{alpha}{beta} fold and a characteristic metal binding motif. A large number of open reading frames identified in genomic sequencing efforts have been annotated as members of this superfamily through sequence comparisons. However, structural and functional studies performed on purified proteins are normally needed to unequivocally include a newly discovered protein in the M{beta}L superfamily. Here we report the spectroscopic characterization of recombinant YcbL, a gene product annotated as a member of the M{beta}L superfamily whose function in vivo remains unknown. By taking advantage of the structural features characterizing the M{beta}L superfamily metal binding motif, we performed spectroscopic studies on Zn(II)- and Co(II)-substituted YcbL to structurally interrogate the metal binding site. The dinuclear center in Co(II)-YcbL was shown to display characteristic electronic absorption features in the visible region, which were also observed in an engineered M{beta}L aimed at mimicking this metal site. Thus, the spectroscopic features reported herein can be employed as a signature to readily identify and characterize the presence of these ubiquitous metal binding sites.

  18. Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

    International Nuclear Information System (INIS)

    Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

    2017-01-01

    Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co 3 O 4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu 2 O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn 3 O 4 , which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O 2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these

  19. Electronic self-organization in layered transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Ritschel, Tobias

    2015-10-30

    The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS{sub 2} both experimentally and theoretically. At first the static charge density wave order in 1T-TaS{sub 2} is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS{sub 2}. Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS{sub 2} in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales. These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures

  20. Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides

    Energy Technology Data Exchange (ETDEWEB)

    Peroni, Marco [Technische Universität München, Department; Lee, Insu [Technische Universität München, Department; Huang, Xiaoyang [Technische Universität München, Department; Baráth, Eszter [Technische Universität München, Department; Gutiérrez, Oliver Y. [Technische Universität München, Department; Lercher, Johannes A. [Technische Universität München, Department; Institute

    2017-08-18

    Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged. J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.

  1. Synthesis, characterization, anti-microbial, DNA binding and cleavage studies of Schiff base metal complexes

    Directory of Open Access Journals (Sweden)

    Poomalai Jayaseelan

    2016-09-01

    Full Text Available A novel Schiff base ligand has been prepared by the condensation between butanedione monoxime with 3,3′-diaminobenzidine. The ligand and metal complexes have been characterized by elemental analysis, UV, IR, 1H NMR, conductivity measurements, EPR and magnetic studies. The molar conductance studies of Cu(II, Ni(II, Co(II and Mn(II complexes showed non-electrolyte in nature. The ligand acts as dibasic with two N4-tetradentate sites and can coordinate with two metal ions to form binuclear complexes. The spectroscopic data of metal complexes indicated that the metal ions are complexed with azomethine nitrogen and oxyimino nitrogen atoms. The binuclear metal complexes exhibit octahedral arrangements. DNA binding properties of copper(II metal complex have been investigated by electronic absorption spectroscopy. Results suggest that the copper(II complex bind to DNA via an intercalation binding mode. The nucleolytic cleavage activities of the ligand and their complexes were assayed on CT-DNA using gel electrophoresis in the presence and absence of H2O2. The ligand showed increased nuclease activity when administered as copper complex and copper(II complex behave as efficient chemical nucleases with hydrogen peroxide activation. The anti-microbial activities and thermal studies have also been studied. In anti-microbial activity all complexes showed good anti-microbial activity higher than ligand against gram positive, gram negative bacteria and fungi.

  2. GRHL3 binding and enhancers rearrange as epidermal keratinocytes transition between functional states.

    Directory of Open Access Journals (Sweden)

    Rachel Herndon Klein

    2017-04-01

    Full Text Available Transcription factor binding, chromatin modifications and large scale chromatin re-organization underlie progressive, irreversible cell lineage commitments and differentiation. We know little, however, about chromatin changes as cells enter transient, reversible states such as migration. Here we demonstrate that when human progenitor keratinocytes either differentiate or migrate they form complements of typical enhancers and super-enhancers that are unique for each state. Unique super-enhancers for each cellular state link to gene expression that confers functions associated with the respective cell state. These super-enhancers are also enriched for skin disease sequence variants. GRHL3, a transcription factor that promotes both differentiation and migration, binds preferentially to super-enhancers in differentiating keratinocytes, while during migration, it binds preferentially to promoters along with REST, repressing the expression of migration inhibitors. Key epidermal differentiation transcription factor genes, including GRHL3, are located within super-enhancers, and many of these transcription factors in turn bind to and regulate super-enhancers. Furthermore, GRHL3 represses the formation of a number of progenitor and non-keratinocyte super-enhancers in differentiating keratinocytes. Hence, chromatin relocates GRHL3 binding and enhancers to regulate both the irreversible commitment of progenitor keratinocytes to differentiation and their reversible transition to migration.

  3. Importance of diffuse metal ion binding to RNA.

    Science.gov (United States)

    Tan, Zhi-Jie; Chen, Shi-Jie

    2011-01-01

    RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding.

  4. Dislocations and Plasticity in bcc Transition Metals at High Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L H; Tang, M; Moriarty, J A

    2009-01-23

    Using first-principles electronic structure calculations, quantum-based atomistic simulations and atomistically informed dislocation dynamics (DD) simulations, we have studied individual dislocation behavior and the multiscale modeling of single-crystal plasticity in the prototype bcc transition metals Ta, Mo and V under both ambient and high pressure conditions. The primary focus in this work is on the pressure-dependent structure, mobility and interaction of a/2<111> screw dislocations, which dominate the plastic deformation properties of these materials. At the electronic scale, first-principles calculations of elasticity, ideal strength and generalized stacking fault energy surfaces have been used to validate quantum-based multi-ion interatomic potentials. At the atomistic scale, these potentials have been used in flexible Green's function boundary condition simulations to study the core structure, Peierls stress {tau}{sub P}, thermally activated kink-pair formation and mobility below {tau}{sub P}, and phonon-drag mobility above {tau}{sub P}. These results have then been distilled into analytic velocity laws and used directly in predictive microscale DD simulations of flow stress and resolved yield stress over wide ranges of pressure, temperature and strain rate.

  5. Quantum dot behavior in transition metal dichalcogenides nanostructures

    Science.gov (United States)

    Luo, Gang; Zhang, Zhuo-Zhi; Li, Hai-Ou; Song, Xiang-Xiang; Deng, Guang-Wei; Cao, Gang; Xiao, Ming; Guo, Guo-Ping

    2017-08-01

    Recently, transition metal dichalcogenides (TMDCs) semiconductors have been utilized for investigating quantum phenomena because of their unique band structures and novel electronic properties. In a quantum dot (QD), electrons are confined in all lateral dimensions, offering the possibility for detailed investigation and controlled manipulation of individual quantum systems. Beyond the definition of graphene QDs by opening an energy gap in nanoconstrictions, with the presence of a bandgap, gate-defined QDs can be achieved on TMDCs semiconductors. In this paper, we review the confinement and transport of QDs in TMDCs nanostructures. The fabrication techniques for demonstrating two-dimensional (2D) materials nanostructures such as field-effect transistors and QDs, mainly based on e-beam lithography and transfer assembly techniques are discussed. Subsequently, we focus on electron transport through TMDCs nanostructures and QDs. With steady improvement in nanoscale materials characterization and using graphene as a springboard, 2D materials offer a platform that allows creation of heterostructure QDs integrated with a variety of crystals, each of which has entirely unique physical properties.

  6. Exciton-polariton condensation in transition metal dichalcogenide bilayer heterostructure

    Science.gov (United States)

    Lee, Ki Hoon; Jeong, Jae-Seung; Min, Hongki; Chung, Suk Bum

    For the bilayer heterostructure system in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon coupling can lead to the emergence of quasiparticles consisting of the spatially indirect exciton and cavity photons known as dipolariton, which can form the Bose-Einstein condensate above a threshold density. Additional physics comes into play when each layer of the bilayer system consists of the transition metal dichalcogenide (TMD) monolayer. The TMD monolayer band structure in the low energy spectrum has two valley components with nontrivial Berry phase, which gives rise to a selection rule in the exciton-polariton coupling, e.g. the exciton from one (the other) valley can couple only to the clockwise (counter-clockwise) polarized photon. We investigate possible condensate phases of exciton-polariton in the bilayer TMD microcavity changing relevant parameters such as detuning, excitation density and interlayer distance. This work was supported in part by the Institute for Basic Science of Korea (IBS) under Grant IBS-R009-Y1 and by the National Research Foundation of Korea (NRF) under the Basic Science Research Program Grant No. 2015R1D1A1A01058071.

  7. Photoconductivity in Transition Metal Doped Bismuth Germanium Oxide

    Science.gov (United States)

    Newkirk, Nolan M.; McCullough, J. S.; Martin, J. J.

    1999-10-01

    Bismuth germanium oxide (BGO) is a photorefractive material that has potential for a number of applications. We are investigating the possibility of tailoring it for specific uses by doping with 3d-ions. . Anti-site bismuth is a native defect in melt-grown BGO. This amphoteric defect dominates the photo-response of undoped BGO and plays a role in transition metal doped samples. The majority of the 3d-ions go into the tetrahedrally bonded Ge-site; thus, Cr would be expected to be in a 4+ state. Instead, it gives up an electron to the anti-site Bi and is in a 5+ state. Strongly persistent photorefractive gratings are observed in BGO:Cr. Photoconductivity measurements were performed on undoped BGO, BGO:V, and BGO:Cr before and after the samples were exposed to 442 nm light. The photoconductivity response roughly matched the optical absorption spectra of the samples. The exposed samples showed additional photo-induced absorption bands and much stronger photocurrents in the same spectral regions. The exposure to blue light appears to convert Cr from the 5+ state to the 4+state.

  8. Band Alignment of 2D Transition Metal Dichalcogenide Heterojunctions

    KAUST Repository

    Chiu, Ming-Hui

    2016-09-20

    It is critically important to characterize the band alignment in semiconductor heterojunctions (HJs) because it controls the electronic and optical properties. However, the well-known Anderson\\'s model usually fails to predict the band alignment in bulk HJ systems due to the presence of charge transfer at the interfacial bonding. Atomically thin 2D transition metal dichalcogenide materials have attracted much attention recently since the ultrathin HJs and devices can be easily built and they are promising for future electronics. The vertical HJs based on 2D materials can be constructed via van der Waals stacking regardless of the lattice mismatch between two materials. Despite the defect-free characteristics of the junction interface, experimental evidence is still lacking on whether the simple Anderson rule can predict the band alignment of HJs. Here, the validity of Anderson\\'s model is verified for the 2D heterojunction systems and the success of Anderson\\'s model is attributed to the absence of dangling bonds (i.e., interface dipoles) at the van der Waal interface. The results from the work set a foundation allowing the use of powerful Anderson\\'s rule to determine the band alignments of 2D HJs, which is beneficial to future electronic, photonic, and optoelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Moessbauer spectroscopy and transition metal chemistry. Fundamentals and applications

    International Nuclear Information System (INIS)

    Guetlich, Philipp; Trautwein, Alfred X.

    2011-01-01

    Moessbauer spectroscopy is a profound analytical method which has nevertheless continued to develop. The authors now present a state-of-the art book which consists of two parts. The first part details the fundamentals of Moessbauer spectroscopy and is based on a book published in 1978 in the Springer series 'Inorganic Chemistry Concepts' by P. Guetlich, R. Link and A.X. Trautwein. The second part covers useful practical aspects of measurements, and the application of the techniques to many problems of materials characterization. The update includes the use of synchroton radiation and many instructive and illustrative examples in fields such as solid state chemistry, biology and physics, materials and the geosciences, as well as industrial applications. Special chapters on magnetic relaxation phenomena (S. Morup) and computation of hyperfine interaction parameters (F. Neese) are also included. An attached CD-ROM with more than 400 full-color PowerPoint images provides self-explanatory examples. The book concentrates on teaching the technique using theory as much as needed and as little as possible. The reader will learn the fundamentals of the technique and how to apply it to many problems of materials characterization. Transition metal chemistry, studied on the basis of the most widely used Moessbauer isotopes, is in the foreground. (orig.)

  10. Hyperdoping Si with transition metals for infrared detection

    Science.gov (United States)

    Mathews, Jay; Liu, Yining; Yang, Wenjie; Hudspeth, Quentin; Malladi, Girish; Efstathiadis, Harry; Williams, James; Warrender, Jeffrey

    Recent advances in the field of laser hyperdoping have produced a new class of materials that could lead the way to silicon-based, CMOS-compatible infrared detectors. Using the method of ion implantation followed by pulsed laser melting (II-PLM), silicon films with impurities at concentrations well above the solid solubility limit can be fabricated. Recent work has centered on using transition metals like Au or Ti as the impurity, as their deep level impurity states broaden into intermediate bands, thereby creating sub-band gap optical absorption. In this work, we report on efforts to develop the fabrication methods for realization of photodetectors from Si:Au and Si:Ti, including etching the materials and forming Ohmic contacts. We also explore the optical and electrical properties of fabricated Si:Au and Si:Ti photodetectors. This work is supported by US Army ARDEC Grant No. W15QKN-16-2-0001 and Office of Naval Research Grant No. N00014-16-1-2864.

  11. Protactinium and the intersection of actinide and transition metal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

    2018-02-12

    The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

  12. Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes

    Science.gov (United States)

    Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Mercadier, Laurent; Majety, Vinay P.; Marinelli, Agostino; Lutman, Alberto; Guetg, Marc W.; Decker, Franz-Josef; Boutet, Sébastien; Aquila, Andy; Koglin, Jason; Koralek, Jake; DePonte, Daniel P.; Kern, Jan; Fuller, Franklin D.; Pastor, Ernest; Fransson, Thomas; Zhang, Yu; Yano, Junko; Yachandra, Vittal K.; Rohringer, Nina; Bergmann, Uwe

    2018-03-01

    We report the observation and analysis of the gain curve of amplified K α x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1 s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1 s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ˜1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ˜1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ˜1020 W /cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.

  13. Surface and subsurface hydrogen: adsorption properties on transition metals and near-surface alloys.

    Science.gov (United States)

    Greeley, Jeff; Mavrikakis, Manos

    2005-03-03

    Periodic, self-consistent DFT-GGA calculations are used to study the thermochemical properties of both surface and subsurface atomic hydrogen on a variety of pure metals and near-surface alloys (NSAs). For surface hydrogen on pure metals, calculated site preferences, adsorption geometries, vibrational frequencies, and binding energies are reported and are found to be in good agreement with available experimental data. On NSAs, defined as alloys wherein a solute is present near the surface of a host metal in a composition different from the bulk composition, surface hydrogen generally binds more weakly than it binds to the pure-metal components composing the alloys. Some of the NSAs even possess the unusual property of binding hydrogen as weakly as the noble metals while, at the same time, dissociating H(2) much more easily. On both NSAs and pure metals, formation of surface hydrogen is generally exothermic with respect to H(2)(g). In contrast, formation of subsurface hydrogen is typically endothermic with respect to gas-phase H(2) (the only exception to this general statement is found for pure Pd). As with surface H, subsurface H typically binds more weakly to NSAs than to the corresponding pure-metal components of the alloys. The diffusion barrier for hydrogen from surface to subsurface sites, however, is usually lower on NSAs compared to the pure-metal components, suggesting that population of subsurface sites may occur more rapidly on NSAs.

  14. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts.

    Science.gov (United States)

    van Oversteeg, Christina H M; Doan, Hoang Q; de Groot, Frank M F; Cuk, Tanja

    2017-01-03

    X-ray absorption studies of the geometric and electronic structure of primarily heterogeneous Co, Ni, and Mn based water oxidation catalysts are reviewed. The X-ray absorption near edge and extended X-ray absorption fine structure studies of the metal K-edge, characterize the metal oxidation state, metal-oxygen bond distance, metal-metal distance, and degree of disorder of the catalysts. These properties guide the coordination environment of the transition metal oxide radical that localizes surface holes and is required to oxidize water. The catalysts are investigated both as-prepared, in their native state, and under reaction conditions, while transition metal oxide radicals are generated. The findings of many experiments are summarized in tables. The advantages of future X-ray experiments on water oxidation catalysts, which include the limited data available of the oxygen K-edge, metal L-edge, and resonant inelastic X-ray scattering, are discussed.

