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Sample records for crystal ligand field

  1. Can the low symmetry crystal (ligand) field parameters be considered compatible and reliable?

    International Nuclear Information System (INIS)

    Rudowicz, C.; Qin, J.

    2004-01-01

    This paper stems from our recent efforts to clarify the inconsistencies between the crystal-field parameter (CFP) data sets reported in the literature for various low symmetry transition ion-host systems. Prompted by the results of these studies, in this paper we consider the intricate properties of CF Hamiltonians, hitherto not fully understood. The term 'low symmetry' here includes the continuous rotational symmetry cases, i.e. hexagonal II, tetragonal II, trigonal II, monoclinic, and triclinic ones, as well as orthorhombic ones. The following fundamental intricate aspects are considered: (1) selection of the axis systems, (2) types of CFPs and their properties, (3) introduction of a new notion of a nominal axis system for the fitted CFP data sets, (4) implications of the Noether's theorem and the algebraic symmetry of CF Hamiltonians, (5) correlation properties among CFP data sets, (6) the rotational degrees of freedom and the reduction of the number of independent CFPs, which are of special importance for triclinic symmetry cases, and (7) extension of the multiple correlated fitting technique, including a quantitative method for CFP data sets comparison. Clarification of these intricate aspects enables us to provide a general framework aimed at achieving an increased compatibility and reliability of CFP data sets for transition ions at low symmetry sites in crystals. This framework may be especially useful for trivalent lanthanides in technologically important low symmetry hosts for which only limited energy-level data are available

  2. Crystallization of protein–ligand complexes

    International Nuclear Information System (INIS)

    Hassell, Anne M.; An, Gang; Bledsoe, Randy K.; Bynum, Jane M.; Carter, H. Luke III; Deng, Su-Jun J.; Gampe, Robert T.; Grisard, Tamara E.; Madauss, Kevin P.; Nolte, Robert T.; Rocque, Warren J.; Wang, Liping; Weaver, Kurt L.; Williams, Shawn P.; Wisely, G. Bruce; Xu, Robert; Shewchuk, Lisa M.

    2007-01-01

    Methods presented for growing protein–ligand complexes fall into the categories of co-expression of the protein with the ligands of interest, use of the ligands during protein purification, cocrystallization and soaking the ligands into existing crystals. Obtaining diffraction-quality crystals has long been a bottleneck in solving the three-dimensional structures of proteins. Often proteins may be stabilized when they are complexed with a substrate, nucleic acid, cofactor or small molecule. These ligands, on the other hand, have the potential to induce significant conformational changes to the protein and ab initio screening may be required to find a new crystal form. This paper presents an overview of strategies in the following areas for obtaining crystals of protein–ligand complexes: (i) co-expression of the protein with the ligands of interest, (ii) use of the ligands during protein purification, (iii) cocrystallization and (iv) soaks

  3. Revealing the consequences and errors of substance arising from the inverse confusion between the crystal (ligand) field quantities and the zero-field splitting ones

    Energy Technology Data Exchange (ETDEWEB)

    Rudowicz, Czesław, E-mail: crudowicz@zut.edu.pl [Institute of Physics, West Pomeranian University of Technology, Al. Piastów 17, 70-310 Szczecin (Poland); Karbowiak, Mirosław [Faculty of Chemistry, University of Wrocław, ul. F. Joliot-Curie 14, 50-383 Wrocław (Poland)

    2015-01-01

    Survey of recent literature has revealed a doubly-worrying tendency concerning the treatment of the two distinct types of Hamiltonians, namely, the physical crystal field (CF), or equivalently ligand field (LF), Hamiltonians and the zero-field splitting (ZFS) Hamiltonians, which appear in the effective spin Hamiltonians (SH). The nature and properties of the CF (LF) Hamiltonians have been mixed up in various ways with those of the ZFS Hamiltonians. Such cases have been identified in a rapidly growing number of studies of the transition-ion based systems using electron magnetic resonance (EMR), optical spectroscopy, and magnetic measurements. These findings have far ranging implications since these Hamiltonians are cornerstones for interpretation of magnetic and spectroscopic properties of the single transition ions in various crystals or molecules as well as the exchange coupled systems (ECS) of transition ions, e.g. single molecule magnets (SMM) or single ion magnets (SIM). The seriousness of the consequences of such conceptual problems and related terminological confusions has reached a level that goes far beyond simple semantic issues or misleading keyword classifications of papers in journals and scientific databases. The prevailing confusion, denoted as the CF=ZFS confusion, pertains to the cases of labeling the true ZFS quantities as purportedly the CF (LF) quantities. Here we consider the inverse confusion between the CF (LF) quantities and the SH (ZFS) ones, denoted the ZFS=CF confusion, which consists in referring to the parameters (or Hamiltonians), which are the true CF (LF) quantities, as purportedly the ZFS (or SH) quantities. Specific cases of the ZFS=CF confusion identified in recent textbooks, reviews and papers, especially SMM- and SIM-related ones, are surveyed and the pertinent misconceptions are clarified. The serious consequences of the terminological confusions include misinterpretation of data from a wide range of experimental techniques and

  4. Intrinsically incompatible crystal (ligand) field parameter sets for transition ions at orthorhombic and lower symmetry sites in crystals and their implications

    Science.gov (United States)

    Rudowicz, C.; Gnutek, P.

    2010-01-01

    Central quantities in spectroscopy and magnetism of transition ions in crystals are crystal (ligand) field parameters (CFPs). For orthorhombic, monoclinic, and triclinic site symmetry CF analysis is prone to misinterpretations due to large number of CFPs and existence of correlated sets of alternative CFPs. In this review, we elucidate the intrinsic features of orthorhombic and lower symmetry CFPs and their implications. The alternative CFP sets, which yield identical energy levels, belong to different regions of CF parameter space and hence are intrinsically incompatible. Only their ‘images’ representing CFP sets expressed in the same region of CF parameter space may be directly compared. Implications of these features for fitting procedures and meaning of fitted CFPs are categorized into negative: pitfalls and positive: blessings. As a case study, the CFP sets for Tm 3+ ions in KLu(WO 4) 2 are analysed and shown to be intrinsically incompatible. Inadvertent, so meaningless, comparisons of incompatible CFP sets result in various pitfalls, e.g., controversial claims about the values of CFPs obtained by other researchers as well as incorrect structural conclusions or faulty systematics of CF parameters across rare-earth ion series based on relative magnitudes of incompatible CFPs. Such pitfalls bear on interpretation of, e.g., optical spectroscopy, inelastic neutron scattering, and magnetic susceptibility data. An extensive survey of pertinent literature was carried out to assess recognition of compatibility problems. Great portion of available orthorhombic and lower symmetry CFP sets are found intrinsically incompatible, yet these problems and their implications appear barely recognized. The considerable extent and consequences of pitfalls revealed by our survey call for concerted remedial actions of researchers. A general approach based on the rhombicity ratio standardization may solve compatibility problems. Wider utilization of alternative CFP sets in the

  5. Intrinsically incompatible crystal (ligand) field parameter sets for transition ions at orthorhombic and lower symmetry sites in crystals and their implications

    International Nuclear Information System (INIS)

    Rudowicz, C.; Gnutek, P.

    2010-01-01

    Central quantities in spectroscopy and magnetism of transition ions in crystals are crystal (ligand) field parameters (CFPs). For orthorhombic, monoclinic, and triclinic site symmetry CF analysis is prone to misinterpretations due to large number of CFPs and existence of correlated sets of alternative CFPs. In this review, we elucidate the intrinsic features of orthorhombic and lower symmetry CFPs and their implications. The alternative CFP sets, which yield identical energy levels, belong to different regions of CF parameter space and hence are intrinsically incompatible. Only their 'images' representing CFP sets expressed in the same region of CF parameter space may be directly compared. Implications of these features for fitting procedures and meaning of fitted CFPs are categorized into negative: pitfalls and positive: blessings. As a case study, the CFP sets for Tm 3+ ions in KLu(WO 4 ) 2 are analysed and shown to be intrinsically incompatible. Inadvertent, so meaningless, comparisons of incompatible CFP sets result in various pitfalls, e.g., controversial claims about the values of CFPs obtained by other researchers as well as incorrect structural conclusions or faulty systematics of CF parameters across rare-earth ion series based on relative magnitudes of incompatible CFPs. Such pitfalls bear on interpretation of, e.g., optical spectroscopy, inelastic neutron scattering, and magnetic susceptibility data. An extensive survey of pertinent literature was carried out to assess recognition of compatibility problems. Great portion of available orthorhombic and lower symmetry CFP sets are found intrinsically incompatible, yet these problems and their implications appear barely recognized. The considerable extent and consequences of pitfalls revealed by our survey call for concerted remedial actions of researchers. A general approach based on the rhombicity ratio standardization may solve compatibility problems. Wider utilization of alternative CFP sets in the

  6. Revealing the consequences and errors of substance arising from the inverse confusion between the crystal (ligand) field quantities and the zero-field splitting ones

    Science.gov (United States)

    Rudowicz, Czesław; Karbowiak, Mirosław

    2015-01-01

    Survey of recent literature has revealed a doubly-worrying tendency concerning the treatment of the two distinct types of Hamiltonians, namely, the physical crystal field (CF), or equivalently ligand field (LF), Hamiltonians and the zero-field splitting (ZFS) Hamiltonians, which appear in the effective spin Hamiltonians (SH). The nature and properties of the CF (LF) Hamiltonians have been mixed up in various ways with those of the ZFS Hamiltonians. Such cases have been identified in a rapidly growing number of studies of the transition-ion based systems using electron magnetic resonance (EMR), optical spectroscopy, and magnetic measurements. These findings have far ranging implications since these Hamiltonians are cornerstones for interpretation of magnetic and spectroscopic properties of the single transition ions in various crystals or molecules as well as the exchange coupled systems (ECS) of transition ions, e.g. single molecule magnets (SMM) or single ion magnets (SIM). The seriousness of the consequences of such conceptual problems and related terminological confusions has reached a level that goes far beyond simple semantic issues or misleading keyword classifications of papers in journals and scientific databases. The prevailing confusion, denoted as the CF=ZFS confusion, pertains to the cases of labeling the true ZFS quantities as purportedly the CF (LF) quantities. Here we consider the inverse confusion between the CF (LF) quantities and the SH (ZFS) ones, denoted the ZFS=CF confusion, which consists in referring to the parameters (or Hamiltonians), which are the true CF (LF) quantities, as purportedly the ZFS (or SH) quantities. Specific cases of the ZFS=CF confusion identified in recent textbooks, reviews and papers, especially SMM- and SIM-related ones, are surveyed and the pertinent misconceptions are clarified. The serious consequences of the terminological confusions include misinterpretation of data from a wide range of experimental techniques and

  7. Specific sequestering agents for the actinides. 2. A ligand field effect in the crystal and molecular structures of tetrakis(catecholato)uranate(IV) and -thorate(IV)

    International Nuclear Information System (INIS)

    Sofen, S.R.; Abu-Dari, K.; Freyberg, D.P.; Raymond, K.N.

    1978-01-01

    The structures of the title compounds, Na 4 [M(C 6 H 4 O 2 ) 4 ] 21H 2 O,M = Th, U, have been determined by single-crystal x-ray diffraction methods using counter data. These isostructural tetrakis(catecholato) complexes are structural archetypes for actinide-specific macrocyclic sequestering agents. The complexes have D/sub 2d/ molecular symmetry. The M--O bond lengths are 2.417(3) and 2.421(3) A for Th and 2.362(3) and 2.389(4) A for U. The ring O--M--O bond angles are 66.8(1) 0 for Th and 67.7(1) 0 for U. The difference in M--O bond lengths for the uranium complex [0.027(5) A] vs. a difference of 0.004(4) A in the thorium complex is attributed to a ligand field effect of the 5f 2 electronic configuration of U(IV) vs. 5f 0 for Th(IV). Green crystals of the uranium complex, obtained from basic aqueous solution, conform to the space group I anti 4 with a = 14.659(3) and c = 9.984(4) A. For 3660 independent data with F 0 2 > 3 sigma(F 0 2 ) full-matrix least-squares refinement with anisotropic thermal parameters for all nonhydrogen atoms converged to unweighted and weighted R factors of 3.8 and 4.5%, respectively. The colorless thorium compound, also obtained from basic aqueous solution, has a = 14.709(4) and c = 9.978(3) A. For 5038 independent data refinement as above converged to unweighted and weighted R factors of 4.3 and 5.3%, respectively. 3 figures, 8 tables

  8. The effective crystal field potential

    CERN Document Server

    Mulak, J

    2000-01-01

    As it results from the very nature of things, the spherical symmetry of the surrounding of a site in a crystal lattice or an atom in a molecule can never occur. Therefore, the eigenfunctions and eigenvalues of any bound ion or atom have to differ from those of spherically symmetric respective free ions. In this way, the most simplified concept of the crystal field effect or ligand field effect in the case of individual molecules can be introduced. The conventional notion of the crystal field potential is narrowed to its non-spherical part only through ignoring the dominating spherical part which produces only a uniform energy shift of gravity centres of the free ion terms. It is well understood that the non-spherical part of the effective potential "seen" by open-shell electrons localized on a metal ion plays an essential role in most observed properties. Light adsorption, electron paramagnetic resonance, inelastic neutron scattering and basic characteristics derived from magnetic and thermal measurements, ar...

  9. Models of protein-ligand crystal structures: trust, but verify

    Science.gov (United States)

    Deller, Marc C.; Rupp, Bernhard

    2015-09-01

    X-ray crystallography provides the most accurate models of protein-ligand structures. These models serve as the foundation of many computational methods including structure prediction, molecular modelling, and structure-based drug design. The success of these computational methods ultimately depends on the quality of the underlying protein-ligand models. X-ray crystallography offers the unparalleled advantage of a clear mathematical formalism relating the experimental data to the protein-ligand model. In the case of X-ray crystallography, the primary experimental evidence is the electron density of the molecules forming the crystal. The first step in the generation of an accurate and precise crystallographic model is the interpretation of the electron density of the crystal, typically carried out by construction of an atomic model. The atomic model must then be validated for fit to the experimental electron density and also for agreement with prior expectations of stereochemistry. Stringent validation of protein-ligand models has become possible as a result of the mandatory deposition of primary diffraction data, and many computational tools are now available to aid in the validation process. Validation of protein-ligand complexes has revealed some instances of overenthusiastic interpretation of ligand density. Fundamental concepts and metrics of protein-ligand quality validation are discussed and we highlight software tools to assist in this process. It is essential that end users select high quality protein-ligand models for their computational and biological studies, and we provide an overview of how this can be achieved.

  10. Effects of size and ligand density on the chirality transfer from chiral-ligand-capped nanoparticles to nematic liquid crystals

    Science.gov (United States)

    Mori, Taizo; Sharma, Anshul; Nemati, Ahlam; Bergquist, Leah; Hegmann, Torsten

    2017-08-01

    Studies of chiroptical effects of chiral ligand-capped gold nanoparticles (Au NPs) are a fascinating and rapidly evolving field in nanomaterial research with promising applications of such chiral metal NPs in catalysis and metamaterials as well as chiral sensing and separation. The aim of our studies was to seek out a system that not only allows the detection and understanding of Au NP chirality but also permits visualization and ranking — considering size, shape and nature as well as density of the ligand shell — of the extent of chirality transfer to a surrounding medium. Nematic liquid crystal (N-LC) phases are an ideal platform to examine these effects, exhibiting characteristic defect textures upon doping with a chiral additive. To test this, we synthesized series of Au NPs capped with two structurally different chiral ligands and studied well-dispersed mixtures in two nematic liquid crystal hosts. Induced circular dichroism (ICD) spectropolarimetry and polarized light optical microscopy (POM) confirmed that all Au NPs induce chiral nematic (N*-LC) phases, and measurements of the helical pitch as well as calculation of the helical twisting power (HTP) in various cell geometries allowed for an insightful ranking of the efficiency of chirality transfer of all Au NPs as well as their free ligands.

  11. Oxidation and crystal field effects in uranium

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Booth, C. H. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shuh, D. K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); van der Laan, G. [Diamond Light Source, Didcot (United Kingdom); Sokaras, D. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States); Weng, T. -C. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States); Yu, S. W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bagus, P. S. [Univ. of North Texas, Denton, TX (United States); Tyliszczak, T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Nordlund, D. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States)

    2015-07-06

    An extensive investigation of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (UO2), uranium trioxide (UO3), and uranium tetrafluoride (UF4). As a result, a discussion of the role of non-spherical perturbations, i.e., crystal or ligand field effects, will be presented.

  12. Selection of ligands for affinity chromatography using quartz crystal biosensor.

    Science.gov (United States)

    Liu, Yang; Tang, Xiaoling; Liu, Feng; Li, Ke'an

    2005-07-01

    This paper described a new strategy for rapid selecting ligands for application in affinity chromatography using a quartz crystal microbalance (QCM) biosensor. An aminoglycoside antibiotic drug, kanamycin (KM), was immobilized on the gold electrodes of the QCM sensor chip. The binding interactions of the immobilized KM with various proteins in solution were monitored as the variations of the resonant frequency of the modified sensor. Such a rapid screen analysis of interactions indicated clearly that KM-immobilized sensor showed strong specific interaction only with lysozyme (LZM). The resultant sensorgrams were rapidly analyzed by using a kinetic analysis software based on a genetic algorithm to derive both the kinetic rate constants (k(ass) and k(diss)) and equilibrium dissociation constants (K(D)) for LZM-KM interactions. The immobilized KM showed higher affinity to LZM with a dissociation constant on the order of 10(-5) M, which is within the range of 10(-4)-10(-8) M and suitable for an affinity ligand. Therefore, KM was demonstrated for the first time as a novel affinity ligand for purification of LZM and immobilized onto the epoxy-activated silica in the presence of a high potassium phosphate concentration. The KM immobilized affinity column has proved useful for a very convenient purification of LZM from chicken egg white. The purity of LZM obtained was higher than 90%, as determined by densitometric scanning of sodium dodecyl sulfate-polyacrylamide gel electrophoresis of purified fraction. These results confirmed that the selected KM ligand is indeed a valuable affinity ligand for purification of LZM. The new screening strategy based on a QCM biosensor is expected to be a promising way for rapid selecting specific ligands for purifying other valuable proteins.