  15. Oxygen effect on the work function of electropositive metal films adsorbed on 4d and 5d-transition metals

    International Nuclear Information System (INIS)

    Kultashev, O.K.; Makarov, A.P.; Rozhkov, S.E.

    1976-01-01

    The thermionic emission method was used to study the effect of oxygen upon the work function of films of electropositive metals, Sc, Y, La and Ba on some monocrystal and polycrystalline specimens of 4d- and 5d-transition metals of groups 4-8 of the Periodic system. It was revealed that when the supports were polycrystalline and monocrystalline specimens of transition metals of Group 5 (niobium and tantalum), the work function phi of films of electropositive adsorbates dropped substantially as compared, e.g., to the phi values on the same faces of tungsten. When the concentration of the electropositive adsorbate exceeds the optimum value (in the absence of oxygen), oxygen exerts an appreciably activating action upon the work function phi of films of electropositive adsorbates on transition metals of the Groups 7 and 8. The activating action of oxygen is assumed to be due to a possibility of formation of surface interstitial structures

  16. MetalionRNA: computational predictor of metal-binding sites in RNA structures.

    Science.gov (United States)

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Boniecki, Michal; Rother, Kristian; Bujnicki, Janusz M

    2012-01-15

    Metal ions are essential for the folding of RNA molecules into stable tertiary structures and are often involved in the catalytic activity of ribozymes. However, the positions of metal ions in RNA 3D structures are difficult to determine experimentally. This motivated us to develop a computational predictor of metal ion sites for RNA structures. We developed a statistical potential for predicting positions of metal ions (magnesium, sodium and potassium), based on the analysis of binding sites in experimentally solved RNA structures. The MetalionRNA program is available as a web server that predicts metal ions for RNA structures submitted by the user. The MetalionRNA web server is accessible at http://metalionrna.genesilico.pl/.

  17. A mononuclear non-heme manganese(IV)-oxo complex binding redox-inactive metal ions.

    Science.gov (United States)

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N; Nam, Wonwoo

    2013-05-01

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal-oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)-oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)-oxo complex binding scandium ions. The Mn(IV)-oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)-oxo complex are markedly influenced by binding of Sc(3+) ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C-H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  18. Polymer derived non-oxide ceramics modified with late transition metals.

    Science.gov (United States)

    Zaheer, Muhammad; Schmalz, Thomas; Motz, Günter; Kempe, Rhett

    2012-08-07

    This tutorial review highlights the methods for the preparation of metal modified precursor derived ceramics (PDCs) and concentrates on the rare non-oxide systems enhanced with late transition metals. In addition to the main synthetic strategies for modified SiC and SiCN ceramics, an overview of the morphologies, structures and compositions of both, ceramic materials and metal (nano) particles, is presented. Potential magnetic and catalytic applications have been discussed for the so manufactured metal containing non-oxide ceramics.

  19. Crystal structure of glucose isomerase in complex with xylitol inhibitor in one metal binding mode.

    Science.gov (United States)

    Bae, Ji-Eun; Kim, In Jung; Nam, Ki Hyun

    2017-11-04

    Glucose isomerase (GI) is an intramolecular oxidoreductase that interconverts aldoses and ketoses. These characteristics are widely used in the food, detergent, and pharmaceutical industries. In order to obtain an efficient GI, identification of novel GI genes and substrate binding/inhibition have been studied. Xylitol is a well-known inhibitor of GI. In Streptomyces rubiginosus, two crystal structures have been reported for GI in complex with xylitol inhibitor. However, a structural comparison showed that xylitol can have variable conformation at the substrate binding site, e.g., a nonspecific binding mode. In this study, we report the crystal structure of S. rubiginosus GI in a complex with xylitol and glycerol. Our crystal structure showed one metal binding mode in GI, which we presumed to represent the inactive form of the GI. The metal ion was found only at the M1 site, which was involved in substrate binding, and was not present at the M2 site, which was involved in catalytic function. The O 2 and O 4 atoms of xylitol molecules contributed to the stable octahedral coordination of the metal in M1. Although there was no metal at the M2 site, no large conformational change was observed for the conserved residues coordinating M2. Our structural analysis showed that the metal at the M2 site was not important when a xylitol inhibitor was bound to the M1 site in GI. Thus, these findings provided important information for elucidation or engineering of GI functions. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Catalytic role of transition metals supported on niobium oxide in O2 activation

    Science.gov (United States)

    Omidvar, Akbar

    2018-03-01

    Metal particles supported on metal oxides (MMO) are promising materials with versatile applications such as catalyst in fuel cell technologies. As one of the transition metal oxides, niobium oxide (NbO) demonstrates a wide interesting properties that make it a potentially applicable in MMO materials. Here, the catalytic activity for the O2 activation of transition metals (Fe, Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) supported on the NbO has been studied theoretically using density functional theory (DFT). The activation of O2 molecule and yielding two separated O atoms is an essential step for the oxygen reduction reaction. Our study demonstrates that the transition metals supported on the NbO can act as driving force for O2 dissociation. Consistent with the prediction of reactivity descriptors, the maximum catalytic activity toward O2 activation is related to the Pt-supported on the NbO metal oxide.

  1. Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

    Energy Technology Data Exchange (ETDEWEB)

    Mellah, B

    2006-11-15

    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

  2. Scaling Relationships for Adsorption Energies of C2 Hydrocarbons on Transition Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G

    2011-08-18

    Using density functional theory calculations we show that the adsorption energies for C{sub 2}H{sub x}-type adsorbates on transition metal surfaces scale with each other according to a simple bond order conservation model. This observation generalizes some recently recognized adsorption energy scaling laws for AH{sub x}-type adsorbates to unsaturated hydrocarbons and establishes a coherent simplified description of saturated as well as unsaturated hydrocarbons adsorbed on transition metal surfaces. A number of potential applications are discussed. We apply the model to the dehydrogenation of ethane over pure transition metal catalysts. Comparison with the corresponding full density functional theory calculations shows excellent agreement.

  3. On the Problem of Metal-Insulator Transitions in Vanadium Oxides

    OpenAIRE

    A. A. Velichko; N. A. Kuldin; G. B. Stefanovich; A. L. Pergament

    2013-01-01

    The problem of metal-insulator transition is considered. It is shown that the Mott criterion aB(nc)1/3≈0.25 is applicable not only to heavily doped semiconductors but also to many other materials, including some transition-metal compounds, such as vanadium oxides (particularly, VO2 and V2O3). The low-temperature transition (“paramagnetic metal—antiferromagnetic insulator”) in vanadium sesquioxide is described on the basis of this concept in terms of an intervening phase, between metal and ins...

  4. Microalloying of transition metal silicides by mechanical activation and field-activated reaction

    Energy Technology Data Exchange (ETDEWEB)

    Munir, Zuhair A [Davis, CA; Woolman, Joseph N [Davis, CA; Petrovic, John J [Los Alamos, NM

    2003-09-02

    Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

  5. Mechanism of decomposition of transition metal organometallic compounds and role of intermediate particles in catalysis

    International Nuclear Information System (INIS)

    Dolgoplosk, B.A.

    1984-01-01

    In the review, containing 105 bibliographic references, ways of decomposition of transition metal organic compounds in the moment of their formation are considered. For methyl, benzyl, trimethylsililmethyl and neophilic derivatives of transition metals (Mo, W, Re, Nb, Ta, Nd, Y) α-decay, which is accompanied by the formation of carbene and carbyne particles, is the determining one. Mechanism of the chain processes of metathesis of olefines and cycloolephines under the effect of carbene complexes of transition metals is discussed. Suppositions are made on chemical nature of elementary acts in the reactions of hydrogenolisis, isomerization of carbon carcass; dehydration and hydration of hydrocarbons

  6. Crystal structure of Yersinia pestis virulence factor YfeA reveals two polyspecific metal-binding sites

    Energy Technology Data Exchange (ETDEWEB)

    Radka, Christopher D.; DeLucas, Lawrence J.; Wilson, Landon S.; Lawrenz, Matthew B.; Perry, Robert D.; Aller, Stephen G.

    2017-06-30

    Gram-negative bacteria use siderophores, outer membrane receptors, inner membrane transporters and substrate-binding proteins (SBPs) to transport transition metals through the periplasm. The SBPs share a similar protein fold that has undergone significant structural evolution to communicate with a variety of differentially regulated transporters in the cell. InYersinia pestis, the causative agent of plague, YfeA (YPO2439, y1897), an SBP, is important for full virulence during mammalian infection. To better understand the role of YfeA in infection, crystal structures were determined under several environmental conditions with respect to transition-metal levels. Energy-dispersive X-ray spectroscopy and anomalous X-ray scattering data show that YfeA is polyspecific and can alter its substrate specificity. In minimal-media experiments, YfeA crystals grown after iron supplementation showed a threefold increase in iron fluorescence emission over the iron fluorescence emission from YfeA crystals grown from nutrient-rich conditions, and YfeA crystals grown after manganese supplementation during overexpression showed a fivefold increase in manganese fluorescence emission over the manganese fluorescence emission from YfeA crystals grown from nutrient-rich conditions. In all experiments, the YfeA crystals produced the strongest fluorescence emission from zinc and could not be manipulated otherwise. Additionally, this report documents the discovery of a novel surface metal-binding site that prefers to chelate zinc but can also bind manganese. Flexibility across YfeA crystal forms in three loops and a helix near the buried metal-binding site suggest that a structural rearrangement is required for metal loading and unloading.

  7. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    Science.gov (United States)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization

  8. High pressure and microwave based synthesis of transition metal pnictides

    Energy Technology Data Exchange (ETDEWEB)

    Pobel, Roman Rupert

    2016-04-11

    The goal of this thesis was to explore the possibilities of synthetic methods that are not very common in current transition metal pnictide research. The substitution of the Ca-site in CaFe{sub 2}As{sub 2} with rare earth elements such as Pr the has been reported to induce superconductivity. However, some inconsistencies in the data suggested a non-intrinsic origin of the observed diamagnetic signal. Furthermore a solubility limit of 13% was found when prepared in an electrical furnace thus leaving a huge part of the physical phase diagram inaccessible. A high pressure/high temperature synthesis was developed to allow access to the whole doping range and an in-depth characterization of this compound was carried out. During the experiments concerning the high pressure synthesis of Ca{sub 1-x}Pr{sub x}Fe{sub 2}As{sub 2} the new ternary iron arsenide CaFe{sub 5}As{sub 3} was identified and classified as a member of the Ca{sub n(n+1)/2}(Fe{sub 1-x}M{sub x}){sub (2+3n)}M'{sub n(n-1)/2}As{sub (n+1)(n+2)/2} (n = 1-3; M =Nb, Pd, Pt; M' = □, Pd, Pt) family. The complete solid solution Ca{sub 1-x}Pr{sub x}Fe{sub 5}As{sub 3} (O ≤ x ≤ 1) was prepared and physically characterized. Furthermore, several useful techniques were developed to aid in future high pressure based investigations of transition metal pnictides. The second part of this thesis concerns a completely different, but equally promising synthetic approach. Microwave based synthesis is a well-established technique in many solution based fields, such as organic, medicinal or nano chemistry. For solid state and materials research several parameters and particularities have to be considered. But when successful, it allows for the reduction of reaction time by several orders of magnitude. It has very rarely been applied in the preparation of pnictides and on1y once in the context of pnictide superconductor research. The possibilities of this method were explored and employed in the preparation of several

  9. Features of order-disorder phase transformation in nonstoichiometric transition metals carbides

    International Nuclear Information System (INIS)

    Emel'yanov, A.N.

    1996-01-01

    Measurements of temperature and electric conductivity of nonstoichiometric transition metals carbides TiC χ and NbC χ in the area of order-disorder phase transformation are carried out. There are certain peculiarities on the temperature and electric conductivity curves of the carbides, connected with the carbon sublattice disordering. On the basis of the anomalies observed on the curves of the temperature conductivity of nonstoichiometric carbides of transition metals above the temperature of the order-disorder transition the existence of the second structural transition is supposed

  10. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    KAUST Repository

    Grytsiuk, Sergii

    2016-05-23

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  11. Atomic volume and semiconducting properties in pnictides of non-magnetic transition metals

    International Nuclear Information System (INIS)

    Chapnik, I.M.

    1978-01-01

    Deviations of atomic volume from additivity are determined for binary compounds of pnictide elements with non-magnetic transition metals. It is shown that metallic properties (in contrast to semiconducting properties) are associated with intensive contraction. It is supposed that the wide range of contraction observed, the overlapping of the metallic and semiconducting ranges of contraction, and the usual absence of one smooth curve for the composition dependence of atomic volume in pnictides of transition metals, are associated with the change of valency state of the pnictide atoms in different compounds. (author)

  12. Phase coexistence in the metal-insulator transition of a VO2 thin film

    International Nuclear Information System (INIS)

    Chang, Y.J.; Koo, C.H.; Yang, J.S.; Kim, Y.S.; Kim, D.H.; Lee, J.S.; Noh, T.W.; Kim, Hyun-Tak; Chae, B.G.

    2005-01-01

    Vanadium dioxide (VO 2 ) shows a metal-insulator transition (MIT) near room temperature, accompanied by an abrupt resistivity change. Since the MIT of VO 2 is known to be a first order phase transition, it is valuable to check metallic and insulating phase segregation during the MIT process. We deposited (100)-oriented epitaxial VO 2 thin films on R-cut sapphire substrates. From the scanning tunneling spectroscopy (STS) spectra, we could distinguish metallic and insulating regions by probing the band gap. Optical spectroscopic analysis also supported the view that the MIT in VO 2 occurs through metal and insulator phase coexistence

  13. Cucumber Metallothionein-Like 2 (CsMTL2 Exhibits Metal-Binding Properties

    Directory of Open Access Journals (Sweden)

    Yu Pan

    2016-11-01

    Full Text Available We identified a novel member of the metallothionein (MT family, Cucumis sativus metallothionein-like 2 (CsMTL2, by screening a young cucumber fruit complementary DNA (cDNA library. The CsMTL2 encodes a putative 77-amino acid Class II MT protein that contains two cysteine (Cys-rich domains separated by a Cys-free spacer region. We found that CsMTL2 expression was regulated by metal stress and was specifically induced by Cd2+ treatment. We investigated the metal-binding characteristics of CsMTL2 and its possible role in the homeostasis and/or detoxification of metals by heterologous overexpression in Escherichia coli cells. Furthermore, we produced a deletion mutant form of the protein, CsMTL2m, that contained the two Cys-rich clusters but lacked the spacer region, in E. coli. We compared the metal-binding properties of CsMTL2 with those of CsMTL2m, the β domain of human metallothionein-like protein 1 (HsMTXb, and phytochelatin-like (PCL heterologously expressed in E. coli using metal-binding assays. We found that E. coli cells expressing CsMTL2 accumulated the highest levels of Zn2+ and Cd2+ of the four transformed cell types, with levels being significantly higher than those of control cells containing empty vector. E. coli cells expressing CsMTL2 had a higher tolerance for cadmium than for zinc ions. These findings show that CsMTL2 improves metal tolerance when heterologously expressed in E. coli. Future studies should examine whether CsMTL2 improves metal tolerance in planta.

  14. Formation of bulk metallic glasses in the Fe-M-Y-B (M = transition metal) system

    Energy Technology Data Exchange (ETDEWEB)

    Huang, X.M. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chang, C.T. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Chang, Z.Y.; Wang, X.D.; Cao, Q.P. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Shen, B.L.; Inoue, A. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Jiang, J.Z. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)], E-mail: jiangjz@zju.edu.cn

    2008-07-28

    In this work, quaternary Fe{sub 72-x}M{sub x}Y{sub 6}B{sub 22} (M = Ni, Co and Mo) bulk metallic glasses (BMGs) have been developed. It is found that a fully amorphous Fe{sub 68}Mo{sub 4}Y{sub 6}B{sub 22} cylindrical rod with 6.5 mm in diameter can be prepared by copper mold injection. These alloys have a high glass transition temperature of about 900 K with high fracture strengths up to about 3 GPa although they are still brittle. Magnetic measurements reveal that they are ferromagnetic at ambient temperature with low coercive force of about 2 A/m, saturation magnetization of about 0.7 T and effective permeability of about 7000 at 100 kHz. The newly developed Fe-based quaternary alloys exhibit excellent combination properties: superior glass forming ability (GFA), high glass transition temperature, and soft magnetic properties, which could have potential applications in electronic industries. Furthermore, the effect of Mo addition on GFA in the Fe-Y-B BMG system has been discussed compared with those of Ni and Co additions.

  15. A New Metal Binding Domain Involved in Cadmium, Cobalt and Zinc Transport

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Aaron T. [Northwestern Univ., Evanston, IL (United States); Barupala, Dulmini [Wayne State Univ., Detroit, MI (United States); Stemmler, Timothy L. [Wayne State Univ., Detroit, MI (United States); Rosenzweig, Amy C. [Northwestern Univ., Evanston, IL (United States)

    2015-07-20

    In the P1B-ATPases, which couple cation transport across membranes to ATP hydrolysis, are central to metal homeostasis in all organisms. An important feature of P1B-ATPases is the presence of soluble metal binding domains (MBDs) that regulate transport activity. Only one type of MBD has been characterized extensively, but bioinformatics analyses indicate that a diversity of MBDs may exist in nature. Here we report the biochemical, structural and functional characterization of a new MBD from the Cupriavidus metallidurans P1B-4-ATPase CzcP (CzcP MBD). The CzcP MBD binds two Cd2+, Co2+ or Zn2+ ions in distinct and unique sites and adopts an unexpected fold consisting of two fused ferredoxin-like domains. Both in vitro and in vivo activity assays using full-length CzcP, truncated CzcP and several variants indicate a regulatory role for the MBD and distinct functions for the two metal binding sites. Moreover, these findings elucidate a previously unknown MBD and suggest new regulatory mechanisms for metal transport by P1B-ATPases.

  16. Binding of Industrial Deposits of Heavy Metals and Arsenic in the Soil by 3-Aminopropyltrimethoxysilane

    Directory of Open Access Journals (Sweden)

    Grzesiak Piotr

    2014-06-01

    Full Text Available The results of the research studies concerning binding of heavy metals and arsenic (HM+As, occurring in soils affected by emissions from Głogów Copper Smelter and Refinery, by silane nanomaterial have been described. The content of heavy metals and arsenic was determined by AAS and the effectiveness of heavy metals and arsenic binding by 3-Aminopropyltrimethoxysilane was examined. The total leaching level of impurities in those fractions was 73.26% Cu, 74.7% – Pb, 79.5% Zn, 65.81% – Cd and 55.55% As. The studies demonstrated that the total binding of heavy metals and arsenic with nanomaterial in all fractions was about as follows: 20.5% Cu, 9.5% Pb, 7.1% Zn, 25.3% Cd and 10.89% As. The results presented how the safety of food can be cultivated around industrial area, as the currently used soil stabilization technique of HM by soil pH does not guarantee their stable blocking in a sorptive complex.

  17. The control of magnetism near metal-to-insulator transitions of VO2 nano-belts

    CSIR Research Space (South Africa)

    Nkosi, SS

    2016-12-01

    Full Text Available The magnetic properties of paramagnetic/weakly ferromagnetic films are strongly affected by the proximity to materials that undergo a metal to insulator phase transition. Here, we show that under the deposition conditions associated with structural...

  18. Semiconductor-metal transition induced by giant Stark effect in blue phosphorene nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Peng-Yu; Chen, Shi-Zhang; Zhou, Wu-Xing; Chen, Ke-Qiu, E-mail: keqiuchen@hnu.edu.cn

    2017-06-28

    The electronic structures and transport properties in monolayer blue phosphorene nanoribbons (BPNRs) with transverse electric field have been studied by using density functional theory and nonequilibrium Green's functions method. The results show that the band gaps of BPNRs with both armchair and zigzag edges are linearly decreased with the increasing of the strength of transverse electric field. A semiconductor-metal transition occurs when the electric field strength reaches to 5 V/nm. The Stark coefficient presents a linear dependency on BPNRs widths, and the slopes of both zBPNRs and aBPNRs are 0.41 and 0.54, respectively, which shows a giant Stark effect occurs. Our studies show that the semiconductor-metal transition originates from the giant Stark effect. - Highlights: • The electronic transport in blue phosphorene nanoribbons. • Semiconductor-metal transition can be observed. • The semiconductor-metal transition originates from the giant Stark effect.

  19. Excited State Dynamics and Semiconductor-to-Metallic Phase Transition of VO2 Thin Film

    National Research Council Canada - National Science Library

    Liu, Huimin

    2004-01-01

    .... Vanadium dioxide shows an ultrafast, passive phase transition (PT) from a monoclinic semiconductor phase to a metallic tetragonal rutile structure when the sample temperature is above 68 degrees C...

  20. Insulator-to-metal transition in vanadium sesquioxide: does the Mott criterion work in this case?

    Science.gov (United States)

    Pergament, Alexander; Stefanovich, Genrikh

    2012-03-01

    It is shown that the Mott criterion expressed by the simple relation a B(n c)1/3 ≈ 0.25 turns out to be quite successful in describing metal-insulator phase transitions not only in heavily doped semiconductors, but also in transition metal oxides such as VO2 and V2O3. It is found in this article that, in the case of a high-temperature transition 'paramagnetic insulator - paramagnetic metal' in vanadium sesquioxide, a B(n c)1/3 = 0.254. Difficulties connected with the analogous description of a low-temperature transition ('paramagnetic metal - antiferromagnetic insulator') in V2O3 are discussed.

  1. Multi-body forces and the energetics of transition metals, alloys, and semiconductors

    International Nuclear Information System (INIS)

    Carlsson, A.E.

    1992-01-01

    Progress over the past year is divided into 3 areas: potential-energy functions for transition-metal aluminides; electronic structure and energetics of complex structures and quasicrystals; and ceramic materials (PdO, PtO)

  2. Single crystal particles of a mesoporous mixed transition metal oxide with a wormhole structure.

    Science.gov (United States)

    Lee, B; Lu, D; Kondo, J N; Domen, K

    2001-10-21

    A new type of mesoporous mixed transition metal oxide of Nb and Ta (NbTa-TIT-1) has been prepared through a two-step calcination, which consists of single crystal particles with wormhole mesoporous structure.

  3. Transition-Metal-Free Multicomponent Benzannulation Reactions for the Construction of Polysubstituted Benzene Derivatives.

    Science.gov (United States)

    Shu, Wen-Ming; Zheng, Kai-Lu; Ma, Jun-Rui; Wu, An-Xin

    2015-11-06

    A transition-metal-free multicomponent benzannulation reaction was developed from readily available ketones, nitro-olefins, and diester acetylenedicarboxylate. This approach provides a straightforward and efficient way to construct polysubstituted benzene derivatives under mild conditions in high yields.

  4. Hydrogen molecule binding to unsaturated metal sites in metal-organic frameworks studied by neutron powder diffraction and inelastic neutron scattering

    Science.gov (United States)

    Liu, Yun; Brown, Craig; Neumann, Dan; Dinca, Mircea; Long, Jeffrey; Peterson, Vanessa; Kepert, Cameron

    2007-03-01

    Metal organic framework (MOF) materials have shown considerable potential for hydrogen storage arising from very large surface areas. However, the low binding energy of hydrogen molecules limits its storage capability to very low temperatures (industrial applications. Using neutron powder diffraction (NPD), we have characterized the hydrogen adsorption sites in a selected series of MOF materials with exposed unsaturated metal ions. Direct binding between the unsaturated metal ions and hydrogen molecules is observed and responsible for the enhanced initial hydrogen adsorption enthalpy. The different metals centers in these MOFs show different binding strength and interaction distances between the hydrogen molecule and metal ions. The organic linker also affects the overall H2 binding strength. Inelastic neutron scattering spectra of H2 in these MOFs are also discussed.

  5. Pressure induced phase transitions in transition metal nitrides: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Anurag; Chauhan, Mamta [Advanced Material Research Lab, Indian Institute of Information Technology and Management, Gwalior 474010 (India); Singh, R.K. [Department of Physics, ITM University, Gurgaon 122017 (India)

    2011-12-15

    We have analyzed the stability of transition metal nitrides (TMNs) XN (X = Ti, Zr, Hf, V, Nb, Ta) in their original rocksalt (B1) and hypothetical CsCl (B2) type phases under high compression. The ground state total energy calculation approach of the system has been used through the generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) type parameterization as exchange correlation functional. In the whole series of nitrides taken into consideration, tantalum nitride is found to be the most stable. We have observed that under compression the original B1-type phase of these nitrides transforms to a B2-type phase. We have also discussed the computation of ground state properties, like the lattice constant (a), bulk modulus (B{sub 0}) and first order pressure derivative of the bulk modulus (B'{sub 0}) of the TMNs and their host elements. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Magnetic phase transition induced by electrostatic gating in two-dimensional square metal-organic frameworks

    Science.gov (United States)

    Wang, Yun-Peng; Li, Xiang-Guo; Liu, Shuang-Long; Fry, James N.; Cheng, Hai-Ping

    2018-03-01

    We investigate theoretically magnetism and magnetic phase transitions induced by electrostatic gating of two-dimensional square metal-organic framework compounds. We find that electrostatic gating can induce phase transitions between homogeneous ferromagnetic and various spin-textured antiferromagnetic states. Electronic structure and Wannier function analysis can reveal hybridizations between transition-metal d orbitals and conjugated π orbitals in the organic framework. Mn-containing compounds exhibit a strong d -π hybridization that leads to partially occupied spin-minority bands, in contrast to compounds containing transition-metal ions other than Mn, for which electronic structure around the Fermi energy is only slightly spin split due to weak d -π hybridization and the magnetic interaction is of the Ruderman-Kittel-Kasuya-Yosida type. We use a ferromagnetic Kondo lattice model to understand the phase transition in Mn-containing compounds in terms of carrier density and illuminate the complexity and the potential to control two-dimensional magnetization.

  7. Aging of iron (hydr)oxides by heat treatment and effects on heavy metal binding

    DEFF Research Database (Denmark)

    Sørensen, Mette Abildgaard; Starckpoole, M. M.; Frenkel, A. I.

    2000-01-01

    Amorphous iron (hydr)oxides are used to remove heavy metals from wastewater and in the treatment of air pollution control residues generated in waste incineration. In this study, iron oxides containing heavy metals (e.g., Pb, Hg, Cr, and Cd) were treated at 50, 600, and 900 °C to simulate...... oxides were transformed to hematite, which had a greater thermodynamic stability but less surface area than the initial products. Heat treatment also caused some volatilization of heavy metals (most notably, Hg). Leaching with water at pH 9 (L/S 10, 24 h) and weak acid extraction showed that heat...... of iron oxides may be advantageous to improve the thermodynamic stability of the product but that thermal treatment at both 600 and 900 °C significantly reduced the binding capacity for heavy metals....

  8. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

    2011-01-01

    We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

  9. Relationship between thermal expansion coefficient and glass transition temperature in metallic glasses

    International Nuclear Information System (INIS)

    Kato, H.; Chen, H.-S.; Inoue, A.

    2008-01-01

    The thermal expansion coefficients of 13 metallic glasses were measured using a thermo-mechanical analyser. A unique correlation was found between the linear thermal expansion coefficient and the glass transition temperature-their product is nearly constant ∼8.24 x 10 -3 . If one assumes the Debye expression for thermal activation, the total linear thermal expansion up to glass transition temperature (T g ) is reduced to 6 x 10 -3 , nearly 25% of that at the fusion of pure metals

  10. The investigation of germanium based compounds, transition metals and isoflavones within foods

    OpenAIRE

    Dowling, Stephen

    2010-01-01

    The body of work here looks not only at how germanium was present in foods but also the ascertainment of chelation behaviour of germanium compounds and also transition metals with flavonoids. The chelation of germanium with flavonoids, or particularly isoflavones, is a completely novel area and gave some interesting results for chelation with isoflavones with transition metals, an area of research that was completely underexploited until recently. (refer to appendix 1) The Fourier Tran...

  11. Substitution effect on metal-insulator transition of K2V8O16

    International Nuclear Information System (INIS)

    Isobe, Masahiko; Koishi, Shigenori; Yamazaki, Satoshi; Yamaura, Jun-ichi; Gotou, Hirotada; Yagi, Takehiko; Ueda, Yutaka

    2009-01-01

    The effect of the substitution of various ions on the metal-insulator (MI) transition at 170 K in K 2 V 8 O 16 has been investigated. Both Rb and Ti form complete solid solution systems: K 2-x Rb x V 8 O 16 and K 2 V 8-y Ti y O 16 , respectively. The substitution of Rb for K or of Ti for V splits the transition into two transitions: the high-temperature transition is a first-order MI transition from a tetragonal structure to a tetragonal structure, and the low-temperature transition is a second-order transition to a monoclinic structure. In K 2-x Rb x V 8 O 16 , the former terminates to an MI transition at around 220 K in Rb 2 V 8 O 16 , while the latter disappears at x > 0.6. In K 2 V 8-y Ti y O 16 , both transitions disappear at y > 0.5. The substitution of Cr for V also results in a similar splitting of the transition and the rapid disappearance of both transitions. The substitution of Na or Ba for K suppresses the MI transition without any splitting of the transition, although the solubility of both ions is limited. These substitution effects reveal that the MI transition of K 2 V 8 O 16 consists of two parts: a first-order MI transition and a parasitic second-order structural transition; the substitution of some ions causes a clear splitting of these transitions, probably due to the difference between the chemical pressure effects on the two transitions. The first-order MI transition is very sensitive to charge randomness, suggesting the charge ordering nature of the MI transition, while the second-order structural transition is very sensitive to both charge and structural randomnesses. (author)

  12. Transition metal rates in latosol twice treated with sewage sludge

    Directory of Open Access Journals (Sweden)

    Ana Tereza Jordão Pigozzo

    2006-05-01

    Full Text Available Agricultural recycling of sewage sludge has been a source of accumulation of heavy metals in the environment which may reach toxic levels and cause serious damage to the biota. Field experiments were undertaken for two agricultural years (2000 and 2002 and effects of two sewage sludge applications were evaluated through the extraction of (essential and non-essential transition metals by diethylenetriaminepentaacetic acid (DTPA extractor in a medium texture dystrophic Dark Red Latosol. Cd, Ni, Co, Pb and Cr were not detected. Application of sewage sludge initially caused a slight pH rise in the soil; later pH lowered and kept itself close to the starting level. It could be concluded that through consecutive sludge application, extractable rates of Fe and Mn in soil samples gradually increased during the two agricultural years in proportion to sewage sludge doses and sampling period. In fact, they were higher than rates of control. Due to low concentrations of soil samples, extractor had a restricted capacity for evaluation of its phytoavailability.A reciclagem agrícola do lodo de esgoto tem provocado o acúmulo de metais pesados no solo e na água, podendo atingir níveis tóxicos e causar danos às plantas cultivadas, aos animais e ao homem, por meio da cadeia trófica. Neste intuito foi desenvolvido o presente experimento, em condições de campo, entre 2000 e 2002, onde foram avaliados os efeitos da aplicação de lodo de esgoto por dois anos, sobre a extração de metais de transição (essenciais e não pelo extrator DTPA em um Latossolo Vermelho distrófico (LVd de textura média. As concentrações dos elementos metálicos: Mn, Fe, Cd, Ni, Co, Pb e Cr não foram detectados pelo método da absorção atômica na solução obtida com o extrator DTPA. A aplicação de lodo de esgoto causou inicialmente pequena elevação no pH do solo, posteriormente a diminuição do mesmo, e manteve-se próximo ao original. Foi possível concluir que, com

  13. Theory of magnetic transition metal nanoclusters on surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lounis, S.