  13. Bosonic fields in crystal manifold

    Energy Technology Data Exchange (ETDEWEB)

    Alencar, G., E-mail: geovamaciel@gmail.com [Departamento de Física, Universidade Federal do Ceará, Caixa Postal 6030, Campus do Pici, 60440-554 Fortaleza, Ceará (Brazil); Tahim, M.O., E-mail: makarius.tahim@uece.br [Universidade Estadual do Ceará, Faculdade de Educação, Ciências e Letras do Sertão Central, Rua Epitácio Pessoa, 2554, 63.900-000 Quixadá, Ceará (Brazil); Landim, R.R., E-mail: renan@fisica.ufc.br [Departamento de Física, Universidade Federal do Ceará, Caixa Postal 6030, Campus do Pici, 60440-554 Fortaleza, Ceará (Brazil); Costa Filho, R.N., E-mail: rai@fisica.ufc.br [Departamento de Física, Universidade Federal do Ceará, Caixa Postal 6030, Campus do Pici, 60440-554 Fortaleza, Ceará (Brazil)

    2013-11-04

    A crystal-like universe made of membranes in extra dimensions in a Randall–Sundrum scenario is studied. A background gravitational metric satisfying the right boundary conditions is considered to study the localization of the scalar, gauge and Kalb–Ramond fields. It is found that the wave function for the fields are Bloch waves. The mass modes equations are calculated allowing us to show the zero-gap mass behavior and the mass dispersion relation for each field. Finally we generalize all these results and consider q-forms in the crystal membrane universe. We add the dilaton interaction in order to guarantee localization of forms. We show that, due to the dimension D, the form q and the dilaton coupling λ, the mass spectrum can be the same for the different bosonic fields studied. Such a result is a different way to see the duality between forms.

  14. Local fields in ionic crystals

    International Nuclear Information System (INIS)

    Claro, F.

    1981-08-01

    Local fields arising from the electronic distortion in perfect ionic crystals are described in terms of multipolar excitations. Field factors for the alkali halides and chalcogenide ions are found to differ significantly from the Lorentz value of 4π/3, the correction size following an exponential dependence on the difference in ionic radii. Local fields are only slightly modified by these corrections however, and together with the Clausius-Mossotti relation may be regarded as accurate to within 2% if the Lorentz value is adopted. (author)

  15. Crystal fields and conduction electrons in praseodymium

    DEFF Research Database (Denmark)

    Clausen, K.N.; Aagaard Sørensen, S.; McEwen, K.A.

    1995-01-01

    The interactions between the crystal-field excitations, the phonons and the conduction electrons in Pr have been studied further. The low-energy satellites to the crystal-field excitations, which are believed to be associated with propagating paramagnon modes in the conduction-electron gas, appear...

  16. Syntheses, crystal structures and magnetic properties of two mixed-valence Co(iii)Co(ii) compounds derived from Schiff base ligands: field-supported single-ion-magnet behavior with easy-plane anisotropy.

    Science.gov (United States)

    Mandal, Shuvankar; Mondal, Suraj; Rajnák, Cyril; Titiš, Ján; Boča, Roman; Mohanta, Sasankasekhar

    2017-10-14

    Two μ-phenoxo-μ 1,1 -azide dinuclear Co III Co II complexes [Co III (N 3 ) 2 L 1 (μ 1,1 -N 3 )Co II (N 3 )]·MeOH (1) and [Co III (N 3 ) 2 L 2 (μ 1,1 -N 3 )Co II (N 3 )]·MeOH (2) (HL 1 and HL 2 are two Schiff base ligands having N 2 O-N 2 O compartments) both possess one hexacoordinate Co(iii) and one pentacoordinate Co(ii) center. DC magnetic susceptibility and magnetization measurements show an appreciable amount of positive magnetic anisotropy (D/hc∼ 40 cm -1 ) that is also confirmed by ab initio CASSCF calculations. AC susceptibility measurements of 1 reveal that it exhibits a slow magnetic relaxation with two relaxation channels. The external magnetic field supports the low-frequency (LF) channel that escapes on heating more progressively than the high-frequency (HF) branch. The relaxation time is as slow as τ = 255 ms at T = 1.9 K and B DC = 0.6 T, where the LF mole fraction is 69%. The complex 2 also displays similar field-supported slow magnetic relaxation with two relaxation channels.

  17. A Guided Inquiry Activity for Teaching Ligand Field Theory

    Science.gov (United States)

    Johnson, Brian J.; Graham, Kate J.

    2015-01-01

    This paper will describe a guided inquiry activity for teaching ligand field theory. Previous research suggests the guided inquiry approach is highly effective for student learning. This activity familiarizes students with the key concepts of molecular orbital theory applied to coordination complexes. Students will learn to identify factors that…

  18. Nuclear receptor ligand-binding domains: reduction of helix H12 dynamics to favour crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Nahoum, Virginie; Lipski, Alexandra; Quillard, Fabien; Guichou, Jean-François [INSERM, U554, 34090 Montpellier (France); Université de Montpellier, CNRS, UMR5048, Centre de Biochimie Structurale (CBS), 34090 Montpellier (France); Boublik, Yvan [CNRS, UMR5237, Centre de Recherche de Biochimie Macromoléculaire (CRBM), 34293 Montpellier (France); Pérez, Efrèn [Universidade de Vigo, Departamento de Quimica Organica, Facultad de Química, 36310 Vigo (Spain); Germain, Pierre [Institut de Génétique et de Biologie Moléculaire et Cellulaire (IGBMC), BP 10142, 67404 Illkirch CEDEX (France); Lera, Angel R. de [Universidade de Vigo, Departamento de Quimica Organica, Facultad de Química, 36310 Vigo (Spain); Bourguet, William, E-mail: bourguet@cbs.cnrs.fr [INSERM, U554, 34090 Montpellier (France); Université de Montpellier, CNRS, UMR5048, Centre de Biochimie Structurale (CBS), 34090 Montpellier (France)

    2008-07-01

    Attempts have been made to crystallize the ligand-binding domain of the human retinoid X receptor in complex with a variety of newly synthesized ligands. An inverse correlation was observed between the ‘crystallizability’ and the structural dynamics of the various receptor–ligand complexes. Crystallization trials of the human retinoid X receptor α ligand-binding domain (RXRα LBD) in complex with various ligands have been carried out. Using fluorescence anisotropy, it has been found that when compared with agonists these small-molecule effectors enhance the dynamics of the RXRα LBD C-terminal helix H12. In some cases, the mobility of this helix could be dramatically reduced by the addition of a 13-residue co-activator fragment (CoA). In keeping with these observations, crystals have been obtained of the corresponding ternary RXRα LBD–ligand–CoA complexes. In contrast, attempts to crystallize complexes with a highly mobile H12 remained unsuccessful. These experimental observations substantiate the previously recognized role of co-regulator fragments in facilitating the crystallization of nuclear receptor LBDs.

  19. Crystal Field Splittings of NdN

    DEFF Research Database (Denmark)

    Warming, E.; Bak, Poul Erik

    1975-01-01

    The crystal field levels of the Nd (J=9/2) ion in NdN have been determined by inelastic neutron scattering. The crystal field parameters obtained by a least-squares fit to the spectra at 80K are: B4=-0.042+or-0.002K and B6=-0.00042+or-0.00002K. This result contrasts with the point charge model used...

  20. Theory of electrolyte crystallization in magnetic field

    DEFF Research Database (Denmark)

    Madsen, Hans Erik Lundager

    2007-01-01

    Crystallization from aqueous solution of a sparingly soluble electrolyte is accelerated by magnetic field if the crystalizing phase is a diamagnetic salt of a weak acid, and crystallization is from neutral or acid solution in ordinary (not heavy) water. Since the effect of Lorentz force is neglig......Crystallization from aqueous solution of a sparingly soluble electrolyte is accelerated by magnetic field if the crystalizing phase is a diamagnetic salt of a weak acid, and crystallization is from neutral or acid solution in ordinary (not heavy) water. Since the effect of Lorentz force...... phenomena. The basis of the theory is a crystal model of a sparingly soluble salt with NaCl structure, where the ions are divalent, and the anion is a base. It is assumed that almost all the anions in the surface layer are protonized, and that an approaching metal ion pushes the proton away...... to a neighbouring anion, which then becomes doubly protonized. If the two protons are in the same spin state, the Pauli principle requires that one of them enter a state of higher energy, which enhances the activation energy and reduces the rate of the process, but even with opposite spins the incoming proton must...

  1. Phase-field crystal simulation facet and branch crystal growth

    Science.gov (United States)

    Chen, Zhi; Wang, Zhaoyang; Gu, Xinrui; Chen, Yufei; Hao, Limei; de Wit, Jos; Jin, Kexin

    2018-05-01

    Phase-field crystal model with one mode is introduced to describe morphological transition. The relationship between growth morphology and smooth density distribution was investigated. The results indicate that the pattern selection of dendrite growth is caused by the competition between interface energy anisotropy and interface kinetic anisotropy based on the 2D phase diagram. When the calculation time increases, the crystal grows to secondary dendrite at the dimensionless undercooling equal to - 0.4. Moreover, when noise is introduced in the growth progress, the symmetry is broken in the growth mode, and there becomes irregular fractal-like growth morphology. Furthermore, the single crystal shape develops into polycrystalline when the noise amplitude is large enough. When the dimensionless undercooling is less than - 0.3, the noise has a significant effect on the growth shape. In addition, the growth velocity of crystal near to liquid phase line is slow, while the shape far away from the liquid adapts to fast growth. Based on the simulation results, the method was proved to be effective, and it can easily obtain different crystal shapes by choosing the different points in 2D phase diagram.

  2. Photoreduction and validation of haem-ligand intermediate states in protein crystals byin situsingle-crystal spectroscopy and diffraction.

    Science.gov (United States)

    Kekilli, Demet; Moreno-Chicano, Tadeo; Chaplin, Amanda K; Horrell, Sam; Dworkowski, Florian S N; Worrall, Jonathan A R; Strange, Richard W; Hough, Michael A

    2017-05-01

    Powerful synergies are available from the combination of multiple methods to study proteins in the crystalline form. Spectroscopies which probe the same region of the crystal from which X-ray crystal structures are determined can give insights into redox, ligand and spin states to complement the information gained from the electron-density maps. The correct assignment of crystal structures to the correct protein redox and ligand states is essential to avoid the misinterpretation of structural data. This is a particular concern for haem proteins, which can occupy a wide range of redox states and are exquisitely sensitive to becoming reduced by solvated electrons generated from interactions of X-rays with water molecules in the crystal. Here, single-crystal spectroscopic fingerprinting has been applied to investigate the laser photoreduction of ferric haem in cytochrome c '. Furthermore, in situ X-ray-driven generation of haem intermediates in crystals of the dye-decolourizing-type peroxidase A (DtpA) from Streptomyces lividans is described.

  3. The use of small-molecule structures to complement protein-ligand crystal structures in drug discovery.

    Science.gov (United States)

    Groom, Colin R; Cole, Jason C

    2017-03-01

    Many ligand-discovery stories tell of the use of structures of protein-ligand complexes, but the contribution of structural chemistry is such a core part of finding and improving ligands that it is often overlooked. More than 800 000 crystal structures are available to the community through the Cambridge Structural Database (CSD). Individually, these structures can be of tremendous value and the collection of crystal structures is even more helpful. This article provides examples of how small-molecule crystal structures have been used to complement those of protein-ligand complexes to address challenges ranging from affinity, selectivity and bioavailability though to solubility.

  4. High resolution crystal structures of unliganded and liganded human liver ACBP reveal a new mode of binding for the acyl-CoA ligand

    DEFF Research Database (Denmark)

    Taskinen, Jukka P; van Aalten, Daan M; Knudsen, Jens

    2007-01-01

    The acyl-CoA binding protein (ACBP) is essential for the fatty acid metabolism, membrane structure, membrane fusion, and ceramide synthesis. Here high resolution crystal structures of human cytosolic liver ACBP, unliganded and liganded with a physiological ligand, myristoyl-CoA are described. The...

  5. Crystal field contribution to Moessbauer isomer shift

    International Nuclear Information System (INIS)

    Singh, Avtar; Shrivastava, K.N.

    1975-01-01

    A new temperature dependent contribution to isomer shift in Fe 3+ (ed 5 ) is proposed. The static crystal field gives rise to a new second-order correction to Mossbauer resonance line and crystal field hamiltonian Hc=B 2 0 Y 2 0 +B 2 2 (Y 22 ) usually used in the study of electronspin resonance is employed. The electron charge density at the nuclear site, responsible for the isomer shift is affected by the crystal field through excitation of an electron from 3d to 4s subshell. Further, temperature dependence is analysed by the variation of crystal field parameters with temperature which occurs as a square in the final result. The importance of the sign of the field parameter (KD) is also realised in the isomer shift studies. Although the proposed new second-order contribution to Moessbauer isomer shift is static in nature, yet it is expected to have important implications in the study of temperature depedence of centre shift of a Moessbauer line. Numerical estimates of the shift are also presented. (author)

  6. High Field Magnetization of Tb Single Crystals

    DEFF Research Database (Denmark)

    Roeland, L. W.; Cock, G. J.; Lindgård, Per-Anker

    1975-01-01

    The magnetization of Tb single crystals was measured in magnetic fields to 34T along the hard direction at temperature of 1.8, 4.2, 65.5 and 77K, and along with easy direction at 4.2 and 77K. The data are compared with the results of a self-consistent spin wave calculation using a phenomenological...

  7. Crystal fields in UO2 - revisited

    Energy Technology Data Exchange (ETDEWEB)

    Nakotte, Heinz [Los Alamos National Laboratory; Rajatram, R [NMSU/UNIV OF N.C.; Kern, S [COLORADO STATE UNIV; Mcqueeney, R J [AMES LAB; Lander, G H [EUROPEAN COMMISIONS, JRC; Robinson, R A [BRAGG INSTITUTE

    2009-01-01

    We performed inelastic neutron scattering (INS) in order to re-investigate the crystal-field ground state and the level splitting in UO{sub 2}. Previous INS studies on UO{sub 2} by Amorelli et al. [Physical Review B 15, 1989, 1856] uncovered four excitations at low temperatures in the 150-180 meV range. Considering the dipole-allowed transitions, only three of these transitions could be explained by the published crystal-field model. Our INS results on a different UO{sub 2} sample revealed that the unaccounted peak at about 180 meV is a spurious one, and thus not intrinsic to UO{sub 2}. In good agreement with Amoretti's results, we corroborated that the ground-state of UO{sub 2} is the {Lambda}{sub 5} triplet, and we computed that the fourth- and six-order crystal field parameters are V{sub 4} = -116 meV and V{sub 6} = 26 meV, respectively. We also studied the INS response of the non-magnetic U{sub 0.4}Th{sub 0.6}O{sub 2}. The splitting for this thorium-doped compound is similar to the one of UO{sub 2}, which orders antiferromagnetically at low temperatures. Therefore, we can conclude that magnetic interactions only weakly perturb the energy level splitting, which is dominated by strong crystal fields.

  8. Crystal structures of the ligand-binding region of uPARAP

    DEFF Research Database (Denmark)

    Yuan, Cai; Jürgensen, Henrik J; Engelholm, Lars H

    2016-01-01

    The proteins of the mannose receptor (MR) family share a common domain organization and have a broad range of biological functions. Urokinase plasminogen activator receptor-associated protein (uPARAP) (or Endo180) is a member of this family and plays an important role in extracellular matrix...... remodelling through interaction with its ligands, including collagens and urokinase plasminogen activator receptor (uPAR). We report the crystal structures of the first four domains of uPARAP (also named the ligand-binding region, LBR) at pH 7.4 in Ca(2+)-bound and Ca(2+)-free forms. The first domain...

  9. Crystal structure and ligand binding properties of the truncated hemoglobin from Geobacillus stearothermophilus.

    Science.gov (United States)

    Ilari, Andrea; Kjelgaard, Peter; von Wachenfeldt, Claes; Catacchio, Bruno; Chiancone, Emilia; Boffi, Alberto

    2007-01-01

    A novel truncated hemoglobin has been identified in the thermophilic bacterium Geobacillus stearothermophilus (Gs-trHb). The protein has been expressed in Escherichia coli, the 3D crystal structure (at 1.5 Angstroms resolution) and the ligand binding properties have been determined. The distal heme pocket displays an array of hydrogen bonding donors to the iron-bound ligands, including Tyr-B10 on one side of the heme pocket and Trp-G8 indole nitrogen on the opposite side. At variance with the highly similar Bacillus subtilis hemoglobin, Gs-trHb is dimeric both in the crystal and in solution and displays several unique structural properties. In the crystal cell, the iron-bound ligand is not homogeneously distributed within each distal site such that oxygen and an acetate anion can be resolved with relative occupancies of 50% each. Accordingly, equilibrium titrations of the oxygenated derivative in solution with acetate anion yield a partially saturated ferric acetate adduct. Moreover, the asymmetric unit contains two subunits and sedimentation velocity ultracentrifugation data confirm that the protein is dimeric.

  10. A ligand-conformation driving chiral generation and symmetry-breaking crystallization of a zinc(II) organoarsonate.

    Science.gov (United States)

    Zhou, Tian-Hua; Zhang, Jian; Zhang, Hai-Xia; Feng, Rui; Mao, Jiang-Gao

    2011-08-21

    An unusual ligand-conformation driving chiral generation and symmetry-breaking crystallization occurred simultaneously in the formation of a layered zinc(II) arsonate Zn(Hcapa)(4,4'-bipy) (1P) and its enantiomorph (1M) without any chiral sources, indicating that the asymmetrical crystallization of the coordination polymer from achiral precursors may be induced by the conformation control of the ligand. This journal is © The Royal Society of Chemistry 2011

  11. Synthesis, characterization and crystal structures of oxovanadium(V complexes derived from similar aroylhydrazone ligands

    Directory of Open Access Journals (Sweden)

    X-Z Zhang

    2015-10-01

    Full Text Available Reaction of [VO(acac2] (acac = acetylacetonate with N’-(5-chloro-2-hydroxybenzylidene-3-methoxybenzohydrazide (H2L1 and N’-(2-hydroxy-4-methoxybenzylidene-4-nitrobenzohydrazide (H2L2 in methanol affords methanol-coordinated mononuclear oxovanadium(V complexes, [VOL1(OMe(MeOH] (1 and [VOL2(OMe(MeOH] (2, respectively. The complexes were characterized by elemental analysis, FT-IR, 1H NMR and 13C NMR spectra. Crystal and molecular structures of the complexes were determined by single crystal X-ray diffraction method. Single crystal X-ray structural studies indicate that the hydrazone ligands coordinate to the VO core through enolate oxygen, phenolate oxygen and azomethine nitrogen. The V atoms in the complexes are in octahedral coordination. Thermal stabilities of the complexes have also been studied. DOI: http://dx.doi.org/10.4314/bcse.v29i3.10

  12. Temperature fields in a growing solar silicon crystal

    Directory of Open Access Journals (Sweden)

    Kondrik A. I.

    2012-06-01

    Full Text Available The optimal thermal terms for growing by Czochralski method Si single-crystals, suitable for making photoelectric energy converters, has been defined by the computer simulation method. Dependences of temperature fields character and crystallization front form on the diameter of the crystal, stage and speed of growing, and also on correlation between diameter and height of the crystal has been studied.