    2007-04-17

    This thesis is motivated by the quest for the understanding and the exploration of complex magnetism provided by atomic scale magnetic clusters deposited on surfaces or embedded in the bulk. Use is made of the density functional theory (DFT). Acting within this framework, we have developed and implemented the treatment of non-collinear magnetism into the Juelich version of the full-potential Korringa-Kohn-Rostoker Green Function (KKR-GF) method. Firstly, the method was applied to 3d transition-metal clusters on different ferromagnetic surfaces. Different types of magnetic clusters where selected. In order to investigate magnetic frustration due to competing interactions within the ad-cluster we considered a (001) oriented surface of fcc metals, a topology which usually does not lead to non-collinear magnetism. We tuned the strength of the magnetic coupling between the ad-clusters and the ferromagnetic surface by varying the substrate from the case of Ni(001) with a rather weak hybridization of the Ni d-states with the adatom d-states to the case of Fe{sub 3ML}/Cu(001) with a much stronger hybridization due to the larger extend of the Fe wavefunctions. On Ni(001), the interaction between the Cr- as well as the Mn-dimer adatoms is of antiferromagnetic nature, which is in competition with the interaction with the substrate atoms. After performing total energy calculations we find that for Cr-dimer the ground state is collinear whereas the Mn-dimer prefers the non-collinear configuration as ground state. Bigger clusters are found to be magnetically collinear. These calculations were extended to 3d multimers on Fe{sub 3ML}/Cu(001). All neighboring Cr(Mn) moments in the compact tetramer are antiferromagnetically aligned in-plane, with the directions slightly tilted towards (outwards from) the substrate to gain some exchange interaction energy. The second type of frustration was investigated employing a Ni(111) surface, a surface with a triangular lattice of atoms, were

  14. Modeling metal binding to soils: the role of natural organic matter.

    Science.gov (United States)

    Gustafsson, Jon Petter; Pechová, Pavlina; Berggren, Dan

    2003-06-15

    The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.

  15. Surface analysis of transition metal oxalates: Damage aspects

    Energy Technology Data Exchange (ETDEWEB)

    Chenakin, S.P., E-mail: chenakin@imp.kiev.ua [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Institute of Metal Physics, Nat. Acad. Sci. of Ukraine, Akad. Vernadsky Blvd. 36, 03680 Kiev (Ukraine); Szukiewicz, R. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Barbosa, R.; Kruse, N. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Voiland School of Chemical Engineering and Bioengineering, Washington State University, 155 Wegner Hall, Pullman, WA 99164-6515 (United States)

    2016-05-15

    Highlights: • Gas evolution from the Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation is studied. • A comparative study of the damage caused by X-rays in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} is carried out. • Effect of Ar{sup +} bombardment on the structure and composition of CoC{sub 2}O{sub 4} is studied. - Abstract: The behavior of transition metal oxalates in vacuum, under X-ray irradiation and low-energy Ar{sup +} ion bombardment was studied. A comparative mass-spectrometric analysis was carried out of gas evolution from the surface of Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation. The rates of H{sub 2}O and CO{sub 2} liberation from the oxalates were found to be in an inverse correlation with the temperatures of dehydration and decomposition, respectively. X-ray photoelectron spectroscopy (XPS) was employed to study the X-ray induced damage in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} by measuring the various XP spectral characteristics and surface composition of the oxalates as a function of time of exposure to X-rays. It was shown that Cu oxalate underwent a significantly faster degradation than Ni oxalate and demonstrated a high degree of X-ray induced reduction from the Cu{sup 2+} to the Cu{sup 1+} chemical state. 500 eV Ar{sup +} sputter cleaning of CoC{sub 2}O{sub 4} for 10 min was found to cause a strong transformation of the oxalate structure which manifested itself in an appreciable alteration of the XP core-level and valence band spectra. The analysis of changes in stoichiometry and comparison of XP spectra of bombarded oxalate with respective spectra of a reference carbonate CoCO{sub 3} implied that the bombardment-induced decomposition of CoC{sub 2}O{sub 4} gave rise to the formation of CoO-like and disordered CoCO{sub 3}-like phases.

  16. Subnanometer to nanometer transition metal CO oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

    2017-12-26

    The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

  17. CO adsorption on transition metal clusters: Trends from density functional theory

    Science.gov (United States)

    Zeinalipour-Yazdi, Constantinos D.; Cooksy, Andrew L.; Efstathiou, Angelos M.

    2008-05-01

    This work reports for the first time the trends for carbon monoxide (CO) chemisorption on transition metal clusters present in supported metal catalysts. In particular, the energetic, structural and infrared adsorption characteristics of linearly (atop) CO adsorbed on transition metal nano-clusters of less than 10 Å in size were explored. Spin-unrestricted density functional theory (DFT) calculations were employed to explore the trends of CO adsorption energy (AM-CO) and C-O vibrational frequency (νCO) for clusters composed of Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt and Au. The effects of the transition metal electronic structure onto the adsorption energy of CO and the vibrational stretching frequency of C-O, and how these chemical parameters can be correlated to the catalytic activity of transition supported metal catalysts that involve the adsorption, surface diffusion, and C-O bond dissociation elementary steps in heterogeneous catalytic surface reactions, are discussed. Our findings show that an increase of the electronic d-shell occupancy and the principal quantum number (n) in transition metals causes an increase in the vibrational stretching frequency of the C-O bond. This trend is inconsistent with the classical Blyholder model for the metal-carbonyl bond.

  18. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

    Energy Technology Data Exchange (ETDEWEB)

    Kunaseth, Manaschai, E-mail: manaschai@nanotec.or.th [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Poldorn, Preeyaporn [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Kungwan, Nawee [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Inntam, Chan [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Jungsuttiwong, Siriporn, E-mail: siriporn.j@ubu.ac.th [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand)

    2017-02-28

    Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp{sup 2}-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt{sub 4} (−2.11 eV) > Pd{sub 4} (−2.05 eV) > Ag{sub 4} (−1.53 eV) > Au{sub 4} (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp{sup 2}-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon

  19. Pressure-driven metal-insulator transition in hematite from dynamical mean-field theory

    Czech Academy of Sciences Publication Activity Database

    Kuneš, Jan; Korotin, D. M.; Korotin, M. A.; Anisimov, V.I.; Werner, P.

    2009-01-01

    Roč. 102, č. 14 (2009), 146402/1-146402/4 ISSN 0031-9007 Institutional research plan: CEZ:AV0Z10100521 Keywords : metal-insulator transitions and other electronic transitions * strongly correlated electron systems * heavy fermions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.328, year: 2009

  20. Planar heterostructures of single-layer transition metal dichalcogenides: Composite structures, Schottky junctions, tunneling barriers, and half metals

    Science.gov (United States)

    Aras, Mehmet; Kılıç, ćetin; Ciraci, S.

    2017-02-01

    Planar composite structures formed from the stripes of transition metal dichalcogenides joined commensurately along their zigzag or armchair edges can attain different states in a two-dimensional (2D), single-layer, such as a half metal, 2D or one-dimensional (1D) nonmagnetic metal and semiconductor. Widening of stripes induces metal-insulator transition through the confinements of electronic states to adjacent stripes, that results in the metal-semiconductor junction with a well-defined band lineup. Linear bending of the band edges of the semiconductor to form a Schottky barrier at the boundary between the metal and semiconductor is revealed. Unexpectedly, strictly 1D metallic states develop in a 2D system along the boundaries between stripes, which pins the Fermi level. Through the δ doping of a narrow metallic stripe one attains a nanowire in the 2D semiconducting sheet or narrow band semiconductor. A diverse combination of constituent stripes in either periodically repeating or finite-size heterostructures can acquire critical fundamental features and offer device capacities, such as Schottky junctions, nanocapacitors, resonant tunneling double barriers, and spin valves. These predictions are obtained from first-principles calculations performed in the framework of density functional theory.

  1. Towards the role of metal ions in the structural variability of proteins: CdII speciation of a metal ion binding loop motif

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szunyogh, Dániel; Gyurcsik, Béla

    2011-01-01

    A de novo designed dodecapeptide (HS), inspired by the metal binding loops of metal-responsive transcriptional activators, was synthesized. The aim was to create a model system for structurally promiscuous and intrinsically unstructured proteins, and explore the effect of metal ions on their stru...... the peptide is exchanging between a number of structures also in its metal ion bound state(s), as indicated by NMR and PAC data. © 2011 The Royal Society of Chemistry....

  2. Substituent Effects on the Coordination Chemistry of Metal-Binding Pharmacophores

    Energy Technology Data Exchange (ETDEWEB)

    Craig, Whitney R. [Department; Baker, Tessa W. [Department; Marts, Amy R. [Department; DeGenova, Daniel T. [Department; Martin, David P. [Department; Reed, Garrett C. [Department; McCarrick, Robert M. [Department; Crowder, Michael W. [Department; Cohen, Seth M. [Department; Tierney, David L. [Department

    2017-09-12

    A combination of XAS, UV–vis, NMR, and EPR was used to examine the binding of a series of α-hydroxythiones to CoCA. All three appear to bind preferentially in their neutral, protonated forms. Two of the three clearly bind in a monodentate fashion, through the thione sulfur alone. Thiomaltol (TM) appears to show some orientational preference, on the basis of the NMR, while it appears that thiopyromeconic acid (TPMA) retains rotational freedom. In contrast, allothiomaltol (ATM), after initially binding in its neutral form, presumably through the thione sulfur, forms a final complex that is five-coordinate via bidentate coordination of ATM. On the basis of optical titrations, we speculate that this may be due to the lower initial pKa of ATM (8.3) relative to those of TM (9.0) and TPMA (9.5). Binding through the thione is shown to reduce the hydroxyl pKa by ~0.7 pH unit on metal binding, bringing only ATM’s pKa close to the pH of the experiment, facilitating deprotonation and subsequent coordination of the hydroxyl. The data predict the presence of a solvent-exchangeable proton on TM and TPMA, and Q-band 2-pulse ESEEM experiments on CoCA + TM suggest that the proton is present. ESE-detected EPR also showed a surprising frequency dependence, giving only a subset of the expected resonances at X-band.

  3. The role of METAMORPhos ligands in transition metal complex formation and catalysis

    NARCIS (Netherlands)

    Oldenhof, S.

    2015-01-01

    Chemists are challenged to develop homogeneous transition metal catalysts that are faster, more selective, cheaper, safer, robust and environmentally benign. This is generally approached by varying the ligands that are coordinated to the applied metal to steer its properties. Traditionally, ligands

  4. Reactivity of Dinitrogen Bound to Mid- and Late-Transition-Metal Centers

    NARCIS (Netherlands)

    Khoenkhoen, N.; de Bruin, B.; Reek, J.N.H.; Dzik, W.I.

    2015-01-01

    This review presents a comprehensive overview of the reactions of N-2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N-2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine,

  5. Stability of Transition-metal Carbides in Liquid Phase Reactions Relevant for Biomass-Based Conversion

    NARCIS (Netherlands)

    Souza Macêdo, L.; Stellwagen, D.R.; Teixeira da Silva, V.; Bitter, J.H.

    2015-01-01

    Transition-metal carbides have been employed for biobased conversions aiming to replace the rare noble metals. However, when reactions are in liquid phase, many authors have observed catalyst deactivation. The main routes of deactivation in liquid phase biobased conversions are coke deposition,

  6. Support effects and catalytic trends for water gas shift activity of transition metals

    DEFF Research Database (Denmark)

    Boisen, Astrid; Janssens, T.V.W.; Schumacher, Nana Maria Pii

    2010-01-01

    Water gas shift activity measurements for 12 transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au) supported on inert MgAl2O4 and Ce0.75Zr0.25O2 are presented, to elucidate the influence of the active metal and the support. The activity is related to the adsorption energy of molecular...

  7. Structures of the Dehydrogenation Products of Methane Activation by 5d Transition Metal Cations

    NARCIS (Netherlands)

    Lapoutre, V.J.F.; Redlich, B.; Meer, A.F.G.; Oomens, J.; Bakker, J.M.; Sweeney, A.; Mookherjee, A.; Armentrout, P.B.

    2013-01-01

    The activation of methane by gas-phase transition metal cations (M+) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H](+) and H-2. However, the structure of the

  8. Structures of the dehydrogenation products of methane activation by 5d transition metal cations

    NARCIS (Netherlands)

    Lapoutre, V. J. F.; Redlich, B.; van der Meer, A. F. G.; Oomens, J.; Bakker, J. M.; Sweeney, A.; Mookherjee, A.; Armentrout, P. B.

    2013-01-01

    The activation of methane by gas-phase transition metal cations (M +) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H]+ and H2. However, the structure of the dehydrogenation

  9. Production by metallothermics of pure alloys of rare earths and transition metals

    International Nuclear Information System (INIS)

    Jourdan, A.

    1988-01-01

    Industrial process of production of high purity master alloys ingots by the thermite process from a rare earth compound which is reduced by a reducing agent like alkaline or alkaline earth metals. The process is characterized by introduction of the transition metal into the initial reaction mixture, at least in part, as a compound than can be reduced by the reducing agent [fr

  10. Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

    NARCIS (Netherlands)

    Armitt, D.J.; Bruce, M.I.; Gaudio, M.; Zaitseva, N.N.; Skelton, B.W.; White, A.H.; Le Guennic, B.; Halet, J.-F.; Fox, M.A.; Roberts, R.L.; Hartl, F.; Low, P.J.

    2008-01-01

    Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of

  11. Binding of monovalent alkali metal ions with negatively charged phospholipid membranes.

    Science.gov (United States)

    Maity, Pabitra; Saha, Baishakhi; Kumar, Gopinatha Suresh; Karmakar, Sanat

    2016-04-01

    We have systematically investigated the effect of various alkali metal ions with negatively charged phospholipid membranes. Size distributions of large unilamellar vesicles have been confirmed using dynamic light scattering. Zeta potential and effective charges per vesicle in the presence of various alkali metal ions have been estimated from the measured electrophoretic mobility. We have determined the intrinsic binding constant from the zeta potential using electrostatic double layer theory. The reasonable and consistent value of the intrinsic binding constant of Na(+), found at moderate NaCl concentration (10-100 mM), indicates that the Gouy-Chapman theory cannot be applied for very high (> 100mM) and very low (concentrations. The isothermal titration calorimetry study has revealed that the net binding heat of interaction of the negatively charged vesicles with monovalent alkali metal ions is small and comparable to those obtained from neutral phosphatidylcholine vesicles. The overall endothermic response of binding heat suggests that interaction is primarily entropy driven. The entropy gain might arise due to the release of water molecules from the hydration layer vicinity of the membranes. Therefore, the partition model which does not include the electrostatic contribution suffices to describe the interaction. The binding constant of Na(+) (2.4 ± 0.1 M(-1)), obtained from the ITC, is in agreement with that estimated from the zeta potential (-2.0 M(-1)) at moderate salt concentrations. Our results suggest that hydration dynamics may play a vital role in the membrane solution interface which strongly affects the ion-membrane interaction. Copyright © 2016 Elsevier B.V. All rights reserved

  12. Characterization of Two Metal Binding Lipoproteins as Vaccine Candidates for Enterococcal Infections.

    Directory of Open Access Journals (Sweden)

    Felipe Romero-Saavedra

    Full Text Available Enterococcus faecium and faecalis are Gram-positive opportunistic pathogens that have become leading causes of nosocomial infections over the last decades. Especially multidrug resistant enterococci have become a challenging clinical problem worldwide. Therefore, new treatment options are needed and the identification of alternative targets for vaccine development has emerged as a feasible alternative to fight the infections caused by these pathogens.We extrapolate the transcriptomic data from a mice peritonitis infection model in E. faecalis to identify putative up-regulated surface proteins under infection conditions in E. faecium. After the bionformatic analyses two metal binding lipoproteins were identified to have a high homology (>72% between the two species, the manganese ABC transporter substrate-binding lipoprotein (PsaAfm, and the zinc ABC transporter substrate-binding lipoprotein (AdcAfm. These candidate lipoproteins were overexpressed in Escherichia coli and purified. The recombinant proteins were used to produce rabbit polyclonal antibodies that were able to induce specific opsonic antibodies that mediated killing of the homologous strain E. faecium E155 as well as clinical strains E. faecium E1162, Enterococcus faecalis 12030, type 2 and type 5. Mice were passively immunized with the antibodies raised against recombinant lipoproteins, showing significant reduction of colony counts in mice livers after the bacterial challenge and demonstrating the efficacy of these metal binding lipoproteins as promising vaccine candidates to treat infections caused by these enterococcal pathogens.Overall, our results demonstrate that these two metal binding lipoproteins elicited specific, opsonic and protective antibodies, with an extensive cross-reactivity and serotype-independent coverage among these two important nocosomial pathogens. Pointing these two protein antigens as promising immunogens, that can be used as single components or as carrier

  13. Electrochemical Characterization of Metal-Binding Properties of Metallothioneins Isolated from M. galloprovincialis

    OpenAIRE

    Raspor, Biserka; Pavičić, Jasenka

    1997-01-01

    Amperometric titrations of defined metallothionein concentrations with the standard CdCl2 solution have been performed in seawater samples at pH > 8, in order to define the metal-binding properties of purified mussel metallothionein component. The concentration of the formed Cd-thionein complex has been assessed in the indirect and direct mode. The results on the available ligand concentration CL for complexing Cd2+ ions and the apparent stability constant K, determined by two procedures are ...