  13. Crystal structure of the urokinase receptor in a ligand-free form

    DEFF Research Database (Denmark)

    Xu, Xiang; Gårdsvoll, Henrik; Yuan, Cai

    2012-01-01

    . The crystal structure of human uPAR in its ligand-free state would clarify this issue, but such information remains unfortunately elusive. We now report the crystal structures of a stabilized, human uPAR (H47C/N259C) in its ligand-free form to 2.4 Å and in complex with amino-terminal fragment (ATF) to 3.2 Å...... represents one of the biologically active conformations of uPAR as defined by extensive biochemical studies. The domain boundary between uPAR DI-DII domains is more flexible than the DII-DIII domain boundary. Two important structural features are highlighted by the present uPAR structure. First, the DI......-DIII domain boundary may face the cell membrane. Second, loop 130-140 of uPAR plays a dynamic role during ligand loading/unloading. Together, these studies provide new insights into uPAR structure-function relationships, emphasizing the importance of the inter-domain dynamics of this modular receptor....

  14. Do Fragments and Crystallization Additives Bind Similarly to Drug-like Ligands?

    Science.gov (United States)

    Drwal, Malgorzata N; Jacquemard, Célien; Perez, Carlos; Desaphy, Jérémy; Kellenberger, Esther

    2017-05-22

    The success of fragment-based drug design (FBDD) hinges upon the optimization of low-molecular-weight compounds (MW additives such as cryoprotectants or buffer components, which are highly abundant in crystal structures, are frequently ignored. Thus, the aim of this study was to investigate the information present in protein complexes with fragments as well as those with additives and how they relate to the binding modes of their drug-like counterparts. We present a thorough analysis of the binding modes of crystallographic additives, fragments, and drug-like ligands bound to four diverse targets of wide interest in drug discovery and highly represented in the Protein Data Bank: cyclin-dependent kinase 2, β-secretase 1, carbonic anhydrase 2, and trypsin. We identified a total of 630 unique molecules bound to the catalytic binding sites, among them 31 additives, 222 fragments, and 377 drug-like ligands. In general, we observed that, independent of the target, protein-fragment interaction patterns are highly similar to those of drug-like ligands and mostly cover the residues crucial for binding. Crystallographic additives are also able to show conserved binding modes and recover the residues important for binding in some of the cases. Moreover, we show evidence that the information from fragments and drug-like ligands can be applied to rescore docking poses in order to improve the prediction of binding modes.

  15. Synthesis, crystal structure and photoluminescence property of Eu/Tb MOFs with mixed polycarboxylate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lu; Zhang, Sheng; Qu, Xiaoni; Yang, Qi [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); Liu, Xiangyu [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021 (China); Wei, Qing; Xie, Gang [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); Chen, Sanping, E-mail: sanpingchen@126.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China)

    2015-11-15

    Lanthanide MOFs, [Eu(TCA)(NDC)·H{sub 2}O]{sub n} (1) and [Tb(TCA)(NDC)·H{sub 2}O]{sub n} (2), have been prepared with the mixed aromatic carboxylate ligands, namely, 4,4′,4″-tricarboxytriphenylamine (H{sub 3}TCA) and 1,4-naphthalenedicarboxylate (H{sub 2}NDC). Single-crystal X-ray diffraction analysis reveals that isomorphic 1 and 2 present pillar-layered 3D framework that Eu/Tb(III) bond with carboxylate in various coordination fashions. Optical investigation indicates that the as-prepared compounds feature characteristic luminescence emission bands of Eu/Tb ions in the visible regions at room temperature. Moreover, compound 2 shows a relatively longer luminescence lifetime (τ=0.342 ms) and significantly enhanced quantum yield (Φ{sub overall}=11%) comparing with those of 1 (τ=0.335 ms, Φ{sub overall}=0.06%). - Graphical abstract: Synoptic: Two Ln-MOFs (Ln=Eu{sup III}, Tb{sup III}) with mixed polycarboxylate ligands present different luminescent properties. - Highlights: • Two Eu/Tb-MOFs with H{sub 3}TCA and H{sub 2}NDC ligands have been obtained. • The ancillary ligand is employed to decrease water molecule coordinate numbers. • 2displays superior quantum yield and lifetime than those of 1.

  16. Synthesis and crystal structure of novel fluorescent 1,3,4-oxadiazole-containing carboxylate ligands

    Science.gov (United States)

    Mikhailov, Igor E.; Popov, Leonid D.; Tkachev, Valery V.; Aldoshin, Sergey M.; Dushenko, Galina A.; Revinskii, Yurii V.; Minkin, Vladimir I.

    2018-04-01

    Novel chelating ligands, 3-(5-aryl-1,3,4-oxadiazol-2-yl)acrylic acids and their zinc complexes were synthesized and their spectral and luminescent properties studied. The compounds intensively (quantum efficiencies φ = 0.18-0.76) luminesce in nonpolar solvents in the blue-green region (λmaxPL = 458-504 nm) of the spectrum. Molecular and crystal structures of 3-[5-(4-dimethylaminophenyl)-1,3,4-oxadiazol-2-yl]acrylic acid were established using X-ray crystallography. In crystal, the infinite chains of the molecules lie in the parallel planes and are arranged by the "head to tail" type to provide for strong π-π stacking interactions between the layers facilitating appearance of high electron transport properties and formation of excimers.

  17. Modelling crystal-field interaction for f-elements in LaCl{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Zhorin, V.V.; Liu, G.K.

    1997-09-01

    The results of crystal field calculations in the framework of exchange charge model (ECM) are reported for trivalent lanthanide and actinide ions doped into LaCl{sub 3}. Whereas the scalar strength of the model crystal field parameters are consistent with that previously determined by fitting the experimental data, the sign of the second-order parameter is found to be negative, in contrast to previous reports. The contribution from long-range electrostatic interactions exceeds that from the nearest neighboring ligands and leads to the negative sign of the second-order crystal field parameter. Other interaction mechanisms including overlap, covalence, and charge exchange are less important to the second order parameter, but dominate the fourth-and sixth-order parameters. This work provides a consistent interpretation of the previously controversial experimental results for both lanthanide and actinide ions in this classical host.

  18. Modeling crystal-field interaction for f-elements in LaCl{sub 3}.

    Energy Technology Data Exchange (ETDEWEB)

    Liu, G. K.; Zhorin, V. V.

    1997-07-14

    The results of crystal field calculations in the framework of exchange charge model (ECM) are reported for trivalent lanthanide and actinide ions doped into LaCl{sub 3}. Whereas the scalar strength of the model crystal field parameters are consistent with that previously determined by fitting the experimental data, the sign of the second-order parameter is found to be negative, in contrast to previous reports. The contribution from long-range electrostatic interactions exceeds that from the nearest neighboring ligands and leads to the negative sign of the second-order crystal field parameter. Other interaction mechanisms including overlap, covalence, and charge exchange are less important to the second order parameter, but dominate the fourth- and sixth-order parameters. This work provides a consistent interpretation of the previously controversial experimental results for both lanthanide and actinide ions in this classical host.

  19. Magnetism and crystal fields in ternary superconductors

    International Nuclear Information System (INIS)

    Shenoy, G.K.; Crabtree, G.W.; Niarchos, D.; Behroozi, F.; Dunlap, B.D.; Hinks, D.; Noakes, D.R.

    1982-01-01

    In this paper, the present state of knowledge of crystalline electric field (CEF) in two important classes of ternary superconductors has been described. It is clear that in understanding the superconducting and magnetic behavior of RERh 4 B 4 , the CEF plays a very important role. Considerable importance has been given to the specific heat Schottky anomalies in deducing the position and degeneracy of various CEF levels. Interpretation of these data is made difficult because of complicated subtraction of lattice, electronic and superconducting specific heats. Furthermore, the purity of the sample is important in such studies. It is known that a few percent of Rh-B/sub x/, RERh 3 B 2 and RERh 6 B 4 are commonly present in RERh 4 B 4 , while Mo-Ch/sub x/, RE-Ch/sub x/ and RE 2 O 2 Ch phases occur in Chevrel phase compounds. Only single-crystal samples will lead to dependable specific heat data

  20. Hydrothermal syntheses, crystal structures, and photophysical properties of two coordination polymers with mixed ligands

    Science.gov (United States)

    Yan, Li; Liu, Chun-Ling

    2017-10-01

    Two novel metal-organic coordination polymers [Cd(ipdt)(m-BDC)·3H2O]n (1) and [Pb(mip)2(NTC) ·2H2O]n (2) [ipdt = 2,6-Dimethoxy-4-(1H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)-phenol, mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC = isophthalic acid, NTC = nicotinic acid] have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 exhibits two-dimensional (2D) layer architecture, and 2 shows 1D chain architecture. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand ipdt, mip and complexes 1-2 are also discussed in detail, which should be acted as potential luminescent material.

  1. Protein Crystal Growth in Gels and Stationary Magnetic Fields

    International Nuclear Information System (INIS)

    Moreno, A.; Quiroz-Garcia, B.; Yokaichiya, F.; Stojanoff, V.; Rudolph, P.

    2007-01-01

    Thaumatin, lysozyme, and ferritin single crystals were grown in solutions and gels without and with surrounding strong stationary magnetic fields. The crystal size, number and alignment in dependence on the induction force were analyzed. The crystal quality, like mosaicity, as function of the magnetic force is discussed by using synchrotron X-ray diffraction analysis

  2. Affinity Interaction between Hexamer Peptide Ligand HWRGWV and Immunoglobulin G Studied by Quartz Crystal Microbalance and Surface Plasmon Resonance

    Science.gov (United States)

    Shen, Fei

    Immunoglobulins (Ig), also referred to as antibodies, act as protective agents against pathogens trying to invade an organism. Human immunoglobulin G (hIgG), as the most prominent immunoglobulin presented in serum and other human fluids, has broad applications in fields like immunotherapy and clinical diagnostics. Staphylococcus aureus Protein A and Streptococcus Protein G are the most common affinity ligands for IgG purifaction and detection. However, drawbacks associated with these two protein ligands have motivated searches for alternative affinity ligands. The hexamer peptide ligand HWRGWV identified from a one-bead-one-peptide combinatorial library synthesized on chromatography resins has demonstrated high affinity and specificity to the Fc fragment of hIgG. A chromatography resin with HWRGWV can purify human IgG (hIgG) from complete minimum essential medium (cMEM) with purities and yields as high as 95%, which are comparable to using Protein A as affinity ligand (4). As a short peptide ligand, HWRGWV can be produced at relatively low costs under good manufacturing practices (GMP) conditions, it is highly robust, less immunogenic and allows for milder elution conditions for the bound antibody (3, 5). Although this short peptide ligand has exhibited promising properties for IgG capture and purification, limited information is available on the intrinsic mechanisms of affinity interaction between the peptide ligand and target protein. In this study, the affinity interaction between hIgG and peptide ligand immobilized on solid surfaces was studied by quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). Compared with previous methods employed for the peptide characterization, QCM and SPR can provide direct measurements of equilibrium adsorption isotherms and rates of adsorption, allowing a complete kinetic and thermodynamics analyses of the ligand-target interactions. New methods were developed to modify gold and silica surfaces of QCM and SPR

  3. Crystal Fields and the Magnetic Properties of Praseodymium and Neodymium

    DEFF Research Database (Denmark)

    Johansson, Torben; Lebech, Bente; Nielsen, Mourits

    1970-01-01

    The magnetic properties of Pr and Nd single crystals have been studied by neutron-diffraction and susceptibility measurements. In contrast to earlier results on polycrystals, monocrystalline Pr is found not to be magnetically ordered, because of crystal field effects, but a magnetic field induces...

  4. Crystal-contact engineering to obtain a crystal form of the Kelch domain of human Keap1 suitable for ligand-soaking experiments

    International Nuclear Information System (INIS)

    Hörer, Stefan; Reinert, Dirk; Ostmann, Katja; Hoevels, Yvette; Nar, Herbert

    2013-01-01

    A mutant of the Kelch domain of the human Keap1 protein has been designed in order to enable the soaking of small-molecule ligands. The apo structure of this mutant is reported at 1.98 Å resolution and the suitability of the crystal system has been demonstrated by the structure of the mutated Keap1 Kelch domain in complex with a cyclic peptide derived from Nrf2. Keap1 is a substrate adaptor protein for a Cul3-dependent ubiquitin ligase complex and plays an important role in the cellular response to oxidative stress. It binds Nrf2 with its Kelch domain and thus triggers the ubiquitinylation and degradation of Nrf2. Oxidative stress prevents the degradation of Nrf2 and leads to the activation of cytoprotective genes. Therefore, Keap1 is an attractive drug target in inflammatory diseases. The support of a medicinal chemistry effort by structural research requires a robust crystallization system in which the crystals are preferably suited for performing soaking experiments. This facilitates the generation of protein–ligand complexes in a routine and high-throughput manner. The structure of human Keap1 has been described previously. In this crystal form, however, the binding site for Nrf2 was blocked by a crystal contact. This interaction was analysed and mutations were introduced to disrupt this crystal contact. One double mutation (E540A/E542A) crystallized in a new crystal form in which the binding site for Nrf2 was not blocked and was accessible to small-molecule ligands. The crystal structures of the apo form of the mutated Keap1 Kelch domain (1.98 Å resolution) and of the complex with an Nrf2-derived peptide obtained by soaking (2.20 Å resolution) are reported

  5. Crystal structure of the ligand-binding domain of the promiscuous EphA4 receptor reveals two distinct conformations

    Energy Technology Data Exchange (ETDEWEB)

    Singla, Nikhil; Goldgur, Yehuda; Xu, Kai; Paavilainen, Sari; Nikolov, Dimitar B.; Himanen, Juha P. (MSKCC); (Turku)

    2010-09-08

    Eph receptors and their ephrin ligands are important mediators of cell-cell communication. They are divided in two subclasses based on their affinities for each other and on sequence conservation. Receptor-ligand binding within each subclass is fairly promiscuous, while binding cross the subclasses happens rarely. EphA4 is an exception to this general rule, since it has long been known to bind both A- and B-class ephrin ligands but the reason for this exceptional behavior has not been worked out at molecular level. Recent structural and biochemical studies on EphA4 ligand-binding domain alone and in complex with its ligands have addressed this question. However, the published structures of EphA4/ephrin complexes differ considerably from each other and strikingly different explanations for the exceptional promiscuity of EphA4 were proposed. To address these contradictory findings, we have determined a crystal structure of the EphA4 ligand-binding domain at 2.3 {angstrom} resolution and show that the receptor has an unprecedented ability to exist in two very different, well-ordered conformations even in the unbound state. Our results suggest that the ligand promiscuity of the Ephs is directly correlated with the structural flexibility of the ligand-binding surface of the receptor.

  6. Two fac-tricarbonylrhenium(I) azadipyrromethene (ADPM) complexes: ligand-substitution effect on crystal structure.

    Science.gov (United States)

    Cibian, Mihaela; Bessette, André; O'Connor, Andrew; Ferreira, Janaina G; Hanan, Garry S

    2015-02-01

    The crystal structures of fac-(acetonitrile-κN)(2-{[3,5-bis(4-methoxyphenyl)-2H-pyrrol-2-ylidene-κN(1)]amino}-3,5-bis(4-methoxyphenyl)-1H-pyrrol-1-ido-κN(1))tricarbonylrhenium(I)-hexane-acetonitrile (2/1/2), [Re(C36H30N3O4)(CH3CN)(CO)3]·0.5C6H14·CH3CN, (2), and fac-(2-{[3,5-bis(4-methoxyphenyl)-2H-pyrrol-2-ylidene-κN(1)]amino}-3,5-bis(4-methoxyphenyl)-1H-pyrrol-1-ido-κN(1))tricarbonyl(dimethyl sulfoxide-κO)rhenium(I), [Re(C36H30N3O4)(C2H6OS)(CO)3], (3), at 150 K are reported. Both complexes display a distorted octahedral geometry, with a fac-Re(CO)3 arrangement and one azadipyrromethene (ADPM) chelating ligand in the equatorial position. One solvent molecule completes the coordination sphere of the Re(I) centre in the remaining axial position. The ADPM ligand shows high flexibility upon coordination, while retaining its π-delocalized nature. Bond length and angle analyses indicate that the differences in the geometry around the Re(I) centre in (2) and (3), and those found in three reported fac-Re(CO)3-ADPM complexes, are dictated mainly by steric factors and crystal packing. Both structures display intramolecular C-H...N hydrogen bonding. Intermolecular interactions of the Csp(2)-H...π and Csp(2)-H...O(carbonyl) types link the discrete monomers into extended chains.

  7. Ligand Field Strengths of Carbon Monoxide and Cyanide in Octahedral Coordination

    National Research Council Canada - National Science Library

    Hummel, Patrick; Oxgaard, Jonas; Goddard, III, William A; Gray, Harry B

    2005-01-01

    Ligand field splittings were extracted from absorption spectra of metal hexacarbonyl and hexacyano complexes over 35 years ago by Gray and coworkers (J. Am. Chem. Soc., 85, 2922 (1963); ibid. 90, 4260, 5713 (1968...

  8. Crystal structure-based virtual screening for novel fragment-like ligands of the human histamine H1 receptor

    NARCIS (Netherlands)

    de Graaf, C.; Kooistra, A.J.; Vischer, H.F.; Katritch, V; Kuijer, M.; Shiroishi, M; Shimamura, T; Iwata, S; Stevens, R.C.; de Esch, I.J.P.; Leurs, R.

    2011-01-01

    The recent crystal structure determinations of druggable class A G protein-coupled receptors (GPCRs) have opened up excellent opportunities in structure-based ligand discovery for this pharmaceutically important protein family. We have developed and validated a customized structure-based virtual

  9. From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields.

    Science.gov (United States)

    Hoffmann, Roald; Alvarez, Santiago; Mealli, Carlo; Falceto, Andrés; Cahill, Thomas J; Zeng, Tao; Manca, Gabriele

    2016-07-27

    We begin with a brief historical review of the development of our understanding of the normal ordering of nd orbitals of a transition metal interacting with ligands, the most common cases being three below two in an octahedral environment, two below three in tetrahedral coordination, and four below one in a square-planar environment. From the molecular orbital construction of these ligand field splittings evolves a strategy for inverting the normal order: the obvious way to achieve this is to raise the ligand levels above the metal d's; that is, make the ligands better Lewis bases. However, things are not so simple, for such metal/ligand level placement may lead to redox processes. For 18-electron octahedral complexes one can create the inverted situation, but it manifests itself in the makeup of valence orbitals (are they mainly on metal or ligands?) rather than energy. One can also see the effect, in small ways, in tetrahedral Zn(II) complexes. We construct several examples of inverted ligand field systems with a hypothetical but not unrealistic AlCH3 ligand and sketch the consequences of inversion on reactivity. Special attention is paid to the square-planar case, exemplified by [Cu(CF3)4](-), in which Snyder had the foresight to see a case of an inverted field, with the empty valence orbital being primarily ligand centered, the dx2-y2 orbital heavily occupied, in what would normally be called a Cu(III) complex. For [Cu(CF3)4](-) we provide theoretical evidence from electron distributions, geometry of the ligands, thermochemistry of molecule formation, and the energetics of abstraction of a CF3 ligand by a base, all consistent with oxidation of the ligands in this molecule. In [Cu(CF3)4](-), and perhaps more complexes on the right side of the transition series than one has imagined, some ligands are σ-noninnocent. Exploration of inverted ligand fields helps us see the continuous, borderless transition from transition metal to main group bonding. We also give

  10. First-row transition metal-pyridine (py)-sulfate [(py)xM](SO4) complexes (M = Ni, Cu and Zn): crystal field theory in action.