  14. Characteristics of the brown hagfish Paramyxine atami transthyretin: Metal ion-dependent thyroid hormone binding.

    Science.gov (United States)

    Suzuki, Shunsuke; Kasai, Kentaro; Nishiyama, Norihito; Ishihara, Akinori; Yamauchi, Kiyoshi

    2017-08-01

    Transthyretin (TTR) is a vertebrate-specific protein involved in thyroid hormone distribution in plasma, and its gene is thought to have emerged by gene duplication from the gene for the ancient TTR-related protein, 5-hydroxyisourate hydrolase, at some early stage of chordate evolution. We investigated the molecular and hormone-binding properties of the brown hagfish Paramyxine atami TTR. The amino acid sequence deduced from the cloned hagfish TTR cDNA shared 33-50% identities with those of other vertebrate TTRs but less than 24% identities with those of vertebrate and deuterostome invertebrate 5-hydroxyisourate hydrolases. Hagfish TTR, as well as lamprey and little skate TTRs, had an N-terminal histidine-rich segment, allowing purification by metal-affinity chromatography. The affinity of hagfish TTR for 3,3',5-triiodo-L-thyronine (T3) was 190 times higher than that for L-thyroxine, with a dissociation constant of 1.5-3.9nM at 4°C. The high-affinity binding sites were strongly sensitive to metal ions. Zn 2+ and Cu 2+ decreased the dissociation constant to one-order of magnitude, whereas a chelator, o-phenanthroline, increased it four times. The number of metal ions (mainly Zn 2+ and Cu 2+ ) was approximately 12/TTR (mol/mol). TTR was also a major T3-binding protein in adult hagfish sera and its serum concentration was approximately 8μM. These results suggest that metal ions and the acquisition of N-terminal histidine-rich segment may cooperatively contribute to the evolution toward an ancient TTR with high T3 binding activity from either 5-hydroxyisourate hydrolase after gene duplication. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Size Controlled Synthesis of Transition Metal Nanoparticles for Catalytic Applications

    KAUST Repository

    Esparza, Angel

    2011-07-07

    Catalysis offers cleaner and more efficient chemical reactions for environmental scientists. More than 90% of industrial processes are performed with a catalyst involved, however research it is still required to improve the catalyst materials. The purpose of this work is to contribute with the development of catalysts synthesis with two different approaches. First, the precise size control of non-noble metals nanoparticles. Second, a new one-pot synthesis method based on a microemulsion system was developed to synthesize size-controlled metal nanoparticles in oxide supports. The one-pot method represents a simple approach to synthesize both support and immobilized nanometer-sized non-noble metal nanoparticles in the same reaction system. Narrow size distribution nickel, cobalt, iron and cobalt-nickel nanoparticles were obtained. High metal dispersions are attainable regardless the metal or support used in the synthesis. Thus, the methodology is adaptable and robust. The sizecontrolled supported metal nanoparticles offer the opportunity to study size effects and metal-support interactions on different catalytic reactions with different sets of metals and supports.

  16. Growth and sacrificial oxidation of transition metal nanolayers

    NARCIS (Netherlands)

    T. Tsarfati,; Zoethout, E.; van de Kruijs, R.; F. Bijkerk,

    2009-01-01

    Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3-4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e(-)

  17. Growth and sacrificial oxidation of transition metal nanolayers

    NARCIS (Netherlands)

    Tsarfati, T.; Tsarfati, Tim; Zoethout, E.; Zoethout, E.; van de Kruijs, Robbert Wilhelmus Elisabeth; Bijkerk, Frederik

    2009-01-01

    Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3–4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e−

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

    Science.gov (United States)

    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.

  19. Can Cyclen Bind Alkali Metal Azides? A DFT Study as a Precursor to Synthesis.

    Science.gov (United States)

    Bhakhoa, Hanusha; Rhyman, Lydia; Lee, Edmond P F; Ramasami, Ponnadurai; Dyke, John M

    2016-03-18

    Can cyclen (1,4,7,10-tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide-cyclen [M(cyclen)N3] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide-cyclen [M(cyclen)2N3] complexes are also investigated. N3(-) is found to bind to a M(+) (cyclen) template to give both end-on and side-on structures. In the end-on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end-on configuration to the cyclen ring. In the side-on structures, the N3 unit is bonded (in a side-on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N3-side-on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N3] to form the sandwich compounds [M(cyclen)2N3] causes the bond strength between the metal and the N3 unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    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.

  1. A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N.; Nam, Wonwoo [Ewha; (Purdue); (Osaka)

    2013-05-29

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  2. Selective metal binding by Vanabin2 from the vanadium-rich ascidian, Ascidia sydneiensis samea.

    Science.gov (United States)

    Kawakami, Norifumi; Ueki, Tatsuya; Matsuo, Koichi; Gekko, Kunihiko; Michibata, Hitoshi

    2006-07-01

    Vanadium-binding proteins, or Vanabins, have recently been isolated from the vanadium-rich ascidian, Ascidia sydneiensis samea. Recent reports indicate that Vanabin2 binds twenty V(IV) ions at pH 7.5, and that it has a novel bow-shaped conformation. However, the role of Vanabin2 in vanadium accumulation by the ascidian has not yet been determined. In the present study, the effects of acidic pH on selective metal binding to Vanabin2 and on the secondary structure of Vanabin2 were examined. Vanabin2 selectively bound to V(IV), Fe(III), and Cu(II) ions under acidic conditions. In contrast, Co(II), Ni(II), and Zn(II) ions were bound at pH 6.5 but not at pH 4.5. Changes in pH had no detectable effect on the secondary structure of Vanabin2 under acidic conditions, as determined by circular dichroism spectroscopy, and little variation in the dissociation constant for V(IV) ions was observed in the pH range 4.5-7.5, suggesting that the binding state of the ligands is not affected by acidification. Taken together, these results suggest that the reason for metal ion dissociation upon acidification is attributable not to a change in secondary structure but, rather, that it is caused by protonation of the amino acid ligands that complex with V(IV) ions.

  3. Adsorption of formaldehyde molecule on the pristine and transition metal doped graphene: First-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xin [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Institute of Theoretical Chemistry, Jilin University, Changchun 130012 (China); Xu, Lei [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); College of Physics, Jilin University, Changchun, 130012 (China); Liu, Lin-Lin; Zhao, Lu-Si; Chen, Chun-Ping [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, 130012 (China); Zhang, Yong [Department of Electrical and Computer Engineering, The University of North Carolina at Charlotte, Charlotte, NC 28223-0001 (United States); Wang, Xiao-Chun, E-mail: wangxiaochun@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun, 130012 (China)

    2017-02-28

    Highlights: • Formaldehyde molecule (H{sub 2}CO) is a common environmental pollutant with strong toxicity. • Total 36 different initial configurations of H{sub 2}CO molecule adsorbing onto three types of substrates have been investigated. • The Ti-doped graphene has the enough binding energy, significant changes in electronic structure, and reasonable short recovery time 10{sup −3} s. • The Ti-doped graphene is a promising candidate for detecting formaldehyde gas. - Abstract: The adsorption of H{sub 2}CO molecule on pristine and transition metal (Ti and V) doped graphene samples were investigated via a first-principles approach based on density functional theory. The most stable adsorption geometry, energy and charge transfer of H{sub 2}CO molecule on pristine and doped graphene are discussed respectively. We have found that Ti and V dopant atoms can significantly enhance the interaction between H{sub 2}CO molecule and graphene. The calculated net electron transfers, electronic density difference images and densities of states give the evidence that the H{sub 2}CO molecules stay on Ti (or V) – doped graphene by chemisorption. After H{sub 2}CO adsorption, there are significant changes in electronic structure near the Fermi level, for both two systems of Ti and V doped graphene. This indicates distinct changes of electron transport properties. We have also found that H{sub 2}CO molecule has a larger absorption energy on V-doped graphene (1.939 eV) compared with Ti-doped graphene (1.120 eV). It is shown that the Ti-doped graphene has enough binding energy, adequate changes in electronic structure and reasonable short recovery time 10{sup −3} s, making it a promising candidate for detecting formaldehyde gas.

  4. Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

    Science.gov (United States)

    Driver, Tom G.

    2011-01-01

    Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

  5. Control of metal-insulator transition in (EDO-TTF)2SbF6

    Science.gov (United States)

    Maesato, Mitsuhiko; Nakano, Yoshiaki; Shao, Xiangfeng; Yoshida, Yukihiro; Yamochi, Hideki; Saito, Gunzi; Moreac, Alain; Ameline, Jean-Claude; Collet, Eric; Uruichi, Mikio; Yakushi, Kyuya

    2009-02-01

    We have examined the temperature dependence of optical reflectance spectra of (EDO-TTF)2SbF6 salt, and succeeded to detect the thermal hysteresis by the reflectance spectra. In order to investigate high pressure effects on the metal-insulator transition of SbF6 salt, we have performed Raman experiments under pressures up to 6 kbar. Drastic changes in the frequencies of charge sensitive C=C stretching modes suggested the pressure-induced reentrant metal-insulator-metal transition at room temperature.

  6. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry

    Digital Repository Service at National Institute of Oceanography (India)

    Chakraborty, P.; Chakraborty, S.; Vudamala, K.; Sarkar, Arindam; Nath, B.N.

    binding phases of tropical estuarine sediments. Materials and Methods: Study area: The sediment samples were collected from the Vembanad Lake in Kerala, west coast of India. It is the longest (stretching about 90 km) and largest brackish-water lake... of the European Communities. International journal of environmental analytical chemistry, 51(1-4), 135-151. Verma, A., & Subramanian, V. (2002). Organic matter and amino acid concentrations in surface sediments of Vembanad Lake–a tropical estuary, west coast...

  7. Observation of excitonic fine structure in a 2D transition-metal dichalcogenide semiconductor.

    Science.gov (United States)

    Shang, Jingzhi; Shen, Xiaonan; Cong, Chunxiao; Peimyoo, Namphung; Cao, Bingchen; Eginligil, Mustafa; Yu, Ting

    2015-01-27

    Two-dimensional (2D) semiconductors, such as transition-metal dichalcogenide monolayers (TMD 1Ls), have attracted increasing attention owing to the underlying fundamental physics (e.g., many body effects) and the promising optoelectronic applications such as light-emitting diodes. Though much progress has been made, intrinsic excitonic states of TMD 1Ls are still highly debated in theory, which thirsts for direct experimental determination. Here, we report unconventional emission and excitonic fine structure in 1L WS2 revealed by electrical doping and photoexcitation, which reflects the interplay of exciton, trion, and other excitonic states. Tunable excitonic emission has been realized in a controllable manner via electrical and/or optical injection of charge carriers. Remarkably enough, the superlinear (i.e., quadratic) emission is unambiguously observed which is attributed to biexciton states, indicating the strong Coulomb interactions in such a 2D material. In a nearly neutral 1L WS2, trions and biexcitons possess large binding energies of ∼ 10-15 and 45 meV, respectively. Moreover, our finding of electrically induced robust emission opens up a possibility to boost the luminous efficiency of emerging 1L TMD light emitting diodes.

  8. Sol-Gel Synthesis and Characterization of Selected Transition Metal Nano-Ferrites

    Directory of Open Access Journals (Sweden)

    Aurelija GATELYTĖ

    2011-09-01

    Full Text Available In the present work, the sinterability and formation of nanosized yttrium iron garnet (Y3Fe5O12, yttrium perovskite ferrite (YFeO3, cobalt, nickel and zinc iron spinel (CoFe2O4, NiFe2O4 and ZnFe2O4, respectively powders by an aqueous sol-gel processes are investigated. The metal ions, generated by dissolving starting materials of transition metals in the diluted acetic acid were complexed by 1,2-ethanediol to obtain the precursors for the transition metal ferrite ceramics. The phase purity of synthesized nano-compounds was characterized by infrared spectroscopy (IR and powder X-ray diffraction analysis (XRD. The microstructural evolution and morphological features of obtained transition metal ferrites were studied by scanning electron microscopy (SEM.http://dx.doi.org/10.5755/j01.ms.17.3.598

  9. Direct determination of monolayer MoS2 and WSe2 exciton binding energies on insulating and metallic substrates

    KAUST Repository

    Park, Soohyung

    2018-01-03

    Understanding the excitonic nature of excited states in two-dimensional (2D) transition-metal dichalcogenides (TMDCs) is of key importance to make use of their optical and charge transport properties in optoelectronic applications. We contribute to this by the direct experimental determination of the exciton binding energy (E b,exc) of monolayer MoS2 and WSe2 on two fundamentally different substrates, i.e. the insulator sapphire and the metal gold. By combining angle-resolved direct and inverse photoelectron spectroscopy we measure the electronic band gap (E g), and by reflectance measurements the optical excitonic band gap (E exc). The difference of these two energies is E b,exc. The values of E g and E b,exc are 2.11 eV and 240 meV for MoS2 on sapphire, and 1.89 eV and 240 meV for WSe2 on sapphire. On Au E b,exc is decreased to 90 meV and 140 meV for MoS2 and WSe2, respectively. The significant E b,exc reduction is primarily due to a reduction of E g resulting from enhanced screening by the metal, while E exc is barely decreased for the metal support. Energy level diagrams determined at the K-point of the 2D TMDCs Brillouin zone show that MoS2 has more p-type character on Au as compared to sapphire, while WSe2 appears close to intrinsic on both. These results demonstrate that the impact of the dielectric environment of 2D TMDCs is more pronounced for individual charge carriers than for a correlated electron–hole pair, i.e. the exciton. A proper dielectric surrounding design for such 2D semiconductors can therefore be used to facilitate superior optoelectronic device function.

  10. Direct determination of monolayer MoS2 and WSe2 exciton binding energies on insulating and metallic substrates

    Science.gov (United States)

    Park, Soohyung; Mutz, Niklas; Schultz, Thorsten; Blumstengel, Sylke; Han, Ali; Aljarb, Areej; Li, Lain-Jong; List-Kratochvil, Emil J. W.; Amsalem, Patrick; Koch, Norbert

    2018-04-01

    Understanding the excitonic nature of excited states in two-dimensional (2D) transition-metal dichalcogenides (TMDCs) is of key importance to make use of their optical and charge transport properties in optoelectronic applications. We contribute to this by the direct experimental determination of the exciton binding energy (E b,exc) of monolayer MoS2 and WSe2 on two fundamentally different substrates, i.e. the insulator sapphire and the metal gold. By combining angle-resolved direct and inverse photoelectron spectroscopy we measure the electronic band gap (E g), and by reflectance measurements the optical excitonic band gap (E exc). The difference of these two energies is E b,exc. The values of E g and E b,exc are 2.11 eV and 240 meV for MoS2 on sapphire, and 1.89 eV and 240 meV for WSe2 on sapphire. On Au E b,exc is decreased to 90 meV and 140 meV for MoS2 and WSe2, respectively. The significant E b,exc reduction is primarily due to a reduction of E g resulting from enhanced screening by the metal, while E exc is barely decreased for the metal support. Energy level diagrams determined at the K-point of the 2D TMDCs Brillouin zone show that MoS2 has more p-type character on Au as compared to sapphire, while WSe2 appears close to intrinsic on both. These results demonstrate that the impact of the dielectric environment of 2D TMDCs is more pronounced for individual charge carriers than for a correlated electron-hole pair, i.e. the exciton. A proper dielectric surrounding design for such 2D semiconductors can therefore be used to facilitate superior optoelectronic device function.

  11. Binding of noble metal clusters with rare gas atoms: theoretical investigation.

    Science.gov (United States)

    Jamshidi, Zahra; Far, Maryam Fakhraei; Maghari, Ali

    2012-12-27

    Binding of noble metal clusters (M(n), M = Cu, Ag, and Au; n = 2-4) with rare gas atoms (Rg = Kr, Xe, and Rn) has been investigated at the density functional (CAM-B3LYP) and ab initio (MP2) levels of theory. The calculation shows significant affinity of neutral metal clusters for interaction with rare gas atoms. The binding energies indicate that gold clusters have the highest and silver clusters have the lowest affinity for interaction with rare gas atoms, and for the same metal clusters, there is a continuous increase in E(b) from Kr to Rn. The M-Rg bonding mechanism have been interpreted by means of the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). According to these theories, the M-Rg bonds are found to be partially electrostatic and partially covalent. EDA results identify that these bonds have less than 40% covalent character and more than 60% electrostatic, and also NBO calculations predict the amount of charge transfer from the lone pair of rare gas to σ* and n*orbitals of metal clusters.

  12. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    Science.gov (United States)

    Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

  13. Transitions in Theory and Practice: Managing Metals in the Circular Economy

    Directory of Open Access Journals (Sweden)

    Melissa Jackson

    2014-07-01

    Full Text Available Transitioning from current resource management practice dominated by linear economic models of consumption and production, to circular models of resource use, will require insights into the stages and processes associated with socio-technical transitions. This paper is concerned with transitions in practice. It explores two frameworks within the transitions literature—the multi-level perspective and transition management theory—for practical guidance to inform a deliberate transition in practice. The critical futures literature is proposed as a source of tools and methods to be used in conjunction with the transition frameworks to influence and enable transitions in practice. This enhanced practical guidance for initiating action is applied to a specific context—transitioning the Australian metals sector towards a circular economy model. This particular transition case study is relevant because the vision of a circular economy model of resource management is gaining traction internationally, Australia is significant globally as a supplier of finite mineral resources and it will also be used in a collaborative research project on Wealth from Waste to investigate possibilities for the circular economy and metals recycling.

  14. Apoprotein Structure and Metal Binding Characterization of a de Novo Designed Peptide, α3DIV, that Sequesters Toxic Heavy Metals.

    Science.gov (United States)

    Plegaria, Jefferson S; Dzul, Stephen P; Zuiderweg, Erik R P; Stemmler, Timothy L; Pecoraro, Vincent L

    2015-05-12

    De novo protein design is a biologically relevant approach that provides a novel process in elucidating protein folding and modeling the metal centers of metalloproteins in a completely unrelated or simplified fold. An integral step in de novo protein design is the establishment of a well-folded scaffold with one conformation, which is a fundamental characteristic of many native proteins. Here, we report the NMR solution structure of apo α3DIV at pH 7.0, a de novo designed three-helix bundle peptide containing a triscysteine motif (Cys18, Cys28, and Cys67) that binds toxic heavy metals. The structure comprises 1067 NOE restraints derived from multinuclear multidimensional NOESY, as well as 138 dihedral angles (ψ, φ, and χ1). The backbone and heavy atoms of the 20 lowest energy structures have a root mean square deviation from the mean structure of 0.79 (0.16) Å and 1.31 (0.15) Å, respectively. When compared to the parent structure α3D, the substitution of Leu residues to Cys enhanced the α-helical content of α3DIV while maintaining the same overall topology and fold. In addition, solution studies on the metalated species illustrated metal-induced stability. An increase in the melting temperatures was observed for Hg(II), Pb(II), or Cd(II) bound α3DIV by 18-24 °C compared to its apo counterpart. Further, the extended X-ray absorption fine structure analysis on Hg(II)-α3DIV produced an average Hg(II)-S bond length at 2.36 Å, indicating a trigonal T-shaped coordination environment. Overall, the structure of apo α3DIV reveals an asymmetric distorted triscysteine metal binding site, which offers a model for native metalloregulatory proteins with thiol-rich ligands that function in regulating toxic heavy metals, such as ArsR, CadC, MerR, and PbrR.

  15. Micro-Capillary Coatings Based on Spiropyran Polymeric Brushes for Metal Ion Binding, Detection, and Release in Continuous Flow

    Directory of Open Access Journals (Sweden)

    Aishling Dunne

    2018-04-01

    Full Text Available Micro-capillaries, capable of light-regulated binding and qualitative detection of divalent metal ions in continuous flow, have been realised through functionalisation with spiropyran photochromic brush-type coatings. Upon irradiation with UV light, the coating switches from the passive non-binding spiropyran form to the active merocyanine form, which binds different divalent metal ions (Zn2+, Co2+, Cu2+, Ni2+, Cd2+, as they pass through the micro-capillary. Furthermore, the merocyanine visible absorbance spectrum changes upon metal ion binding, enabling the ion uptake to be detected optically. Irradiation with white light causes reversion of the merocyanine to the passive spiropyran form, with simultaneous release of the bound metal ion from the micro-capillary coating.

  16. Long Spin-Relaxation Times in a Transition-Metal Atom in Direct Contact to a Metal Substrate.

    Science.gov (United States)

    Hermenau, Jan; Ternes, Markus; Steinbrecher, Manuel; Wiesendanger, Roland; Wiebe, Jens

    2018-03-14

    Long spin-relaxation times are a prerequisite for the use of spins in data storage or nanospintronics technologies. An atomic-scale solid-state realization of such a system is the spin of a transition-metal atom adsorbed on a suitable substrate. For the case of a metallic substrate, which enables the direct addressing of the spin by conduction electrons, the experimentally measured lifetimes reported to date are on the order of only hundreds of femtoseconds. Here, we show that the spin states of iron atoms adsorbed directly on a conductive platinum substrate have a surprisingly long spin-relaxation time in the nanosecond regime, which is comparable to that of a transition metal atom decoupled from the substrate electrons by a thin decoupling layer. The combination of long spin-relaxation times and strong coupling to conduction electrons implies the possibility to use flexible coupling schemes to process the spin information.

  17. Long Spin-Relaxation Times in a Transition-Metal Atom in Direct Contact to a Metal Substrate

    Science.gov (United States)

    Hermenau, Jan; Ternes, Markus; Steinbrecher, Manuel; Wiesendanger, Roland; Wiebe, Jens

    2018-03-01

    Long spin relaxation times are a prerequisite for the use of spins in data storage or nanospintronics technologies. An atomic-scale solid-state realization of such a system is the spin of a transition metal atom adsorbed on a suitable substrate. For the case of a metallic substrate, which enables directly addressing the spin by conduction electrons, the experimentally measured lifetimes reported to date are on the order of only hundreds of femtoseconds. Here, we show that the spin states of iron atoms adsorbed directly on a conductive platinum substrate have an astonishingly long spin relaxation time in the nanosecond regime, which is comparable to that of a transition metal atom decoupled from the substrate electrons by a thin decoupling layer. The combination of long spin relaxation times and strong coupling to conduction electrons implies the possibility to use flexible coupling schemes in order to process the spin-information.

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

    Science.gov (United States)

    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. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

  19. Selective metal binding to Cys-78 within endonuclease V causes an inhibition of catalytic activities without altering nontarget and target DNA binding

    International Nuclear Information System (INIS)

    Prince, M.A.; Friedman, B.; Gruskin, E.A.; Schrock, R.D. III; Lloyd, R.S.

    1991-01-01

    T4 endonuclease V is a pyrimidine dimer-specific DNA repair enzyme which has been previously shown not to require metal ions for either of its two catalytic activities or its DNA binding function. However, we have investigated whether the single cysteine within the enzyme was able to bind metal salts and influence the various activities of this repair enzyme. A series of metals (Hg2+, Ag+, Cu+) were shown to inactivate both endonuclease Vs pyrimidine dimer-specific DNA glycosylase activity and the subsequent apurinic nicking activity. The binding of metal to endonuclease V did not interfere with nontarget DNA scanning or pyrimidine dimer-specific binding. The Cys-78 codon within the endonuclease V gene was changed by oligonucleotide site-directed mutagenesis to Thr-78 and Ser-78 in order to determine whether the native cysteine was directly involved in the enzyme's DNA catalytic activities and whether the cysteine was primarily responsible for the metal binding. The mutant enzymes were able to confer enhanced ultraviolet light (UV) resistance to DNA repair-deficient Escherichia coli at levels equal to that conferred by the wild type enzyme. The C78T mutant enzyme was purified to homogeneity and shown to be catalytically active on pyrimidine dimer-containing DNA. The catalytic activities of the C78T mutant enzyme were demonstrated to be unaffected by the addition of Hg2+ or Ag+ at concentrations 1000-fold greater than that required to inhibit the wild type enzyme. These data suggest that the cysteine is not required for enzyme activity but that the binding of certain metals to that amino acid block DNA incision by either preventing a conformational change in the enzyme after it has bound to a pyrimidine dimer or sterically interfering with the active site residue's accessibility to the pyrimidine dimer

  20. [Transition metal mediated transformations of small molecules]. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Sen, A.

    1992-10-01

    Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of {alpha}-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors when doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.

  1. Study of distorted octahedral structure in 3d transition metal complexes using XAFS

    Science.gov (United States)

    Gaur, A.; Nitin Nair, N.; Shrivastava, B. D.; Das, B. K.; Chakrabortty, Monideepa; Jha, S. N.; Bhattacharyya, D.

    2018-01-01

    Distortion in octahedral structure of 3d transition metal complexes (Mn, Fe, Co, Ni, Cu, Zn) has been studied using XAFS showing divergent nature of Cu complex. EXAFS analysis showed elongated metal-oxygen bonds for Cu complex leading to more distorted structure. Derivative XANES spectrum at Cu K-edge exhibits splitting of main edge which is correlated to elongated Cu-O bond length. Using these coordination geometry around metal centers, theoretical XANES spectra have been generated and features observed have been correlated to the corresponding metals p-DOS. It has been shown that distorted octahedral field in Cu complex is responsible for splitting of p-DOS.

  2. Correlation functions between specific volume and stoichiometry for transition metal nitrides

    International Nuclear Information System (INIS)

    Soto, G.; Aparicio, E.; Avalos-Borja, M.

    2005-01-01

    A methodology is proposed to correlate the structural aspects of transition metal nitrides (TMN) to the stoichiometric ratio: x = [N]/[M]. The method is based on a numeric figure, υ, given by the difference between the atomic concentrations of nitride and parent metal normalized to the atomic concentration of parent metal. Numerical regression is used to construct interpolating functions for υ(x) using as input the available data for TMN in two well-recognized databases (ICDD and ICSD). In summary we obtain functions of x that describe the deformation caused in the parent metal lattice by the nitrogen assimilation. The results are attractive, since TMN show remarkable trends

  3. Optical and electrical experiments at some transition-metal oxide foil-electrolyte interfaces

    International Nuclear Information System (INIS)

    Sari, S.O.; Ahlgren, W.L.

    1977-01-01

    Metal-oxide layers formed from transition-metal foils oxidized by heating in air have been examined for their photoelectrolytic response. The metals examined are Y, Ti, Zr, Hf, V, Nb, Ta, Mo, W, and Pt. Weak photoeffects are observed for oxide layers of all of these metals. Sizable light-dependent oxygen gas evolution rates are found in Ti and also in W oxides. The spectral dependence of the oxygen response in these compounds is investigated, and interpretation is given of these experiments

  4. Study of the metal-insulator transition and superconducting correlations of a generalized Hubbard model

    Science.gov (United States)

    Arrachea, Liliana; Aligia, A. A.; Gagliano, E.

    1996-02-01

    We study the metal-insulator transition of a generalized Hubbard model in which the magnitude of the nearest-neighbor hopping depends on the occupations of the sites involved. Numerical results for finite chains at half-filling show that when 0 0 for which the system is metallic. This is consistent with a Hartree-Fock calculation. The metallic phase collapses to one point, U = 0, in the Hubbard limit. In the metallic phase we obtain that the superconducting correlations are the dominant ones, at least for doped systems.

  5. First-principles study of doping effect on the phase transition of zinc oxide with transition metal doped

    International Nuclear Information System (INIS)

    Wu, Liang; Hou, Tingjun; Wang, Yi; Zhao, Yanfei; Guo, Zhenyu; Li, Youyong; Lee, Shuit-Tong

    2012-01-01

    Highlights: ► We study the doping effect on B4, B1 structures and phase transition of ZnO. ► We calculate the phase transition barrier and phase transition path of doped ZnO. ► The transition metal doping decreases the bulk modulus and phase transition pressure. ► The magnetic properties are influenced by the phase transition process. - Abstract: Zinc oxide (ZnO) is a promising material for its wide application in solid-state devices. With the pressure raised from an ambient condition, ZnO transforms from fourfold wurtzite (B4) to sixfold coordinated rocksalt (B1) structure. Doping is an efficient approach to improve the structures and properties of materials. Here we use density-functional theory (DFT) to study doped ZnO and find that the transition pressure from B4 phase to B1 phase of ZnO always decreases with different types of transition metal (V, Cr, Mn, Fe, Co, or Ni) doped, but the phase transition path is not affected by doping. This is consistent with the available experimental results for Mn-doped ZnO and Co-doped ZnO. Doping in ZnO causes the lattice distortion, which leads to the decrease of the bulk modulus and accelerates the phase transition. Mn-doped ZnO shows the strongest magnetic moment due to its half filled d orbital. For V-doped ZnO and Cr-doped ZnO, the magnetism is enhanced by phase transition from B4 to B1. But for Mn-doped ZnO, Fe-doped ZnO, Co-doped ZnO, and Ni-doped ZnO, B1 phase shows weaker magnetic moment than B4 phase. These results can be explained by the amount of charge transferred from the doped atom to O atom. Our results provide a theoretical basis for the doping approach to change the structures and properties of ZnO.

  6. Semiconductor-to-metal transition in trans-polyacetylene (the role of correlated solitons

    Directory of Open Access Journals (Sweden)

    S. A. Ketabi

    2004-06-01

    Full Text Available  In this study the nature of transition to metallic regime in trans-polyacetylene (trans-PA is investigated. Based on Su-Schrieffer-Heeger (SSH model and the use of Continued - Fraction Representation (CFR as well as Lanczos algorithm procedure, we studied the effects of some selected soliton distributions on the semiconductor-to-metal transition in trans-PA.We found that,this transition occurs only when there exists a soliton sublattice in trans-PA, disordered soliton distributions and soliton clustering are the origin of the metallic transition in trans-PA, that is consistent with the experimental data. Our results show that in the presence of correlation between solitons, the disorder in accompanying single soliton distributions plays a crucial role in inducing the transition to metallic regime, so that in contrast to Anderson’s localization theorem, the electronic states near the Fermi level are extended, that is the most significant criteria for the metallic regime .