    Science.gov (United States)

    Roy, Mrittika; Pham, Duyen N K; Kreider-Mueller, Ava; Golen, James A; Manke, David R

    2018-03-01

    The crystal structures of three first-row transition metal-pyridine-sulfate complexes, namely catena-poly[[tetrakis(pyridine-κN)nickel(II)]-μ-sulfato-κ 2 O:O'], [Ni(SO 4 )(C 5 H 5 N) 4 ] n , (1), di-μ-sulfato-κ 4 O:O-bis[tris(pyridine-κN)copper(II)], [Cu 2 (SO 4 ) 2 (C 5 H 5 N) 6 ], (2), and catena-poly[[tetrakis(pyridine-κN)zinc(II)]-μ-sulfato-κ 2 O:O'-[bis(pyridine-κN)zinc(II)]-μ-sulfato-κ 2 O:O'], [Zn 2 (SO 4 ) 2 (C 5 H 5 N) 6 ] n , (3), are reported. Ni compound (1) displays a polymeric crystal structure, with infinite chains of Ni II atoms adopting an octahedral N 4 O 2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. Cu compound (2) features a dimeric molecular structure, with the Cu II atoms possessing square-pyramidal N 3 O 2 coordination environments that contain three pyridine ligands and two bridging sulfate ligands. Zn compound (3) exhibits a polymeric crystal structure of infinite chains, with two alternating zinc coordination environments, i.e. octahedral N 4 O 2 coordination involving four pyridine ligands and two bridging sulfate ligands, and tetrahedral N 2 O 2 coordination containing two pyridine ligands and two bridging sulfate ligands. The observed coordination environments are consistent with those predicted by crystal field theory.

  11. Enhancement of crystal homogeneity of protein crystals under application of an external alternating current electric field

    Energy Technology Data Exchange (ETDEWEB)

    Koizumi, H.; Uda, S.; Fujiwara, K.; Nozawa, J. [Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577 (Japan); Tachibana, M. [Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama, 236-0027 (Japan); Kojima, K. [Department of Education, Yokohama Soei University, 1 Miho-tyou, Midori-ku, Yokohama, 226-0015 (Japan)

    2014-10-06

    X-ray diffraction rocking-curve measurements were performed on tetragonal hen egg white (HEW) lysozyme crystals grown with and without the application of an external alternating current (AC) electric field. The crystal quality was assessed by the full width at half maximum (FWHM) value for each rocking curve. For two-dimensional maps of the FWHMs measured on the 440 and the 12 12 0 reflection, the crystal homogeneity was improved under application of an external electric field at 1 MHz, compared with that without. In particular, the significant improvement of the crystal homogeneity was observed for the 12 12 0 reflection.

  12. Characteristic Ligand-Induced Crystal Forms of HIV-1 Protease Complexes: A Novel Discovery of X-Ray Crystallography

    International Nuclear Information System (INIS)

    Olajuyigbe, Folasade M.; Geremia, Silvano

    2009-10-01

    Mixtures of saquinavir (SQV) and ritonavir (RTV) were cocrystallized with HIV-1 protease (PR) in an attempt to compare their relative potencies using a crystallographic approach and factors responsible for the respective crystal forms obtained were examined. The mixture ratio of the SQV/RTV was in the range of 1:1 to 1:50 with increasing concentration of dimethyl sulphoxide (DMSO) used. Two crystal forms of PR complexes were obtained. At concentrations of 0.8 and 1.2 % DMSO using 1:1 and 1:15 ratios of SQV/RTV, the crystal form was monoclinic while increasing the concentration of DMSO to 3.2 and 5.0% using 1:15 and 1:50 ratios of SQV/RTV, the orthorhombic crystal form was obtained. The high resolution X-ray crystal structures of the PR/ inhibitor complexes reveal that crystal forms with respective space groups are dependent on the occupancy of either SQV or RTV in the active site of the PR. The occupancy of either of the PR inhibitors in the active site of PR has interestingly demonstrated unique cooperativity effects in crystallization of protein-ligand complexes. The crystal forms obtained were also related to the concentration of DMSO and ammonium sulphate in crystallization, and storage conditions of purified PR. Surprisingly, the relative occupancies of these inhibitors in the active site suggested a competition between the two inhibitors which were not inhibition constants related. Analysis of the structures in both crystal forms show no difference in DMSO content but at higher concentration of DMSO (3.2 - 5.0%) in the orthorhombic crystal forms, there were protein-sulphate interactions which were absent in the monoclinic forms with lower concentration (0.8 - 1.2%) of DMSO. This work has clearly demonstrated that there is cooperativity in crystallization and the conditions of crystallization influence specific intermolecular contacts in crystal packing (crystal form). (author)

  13. Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

    Directory of Open Access Journals (Sweden)

    Hiroshi Yao

    2016-10-01

    Full Text Available Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R-/(S-2-phenylpropane-1-thiol, (R-/(S-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of

  14. Optical and dielectric studies of KH2PO4 crystal influenced by organic ligand of citric acid and l-valine: A single crystal growth and comparative study

    Directory of Open Access Journals (Sweden)

    Mohd Anis

    Full Text Available In the present study pure, citric acid (CA and l-valine (LV doped potassium dihydrogen phosphate (KDP crystals have been grown with the aim to investigate the nonlinear optical applications facilitated by UV–visible, third order nonlinear optical (TONLO and dielectric properties. The structural parameters of grown crystals have been confirmed by single crystal X-ray diffraction analysis. The enhancement in optical transparency of KDP crystal due to addition of CA and LV has been examined within 200–900 nm by means of UV–visible spectral analysis. In addition, the transmittance data have been used to evaluate the effect of dopants on reflectance, refractive index and extinction coefficient of grown crystals in the visible region. The Z-scan analysis has been performed at 632.8 nm to identify the nature of photoinduced nonlinear refraction and nonlinear absorption in doped KDP crystals. The influence of π-bonded ligand of dopant CA and LV on TONLO susceptibility (χ3, refractive index (n2 and absorption coefficient (β of KDP crystals has been evaluated to discuss laser assisted device applications. The decrease in dielectric constant and dielectric loss of KDP crystal due to addition of CA and LV has been explored using the temperature dependent dielectric studies. Keywords: Crystal growth, Nonlinear optical materials, UV–visible studies, Z-scan analysis, Dielectric studies

  15. Near-field probing of photonic crystals

    NARCIS (Netherlands)

    Flück, E.; Hammer, Manfred; Vos, Willem L.; van Hulst, N.F.; Kuipers, L.

    2004-01-01

    Photonic crystals form an exciting new class of optical materials that can greatly affect optical propagation and light emission. As the relevant length scale is smaller than the wavelength of light, sub-wavelength detection forms an important ingredient to obtain full insight in the physical

  16. Field renormalization in photonic crystal waveguides

    DEFF Research Database (Denmark)

    Colman, Pierre

    2015-01-01

    A novel strategy is introduced in order to include variations of the nonlinearity in the nonlinear Schro¨dinger equation. This technique, which relies on renormalization, is in particular well adapted to nanostructured optical systems where the nonlinearity exhibits large variations up to two...... Schro¨dinger equation is an occasion for physics-oriented considerations and unveils the potential of photonic crystal waveguides for the study of new nonlinear propagation phenomena....

  17. Field induced heliconical structure of cholesteric liquid crystal

    Science.gov (United States)

    Lavrentovich, Oleg D.; Shiyanovsii, Sergij V.; Xiang, Jie; Kim, Young-Ki

    2017-06-27

    A diffraction grating comprises a liquid crystal (LC) cell configured to apply an electric field through a cholesteric LC material that induces the cholesteric LC material into a heliconical state with an oblique helicoid director. The applied electric field produces diffracted light from the cholesteric LC material within the visible, infrared or ultraviolet. The axis of the heliconical state is in the plane of the liquid crystal cell or perpendicular to the plane, depending on the application. A color tuning device operates with a similar heliconical state liquid crystal material but with the heliconical director axis oriented perpendicular to the plane of the cell. A power generator varies the strength of the applied electric field to adjust the wavelength of light reflected from the cholesteric liquid crystal material within the visible, infrared or ultraviolet.

  18. Optical properties of 3d-ions in crystals spectroscopy and crystal field analysis

    CERN Document Server

    Brik, Mikhail

    2013-01-01

    "Optical Properties of 3d-Ions in Crystals: Spectroscopy and Crystal Field Analysis" discusses spectral, vibronic and magnetic properties of 3d-ions in a wide range of crystals, used as active media for solid state lasers and potential candidates for this role. Crystal field calculations (including first-principles calculations of energy levels and absorption spectra) and their comparison with experimental spectra, the Jahn-Teller effect, analysis of vibronic spectra, materials science applications are systematically presented. The book is intended for researchers and graduate students in crystal spectroscopy, materials science and optical applications. Dr. N.M. Avram is an Emeritus Professor at the Physics Department, West University of Timisoara, Romania; Dr. M.G. Brik is a Professor at the Institute of Physics, University of Tartu, Estonia.

  19. Mapping the absolute electromagnetic field strength of individual field components inside a photonic crystal

    NARCIS (Netherlands)

    Denis, T.; Reijnders, B.; Lee, J.H.H.; Vos, Willem L.; Boller, Klaus J.; van der Slot, Petrus J.M.

    2013-01-01

    We present a method to map the absolute electromagnetic field strength inside photonic crystals. We demonstrate our method by applying it to map the electric field component Ez of a two-dimensional photonic crystal slab at microwave frequencies. The slab is placed between two mirrors to create a

  20. Zinc(II) halide complexes with 2-methoxyaniline ligand: Synthesis, characterization, thermal analyses, crystal structure determination and luminescent properties

    Science.gov (United States)

    Amani, Vahid

    2018-03-01

    Three new mononuclear zinc(II) complexes, [Zn(2-MeO-C6H4NH2)2X2] (X is Cl in 1, Br in 2 and I in 3), were prepared from the reactions of ZnX2 with 2-methoxyaniline (2-MeO-C6H4NH2) ligand in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurements by slow evaporation of methanol solution at room temperature. The three complexes were thoroughly characterized by thermogravimetric analysis, elemental analysis (CHNO), spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the zinc(II) cation is four-coordinated in a distorted tetrahedral configuration by two N atoms from two 2-methoxyanyline ligands and two halide anions. Also, in these complexes intermolecular interactions, for example Nsbnd H⋯X hydrogen bonds (in 1-3), Csbnd H⋯X hydrogen bonds (in 3), Csbnd H⋯π interactions (in 1 and 2) and π⋯π interactions (in 3), are effective in the stabilization of the crystal structures. In addition, the luminescence spectra of all complexes in methanolic solution show that the intensity of their emission bands is stronger than that for free 2-methoxyaniline ligand.

  1. Integral parameters of crystal field for RE spectra

    International Nuclear Information System (INIS)

    Kustov, E.F.; Maketov, T.K.; Prgevudsky, A.K.; Steczko, G.

    1980-01-01

    The integral parameters of the crystal field are introduced for the interpretation of the spectra of RE ions in various crystals. The main formula of the method, the expression of the parameters for various states of Ce, Pr, Nd, Eu, Tb, Er, Tu, and Yb are determined. Integral parameters of A 2 , A 4 , A 6 and parameter of the spin-orbit interaction xi are calculated for 40 laser crystals with Nd, Er. An interpretation of the symmetry of the Eu 3+ centres of the NaBaZn silicate glass is given using integral parameters A 2 , A 4 . (author)

  2. Reversible Single-Crystal-to-Single-Crystal Structural Transformation in a Mixed-Ligand 2D Layered Metal-Organic Framework: Structural Characterization and Sorption Study

    Directory of Open Access Journals (Sweden)

    Chih-Chieh Wang

    2017-12-01

    Full Text Available A 3D supramolecular network, [Cd(bipy(C4O4(H2O2]·3H2O (1 (bipy = 4,4′-bipyridine and C4O42− = dianion of H2C4O4, constructed by mixed-ligand two-dimensional (2D metal-organic frameworks (MOFs has been reported and structurally determined by the single-crystal X-ray diffraction method and characterized by other physicochemical methods. In 1, the C4O42− and bipy both act as bridging ligands connecting the Cd(II ions to form a 2D layered MOF, which are then extended to a 3D supramolecular network via the mutually parallel and interpenetrating arrangements among the 2D-layered MOFs. Compound 1 shows a two-step dehydration process with weight losses of 11.0% and 7.3%, corresponding to the weight-loss of three guest and two coordinated water molecules, respectively, and exhibits an interesting reversible single-crystal-to-single-crystal (SCSC structural transformation upon de-hydration and re-hydration for guest water molecules. The SCSC structural transformation have been demonstrated and monitored by single-crystal and X-ray powder diffraction, and thermogravimetic analysis studies.

  3. Application of X-ray single crystal diffractometry to investigation of Np(5) complexes with n-donor ligands

    International Nuclear Information System (INIS)

    Andreev, G.

    2007-01-01

    Full text of publication follows. We present here some results of application of conventional X-ray single crystal diffractometry to the research on the interaction of Np(V) with N-donor ligands. Compounds that can coordinate to actinides through one or several nitrogen atoms are of a great variety and occur widely in the biosphere. For example, imidazole, pyridine and their derivatives are the building blocks of many biologically important molecules; triazines are known to occur in some aquatic plants. The presence of anthropogenic organic agents like amine-N-carboxylic acids in surface waters has the potential to re-mobilize metals from sediments and aquifers and to influence their bioavailability. The interaction of radionuclides with such ligands needs to be studied in detail to give fundamental understanding the conditions of the incorporation of long lived a-emitters (Np and Pu primarily) into the food chain. Another aspect of the same problem is the design of new chelating ligands for selective co-ordination of actinide ions as an alternative to the traditional sequestering agents. The problem of the separation of long-lived minor actinides and their transmutation also calls for design of new highly selective ligands for solvent extraction. Polydentate N-donor ligands are now considered to be very promising. A detailed study of structural chemistry is crucial for understanding the relationship between the architecture of the ligands and their binding affinity for actinides. The X-ray single crystal diffractometry became conventional technique as applied to the investigation of actinides in spite of difficulties regarding safe handling of radionuclides. This technique provides unambiguous information about modes of the ligand co-ordination to the metal ion and geometrical parameters of complexes. Moreover, the employment of a synchrotron radiation shows considerable promise for determination of solid state structures as well as obtaining structural

  4. Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

    Science.gov (United States)

    Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

    2016-01-26

    Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

  5. Magnetic Field Applications in Semiconductor Crystal Growth and Metallurgy

    Science.gov (United States)

    Mazuruk, Konstantin; Ramachandran, Narayanan; Grugel, Richard; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    The Traveling Magnetic Field (TMF) technique, recently proposed to control meridional flow in electrically conducting melts, is reviewed. In particular, the natural convection damping capability of this technique has been numerically demonstrated with the implication of significantly improving crystal quality. Advantages of the traveling magnetic field, in comparison to the more mature rotating magnetic field method, are discussed. Finally, results of experiments with mixing metallic alloys in long ampoules using TMF is presented

  6. On the laws of disordering of the Ln3+ -ion crystal field in insulating crystals

    International Nuclear Information System (INIS)

    Kaminskij, A.A.

    1988-01-01

    Results of the study of fundamental regularities, which cause crystal field (CF) disordering on Ln 3+ ions in dielectric crystals are summed up. Analysis and systematization of the investigation results of atomic structure of disordered laser crystals and conducted investigations on spectroscopic properties and induced radiation (IR) permitted to come to the conclusion that the nature of disordering on CF is related to two fundamental regularities. The first regularity- the structural-dynamic one- is pronounced in numerous nonstoichiometric phases; the second one - determines spectroscopic properties and IR character

  7. Crystal field and crossover effects in the scheelite structure

    Energy Technology Data Exchange (ETDEWEB)

    Kazei, Z.A. [Physics Department, Moscow State University, 119992 Moscow (Russian Federation)]. E-mail: kazei@plms.phys.msu.su; Snegirev, V.V. [Physics Department, Moscow State University, 119992 Moscow (Russian Federation); Andreenko, A.S. [Physics Department, Moscow State University, 119992 Moscow (Russian Federation); Kondratiev, O.D. [Physics Department, Moscow State University, 119992 Moscow (Russian Federation)

    2006-05-15

    The Zeeman effect, magnetization and differential magnetic susceptibility of a DyLiF{sub 4} crystal are investigated experimentally and theoretically in pulsed magnetic fields. Energy level crossing of the Dy{sup 3+} ion is found for H-parallel [0 0 1], resulting in peaks of the differential magnetic susceptibility dM/dH and inflection points in the magnetization curves M(H) at low temperatures. Magnetic anomalies at the crossover in DyLiF{sub 4} are shown to be sensitive to the electron structure of the Dy{sup 3+} ion, which allows this effect to be used for refining the crystal field parameters.

  8. Crystal field in rare-earth metals and intermetallic compounds

    International Nuclear Information System (INIS)

    Ray, D.K.

    1978-01-01

    Reasons for the success of the crystal-field model for the rare-earth metals and intermetallic compounds are discussed. A review of some of the available experimental results is made with emphasis on cubic intermetallic compounds. Various sources of the origin of the crystal field in these metals are discussed in the background of the recent APW picture of the conduction electrons. The importance of the non-spherical part of the muffin-tin potential on the single-ion anisotropy is stressed. (author)

  9. Fine structure of fields in 2D photonic crystal waveguides

    DEFF Research Database (Denmark)

    Lavrinenko, Andrei; Volkov, V. S.; Bozhevolnyi, S. I.

    2006-01-01

    We resolve fine structure of fields in a single-row missing photonic crystal waveguide by finite-difference time-domain modelling and SNOM measurements. Both linear dispersion and slow-light regimes in proximity of the cutoff are addressed in the analysis.......We resolve fine structure of fields in a single-row missing photonic crystal waveguide by finite-difference time-domain modelling and SNOM measurements. Both linear dispersion and slow-light regimes in proximity of the cutoff are addressed in the analysis....

  10. Correlation theory of crystal field and anisotropic exchange effects

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    1985-01-01

    A general theory for including correlation effects in static and dynamic properties is presented in terms of Raccah or Stevens operators. It is explicitly developed for general crystal fields and anisotropic interactions and systems with several sublattices, like the rare earth compounds. The the......A general theory for including correlation effects in static and dynamic properties is presented in terms of Raccah or Stevens operators. It is explicitly developed for general crystal fields and anisotropic interactions and systems with several sublattices, like the rare earth compounds...... on the susceptibility, the first and second moment frequencies and the line shape are calculated self-consistently....