  7. Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

    Energy Technology Data Exchange (ETDEWEB)

    Achatz, Philipp

    2009-05-15

    During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n{sub c} for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers ({approx} 500 cm{sup -1}) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g{sub c}. The granularity also influences significantly the superconducting properties by introducing the superconducting gap {delta} in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the

  8. Surface free energy of alkali and transition metal nanoparticles

    International Nuclear Information System (INIS)

    Aqra, Fathi; Ayyad, Ahmed

    2014-01-01

    Graphical abstract: Size dependent surface free energy of spherical, cubic and disk Au nanoparticles. - Highlights: • A model to account for the surface free energy of metallic nanoparticles is described. • The model requires only the cohesive energy of the nanoparticle. • The surface free energy of a number of metallic nanoparticles has been calculated, and the obtained values agree well with existing data. • Surface energy falls down very fast when the number of atoms is less than hundred. • The model is applicable to any metallic nanoparticle. - Abstract: This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data

  9. The recent development of efficient Earth-abundant transition-metal nanocatalysts.

    Science.gov (United States)

    Wang, Dong; Astruc, Didier

    2017-02-06

    Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

  10. TRANSITION METAL TRANSPORT IN PLANTS AND ASSOCIATED ENDOSYMBIONTS: ARBUSCULAR MYCORRHIZAL FUNGI AND RHIZOBIA

    Directory of Open Access Journals (Sweden)

    Manuel González-Guerrero

    2016-07-01

    Full Text Available Transition metals such as iron, copper, zinc, or molybdenum, are essential nutrients for plants. These elements are involved in almost every biological process, including photosynthesis, tolerance to biotic and abiotic stress, or symbiotic nitrogen fixation. However, plants often grow in soils with limiting metallic oligonutrient bioavailability. Consequently, to ensure the proper metal levels, plants have developed a complex metal uptake and distribution system, that not only involves the plant itself, but also its associated microorganisms. These microorganisms can simply increase metal solubility in soils and making them more accessible to the host plant, as well as induce the plant metal deficiency response, or deliver directly transition elements to cortical cells. Other, instead of providing metals can act as metal sinks, such as endosymbiotic rhizobia in legume nodules that requires relatively large amounts to carry out nitrogen fixation. In this review, we propose to do an overview of metal transport mechanisms in the plant-microbe system, emphasizing the role of arbuscular mycorrhizal fungi and endosymbiotic rhizobia.

  11. Transition metal catalysed Grignard-like allylic activation across ...

    Indian Academy of Sciences (India)

    Unknown

    Contemporary chemistry is characterized by the number and variety of topics, which cut across traditional divides. The interest in combining transition and main group elements to generate new structural motifs, often clusters, provides distinct opportunities in the field of catalysis. In this direction, ligand-assisted ...

  12. Metal (Pb, Cd, and Zn) Binding to Diverse Organic Matter Samples and Implications for Speciation Modeling.

    Science.gov (United States)

    Chen, Weibin; Guéguen, Céline; Smith, D Scott; Galceran, Josep; Puy, Jaume; Companys, Encarnació

    2018-04-03

    This study evaluated the influence of dissolved organic matter (DOM) properties on the speciation of Pb, Zn, and Cd. A total of six DOM samples were categorized into autochthonous and allochthonous sources based on their absorbance and fluorescence properties. The concentration of free metal ions ( C M 2+ ) measured by titration using the absence of gradients and Nernstian equilibrium stripping (AGNES) method was compared with that predicted by the Windermere humic aqueous model (WHAM). At the same binding condition (pH, dissolved organic carbon, ionic strength, and total metal concentration) the allochthonous DOM showed a higher level of Pb binding than the autochthonous DOM (84- to 504-fold C Pb 2+ variation). This dependency, however, was less pronounced for Zn (12- to 74-fold C Zn 2+ variation) and least for Cd (2- to 14-fold C Cd 2+ variation). The WHAM performance was affected by source variation through the active DOM fraction ( F). The commonly used F = 1.3 provided reliable C Pb 2+ for allochthonous DOMs and acceptable C Cd 2+ for all DOM, but it significantly under-predicted C Pb 2+ and C Zn 2+ for autochthonous DOM. Adjusting F improved C M 2+ predictions, but the optimum F values were metal-specific (e.g., 0.03-1.9 for Pb), as shown by linear correlations with specific optical indexes. The results indicate a potential to improve WHAM by incorporating rapid measurement of DOM optical properties for site-specific F.

  13. Earthworm Lumbricus rubellus MT-2: Metal Binding and Protein Folding of a True Cadmium-MT

    Directory of Open Access Journals (Sweden)

    Gregory R. Kowald

    2016-01-01

    Full Text Available Earthworms express, as most animals, metallothioneins (MTs—small, cysteine-rich proteins that bind d10 metal ions (Zn(II, Cd(II, or Cu(I in clusters. Three MT homologues are known for Lumbricus rubellus, the common red earthworm, one of which, wMT-2, is strongly induced by exposure of worms to cadmium. This study concerns composition, metal binding affinity and metal-dependent protein folding of wMT-2 expressed recombinantly and purified in the presence of Cd(II and Zn(II. Crucially, whilst a single Cd7wMT-2 species was isolated from wMT-2-expressing E. coli cultures supplemented with Cd(II, expressions in the presence of Zn(II yielded mixtures. The average affinities of wMT-2 determined for either Cd(II or Zn(II are both within normal ranges for MTs; hence, differential behaviour cannot be explained on the basis of overall affinity. Therefore, the protein folding properties of Cd- and Zn-wMT-2 were compared by 1H NMR spectroscopy. This comparison revealed that the protein fold is better defined in the presence of cadmium than in the presence of zinc. These differences in folding and dynamics may be at the root of the differential behaviour of the cadmium- and zinc-bound protein in vitro, and may ultimately also help in distinguishing zinc and cadmium in the earthworm in vivo.

  14. Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties

    Science.gov (United States)

    Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

    2016-01-01

    Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs. PMID:27686869

  15. Characterization of Metal Binding in the Active Sites of acireductone dioxygenase Isoforms from Klebsiella ATCC 8724

    Energy Technology Data Exchange (ETDEWEB)

    S Chai; T Ju; M Dang; R Goldsmith; M Maroney; T Pochapsky

    2011-12-31

    The two acireductone dioxygenase (ARD) isozymes from the methionine salvage pathway of Klebsiella ATCC 8724 present an unusual case in which two enzymes with different structures and distinct activities toward their common substrates (1,2-dihydroxy-3-oxo-5-(methylthio)pent-1-ene and dioxygen) are derived from the same polypeptide chain. Structural and functional differences between the two isozymes are determined by the type of M{sup 2+} metal ion bound in the active site. The Ni{sup 2+}-bound NiARD catalyzes an off-pathway shunt from the methionine salvage pathway leading to the production of formate, methylthiopropionate, and carbon monoxide, while the Fe{sup 2+}-bound FeARD catalyzes the on-pathway formation of methionine precursor 2-keto-4-methylthiobutyrate and formate. Four potential protein-based metal ligands were identified by sequence homology and structural considerations. Based on the results of site-directed mutagenesis experiments, X-ray absorption spectroscopy (XAS), and isothermal calorimetry measurements, it is concluded that the same four residues, His96, His98, Glu102 and His140, provide the protein-based ligands for the metal in both the Ni- and Fe-containing forms of the enzyme, and subtle differences in the local backbone conformations trigger the observed structural and functional differences between the FeARD and NiARD isozymes. Furthermore, both forms of the enzyme bind their respective metals with pseudo-octahedral geometry, and both may lose a histidine ligand upon binding of substrate under anaerobic conditions. However, mutations at two conserved nonligand acidic residues, Glu95 and Glu100, result in low metal contents for the mutant proteins as isolated, suggesting that some of the conserved charged residues may aid in transfer of metal from in vivo sources or prevent the loss of metal to stronger chelators. The Glu100 mutant reconstitutes readily but has low activity. Mutation of Asp101 results in an active enzyme that incorporates

  16. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)

    a

    donor and it forms binuclear octahedral metal complexes, possessing alkoxide bridging. Cobalt(II) complex exhibits thermochromism. Antimicrobial studies on ..... coordination. N1 or N3 may be involved in this process (Figure 1) [18-20]. (iii) Positive shifts in ν(C-O) and ν(N-H) are strong indications of the participation of the.

  17. Schiff base transition metal complexes for Suzuki–Miyaura cross ...

    Indian Academy of Sciences (India)

    RASHEEDA M ANSARI

    2017-08-19

    Aug 19, 2017 ... Abstract. Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of ...

  18. A new Mannich base and its transition metal (II) complexes ...

    Indian Academy of Sciences (India)

    Unknown

    some metal complexes of this type of Mannich base and investigate its bonding characteristics. We herein report a new Mannich base, N-(1-morpholinoben- zyl) semicarbazide formed by the three-component condensation, containing active hydrogen on nitro- gen (morpholine), benzaldehyde and semicarbazide.

  19. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal...

  20. Schiff base transition metal complexes for Suzuki–Miyaura cross ...

    Indian Academy of Sciences (India)

    Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of azomethine group.

  1. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    Science.gov (United States)

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  2. Volume variation of Gruneisen parameters of fcc transition metals

    Indian Academy of Sciences (India)

    Unknown

    average discrepancy between the values of γ measured by various methods for 23 metals. Experimentally only the total Gruneisen parameter can be measured. The total. Gruneisen parameter is the sum of lattice, electronic and probably magnetic contribution. The letter term is present in palladium (White and Pawlok 1970) ...

  3. Transition Metal Sulfide Hydrogen Evolution Catalysts for Hydrobromic Acid Electrolysis

    NARCIS (Netherlands)

    Ivanovskaya, Anna; Singh, Nirala; Liu, Ru-Fen; Kreutzer, Haley; Baltrusaitis, Jonas; Nguyen, Trung Van; Metiu, Horia; McFarland, Eric

    2013-01-01

    Mixed metal sulfides containing combinations of W, Fe, Mo, Ni, and Ru were synthesized and screened for activity and stability for the hydrogen evolution reaction (HER) in aqueous hydrobromic acid (HBr). Co- and Ni-substituted RuS2 were identified as potentially active HER electrocatalysts by

  4. Transition metal chemistry of hydroxy(–OH)-rich molecules ...

    Indian Academy of Sciences (India)

    Administrator

    Appropriately designed hydroxy(–OH) containing Schiff's base and Mannich base molecules have been recently found to be important for development of the coordination chemistry of a number of metal ions in the biomimetic chemistry of metalloenzymes. In this context, our group has studied the coordination role of these ...

  5. Computational study of 5d transition metal mononitrides and ...

    Indian Academy of Sciences (India)

    Administrator

    Density functional method; 5d-metal; mononitrides; monoborides. 1. Introduction. Clusters containing a few to thousands of atoms are of scientific importance. In this regime, their physical and chemical properties change with their size. Therefore, the clusters often demonstrate many unexpected characteris- tics different from ...

  6. Synthesis of first row transition metal carboxylate complexes by ring ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 2 ... Metal carboxylates; ring opening reactions; cyclic anhydrides; structural study. Abstract. Hydrolytic and solvolytic ring opening reactions of phthalic anhydride, pyromellitic dianhydride and 2,3-pyridine dicarboxylic anhydride in the presence of various ...

  7. Sub-chronic toxicological studies of transition metal complexes of ...

    African Journals Online (AJOL)

    However, Naproxen metal complexes showed comparatively lower side effects than naproxen. Hematological report suggested that naproxen was in process of initiating inflammation which was justified by decreasing the mean value hemoglobin and hematocrit level and increasing the white blood cells level. There were ...

  8. Textural and morphological studies of transition metal doped SBA ...

    Indian Academy of Sciences (India)

    rials with short and open channels are well explored because they are more ..... is important to note that the increase in unit cell con- stant, ao is not .... The strik- ing improvement in textural parameters suggests that the metal salts promote the silica condensation as a result possesses thicker pore walls. 3.3 TG Analysis.

  9. Schiff base transition metal complexes for Suzuki–Miyaura cross

    Indian Academy of Sciences (India)

    Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of azomethine group.

  10. Synthesis, spectral characterization of Schiff base transition metal ...

    Indian Academy of Sciences (India)

    The UV-Vis, magnetic susceptibility and ESR spectral data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The redox behaviour of copper and vanadyl complexes was studied by cyclic voltammetry. Antimicrobial screening tests ...

  11. Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

    KAUST Repository

    Dong, Liang

    2016-12-30

    Two-dimensional (2D) materials that display robust ferromagnetism have been pursued intensively for nanoscale spintronic applications, but suitable candidates have not been identified. Here we present theoretical predictions on the design of ordered double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless of the surface terminations (T = O, OH, and F), as well as in Hf2MnC2O2 and Hf2VC2O2 monolayers. The high magnetic moments (3–4 μB/unit cell) and high Curie temperatures (495–1133 K) of these MXenes are superior to those of existing 2D ferromagnetic materials. Furthermore, semimetal-to-semiconductor and ferromagnetic-to-antiferromagnetic phase transitions are predicted to occur in these materials in the presence of small or moderate tensile in-plane strains (0–3%), which can be externally applied mechanically or internally induced by the choice of transition metals.

  12. Global transcriptome and deletome profiles of yeast exposed to transition metals.

    Directory of Open Access Journals (Sweden)

    Yong Hwan Jin

    2008-04-01

    Full Text Available A variety of pathologies are associated with exposure to supraphysiological concentrations of essential metals and to non-essential metals and metalloids. The molecular mechanisms linking metal exposure to human pathologies have not been clearly defined. To address these gaps in our understanding of the molecular biology of transition metals, the genomic effects of exposure to Group IB (copper, silver, IIB (zinc, cadmium, mercury, VIA (chromium, and VB (arsenic elements on the yeast Saccharomyces cerevisiae were examined. Two comprehensive sets of metal-responsive genomic profiles were generated following exposure to equi-toxic concentrations of metal: one that provides information on the transcriptional changes associated with metal exposure (transcriptome, and a second that provides information on the relationship between the expression of approximately 4,700 non-essential genes and sensitivity to metal exposure (deletome. Approximately 22% of the genome was affected by exposure to at least one metal. Principal component and cluster analyses suggest that the chemical properties of the metal are major determinants in defining the expression profile. Furthermore, cells may have developed common or convergent regulatory mechanisms to accommodate metal exposure. The transcriptome and deletome had 22 genes in common, however, comparison between Gene Ontology biological processes for the two gene sets revealed that metal stress adaptation and detoxification categories were commonly enriched. Analysis of the transcriptome and deletome identified several evolutionarily conserved, signal transduction pathways that may be involved in regulating the responses to metal exposure. In this study, we identified genes and cognate signaling pathways that respond to exposure to essential and non-essential metals. In addition, genes that are essential for survival in the presence of these metals were identified. This information will contribute to our

  13. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  14. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    Science.gov (United States)

    Iyer, Vivekanantan S.; Vollhardt, K. Peter C.

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  15. Using a Semiconductor-to-Metal Transition to Control Optical Transmission through Subwavelength Hole Arrays

    Directory of Open Access Journals (Sweden)

    E. U. Donev

    2008-01-01

    Full Text Available We describe a simple configuration in which the extraordinary optical transmission effect through subwavelength hole arrays in noble-metal films can be switched by the semiconductor-to-metal transition in an underlying thin film of vanadium dioxide. In these experiments, the transition is brought about by thermal heating of the bilayer film. The surprising reverse hysteretic behavior of the transmission through the subwavelength holes in the vanadium oxide suggest that this modulation is accomplished by a dielectric-matching condition rather than plasmon coupling through the bilayer film. The results of this switching, including the wavelength dependence, are qualitatively reproduced by a transfer matrix model. The prospects for effecting a similar modulation on a much faster time scale by using ultrafast laser pulses to trigger the semiconductor-to-metal transition are also discussed.

  16. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    International Nuclear Information System (INIS)

    Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

    2011-01-01

    Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

  17. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    Science.gov (United States)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  18. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2

    KAUST Repository

    Zhang, Chendong

    2015-09-21

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment.

  19. Influence of the inert and active ion bombardment on structure of the transition metal thin films

    CERN Document Server

    Blazhevich, S; Martynov, I; Neklyudov, I

    2002-01-01

    The results of the experimental research of the inert (He, Ne, Ar, Kr, Xe) and active (O, N) ion impact on the transition metal structure are presented. Thin high-purity (99.999 at.%) films of nickel, chrome and iron were used in the experiment. The bombardment was realized under room temperature at high vacuum (P<1x10 sup - sup 7 Pa) by a separated ion beam of 10-10 sup 3 keV. As a main result of the experiment, the full absence of crystal matrix changes was ascertained for all the transition metals irradiated by inert gas ions. The chemical nature of the crystal structure changes observed in transition metals being under active ion bombardment was found out too.

  20. A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction

    DEFF Research Database (Denmark)

    Skulason, Egill; Bligaard, Thomas; Gudmundsdottir, Sigrıdur

    2012-01-01

    Theoretical studies of the possibility of forming ammonia electrochemically at ambient temperature and pressure are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction...... of N2 admolecules and N adatoms on several close-packed and stepped transition metal surfaces in contact with an acidic electrolyte. Trends in the catalytic activity were calculated for a range of transition metal surfaces and applied potentials under the assumption that the activation energy barrier...... scales with the free energy difference in each elementary step. The most active surfaces, on top of the volcano diagrams, are Mo, Fe, Rh, and Ru, but hydrogen gas formation will be a competing reaction reducing the faradaic efficiency for ammonia production. Since the early transition metal surfaces...

  1. Uniaxial pressure-induced half-metallic ferromagnetic phase transition in LaMnO3

    Science.gov (United States)

    Rivero, Pablo; Meunier, Vincent; Shelton, William

    2016-03-01

    We use first-principles theory to predict that the application of uniaxial compressive strain leads to a transition from an antiferromagnetic insulator to a ferromagnetic half-metal phase in LaMnO3. We identify the Q2 Jahn-Teller mode as the primary mechanism that drives the transition, indicating that this mode can be used to tune the lattice, charge, and spin coupling. Applying ≃6 GPa of uniaxial pressure along the [010] direction activates the transition to a half-metallic pseudocubic state. The half-metallicity opens the possibility of producing colossal magnetoresistance in the stoichiometric LaMnO3 compound at significantly lower pressure compared to recently observed investigations using hydrostatic pressure.

  2. Development of dissimilar metal transition joint by hot roll bonding technique

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki.

    1994-01-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

  3. Development of dissimilar metal transition joint by hot roll bonding technique

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko.

    1995-01-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

  4. Dimensional effects in a disordered system near metal-insulator transitions and superconductor-insulator transitions; Effets dimensionnels dans un systeme desordonne au voisinage des transitions metal-isolant et supraconducteur-isolant

    Energy Technology Data Exchange (ETDEWEB)

    Akiko Marrache-Kikuchi, C

    2006-02-15

    Low temperature transport in disordered conducting materials implies quantum interference, Coulomb repulsion, and superconducting fluctuations. Since 2-D is the lower critical dimension for the existence of metallic and superconducting states, we have studied two quantum phase transitions - the Superconductor-to-Insulator Transition (SIT) and the Metal-to-Insulator Transition (MIT) - when the thickness of a disordered system - here a-NbSi - is lowered. The underlying problem is the transition between the different states and the conditions for a 2-D metal to exist. We have studied the field and disorder-induced SIT. The principal characteristics we have observed (renormalization, role of the field orientation) are well explained by M.P.A. Fisher's theory. However, we do not find the critical exponents values and a universal resistance at the transition as predicted by this theory. Concerning the MIT, we have decreased the thickness of a metallic system to reach the dimension 2 and an insulating state. In both transitions, the passage to the insulating state clearly shows the existence of dissipative states at zero temperature that are not predicted by conventional theories. We propose an interpretation of all our results that implies the existence of a novel phase in 2-D, a Bose Metal, between the superconducting and the metallic states. This new state has been predicted by recent theories. We trace the corresponding phase diagram for the model system NbSi with respect to concentration and film thickness. In the second appendix it is shown how superconducting thin films of Nb{sub x}Si{sub 1-x} are used to make transition edge sensors used in the particle detection field. (author)

  5. Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects.

    Science.gov (United States)

    Ngan, Vu Thi; Janssens, Ewald; Claes, Pieterjan; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

    2015-07-21

    Mass spectrometry experiments show an exceptionally weak bonding between Si7Mn(+) and rare gas atoms as compared to other exohedrally transition metal (TM) doped silicon clusters and other SinMn(+) (n = 5-10) sizes. The Si7Mn(+) cluster does not form Ar complexes and the observed fraction of Xe complexes is low. The interaction of two cluster series, SinMn(+) (n = 6-10) and Si7TM(+) (TM = Cr, Mn, Cu, and Zn), with Ar and Xe is investigated by density functional theory calculations. The cluster-rare gas binding is for all clusters, except Si7Mn(+) and Si7Zn(+), predominantly driven by short-range interaction between the TM dopant and the rare gas atoms. A high s-character electron density on the metal atoms in Si7Mn(+) and Si7Zn(+) shields the polarization toward the rare gas atoms and thereby hinders formation of short-range complexes. Overall, both Ar and Xe complexes are similar except that the larger polarizability of Xe leads to larger binding energies.

  6. Review of thermodinamic and mechanical properties of hydrogen-transition metal systems

    International Nuclear Information System (INIS)

    Mathias, H.; Katz, Y.

    1978-04-01

    A large body of fundamental and empirical knowledge has been acquired during many years of research concerning the interactions between hydrogen and metals, the location of hydrogen in metal structures, its mobility in metals and its influence on mechanical properties of metals. Much progress has been made in the understanding of related phenomena, and various theories have been proposed, but considerable disagreement still exist about basic mechanisms involved. The growing interest in these subjects and their important role in science and technology are well documented by many reviews and symposia. A general survey of these topics with reference to experimental results and theories related to thermodynamic and mechanical properties of hydrogen-transition metal systems, such as H-Pd, H-Ti, H-Fe etc. is given in the present review. Special emphasis is given to hydrogen embrittlement of metals

  7. Evolutionary Implications of Metal Binding Features in Different Species’ Prion Protein: An Inorganic Point of View

    Directory of Open Access Journals (Sweden)

    Diego La Mendola

    2014-05-01

    Full Text Available Prion disorders are a group of fatal neurodegenerative conditions of mammals. The key molecular event in the pathogenesis of such diseases is the conformational conversion of prion protein, PrPC, into a misfolded form rich in β-sheet structure, PrPSc, but the detailed mechanistic aspects of prion protein conversion remain enigmatic. There is uncertainty on the precise physiological function of PrPC in healthy individuals. Several evidences support the notion of its role in copper homeostasis. PrPC binds Cu2+ mainly through a domain composed by four to five repeats of eight amino acids. In addition to mammals, PrP homologues have also been identified in birds, reptiles, amphibians and fish. The globular domain of protein is retained in the different species, suggesting that the protein carries out an essential common function. However, the comparison of amino acid sequences indicates that prion protein has evolved differently in each vertebrate class. The primary sequences are strongly conserved in each group, but these exhibit a low similarity with those of mammals. The N-terminal domain of different prions shows tandem amino acid repeats with an increasing amount of histidine residues going from amphibians to mammals. The difference in the sequence affects the number of copper binding sites, the affinity and the coordination environment of metal ions, suggesting that the involvement of prion in metal homeostasis may be a specific characteristic of mammalian prion protein. In this review, we describe the similarities and the differences in the metal binding of different species’ prion protein, as revealed by studies carried out on the entire protein and related peptide fragments.

  8. Raman scattering in transition metal compounds: Titanium and compounds of titanium

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, J.; Ederer, D.L.; Shu, T. [Tulane Univ., New Orleans, LA (United States)] [and others

    1997-04-01

    The transition metal compounds form a very interesting and important set of materials. The diversity arises from the many states of ionization the transition elements may take when forming compounds. This variety provides ample opportunity for a large class of materials to have a vast range of electronic and magnetic properties. The x-ray spectroscopy of the transition elements is especially interesting because they have unfilled d bands that are at the bottom of the conduction band with atomic like structure. This group embarked on the systematic study of transition metal sulfides and oxides. As an example of the type of spectra observed in some of these compounds they have chosen to showcase the L{sub II, III} emission and Raman scattering in some titanium compounds obtained by photon excitation.

  9. On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2011-08-22

    Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

  10. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina

    2013-01-01

    remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold...... substrate surfaces and gold-coated atomic force microscopy tips. The coordination and bond breaking between terpyridine and osmium are followed in situ by electrochemically controlled atomic force microscopy at the single-molecule level. The redox state of the central metal atom is found to have......Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level...

  11. Systematic group-specific trends for point defects in bcc transition metals: An ab initio study

    International Nuclear Information System (INIS)

    Nguyen-Manh, D.; Dudarev, S.L.; Horsfield, A.P.

    2007-01-01

    Density functional theory calculations have been performed to study the systematic trends of point defect behaviours in bcc transition metals. We found that in all non-magnetic bcc transition metals, the most stable self-interstitial atom (SIAs) defect configuration has the symmetry. The calculated formation energy differences between the dumbbell and the lowest-energy configuration of metals in group 5B (V, Nb, Ta) are consistently larger than those of the corresponding element in group 6B (Cr, Mo, W). The predicted trends of SIA defects are fundamentally different from those in ferromagnetic α-Fe and correlate very well with the pronounced group-specific variation of thermally activated migration of SIAs under irradiation depending on the position of bcc metals in the periodic table

  12. Pressure-driven insulator-metal transition in cubic phase UO2

    Science.gov (United States)

    Huang, Li; Wang, Yilin; Werner, Philipp

    2017-09-01

    Understanding the electronic properties of actinide oxides under pressure poses a great challenge for experimental and theoretical studies. Here, we investigate the electronic structure of cubic phase uranium dioxide at different volumes using a combination of density functional theory and dynamical mean-field theory. The ab initio calculations predict an orbital-selective insulator-metal transition at a moderate pressure of ∼45 GPa. At this pressure the uranium's 5f 5/2 state becomes metallic, while the 5f 7/2 state remains insulating up to about 60 GPa. In the metallic state, we observe a rapid decrease of the 5f occupation and total angular momentum with pressure. Simultaneously, the so-called “Zhang-Rice state”, which is of predominantly 5f 5/2 character, quickly disappears after the transition into the metallic phase.

  13. Frontiers of 4d- and 5d-transition metal oxides

    CERN Document Server

    Cao, Gang

    2013-01-01

    This book is aimed at advanced undergraduates, graduate students and other researchers who possess an introductory background in materials physics and/or chemistry, and an interest in the physical and chemical properties of novel materials, especially transition metal oxides.New materials often exhibit novel phenomena of great fundamental and technological importance. Contributing authors review the structural, physical and chemical properties of notable 4d- and 5d-transition metal oxides discovered over the last 10 years. These materials exhibit extraordinary physical properties that differ s

  14. Transition-metal-catalyzed hydrogen-transfer annulations: access to heterocyclic scaffolds.

    Science.gov (United States)

    Nandakumar, Avanashiappan; Midya, Siba Prasad; Landge, Vinod Gokulkrishna; Balaraman, Ekambaram

    2015-09-14

    The ability of hydrogen-transfer transition-metal catalysts, which enable increasingly rapid access to important structural scaffolds from simple starting materials, has led to a plethora of research efforts on the construction of heterocyclic scaffolds. Transition-metal-catalyzed hydrogen-transfer annulations are environmentally benign and highly atom-economical as they release of water and hydrogen as by-product and utilize renewable feedstock alcohols as starting materials. Recent advances in this field with respect to the annulations of alcohols with various nucleophilic partners, thus leading to the formation of heterocyclic scaffolds, are highlighted herein. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Lattice vibrational properties of transition metal carbides (TiC, ZrC ...

    Indian Academy of Sciences (India)

    Transition metal carbides (TiC, ZrC, HfC, NbC and TaC) are complex crystals with significant ionic, ... ×(S + K + Y mC Y m)−1(TT + Y mC Zm),. (1) where K ... Lattice vibrational properties of transition metal carbides. Table 1. Model parameters for TiC, ZrC and HfC. TiC. ZrC. HfC f0(r0). 0.0250. 0.0300. 0.0070 r0f0(r0). −0.3240.

  16. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

    2011-01-01

    Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site......) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution...

  17. Transition-metal ions in Nd-doped glasses: spectra and effects on Nd fluorescence

    International Nuclear Information System (INIS)

    Stokowski, S.E.; Krashkevich, D.

    1985-01-01

    We have measured transition-metal ion (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) spectra and their effects on Nd fluorescence quenching in Nd-doped phosphate and silicate glasses. Our purpose was to determine the maximum allowable impurity content given particular limits on the absorption loss at 1053 nm and the Nd fluorescence quenching rate. To keep the absorption loss -1 the transition-metal impurity content should be kept below 0.5 ppMw. To keep the increase in the Nd fluorescence decay rate below 1%, the impurity content should be 20 cm -3

  18. Suppression of angular forces in collisions of non-S-state transition metal atoms

    International Nuclear Information System (INIS)

    Krems, R.V.; Klos, J.; Rode, M.F.; Szczesniak, M.M.; Chalasinski, G.; Dalgarno, A.

    2005-01-01

    Angular momentum transfer is expected to occur rapidly in collisions of atoms in states of nonzero angular momenta due to the large torque of angular forces. We show that despite the presence of internal angular momenta transition metal atoms interact in collisions with helium effectively as spherical atoms and angular momentum transfer is slow. Thus, magnetic trapping and sympathetic cooling of transition metal atoms to ultracold temperatures should be readily achievable. Our results open up new avenues of research with a broad class of ultracold atoms

  19. Electric field-triggered metal-insulator transition resistive switching of bilayered multiphasic VOx

    Science.gov (United States)

    Won, Seokjae; Lee, Sang Yeon; Hwang, Jungyeon; Park, Jucheol; Seo, Hyungtak

    2018-01-01

    Electric field-triggered Mott transition of VO2 for next-generation memory devices with sharp and fast resistance-switching response is considered to be ideal but the formation of single-phase VO2 by common deposition techniques is very challenging. Here, VOx films with a VO2-dominant phase for a Mott transition-based metal-insulator transition (MIT) switching device were successfully fabricated by the combined process of RF magnetron sputtering of V metal and subsequent O2 annealing to form. By performing various material characterizations, including scanning transmission electron microscopy-electron energy loss spectroscopy, the film is determined to have a bilayer structure consisting of a VO2-rich bottom layer acting as the Mott transition switching layer and a V2O5/V2O3 mixed top layer acting as a control layer that suppresses any stray leakage current and improves cyclic performance. This bilayer structure enables excellent electric field-triggered Mott transition-based resistive switching of Pt-VOx-Pt metal-insulator-metal devices with a set/reset current ratio reaching 200, set/reset voltage of less than 2.5 V, and very stable DC cyclic switching upto 120 cycles with a great set/reset current and voltage distribution less than 5% of standard deviation at room temperature, which are specifications applicable for neuromorphic or memory device applications. [Figure not available: see fulltext.

  20. Cellulose Nanocrystals Obtained from Rice By-Products and Their Binding Potential to Metallic Ions

    Directory of Open Access Journals (Sweden)

    Vanessa L. Albernaz

    2015-01-01

    Full Text Available The present study aimed to develop and optimize a method to obtain cellulose nanocrystals from the agricultural by-products rice husk and straw and to evaluate their electrostructural modifications in the presence of metallic ions. First, different particle formation conditions and routes were tested and analyzed by spectrophotometry, dynamic light scattering (DLS, and Zeta potential measurements. Then, electrostructural effects of ions Na(I, Cd(II, and Al(III on the optimized nanoparticles were analyzed by atomic force microscopy (AFM, scanning electron microscopy (SEM, and electrical conductivity (EC assessments. The produced cellulose nanocrystals adopted a rod-like shape. AFM height distribution and EC data indicated that the nanocrystals have more affinity in binding with Na(I > Al(III > Cd(II. These data suggest that the use of these cellulose nanocrystals in the bioremediation field is promising, both in metal sorption from wastewater and as an alternative for water desalination.