  11. Thermal conductivity of niobium single crystals in a magnetic field

    International Nuclear Information System (INIS)

    Gladun, C.; Vinzelberg, H.

    1980-01-01

    The thermal conductivity in longitudinal magnetic fields up to 5 T and in the temperature range 3.5 to 15 K is measured in two high purity niobium single crystals having residual resistivity ratios of 22700 and 19200 and orientations of the rod axis [110] and [100]. The investigations show that by means of the longitudinal magnetic field the thermal conductivity may decrease only to a limiting value. In the crystal directions [110] and [100] for the ratio of the thermal conductivity in zero field and the thermal conductivity in the saturation field the temperature-independent factors 1.92 and 1.27, respectively, are determined. With the aid of these factors the thermal conductivity in the normal state is evaluated from the measured values of thermal conductivity below Tsub(c) in the magnetic field. The different conduction and scattering mechanisms are discussed. (author)

  12. Electromagnetic Field Effects in Semiconductor Crystal Growth

    Science.gov (United States)

    Dulikravich, George S.

    1996-01-01

    This proposed two-year research project was to involve development of an analytical model, a numerical algorithm for its integration, and a software for the analysis of a solidification process under the influence of electric and magnetic fields in microgravity. Due to the complexity of the analytical model that was developed and its boundary conditions, only a preliminary version of the numerical algorithm was developed while the development of the software package was not completed.

  13. Crystallization of Calcium Carbonate in a Large Scale Field Study

    Science.gov (United States)

    Ueckert, Martina; Wismeth, Carina; Baumann, Thomas

    2017-04-01

    The long term efficiency of geothermal facilities and aquifer thermal energy storage in the carbonaceous Malm aquifer in the Bavarian Molasse Basin is seriously affected by precipitations of carbonates. This is mainly caused by pressure and temperature changes leading to oversaturation during production. Crystallization starts with polymorphic nuclei of calcium carbonate and is often described as diffusion-reaction controlled. Here, calcite crystallization is favoured by high concentration gradients while aragonite crystallization is occurring at high reaction rates. The factors affecting the crystallization processes have been described for simplified, well controlled laboratory experiments, the knowledge about the behaviour in more complex natural systems is still limited. The crystallization process of the polymorphic forms of calcium carbonate were investigated during a heat storage test at our test site in the eastern part of the Bavarian Molasse Basin. Complementary laboratory experiments in an autoclave were run. Both, field and laboratory experiments were conducted with carbonaceous tap water. Within the laboratory experiments additionally ultra pure water was used. To avoid precipitations of the tap water, a calculated amount of {CO_2} was added prior to heating the water from 45 - 110°C (laboratory) resp. 65 - 110°C (field). A total water volume of 0.5 L (laboratory) resp. 1 L (field) was immediately sampled and filtrated through 10 - 0.1

  14. Synthesis and Crystal Structures of Ni(II)/(III) and Zn(II) Complexes with Schiff Base Ligands

    International Nuclear Information System (INIS)

    Koo, Bon Kweon

    2013-01-01

    Coordination polymers are of great interest due to their intriguing structural motifs and potential applications in optical, electronic, magnetic, and porous materials. The most commonly used strategy for designing such materials relies on the utilization of multidentate N- or Odonor ligands which have the capacity to bridge between metal centers to form polymeric structures. The Schiff bases with N,O,S donor atoms are an useful source as they are readily available and easily form stable complexes with most transition metal ions. Schiff bases are also important intermediates in synthesis of some bioactive compounds and are potent anti-bacterial, anti-fungal, anticancer and antiviral compounds. In this work, the Schiff bases, Hapb and Hbpb, derived from 2-acetylpyridene or 2-benzoylpyridine and benzhydrazide were taken as trifunctional (N,N,O) monobasic ligand (Scheme 1). This ligand is of important because the π-delocalization of charge and the configurational flexibility of their molecular chain can give rise to a great variety of coordination modes. Although many metal.Schiff base complexes have been reported, the 1D, 2D, and 3D networks of coordination polymers linked through the bridging of ligands such as dicyanamide, N(CN) 2 - as coligand have been little published. In the process of working to extend the dimensionality of the metal-Schiff base complexes using benzilic acid as a bridging ligand, we obtained three simple metal (II)/(III) complexes of acetylpyridine/2-benzoyl pyridine based benzhydrazide ligand. Therefore, we report here the synthesis and crystal structures of the complexes

  15. Synthesis and Crystal Structures of Ni(II)/(III) and Zn(II) Complexes with Schiff Base Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Bon Kweon [Catholic Univ., of Daegu, Daegu (Korea, Republic of)

    2013-12-15

    Coordination polymers are of great interest due to their intriguing structural motifs and potential applications in optical, electronic, magnetic, and porous materials. The most commonly used strategy for designing such materials relies on the utilization of multidentate N- or Odonor ligands which have the capacity to bridge between metal centers to form polymeric structures. The Schiff bases with N,O,S donor atoms are an useful source as they are readily available and easily form stable complexes with most transition metal ions. Schiff bases are also important intermediates in synthesis of some bioactive compounds and are potent anti-bacterial, anti-fungal, anticancer and antiviral compounds. In this work, the Schiff bases, Hapb and Hbpb, derived from 2-acetylpyridene or 2-benzoylpyridine and benzhydrazide were taken as trifunctional (N,N,O) monobasic ligand (Scheme 1). This ligand is of important because the π-delocalization of charge and the configurational flexibility of their molecular chain can give rise to a great variety of coordination modes. Although many metal.Schiff base complexes have been reported, the 1D, 2D, and 3D networks of coordination polymers linked through the bridging of ligands such as dicyanamide, N(CN){sub 2}{sup -} as coligand have been little published. In the process of working to extend the dimensionality of the metal-Schiff base complexes using benzilic acid as a bridging ligand, we obtained three simple metal (II)/(III) complexes of acetylpyridine/2-benzoyl pyridine based benzhydrazide ligand. Therefore, we report here the synthesis and crystal structures of the complexes.

  16. Crystallization and preliminary X-ray crystallographic study of the extracellular domain of the 4-1BB ligand, a member of the TNF family

    International Nuclear Information System (INIS)

    Byun, Jung-Sue; Kim, Dong-Uk; Ahn, Byungchan; Kwon, Byoung Se; Cho, Hyun-Soo

    2005-01-01

    The extracellular domain of the 4-1BB ligand fused with glutathione-S-transferase was expressed in Escherichia coli (Origami) and purified by using affinity and ion-exchange column chromatographic methods. Crystals of the 4-1BB ligand were obtained at 290 K by the hanging-drop vapour-diffusion method. The 4-1BB ligand, a member of the tumour necrosis factor (TNF) family, is an important co-stimulatory molecule that plays a key role in the clonal expansion and survival of CD8+ T cells. Signalling through binding of the 4-1BB ligand and 4-1BB has been reported to enhance CD8+ T-cell expansion and protect activated CD8+ T cells from death. The 4-1BB ligand is an integral protein expressed on activated antigen-presenting cells. The extracellular domain of the 4-1BB ligand fused with glutathione-S-transferase was expressed in Escherichia coli (Origami) and purified by using affinity and ion-exchange column chromatographic methods. Crystals of the 4-1BB ligand were obtained at 290 K by the hanging-drop vapour-diffusion method. X-ray diffraction data were collected from these crystals to 2.8 Å resolution and the crystals belong to space group C2, with unit-cell parameters a = 114.6, b = 73.8, c = 118.50 Å, β = 115.5°

  17. Crystal structure of a mixed-ligand dinuclear Ba—Zn complex with 2-methoxyethanol having triphenylacetate and chloride bridges

    Directory of Open Access Journals (Sweden)

    Józef Utko

    2015-07-01

    Full Text Available The dinuclear barium–zinc complex, μ-chlorido-1:2κ2Cl:Cl-chlorido-2κCl-bis(2-methoxyethanol-1κObis(2-methoxyethanol-1κ2O,O′bis(μ-triphenylacetato-1:2κ2O:O′bariumzinc, [BaZn(C20H15O22Cl2(C3H8O24], has been synthesized by the reaction of barium triphenylacetate, anhydrous zinc chloride and 2-methoxyethanol in the presence of toluene. The barium and zinc metal cations in the dinuclear complex are linked via one chloride anion and carboxylate O atoms of the triphenylacetate ligands, giving a Ba...Zn separation of 3.9335 (11 Å. The irregular nine-coordinate BaO8Cl coordination centres comprise eight O-atom donors, six of them from 2-methoxyethanol ligands (four from two bidentate O,O′-chelate interactions and two from monodentate interactions, two from bridging triphenylacetate ligands and one from a bridging Cl donor. The distorted tetrahedral coordination sphere of zinc comprises two O-atom donors from the triphenylacetate ligands and two Cl donors (one bridging and one terminal. In the crystal, O—H...Cl, O—H...O and C—H...Cl intermolecular interactions form a layered structure, lying parallel to (001.

  18. Dispersive crystal field excitations and quadrupolar interactions in UPd3.

    Science.gov (United States)

    Le, M D; McEwen, K A; Rotter, M; Jensen, J; Bewley, R I; Guidi, T; Fort, D

    2012-01-25

    We report inelastic neutron scattering measurements and random phase approximation calculations of the dispersive crystal field excitations of UPd(3). The measured spectra at lower energies agree with those calculated using quadrupolar interaction parameters deduced from bulk and x-ray scattering measurements. The more intense excitations arising from the hexagonal sites were used to obtain exchange parameters which proved to be anisotropic.

  19. Dispersive crystal field excitations and quadrupolar interactions in UPd3

    OpenAIRE

    Le, M.D.; McEwen, K.A.; Rotter, M.; Jensen, J.; Bewley, R.I.; Guidi, T.; Fort, D

    2012-01-01

    We report inelastic neutron scattering measurements and random phase approximation calculations of the dispersive crystal field excitations of UPd3. The measured spectra at lower energies agree with those calculated using quadrupolar interaction parameters deduced from bulk and x ray scattering measurements. The more intense excitations arising from the hexagonal sites were used to obtain exchange parameters which proved to be anisotropic

  20. Crystal structure of a multi-domain human smoothened receptor in complex with a super stabilizing ligand

    Science.gov (United States)

    Zhang, Xianjun; Zhao, Fei; Wu, Yiran; Yang, Jun; Han, Gye Won; Zhao, Suwen; Ishchenko, Andrii; Ye, Lintao; Lin, Xi; Ding, Kang; Dharmarajan, Venkatasubramanian; Griffin, Patrick R.; Gati, Cornelius; Nelson, Garrett; Hunter, Mark S.; Hanson, Michael A.; Cherezov, Vadim; Stevens, Raymond C.; Tan, Wenfu; Tao, Houchao; Xu, Fei

    2017-05-01

    The Smoothened receptor (SMO) belongs to the Class Frizzled of the G protein-coupled receptor (GPCR) superfamily, constituting a key component of the Hedgehog signalling pathway. Here we report the crystal structure of the multi-domain human SMO, bound and stabilized by a designed tool ligand TC114, using an X-ray free-electron laser source at 2.9 Å. The structure reveals a precise arrangement of three distinct domains: a seven-transmembrane helices domain (TMD), a hinge domain (HD) and an intact extracellular cysteine-rich domain (CRD). This architecture enables allosteric interactions between the domains that are important for ligand recognition and receptor activation. By combining the structural data, molecular dynamics simulation, and hydrogen-deuterium-exchange analysis, we demonstrate that transmembrane helix VI, extracellular loop 3 and the HD play a central role in transmitting the signal employing a unique GPCR activation mechanism, distinct from other multi-domain GPCRs.

  1. Mononuclear mercury(II) complexes containing bipyridine derivatives and thiocyanate ligands: Synthesis, characterization, crystal structure determination, and luminescent properties

    Science.gov (United States)

    Amani, Vahid; Alizadeh, Robabeh; Alavije, Hanieh Soleimani; Heydari, Samira Fadaei; Abafat, Marzieh

    2017-08-01

    A series of mercury(II) complexes, [Hg(Nsbnd N)(SCN)2] (Nsbnd N is 4,4‧-dimethyl-2,2‧-bipyridine in 1, 5,5‧-dimethyl-2,2‧-bipyridine in 2, 6,6‧-dimethyl-2,2‧-bipyridine in 3 and 6-methyl-2,2‧-bipyridine in 4), were prepared from the reactions of Hg(SCN)2 with mentioned ligands in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurement by methanol diffusion into a DMSO solution. The four complexes were thoroughly characterized by spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), elemental analysis (CHNS) and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the mercury(II) cation is four-coordinated in a distorted tetrahedral configuration by two S atoms from two thiocyanate anions and two N atoms from one chelating 2,2‧-bipyridine derivative ligand. Also, in these complexes intermolecular interactions, for example Csbnd H⋯N hydrogen bonds (in 1-4), Csbnd H⋯S hydrogen bonds (in 1, 2 and 4), π … π interactions (in 2-4), Hg⋯N interactions (in 2) and S⋯S interactions (in 4), are effective in the stabilization of the crystal structures and the formation of the 3D supramolecular complexes. Furthermore, the luminescence spectra of the title complexes show that the intensity of their emission bands are stronger than the emission bands for the free bipyridine derivative ligands.

  2. Key role of higher order symmetry and electrostatic ligand field design in the magnetic relaxation of low-coordinate Er(iii) complexes.

    Science.gov (United States)

    Singh, Saurabh Kumar; Pandey, Bhawana; Velmurugan, Gunasekaran; Rajaraman, Gopalan

    2017-09-12

    The conceptual framework of electrostatic ligand field modulation based on oblate/prolate type electron density of lanthanide ions is one of the most successful approaches to enhance barrier height in lanthanide-based single-ion magnets. Recently, a tetra coordinated [Er{N(SiMe 3 ) 2 }s 3 Cl]·2THF (1) complex with an unfavourable ligand field showed slow relaxation of magnetization in zero field and challenges the concept of electrostatic ligand field modulation. To unravel the magnetic relaxation in this complex, we carried out a detailed theoretical investigation on three Er(iii) complexes belonging to the same family of single-ion magnets. The CASSCF/PT2 + RASSI-SO approach highlights that the concept of electrostatic ligand field modulation based on oblate/prolate type is still valid in these complexes, and the relaxation dynamics observed can be rationalized by accounting for both the symmetry and geometrical distortions around the Er(iii) ion. Using ab initio computed blockade barriers and crystal field analysis, we analysed the key components of the magnetic relaxation. Our study suggests that in these structures, the Er(iii) ion shifted out of the triangular plane formed by the three nitrogen donor atoms and this out-of-plane shift (τ) significantly influences the slow-relaxation of magnetization. In order to gain deeper insights into the nature of metal-ligand bonding, and to predict quantitatively the strength of the axial and equatorial ligand field, ELF, QTAIM, and EDA analysis were carried out in these complexes. Our findings highlight that the molecules possessing large barrier height for magnetic relaxation are due to the combined effect of a favourable ligand field and the symmetry around the Er(iii) ion. To understand the intricate role of both effects, several robust magneto-structural correlations were developed. Besides, the lanthanide-halogen covalency was also found to play a vital role in controlling the magnetic anisotropy and thus the

  3. Organic field-effect transistors using single crystals.

    Science.gov (United States)

    Hasegawa, Tatsuo; Takeya, Jun

    2009-04-01

    Organic field-effect transistors using small-molecule organic single crystals are developed to investigate fundamental aspects of organic thin-film transistors that have been widely studied for possible future markets for 'plastic electronics'. In reviewing the physics and chemistry of single-crystal organic field-effect transistors (SC-OFETs), the nature of intrinsic charge dynamics is elucidated for the carriers induced at the single crystal surfaces of molecular semiconductors. Materials for SC-OFETs are first reviewed with descriptions of the fabrication methods and the field-effect characteristics. In particular, a benchmark carrier mobility of 20-40 cm 2 Vs -1 , achieved with thin platelets of rubrene single crystals, demonstrates the significance of the SC-OFETs and clarifies material limitations for organic devices. In the latter part of this review, we discuss the physics of microscopic charge transport by using SC-OFETs at metal/semiconductor contacts and along semiconductor/insulator interfaces. Most importantly, Hall effect and electron spin resonance (ESR) measurements reveal that interface charge transport in molecular semiconductors is properly described in terms of band transport and localization by charge traps.

  4. Organic field-effect transistors using single crystals

    Directory of Open Access Journals (Sweden)

    Tatsuo Hasegawa and Jun Takeya

    2009-01-01

    Full Text Available Organic field-effect transistors using small-molecule organic single crystals are developed to investigate fundamental aspects of organic thin-film transistors that have been widely studied for possible future markets for 'plastic electronics'. In reviewing the physics and chemistry of single-crystal organic field-effect transistors (SC-OFETs, the nature of intrinsic charge dynamics is elucidated for the carriers induced at the single crystal surfaces of molecular semiconductors. Materials for SC-OFETs are first reviewed with descriptions of the fabrication methods and the field-effect characteristics. In particular, a benchmark carrier mobility of 20–40 cm2 Vs−1, achieved with thin platelets of rubrene single crystals, demonstrates the significance of the SC-OFETs and clarifies material limitations for organic devices. In the latter part of this review, we discuss the physics of microscopic charge transport by using SC-OFETs at metal/semiconductor contacts and along semiconductor/insulator interfaces. Most importantly, Hall effect and electron spin resonance (ESR measurements reveal that interface charge transport in molecular semiconductors is properly described in terms of band transport and localization by charge traps.

  5. Crystal orientation effects on wurtzite quantum well electromechanical fields

    DEFF Research Database (Denmark)

    Duggen, Lars; Willatzen, Morten

    2010-01-01

    in the literature for semiconductors, is inaccurate for ZnO/MgZnO heterostructures where shear-strain components play an important role. An interesting observation is that a growth direction apart from [1̅ 21̅ 0] exists for which the electric field in the quantum well region becomes zero. This is important for, e......A one-dimensional continuum model for calculating strain and electric field in wurtzite semiconductor heterostructures with arbitrary crystal orientation is presented and applied to GaN/AlGaN and ZnO/MgZnO heterostructure combinations. The model is self-consistent involving feedback couplings...... of spontaneous polarization, strain, and electric field. Significant differences between fully coupled and semicoupled models are found for the longitudinal and shear-strain components as a function of the crystal-growth direction. In particular, we find that the semicoupled model, typically used...

  6. Field-controlled structures in ferromagnetic cholesteric liquid crystals.

    Science.gov (United States)

    Medle Rupnik, Peter; Lisjak, Darja; Čopič, Martin; Čopar, Simon; Mertelj, Alenka

    2017-10-01

    One of the advantages of anisotropic soft materials is that their structures and, consequently, their properties can be controlled by moderate external fields. Whereas the control of materials with uniform orientational order is straightforward, manipulation of systems with complex orientational order is challenging. We show that a variety of structures of an interesting liquid material, which combine chiral orientational order with ferromagnetic one, can be controlled by a combination of small magnetic and electric fields. In the suspensions of magnetic nanoplatelets in chiral nematic liquid crystals, the platelet's magnetic moments orient along the orientation of the liquid crystal and, consequently, the material exhibits linear response to small magnetic fields. In the absence of external fields, orientations of the liquid crystal and magnetization have wound structure, which can be either homogeneously helical, disordered, or ordered in complex patterns, depending on the boundary condition at the surfaces and the history of the sample. We demonstrate that by using different combinations of small magnetic and electric fields, it is possible to control reversibly the formation of the structures in a layer of the material. In such a way, different periodic structures can be explored and some of them may be suitable for photonic applications. The material is also a convenient model system to study chiral magnetic structures, because it is a unique liquid analog of a solid helimagnet.

  7. A new cadmium(II) complex with bridging dithiolate ligand: Synthesis, crystal structure and antifungal activity study

    Science.gov (United States)

    Singh, Mahesh Kumar; Sutradhar, Sanjit; Paul, Bijaya; Adhikari, Suman; Laskar, Folguni; Butcher, Raymond J.; Acharya, Sandeep; Das, Arijit

    2017-07-01

    A new polymeric complex of Cd(II) with 1,1-dicyanoethylene- 2,2-dithiolate [ i-MNT2- = {S2C:C(CN)2}2- ] as a bridging ligand has been synthesized and characterized on the basis of spectroscopy and single-crystal X-ray diffraction analysis. Single crystal X-ray diffraction analysis reveals that the Cadmium (II) complex is six coordinated 1D polymeric in nature. Biological screening effects in vitro of the synthesized polymeric complex has been tested against five fungi Synchitrium endobioticum, Pyricularia oryzae, Helminthosporium oryzae, Candida albicans(ATCC10231), Trichophyton mentagrophytes by the disc diffusion method. In vitro antifungal screening indicates that the complex exhibits fungistatic and fungicidal antifungal activity whereas K2i-MNT.H2O became silent on Synchitrium endobioticum, Pyricularia oryzae, Helminthosporium oryzae, Candida albicans (ATCC10231), Trichophyton mentagrophytes.

  8. A new copper(II) Schiff base complex containing asymmetrical tetradentate N2O2 Schiff base ligand: Synthesis, characterization, crystal structure and DFT study

    Science.gov (United States)

    Grivani, Gholamhossein; Baghan, Sara Husseinzadeh; Vakili, Mohammad; Khalaji, Aliakbar Dehno; Tahmasebi, Vida; Eigner, Václav; Dušek, Michal

    2015-02-01

    A new copper (II) Schiff base complex, CuL1, was prepared from the reaction of asymmetrical Schiff base ligand of L1 and Cu(OAC)2 (L1 = salicylidene imino-ethylimino-pentan-2-one). The Schiff base ligand, L1, and its copper (II) complex, CuL1, have been characterized by elemental analysis (CHN) and FT-IR and UV-vis spectroscopy. In addition, 1H NMR was employed for characterization of the ligand. Thermogrametric analysis of the CuL1 reveals its thermal stability and its decomposition pattern shows that it is finally decomposed to the copper oxide (CuO). The crystal structure of CuL1 was determined by the single crystal X-ray analysis. The CuL1 complex crystallizes in the monoclinic system, with space group P21/n and distorted square planar coordination around the metal ion. The Schiff base ligand of L1 acts as a chelating ligand and coordinates via two nitrogen and two oxygen atoms to the copper (II) ion with C1 symmetry. The structure of the CuL1 complex was also studied theoretically at different levels of DFT and basis sets. According to calculated results the Csbnd O bond length of the salicylate fragment is slightly higher than that in the acetylacetonate fragment of ligand, which could be interpreted by resonance increasing between phenyl and chelated rings in ligand in relative to the acetylacetonate fragment.

  9. Crystal structures and luminescence of two cadmium-carboxylate cluster-based compounds with mixed ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui-Fang; Lei, Qian; Wang, Yu-Ling; Yin, Shun-Gao; Liu, Qing-Yan [College of Chemistry and Chemical Engineering and Key Lab. of Functional Small Organic Molecule of Ministry of Education, Jiangxi Normal Univ., Nanchang (China)

    2017-04-04

    Reactions of Cd(NO{sub 3}){sub 2}.4H{sub 2}O with 2-quinolinecarboxylic acid (H-QLC) in the presence of 1,4-benzenedicarboxylic acid (H{sub 2}-BDC) or 1,3,5-benzenetricarboxylic acid (H-BTC) in DMF/H{sub 2}O solvent afforded two compounds, namely, [Cd(QLC)(BDC){sub 1/2}(H{sub 2}O)]{sub n} (1) and [Cd(QLC)(BTC){sub 1/3}]{sub n} (2). Both compounds are two-dimensional (2D) frameworks but feature different cadmium-carboxylate clusters as a result of the presence of the polycarboxylate ligands with different geometries and coordination preference. The dinuclear Cd{sub 2}(QLC){sub 2} units in 1 are bridged by the pairs of bridging water ligands to give a one-dimensional (1D) chain, which is further linked by the second ligand of BDC{sup 2-} to form a 2D structure. Compound 2 is constructed from unique hexanuclear macrometallacyclic Cd{sub 6}(QLC){sub 6} clusters, which are linked by the surrounding BTC{sup 3-} ligands to generate a 2D structure. Photoluminescence studies showed both compounds exhibit ligand-centered luminescent emissions with emission maxima at 405 and 401 nm, respectively. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Ligand field density functional theory for the prediction of future domestic lighting.

    Science.gov (United States)

    Ramanantoanina, Harry; Urland, Werner; García-Fuente, Amador; Cimpoesu, Fanica; Daul, Claude

    2014-07-28

    We deal with the computational determination of the electronic structure and properties of lanthanide ions in complexes and extended structures having open-shell f and d configurations. Particularly, we present conceptual and methodological issues based on Density Functional Theory (DFT) enabling the reliable calculation and description of the f → d transitions in lanthanide doped phosphors. We consider here the optical properties of the Pr(3+) ion embedded into various solid state fluoride host lattices, for the prospection and understanding of the so-called quantum cutting process, being important in the further quest of warm-white light source in light emitting diodes (LED). We use the conceptual formulation of the revisited ligand field (LF) theory, fully compatibilized with the quantum chemistry tools: LFDFT. We present methodological advances for the calculations of the Slater-Condon parameters, the ligand field interaction and the spin-orbit coupling constants, important in the non-empirical parameterization of the effective Hamiltonian adjusted from the ligand field theory. The model shows simple procedure using less sophisticated computational tools, which is intended to contribute to the design of modern phosphors and to help to complement the understanding of the 4f(n) → 4f(n-1)5d(1) transitions in any lanthanide system.

  11. Magnetic field measurements based on Terfenol coated photonic crystal fibers.

    Science.gov (United States)

    Quintero, Sully M M; Martelli, Cicero; Braga, Arthur M B; Valente, Luiz C G; Kato, Carla C

    2011-01-01

    A magnetic field sensor based on the integration of a high birefringence photonic crystal fiber and a composite material made of Terfenol particles and an epoxy resin is proposed. An in-fiber modal interferometer is assembled by evenly exciting both eigenemodes of the HiBi fiber. Changes in the cavity length as well as the effective refractive index are induced by exposing the sensor head to magnetic fields. The magnetic field sensor has a sensitivity of 0.006 (nm/mT) over a range from 0 to 300 mT with a resolution about ±1 mT. A fiber Bragg grating magnetic field sensor is also fabricated and employed to characterize the response of Terfenol composite to the magnetic field.

  12. Pulsed zero field NMR of solids and liquid crystals

    International Nuclear Information System (INIS)

    Thayer, A.M.

    1987-02-01

    This work describes the development and applications to solids and liquid crystals of zero field nuclear magnetic resonance (NMR) experiments with pulsed dc magnetic fields. Zero field NMR experiments are one approach for obtaining high resolution spectra of amorphous and polycrystalline materials which normally (in high field) display broad featureless spectra. The behavior of the spin system can be coherently manipulated and probed in zero field with dc magnetic field pulses which are employed in a similar manner to radiofrequency pulses in high field NMR experiments. Nematic phases of liquid crystalline systems are studied in order to observe the effects of the removal of an applied magnetic field on sample alignment and molecular order parameters. In nematic phases with positive and negative magnetic susceptibility anisotropies, a comparison between the forms of the spin interactions in high and low fields is made. High resolution zero field NMR spectra of unaligned smectic samples are also obtained and reflect the symmetry of the liquid crystalline environment. These experiments are a sensitive measure of the motionally induced asymmetry in biaxial phases. Homonuclear and heteronuclear solute spin systems are compared in the nematic and smectic phases. Nonaxially symmetric dipolar couplings are reported for several systems. The effects of residual fields in the presence of a non-zero asymmetry parameter are discussed theoretically and presented experimentally. Computer programs for simulations of these and other experimental results are also reported. 179 refs., 75 figs

  13. A new crystal form of human tear lipocalin reveals high flexibility in the loop region and induced fit in the ligand cavity

    Energy Technology Data Exchange (ETDEWEB)

    Breustedt, Daniel A.; Chatwell, Lorenz; Skerra, Arne, E-mail: skerra@wzw.tum.de [Munich Center for Integrated Protein Science, CIPS-M, and Lehrstuhl für Biologische Chemie, Technische Universität München, 85350 Freising-Weihenstephan (Germany)

    2009-10-01

    The crystal structure of tear lipocalin determined in space group P2{sub 1} revealed large structural deviations from the previously solved X-ray structure in space group C2, especially in the loop region and adjoining parts of the β-barrel which give rise to the ligand-binding site. These findings illustrate a novel mechanism for promiscuity in ligand recognition by the lipocalin protein family. Tear lipocalin (TLC) with the bound artificial ligand 1,4-butanediol has been crystallized in space group P2{sub 1} with four protein molecules in the asymmetric unit and its X-ray structure has been solved at 2.6 Å resolution. TLC is a member of the lipocalin family that binds ligands with diverse chemical structures, such as fatty acids, phospholipids and cholesterol as well as microbial siderophores and the antibiotic rifampin. Previous X-ray structural analysis of apo TLC crystallized in space group C2 revealed a rather large bifurcated ligand pocket and a partially disordered loop region at the entrace to the cavity. Analysis of the P2{sub 1} crystal form uncovered major conformational changes (i) in β-strands B, C and D, (ii) in loops 1, 2 and 4 at the open end of the β-barrel and (iii) in the extended C-terminal segment, which is attached to the β-barrel via a disulfide bridge. The structural comparison indicates high conformational plasticity of the loop region as well as of deeper parts of the ligand pocket, thus allowing adaptation to ligands that differ vastly in size and shape. This illustrates a mechanism for promiscuity in ligand recognition which may also be relevant for some other physiologically important members of the lipocalin protein family.

  14. A new crystal form of human tear lipocalin reveals high flexibility in the loop region and induced fit in the ligand cavity

    International Nuclear Information System (INIS)

    Breustedt, Daniel A.; Chatwell, Lorenz; Skerra, Arne

    2009-01-01

    The crystal structure of tear lipocalin determined in space group P2 1 revealed large structural deviations from the previously solved X-ray structure in space group C2, especially in the loop region and adjoining parts of the β-barrel which give rise to the ligand-binding site. These findings illustrate a novel mechanism for promiscuity in ligand recognition by the lipocalin protein family. Tear lipocalin (TLC) with the bound artificial ligand 1,4-butanediol has been crystallized in space group P2 1 with four protein molecules in the asymmetric unit and its X-ray structure has been solved at 2.6 Å resolution. TLC is a member of the lipocalin family that binds ligands with diverse chemical structures, such as fatty acids, phospholipids and cholesterol as well as microbial siderophores and the antibiotic rifampin. Previous X-ray structural analysis of apo TLC crystallized in space group C2 revealed a rather large bifurcated ligand pocket and a partially disordered loop region at the entrace to the cavity. Analysis of the P2 1 crystal form uncovered major conformational changes (i) in β-strands B, C and D, (ii) in loops 1, 2 and 4 at the open end of the β-barrel and (iii) in the extended C-terminal segment, which is attached to the β-barrel via a disulfide bridge. The structural comparison indicates high conformational plasticity of the loop region as well as of deeper parts of the ligand pocket, thus allowing adaptation to ligands that differ vastly in size and shape. This illustrates a mechanism for promiscuity in ligand recognition which may also be relevant for some other physiologically important members of the lipocalin protein family

  15. Identification of Histamine H3 Receptor Ligands Using a New Crystal Structure Fragment-based Method

    DEFF Research Database (Denmark)

    Frandsen, Ida Osborn; Boesgaard, Michael W; Fidom, Kimberley

    2017-01-01

    Virtual screening offers an efficient alternative to high-throughput screening in the identification of pharmacological tools and lead compounds. Virtual screening is typically based on the matching of target structures or ligand pharmacophores to commercial or in-house compound catalogues. This ...

  16. Crystal-field magnetic anisotropy of dilute dysprosium or erbium in yttrium single crystals

    DEFF Research Database (Denmark)

    Høg, J.; Touborg, P.

    1974-01-01

    Magnetization measurements have been performed between 1.3 and 300 K in fields up to 50 × 105 A/m in the a, b, and c directions of hcp crystals of pure Y and Y doped with 0.14-at.% Dy or 0.14-at.% Er, using the Faraday method and a vibrating-sample method. The characteristic behavior of both...

  17. Liquid Crystals for Organic Field-Effect Transistors

    Science.gov (United States)

    O'Neill, Mary; Kelly, Stephen M.

    Columnar, smectic and lamellar polymeric liquid crystals are widely recognized as very promising charge-transporting organic semiconductors due to their ability to spontaneously self-assemble into highly ordered domains in uniform thin films over large areas. The transport properties of smectic and columnar liquid crystals are discussed in Chaps. 2 (10.1007/978-90-481-2873-0_2) and 3 (10.1007/978-90-481-2873-0_3). Here we examine their application to organic field-effect transistors (OFETs): after a short introduction in Sect. 9.1 we introduce the OFET configuration and show how the mobility is measured in Sect. 9.2. Section 9.3 discusses polymeric liquid crystalline semiconductors in OFETs. We review research that shows that annealing of polymers in a fluid mesophase gives a more ordered microcrystalline morphology on cooling than that kinetically determined by solution processing of the thin film. We also demonstrate the benefits of monodomain alignment and show the application of liquid crystals in light-emitting field-effect transistors. Some columnar and smectic phases are highly ordered with short intermolecular separation to give large π-π coupling. We discuss their use in OFETs in Sects. 9.4, and 9.5 respectively. Section 9.6 summarises the conclusions of the chapter.

  18. Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV alkoxide pincer complex

    Directory of Open Access Journals (Sweden)

    Jakub Pedziwiatr

    2017-02-01

    Full Text Available This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-bis[(diethyl etherlithium], [Li2Br2(C24H33N3(C4H10O2] (1 and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-1κ3N,N′,N′′;4κ3N,N′,N′′-tetra-μ-isopropanolato-1:2κ4O:O;3:4κ4O:O-diisopropanolato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N32(C3H7O6] or {[NHNNH]Ti(OiPr3(LiBr2}2 (2. Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O fragment bonded to them, with the Li atom adopting a distorted tetrahedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octahedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12/0.372 (12], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetrahedral coordination as in 1. The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4. The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N—H groups, no hydrogen bonding

  19. Crystallization and crystallographic analysis of the ligand-binding domain of the Pseudomonas putida chemoreceptor McpS in complex with malate and succinate

    International Nuclear Information System (INIS)

    Gavira, J. A.; Lacal, J.; Ramos, J. L.; García-Ruiz, J. M.; Krell, T.; Pineda-Molina, E.

    2012-01-01

    The crystallization of the ligand-binding domain of the methyl-accepting chemotaxis protein chemoreceptor McpS (McpS-LBD) is reported. Methyl-accepting chemotaxis proteins (MCPs) are transmembrane proteins that sense changes in environmental signals, generating a chemotactic response and regulating other cellular processes. MCPs are composed of two main domains: a ligand-binding domain (LBD) and a cytosolic signalling domain (CSD). Here, the crystallization of the LBD of the chemoreceptor McpS (McpS-LBD) is reported. McpS-LBD is responsible for sensing most of the TCA-cycle intermediates in the soil bacterium Pseudomonas putida KT2440. McpS-LBD was expressed, purified and crystallized in complex with two of its natural ligands (malate and succinate). Crystals were obtained by both the counter-diffusion and the hanging-drop vapour-diffusion techniques after pre-incubation of McpS-LBD with the ligands. The crystals were isomorphous and belonged to space group C2, with two molecules per asymmetric unit. Diffraction data were collected at the ESRF synchrotron X-ray source to resolutions of 1.8 and 1.9 Å for the malate and succinate complexes, respectively

  20. Protein-Ligand Informatics Force Field (PLIff): Toward a Fully Knowledge Driven "Force Field" for Biomolecular Interactions.

    Science.gov (United States)

    Verdonk, Marcel L; Ludlow, R Frederick; Giangreco, Ilenia; Rathi, Prakash Chandra

    2016-07-28

    The Protein Data Bank (PDB) contains a wealth of data on nonbonded biomolecular interactions. If this information could be distilled down to nonbonded interaction potentials, these would have some key advantages over standard force fields. However, there are some important outstanding issues to address in order to do this successfully. This paper introduces the protein-ligand informatics "force field", PLIff, which begins to address these key challenges ( https://bitbucket.org/AstexUK/pli ). As a result of their knowledge-based nature, the next-generation nonbonded potentials that make up PLIff automatically capture a wide range of interaction types, including special interactions that are often poorly described by standard force fields. We illustrate how PLIff may be used in structure-based design applications, including interaction fields, fragment mapping, and protein-ligand docking. PLIff performs at least as well as state-of-the art scoring functions in terms of pose predictions and ranking compounds in a virtual screening context.

  1. EMR-related problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians

    Directory of Open Access Journals (Sweden)

    Rudowicz Czesław

    2015-07-01

    Full Text Available The interface between optical spectroscopy, electron magnetic resonance (EMR, and magnetism of transition ions forms the intricate web of interrelated notions. Major notions are the physical Hamiltonians, which include the crystal field (CF (or equivalently ligand field (LF Hamiltonians, and the effective spin Hamiltonians (SH, which include the zero-field splitting (ZFS Hamiltonians as well as to a certain extent also the notion of magnetic anisotropy (MA. Survey of recent literature has revealed that this interface, denoted CF (LF ↔ SH (ZFS, has become dangerously entangled over the years. The same notion is referred to by three names that are not synonymous: CF (LF, SH (ZFS, and MA. In view of the strong need for systematization of nomenclature aimed at bringing order to the multitude of different Hamiltonians and the associated quantities, we have embarked on this systematization. In this article, we do an overview of our efforts aimed at providing a deeper understanding of the major intricacies occurring at the CF (LF ↔ SH (ZFS interface with the focus on the EMR-related problems for transition ions.

  2. Syntheses, crystal structures, anticancer activities of three reduce Schiff base ligand based transition metal complexes

    Science.gov (United States)

    Chang, Hui-Qin; Jia, Lei; Xu, Jun; Zhu, Tao-Feng; Xu, Zhou-Qing; Chen, Ru-Hua; Ma, Tie-Liang; Wang, Yuan; Wu, Wei-Na

    2016-02-01

    Three nickel(II) complexes, [Ni2(L1)2(tren)2(H2O)](ClO4)3 (1), [NiL2(tren)2](ClO4)·2.5H2O (2), [NiL2(tren)2]I·1.5H2O·CH3OH (3) based on amino acid reduced Schiff ligands are synthesized and characterized by physico-chemical and spectroscopic methods. The results show that in all complexes, the amino acid ligand is deprotonated and acts as an anionic ligand. In the dinuclear complex 1, each Ni(II) atom has a distorted octahedron geometry while with different coordination environment. However, the complexes 2 and 3 are mononuclear, almost with the same coordination environment. Furthermore, in vitro experiments are carried out, including MTT assay, Annexin V/PI flow cytometry and western blotting, to assess whether the complexes have antitumor effect. And the results show that all the three complexes have moderate anticancer activity towards human hepatic cancer (HepG2), human cervical cancer (HeLa) and human prostate (PC3) cell lines, in a concentration dependent way. The complex 1 exhibit higher cytotoxicity than the other two complexes and can induce human hepatic cancer cell (HepG2) to cell apoptosis by activating caspase 3.

  3. Infrared transmission study of Pr.sub.2./sub.CuO.sub.4./sub. crystal-field excitations

    Czech Academy of Sciences Publication Activity Database

    Riou, G.; Jandl, S.; Poirier, M.; Nekvasil, Vladimír; Diviš, M.; Fournier, P.; Greene, R. L.; Zhigunov, D. I.; Barilo, S. N.

    2001-01-01

    Roč. 23, - (2001), s. 179-182 ISSN 1434-6028 R&D Projects: GA ČR GA202/00/1602; GA ČR GA202/99/0184 Grant - others:GA UK(XC) 145/2000/B-FYZ; DMR(XX) 9732796 Institutional research plan: CEZ:AV0Z1010914 Keywords : optical properties * crystal and ligand fields * other cuprates Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.811, year: 2001

  4. Variable valence ion spectra in a crystal field

    International Nuclear Information System (INIS)

    Ghiordanescu, V.

    1979-01-01

    Using the Cadmium chloride as a host lattice, the optical spectra and RES of Mnsup(2+) were studied and the following results were obtained: a) By controlled dopings, the absorbtion and excitation spectra of ion Mnsup(2+) in CdCl 2 within the concentration range between 0.01 M and 25 M were plotted. Thus, the band structure for small concentrations was pointed out to differ from the structure observed for high concentrations. In the literature, this effect has not been observed on similar compounds, due to the small intensity values of the absorbtion spectra. b) Considering that for CdCl 2 :Mnsup(2+) 0.1 M, the optical spectra correspond to the isolated ion in the lattice, the energy levels were evaluated using electrostatic and spin-orbit terms in a perturbation calculation of the crystal field approximation. c) The calculation of parameter a which represents the effect of the cubic field in the spjn Hamiltonian of Mnsup(2+), is closer to the experjmental value -0.5.10 -4 cm -1 of the crystal field Dq and zeta parameters are used, respectively, parameters of the spin-orbit interaction obtained under b). d) The coupling effects of spins into more concentrated crystals with Mn 2+ are a function of temperature. The emjssion yield was given a quasi-cantitative evaluation in thjs paper as a function of temperature and concentratjon on the basis of which the isolated centers of Mn 2+ were found to display ectra whose intensity vary with temperature according to the Laporte forbidden transitions and spin rule theory, and the clusters including Mn 2+ - Mn 2+ pairs provide spectra whose intensity vary with the strength of the spin-spin coupling. (author)

  5. Crystal Structure of Epiphyas Postvittana Takeout 1 With Bound Ubiquinone Supports a Role As Ligand Carriers for Takeout Proteins in Insects

    Energy Technology Data Exchange (ETDEWEB)

    Hamiaux, C.; Stanley, D.; Greenwood, D.R.; Baker, E.N.; Newcomb, R.D.

    2009-05-19

    Takeout (To) proteins are found exclusively in insects and have been proposed to have important roles in various aspects of their physiology and behavior. Limited sequence similarity with juvenile hormone-binding proteins (JHBPs), which specifically bind and transport juvenile hormones in Lepidoptera, suggested a role for To proteins in binding hydrophobic ligands. We present the first crystal structure of a To protein, EpTo1 from the light brown apple moth Epiphyas postvittana, solved in-house by the single-wavelength anomalous diffraction technique using sulfur anomalous dispersion, and refined to 1.3 {angstrom} resolution. EpTo1 adopts the unusual {alpha}/{beta}-wrap fold, seen only for JHBP and several mammalian lipid carrier proteins, a scaffold tailored for the binding and/or transport of hydrophobic ligands. EpTo1 has a 45 {angstrom} long, purely hydrophobic, internal tunnel that extends for the full length of the protein and accommodates a bound ligand. The latter was shown by mass spectrometry to be ubiquinone-8 and is probably derived from Escherichia coli. The structure provides the first direct experimental evidence that To proteins are ligand carriers; gives insights into the nature of endogenous ligand(s) of EpTo1; shows, by comparison with JHBP, a basis for different ligand specificities; and suggests a mechanism for the binding/release of ligands.

  6. Synthesis, crystal structure and cytotoxic activity of ruthenium(II) piano-stool complex with N,N-chelating ligand

    Science.gov (United States)

    Rogala, Patrycja; Jabłońska-Wawrzycka, Agnieszka; Kazimierczuk, Katarzyna; Borek, Agnieszka; Błażejczyk, Agnieszka; Wietrzyk, Joanna; Barszcz, Barbara

    2016-12-01

    A mononuclear compound of the general formula [(η6-p-cymene)RuIICl(2,2‧-PyBIm)]PF6 has been synthesized from a bidentate N,N-donor ligand, viz. 2,-(2‧-pyridyl)benzimidazole (2,2‧-PyBIm) and the corresponding chloro-complex [(η6-p-cymene)Ru(μ-Cl)Cl]2 (precursor). The isolated coordination compound was characterized by IR, UV-vis and 1H, 13C NMR spectroscopies. The single crystal X-ray analysis of the complex reveals that the asymmetric part of the unit cell consists of two symmetrically independent, [(η6-p-cymene)RuCl(2,2‧-PyBIm)]+ cationic complexes. Each cation exhibits a pseudo-octahedral three-legged piano-stool geometry, in which three "legs" are occupied by one chloride ion and two nitrogen donor atoms of the chelating ligand 2,2‧-PyBIm. The Hirshfeld surface analysis of obtained complex was determined, too. The ionic nature of the compound is identified by a strong band at around 830 cm-1 due to the νP-F stretching mode of the PF6- counter ion. The electronic spectrum of this monomeric complex displays high intensity bands in the ultraviolet region assignable to π→π*/n→π* transitions, as well as a band attributable to the metal-to-ligand charge transfer (MLCT) dπ(Ru)→π*(L) transition. Additionally, the complex has been screened for its cytotoxicity against three human cancer lines: non-small cell lung carcinoma (A549), colon adenocarcinoma (HT29) and breast adenocarcinoma (MCF-7) as well as normal mice fibroblast cells (BALB/3T3). The complex demonstrated a moderate antiproliferative activity against the cell lines tested.

  7. Acetate Ligands Determine the Crystal Structure of CdSe Nanoplatelets - a Density Functional Theory study

    NARCIS (Netherlands)

    Koster, R.S.; Fang, C.M.; van Blaaderen, A.; Dijkstra, M.; van Huis, M.A.

    2016-01-01

    Cadmium selenide (CdSe) nanoplatelets of a few atomic layers thick exhibit extremely sharp photoluminescence peaks and are synthesized in the zinc blende crystal structure, whereas the most stable bulk polymorph of CdSe is the wurtzite structure. These platelets can be synthesized very

  8. Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands.

    Science.gov (United States)

    Shafaatian, Bita; Ozbakzaei, Zahra; Notash, Behrouz; Rezvani, S Ahmad

    2015-04-05

    A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1 M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150 mV s(-1) scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Using Quartz Crystal Microbalance for Field Measurement of Liquid Viscosities

    Directory of Open Access Journals (Sweden)

    Qingsong Bai

    2016-01-01

    Full Text Available The field measurement of liquid viscosities, especially the high viscous liquids, is challenging and often requires expensive equipment, long processing time, and lots of reagent. We use quartz crystal microbalances (QCMs operating in solution which are also sensitive to the viscosity and density of the contacting solution. QCMs are typically investigated for sensor applications in which one surface of QCM completely immersed in Newtonian liquid, but the viscous damping in liquids would cause not only large frequency shifts but also large losses in the quality factor Q leading to instability and even cessation of oscillation. A novel mass-sensitivity-based method for field measurement of liquid viscosities using a QCM is demonstrated in this paper and a model describing the influence of the liquid properties on the oscillation frequency is established as well. Two groups of verified experiments were performed and the experimental results show that the presented method is effective and possesses potential applications.

  10. Crystal structure and ligand affinity of avidin in the complex with 4‧-hydroxyazobenzene-2-carboxylic acid

    Science.gov (United States)

    Strzelczyk, Paweł; Bujacz, Grzegorz

    2016-04-01

    Avidin is a protein found in egg white that binds numerous organic compounds with high affinity, especially biotin and its derivatives. Due to its extraordinary affinity for its ligands, avidin is extensively used in biotechnology. X-ray crystallography and fluorescence-based biophysical techniques were used to show that avidin binds the dye 4‧-hydroxyazobenzene-2-carboxylic acid (HABA) with a lower affinity than biotin. The apparent dissociation constant determined for the avidin complex with HABA by microscale thermophoresis (MST) is 4.12 μM. The crystal structure of avidin-HABA complex was determined at a resolution of 2.2 Å (PDB entry 5chk). The crystals belong to a hexagonal system, in the space group P6422. In that structure, the hydrazone tautomer of HABA is bound at the bottom part of the central calyx near the polar residues. We show interactions of the dye with avidin and compare them with the previously reported avidin-biotin complex.

  11. Two organoantimony (V) coordination complexes modulated by isomers of trifluoromethylbenzoate ligands: Syntheses, crystal structure, photodegradation properties

    Science.gov (United States)

    Zhang, Xiao-Yin; Cui, Lian-sheng; Zhang, Xia; Jin, Fan; Fan, Yu-Hua

    2017-04-01

    Two organoantimony (V) coordination complexes, namely Ph3Sb(2-tmbc) (1) and Ph3Sb(3-tmbc) (2) (2-tmbc = 2-(trifluoromethyl)benzoic carboxyl, 3-tmbc = 3-(trifluoromethyl)benzoic carboxyl) have been synthesized and characterized by IR spectra, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that complexes 1 and 2 show different architectures by the intermolecular hydrogen bonds (Csbnd H⋯F), complex 1 displays an 1D straight chain structure, while complex 2 shows an 1D zigzag chain structure. The photodegradation properties of complexes 1 and 2 has been investigated in organic dyes (RhB, MV, MB) the results indicated that the two complexes are good candidates for the photocatalytic degradation of three dyes. The tentative photocatalytic degradations mechanism is discussed.

  12. Two new coordination polymers based on tartaric acid ligand: Syntheses, crystal structure and thermal stability

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Fei-Yan; Lan, You-Zhao, E-mail: sky37@zjnu.cn; Han, Min-Min; Feng, Yun-Long, E-mail: lyzhao@zjnu.cn [Zhejiang Normal University, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry (China)

    2016-09-15

    Two new coordination polymers [Cd{sub 3}(D-Tar){sub 3}]{sub n} (1) and [Pb(meso-Tar)]{sub n} (2) (H{sub 2}Tar = tartaric acid) have been synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. 1 crystallizes in the C222{sub 1} chiral space group and shows a 3D (4,4)-connected net with the (4.6.8{sup 4}){sub 4}(4.6{sup 2}.8{sup 2}.10)(4.6{sup 2}.8{sup 3})(4.6{sup 3}.8{sup 2})(4.6{sup 3}.8{sup 2}){sub 4}(4.8{sup 5}){sub 2} topology. 2 possesses a 3D (4,4)-connected net with the (4{sup 3}.6{sup 2}.8) topology. In addition, the thermogravimetric analyses (TGA) results for polymers are discussed.

  13. Correlation between crystal structure and mobility in organic field-effect transistors based on single crystals of tetrathiafulvalene derivatives.

    Science.gov (United States)

    Mas-Torrent, Marta; Hadley, Peter; Bromley, Stefan T; Ribas, Xavi; Tarrés, Judit; Mas, Montserrat; Molins, Elies; Veciana, Jaume; Rovira, Concepció

    2004-07-14

    Recently, it was reported that crystals of the organic material dithiophene-tetrathiafulvalene (DT-TTF) have a high field-effect charge carrier mobility of 1.4 cm(2)/(V x s). These crystals were formed by a simple drop-casting method, making this material interesting to investigate for possible applications in low-cost electronics. Here, organic single-crystal field-effect transistors based on materials related to DT-TTF are presented and a clear correlation between the crystal structure and the electrical characteristics is observed. The observed relationship between the mobilities in the different crystal structures is strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals. The most suitable materials described here exhibit mobilities that are among the highest reported for organic field-effect transistors and that are the highest reported for solution-processed materials.

  14. Influence of magnetic field on the morphology of the andrographolide crystal from supercritical carbon dioxide extraction crystallization

    Science.gov (United States)

    Chen, Kexun; Zhang, Xingyuan; Pan, Jian; Zhang, Wencheng; Yong, Ji; Yin, Wenhong

    2003-10-01

    In this paper, a supercritical fluid extraction-crystallization of andrographolide, a kind of Chinese traditional medicine, was investigated. We have studied the extraction-crystallization process with or without magnet in the extractor, respectively. It was found that the presence of magnetic field is an important factor influencing the quality of the products. SEM images showed that the crystal was slice-like in shape, and many slices reunited together in the absence of magnet. Further research showed that pressure had a certain effect on the morphology of the crystal.

  15. Control of active liquid crystals with a magnetic field.

    Science.gov (United States)

    Guillamat, Pau; Ignés-Mullol, Jordi; Sagués, Francesc

    2016-05-17

    Living cells sense the mechanical features of their environment and adapt to it by actively remodeling their peripheral network of filamentary proteins, known as cortical cytoskeleton. By mimicking this principle, we demonstrate an effective control strategy for a microtubule-based active nematic in contact with a hydrophobic thermotropic liquid crystal. By using well-established protocols for the orientation of liquid crystals with a uniform magnetic field, and through the mediation of anisotropic shear stresses, the active nematic reversibly self-assembles with aligned flows and textures that feature orientational order at the millimeter scale. The turbulent flow, characteristic of active nematics, is in this way regularized into a laminar flow with periodic velocity oscillations. Once patterned, the microtubule assembly reveals its intrinsic length and time scales, which we correlate with the activity of motor proteins, as predicted by existing theories of active nematics. The demonstrated commanding strategy should be compatible with other viable active biomaterials at interfaces, and we envision its use to probe the mechanics of the intracellular matrix.

  16. Crystallization and preliminary X-ray crystallographic analysis of peptide deformylase (PDF) from Bacillus cereus in ligand-free and actinonin-bound forms

    International Nuclear Information System (INIS)

    Park, Joon Kyu; Moon, Jin Ho; Kim, Jae-Hong; Kim, Eunice EunKyeong

    2004-01-01

    Peptide deformylase (PDF) from B. cereus has been overexpressed, purified and crystallized in ligand-free and actinonin-bound forms. Diffraction data have been collected from these crystals to 1.7 and 2.0 Å resolution, respectively. In bacteria, protein expression initiates with an N-formyl group and this needs to be removed in order to ensure proper bacterial growth. These formylation and deformylation processes are unique to eubacteria; therefore, inhibition of these would provide a novel antibacterial therapy. Deformylation is carried out by peptide deformylase (PDF). PDF from Bacillus cereus, one of the major pathogenic bacteria, was cloned into expression plasmid pET-28a (Novagen), overexpressed in Escherichia coli BL21 (DE3) and purified to high quality. Crystals have been obtained of both ligand-free PDF and PDF to which actinonin, a highly potent naturally occurring inhibitor, is bound. Both crystals belong to space group P2 1 2 1 2 1 , with unit-cell parameters a = 42.72, b = 44.04, c = 85.19 Å and a = 41.31, b = 44.56, c = 84.47 Å, respectively. Diffraction data were collected to 1.7 Å resolution for the inhibitor-free crystals and to 2.0 Å resolution for the actinonin-bound crystals

  17. Flood field uniformity testing - effects of crystal hydration

    International Nuclear Information System (INIS)

    Dimcheva, M.; Sergieva, S.; Doldurova, M.; Jovanovska, A.

    2012-01-01

    The most basic and sensitive routine quality control (QC) of gamma camera is that of intrinsic flood-field uniformity. The routine QC test must be assessed daily and any nonuniformity must be eliminated before patient testing to eliminate artifacts and false positive or false-negative patient results. The purpose of this study was to compare uniformity analysis results for scintillation crystal hydration with symmetric and asymmetric energy window on the Siemens Symbia T2 SPECTCT camera. Integral and differential uniformity analysis was performed by placing a point source 99m Tc in front of the detector with removed collimator to measure the effect of correction matrix, a count rate and activity volume on intrinsic uniformity. A 15% energy window set symmetrically over the 99m Tc photo peak is equivalent to 140±10% keV or a window spanning 126-154 keV. The results, received from Detector 2 gave the following uniformity parameter values: Both asymmetric energy window images show clearly multiple focal spots due to crystal hydration: discrete hot spots in the asymmetric low window image and discrete cold spots in the asymmetric high window image. The above results are not seen yet on the symmetric window image. We had replaced Detector 2 in order to avoid spots become visible in flood images obtained with the clinical energy window. The uniformity of a gamma camera is maybe the most important parameter that expresses the quality of the camera's performance. Non uniform areas in the field of view can result in misdiagnosed patients and low quality of clinical services. (authors)

  18. Ligand field theory and the origin of life as an emergent feature of the periodic table of elements.

    Science.gov (United States)

    Morowitz, Harold J; Srinivasan, Vijayasarathy; Smith, Eric

    2010-08-01

    The assumption that all biological catalysts are either proteins or ribozymes leads to an outstanding enigma of biogenesis-how to determine the synthetic pathways to the monomers for the efficient formation of catalytic macromolecules in the absence of any such macromolecules. The last 60 years have witnessed chemists developing an understanding of organocatalysis and ligand field theory, both of which give demonstrable low-molecular-weight catalysts. We assume that transition-metal-ligand complexes are likely to have occurred in the deep ocean trenches by the combination of naturally occurring oceanic metals and ligands synthesized from the emergent CO(2), H(2), NH(3), H(2)S, and H(3)PO(4). We are now in a position to investigate experimentally the metal-ligand complexes, their catalytic function, and the reaction networks that could have played a role in the development of metabolism and life itself.

  19. Crystal structures of Lymphocytic choriomeningitis virus endonuclease domain complexed with diketo-acid ligands

    Directory of Open Access Journals (Sweden)

    Magali Saez-Ayala

    2018-03-01

    Full Text Available The Arenaviridae family, together with the Bunyaviridae and Orthomyxoviridae families, is one of the three negative-stranded RNA viral families that encode an endonuclease in their genome. The endonuclease domain is at the N-terminus of the L protein, a multifunctional protein that includes the RNA-dependent RNA polymerase. The synthesis of mRNA in arenaviruses is a process that is primed by capped nucleotides that are `stolen' from the cellular mRNA by the endonuclease domain in cooperation with other domains of the L protein. This molecular mechanism has been demonstrated previously for the endonuclease of the prototype Lymphocytic choriomeningitis virus (LCMV. However, the mode of action of this enzyme is not fully understood as the original structure did not contain catalytic metal ions. The pivotal role played by the cap-snatching process in the life cycle of the virus and the highly conserved nature of the endonuclease domain make it a target of choice for the development of novel antiviral therapies. Here, the binding affinities of two diketo-acid (DKA compounds (DPBA and L-742,001 for the endonuclease domain of LCMV were evaluated using biophysical methods. X-ray structures of the LCMV endonuclease domain with catalytic ions in complex with these two compounds were determined, and their efficacies were assessed in an in vitro endonuclease-activity assay. Based on these data and computational simulation, two new DKAs were synthesized. The LCMV endonuclease domain exhibits a good affinity for these DKAs, making them a good starting point for the design of arenavirus endonuclease inhibitors. In addition to providing the first example of an X-ray structure of an arenavirus endonuclease incorporating a ligand, this study provides a proof of concept that the design of optimized inhibitors against the arenavirus endonuclease is possible.

  20. Syntheses, crystal structures, and properties of four coordination polymers based on mixed multi-N donor and polycarboxylate ligands

    Science.gov (United States)

    Chen, Shui-Sheng; Guo, Xing-Zhe; Zhao, Yue; Li, Wei-Dong

    2018-02-01

    Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)-5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV-vis absorption spectra of 1 - 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.

  1. Crystal-fields at rare-earth sites in R2Fe14B compounds

    International Nuclear Information System (INIS)

    Adam, S.; Adam, G.; Burzo, E.

    1985-12-01

    Crystal-field effects are expected to be important in R 2 Fe 14 B compounds. Within a model-independent approach, it is proved that four distinct rare-earth sites exist with respect to the crystalline electric fields, namely, R(4f; z=0), R(4f; z=0.5 c), R(4g; z=0), and R(4g; z=0.5 c), and relationships are established between the corresponding crystal-fields coefficients. Further, generalized Stevens parametrizations of the crystal field coefficients are derived at three levels of approximation for the interatomic forces inside the crystal. A crystal lattice dressing effect upon the radial electronic integrals is found to occur, the magnitude of which depends on the deviation of the interatomic forces from Coulombian. Finally, computation of crystal-field coefficients in Nd 2 Fe 14 B leads to results which raise questions about the validity of the simple Coulomb point-charge model. (author)

  2. Modeling nuclear field shift isotope fractionation in crystals

    Science.gov (United States)

    Schauble, E. A.

    2013-12-01

    In this study nuclear field shift fractionations in solids (and chemically similar liquids) are estimated using calibrated density functional theory calculations. The nuclear field shift effect is a potential driver of mass independent isotope fractionation(1,2), especially for elements with high atomic number such as Hg, Tl and U. This effect is caused by the different shapes and volumes of isotopic nuclei, and their interactions with electronic structures and energies. Nuclear field shift isotope fractionations can be estimated with first principles methods, but the calculations are computationally difficult, limiting most theoretical studies so far to small gas-phase molecules and molecular clusters. Many natural materials of interest are more complex, and it is important to develop ways to estimate field shift effects that can be applied to minerals, solutions, in biomolecules, and at mineral-solution interfaces. Plane-wave density functional theory, in combination with the projector augmented wave method (DFT-PAW), is much more readily adapted to complex materials than the relativistic all-electron calculations that have been the focus of most previous studies. DFT-PAW is a particularly effective tool for studying crystals with periodic boundary conditions, and may also be incorporated into molecular dynamics simulations of solutions and other disordered phases. Initial calibrations of DFT-PAW calculations against high-level all-electron models of field shift fractionation suggest that there may be broad applicability of this method to a variety of elements and types of materials. In addition, the close relationship between the isomer shift of Mössbauer spectroscopy and the nuclear field shift isotope effect makes it possible, at least in principle, to estimate the volume component of field shift fractionations in some species that are too complex even for DFT-PAW models, so long as there is a Mössbauer isotope for the element of interest. Initial results

  3. An Overview of Hardware for Protein Crystallization in a Magnetic Field

    Directory of Open Access Journals (Sweden)

    Er-Kai Yan

    2016-11-01

    Full Text Available Protein crystallization under a magnetic field is an interesting research topic because a magnetic field may provide a special environment to acquire improved quality protein crystals. Because high-quality protein crystals are very useful in high-resolution structure determination using diffraction techniques (X-ray, neutron, and electron diffraction, research using magnetic fields in protein crystallization has attracted substantial interest; some studies have been performed in the past two decades. In this research field, the hardware is especially essential for successful studies because the environment is special and the design and utilization of the research apparatus in such an environment requires special considerations related to the magnetic field. This paper reviews the hardware for protein crystallization (including the magnet systems and the apparatus designed for use in a magnetic field and progress in this area. Future prospects in this field will also be discussed.

  4. Synthesis, characterization, and crystal structures of diruthenium complexes containing bridging salicylato ligands

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Mingxuan; Yau, Chun Huan; Hu, Yuxin; Tan, Yong Leng Kelvin [Hwa Chong Institution (Singapore); Li, Yingzhou; Ganguly, Rakesh; Leong, Weng Kee [Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (Singapore)

    2017-08-03

    The thermal reaction of Ru{sub 3}(CO){sub 12} (1) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru{sub 2}(CO){sub 4}(μ-O{sub 2}CC{sub 6}H{sub 4}OH){sub 2}L{sub 2} (2) [L = PPh{sub 3} (2a). C{sub 5}H{sub 5}N (2b); (CH{sub 3}){sub 2}SO (2c)]. Complex 2b was further reacted with the aromatic dimmines 2,2'-dipyridine or 1,10-phenanthroline to give the cationic diruthenium complexes [Ru{sub 2}(CO){sub 2}(μ-CO){sub 2}(μ-O{sub 2}CC{sub 6}H{sub 4}OH)(N intersection N){sub 2}]{sup +} (3) [(N intersection N) = 2,2'-dipyridine (3a); 1,10-phenanthroline (3b)], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a-2b and 3a-3b, single-crystal X-ray diffraction studies were also carried out. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Crystal Structure of the Ligand Binding Suppressor Domain of Type 1 Inositol 1,4,5-Trisphosphate Receptor

    Energy Technology Data Exchange (ETDEWEB)

    Bosanac, Ivan; Yamazaki, Haruka; Matsu-ura, Toru; Michikawa, Takayuki; Mikoshiba, Katsuhiko; Ikura, Mitsuhiko (U. of Texas-SMED)

    2010-11-10

    Binding of inositol 1,4,5-trisphosphate (IP{sub 3}) to the amino-terminal region of IP{sub 3} receptor promotes Ca{sup 2+} release from the endoplasmic reticulum. Within the amino terminus, the first 220 residues directly preceding the IP{sub 3} binding core domain play a key role in IP{sub 3} binding suppression and regulatory protein interaction. Here we present a crystal structure of the suppressor domain of the mouse type 1 IP{sub 3} receptor at 1.8 {angstrom}. Displaying a shape akin to a hammer, the suppressor region contains a Head subdomain forming the {beta}-trefoil fold and an Arm subdomain possessing a helix-turn-helix structure. The conserved region on the Head subdomain appeared to interact with the IP{sub 3} binding core domain and is in close proximity to the previously proposed binding sites of Homer, RACK1, calmodulin, and CaBP1. The present study sheds light onto the mechanism underlying the receptor's sensitivity to the ligand and its communication with cellular signaling proteins.

  6. Synthesis, crystal structures, luminescence and catalytic properties of two d¹⁰ metal coordination polymers constructed from mixed ligands.

    Science.gov (United States)

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-15

    Two new coordination polymers [Cd(bmb)(hmph)]n (1), {[Ag(bmb)]·H2btc}n (2) (bmb=1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2hmph=homophthalic acid, H3btc=1,3,5-benzenetetracarboxylic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA, XRPD and elemental analysis. Complex 1 features a 3D threefold interpenetrating dia array with a 4-connected 6(6) topology. Complex 2 shows a 1D helix chain structure connected by L1 ligands, which is finally extended into a rarely 2D 4L2 supramolecular network via C-H⋯O hydrogen bond interactions. In addition, the luminescence and catalytic properties of the two complexes for the degradation of the methyl orange azo dye in a Fenton-like process were presented. The degradation efficiency of the methyl orange azo dye for 1 and 2 are 56% and 96%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Crystal structure and dynamics of a lipid-induced potential desensitized-state of a pentameric ligand-gated channel

    Energy Technology Data Exchange (ETDEWEB)

    Basak, Sandip [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States; Schmandt, Nicolaus [Department of Neuroscience, School of Medicine, Case Western Reserve University, Cleveland, United States; Gicheru, Yvonne [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States; Chakrapani, Sudha [Department of Physiology and Biophysics, School of Medicine, Case Western Reserve University, Cleveland, United States

    2017-03-06

    Desensitization in pentameric ligand-gated ion channels plays an important role in regulating neuronal excitability. Here, we show that docosahexaenoic acid (DHA), a key ω-3 polyunsaturated fatty acid in synaptic membranes, enhances the agonist-induced transition to the desensitized state in the prokaryotic channel GLIC. We determined a 3.25 Å crystal structure of the GLIC-DHA complex in a potentially desensitized conformation. The DHA molecule is bound at the channel-periphery near the M4 helix and exerts a long-range allosteric effect on the pore across domain-interfaces. In this previously unobserved conformation, the extracellular-half of the pore-lining M2 is splayed open, reminiscent of the open conformation, while the intracellular-half is constricted, leading to a loss of both water and permeant ions. These findings, in combination with spin-labeling/EPR spectroscopic measurements in reconstituted-membranes, provide novel mechanistic details of desensitization in pentameric channels.

  8. Synthesis, Crystal Structures, and Photoluminescent Properties of Two Supramolecular Architectures Based on Difunctional Ligands Containing Imidazolyl and Carboxyl Groups

    Directory of Open Access Journals (Sweden)

    Mei-An Zhu

    2017-07-01

    Full Text Available Two new supramolecular architectures, namely, [Cd(L12(H2O]n (1 and [Ni(L22(H2O]n (2, were synthesized by the reaction of corresponding metal salts of CdCl2·2.5H2O and NiCl2·6H2O with 2-(1H-imidazol-4-ylbenzoic acid (HL1 and 3-(1H-imidazol-4-ylbenzoic acid (HL2 respectively, and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and powder X-ray diffraction (PXRD. Both HL1 and HL2 ligands are deprotonated to be L1- and L2- anions that coordinate with Cd(II and Ni(II atoms to form two-dimensional (2D layer structure. Topologically, complex 1 is a 2D network with (4, 4 sql topology, while 2 is a typical 63-hcb topology net. Complex 1 exhibits intense light blue emission in the solid state at room temperature.

  9. X-ray Crystal Structure of the Novel Enhanced-Affinity Glucocorticoid Agonist Fluticasone Furoate in the Glucocorticoid Receptor−Ligand Binding Domain

    Energy Technology Data Exchange (ETDEWEB)

    Biggadike, Keith; Bledsoe, Randy K.; Hassell, Anne M.; Kirk, Barrie E.; McLay, Iain M.; Shewchuk, Lisa M.; Stewart, Eugene L. (GSKNC); (GSK)

    2008-07-08

    An X-ray crystal structure is reported for the novel enhanced-affinity glucocorticoid agonist fluticasone furoate (FF) in the ligand binding domain of the glucocorticoid receptor. Comparison of this structure with those of dexamethasone and fluticasone propionate shows the 17{alpha} furoate ester to occupy more fully the lipophilic 17{alpha} pocket on the receptor, which may account for the enhanced glucocorticoid receptor binding of FF.

  10. Crystal Fields in Dilute Rare-Earth Metals Obtained from Magnetization Measurements on Dilute Rare-Earth Alloys

    DEFF Research Database (Denmark)

    Touborg, P.; Høg, J.

    1974-01-01

    Crystal field parameters of Tb, Dy, and Er in Sc, Y, and Lu are summarized. These parameters are obtained from magnetization measurements on dilute single crystals, and successfully checked by a number of different methods. The crystal field parameters vary unpredictably with the rare-earth solut....... B40, B60, and B66 are similar in Y and Lu. Crystal field parameters for the pure metals Tb, Dy, and Er are estimated from the crystal fields in Y and Lu....

  11. Synthesis, Crystal Structure and Luminescent Property of A Novel Cd(II) Coordination Polymer with Bis-imidazole Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yong Hong [Huaibei Normal Univ., Huaibei (China)

    2013-04-15

    The key to the successful design of metal-organic coordination polymers is the judicious selection of organic ligand. Recently, polydentate aromatic nitrogen heterocyclic ligands with five-membered rings have been well-studied in the construction of supramolecular structure for their N-coordinated sites apt to coordinating to transition metals. Similar to six-membered N-heterocyclic ligands, the azole-based five-membered N-heterocyclic ligands, such as imidazoles, triazoles and tetrazoles have been extensively employed in the construction of various coordination polymers with diverse topologies and interesting properties. The bis(azole) ligands in which N-donor azole rings (imidazole, triazole, or tetrazole) are separated by alkyl, (CH{sub 2}){sub n}, spacers are good choices for flexible bridging ligands. The conformational flexibility of the spacers makes the ligands adaptable to various coordination networks with one-, two-, and three dimensional structures.

  12. Hybridisation and crystal field in YbPd2Si2

    International Nuclear Information System (INIS)

    Bonville, P.; Hammann, J.; Hodges, J.A.; Imbert, P.; Jehanno, G.

    1990-01-01

    Experimental data in the Kondo lattice YbPd 2 Si 2 is compared with the results of a hybridisation model, based on the large-degeneracy expansion approximation, which takes into account the crystal field level splittings of the Yb ion. We show that satisfactory agreement is obtained with a unique set of crystal field and hybridisation parameters

  13. Effect of pressure on the crystal field splitting in rare earth pnictides and chalcogenides

    International Nuclear Information System (INIS)

    Schirber, J.E.; Weaver, H.T.

    1978-01-01

    The experimental situation for the pressure dependence of the crystal field of praseodymium pnictides and chalcogenides is reviewed and compared with the predictions of the point charge model. The problem of separating exchange and crystal field contributions from the measured NMR frequency shift or susceptibility measurements is discussed as well as problems explaining these effects with conduction electron related models

  14. Method to map individual electromagnetic field components inside a photonic crystal

    NARCIS (Netherlands)

    Denis, T.; Reijnders, B.; Lee, J.H.H.; van der Slot, Petrus J.M.; Vos, Willem L.; Boller, Klaus J.

    2012-01-01

    We present a method to map the absolute electromagnetic field strength inside photonic crystals. We apply the method to map the dominant electric field component Ez of a two-dimensional photonic crystal slab at microwave frequencies. The slab is placed between two mirrors to select Bloch standing

  15. Crystal fields at light rare-earth ions in Y and Lu

    DEFF Research Database (Denmark)

    Touborg, P.; Nevald, Rolf; Johansson, Torben

    1978-01-01

    Crystal-field parameters have been deduced for the light rare-earth solutes Ce, Pr, and Nd in Y or Lu hosts from measurements of the paramagnetic susceptibilities. In the analysis all multiplets in the lowest LS term were included. For a given host, crystal-field parameters divided by Stevens...

  16. The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study.

    Science.gov (United States)

    Lukens, W W; Speldrich, M; Yang, P; Duignan, T J; Autschbach, J; Kögerler, P

    2016-07-28

    The electronic structures of 4f(3)/5f(3) Cp''3M and Cp''3M·alkylisocyanide complexes, where Cp'' is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal-ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(iii) and uranium(iii) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. While interaction with the isocyanide π*-orbitals lowers the energies of the 5fxz(2) and 5fyz(2)-orbitals, spin-orbit coupling greatly reduces the population of 5fxz(2) and 5fyz(2) in the ground state.

  17. Ligand size is a major determinant of specificity in periplasmic oxyanion-binding proteins: the 1.2 A resolution crystal structure of Azotobacter vinelandii ModA.

    Science.gov (United States)

    Lawson, D M; Williams, C E; Mitchenall, L A; Pau, R N

    1998-12-15

    . Periplasmic receptors constitute a diverse class of binding proteins that differ widely in size, sequence and ligand specificity. Nevertheless, almost all of them display a common beta/alpha folding motif and have similar tertiary structures consisting of two globular domains. The ligand is bound at the bottom of a deep cleft, which lies at the interface between these two domains. The oxyanion-binding proteins are notable in that they can discriminate between very similar ligands. . Azotobacter vinelandii is unusual in that it possesses two periplasmic molybdate-binding proteins. The crystal structure of one of these with bound ligand has been determined at 1.2 A resolution. It superficially resembles the structure of sulphate-binding protein (SBP) from Salmonella typhimurium and uses a similar constellation of hydrogen-bonding interactions to bind its ligand. However, the detailed interactions are distinct from those of SBP and the more closely related molybdate-binding protein of Escherichia coli. . Despite differences in the residues involved in binding, the volumes of the binding pockets in the A. vinelandii and E. coli molybdate-binding proteins are similar and are significantly larger than that of SBP. We conclude that the discrimination between molybdate and sulphate shown by these binding proteins is largely dependent upon small differences in the sizes of these two oxyanions.

  18. Crystallization and preliminary crystal structure analysis of the ligand-binding domain of PqsR (MvfR), the Pseudomonas quinolone signal (PQS) responsive quorum-sensing transcription factor of Pseudomonas aeruginosa

    International Nuclear Information System (INIS)

    Xu, Ningna; Yu, Shen; Moniot, Sébastien; Weyand, Michael; Blankenfeldt, Wulf

    2012-01-01

    The ligand-binding domain of the transcription factor PqsR from P. aeruginosa has been crystallized and initial phases have been obtained using SAD data from seleno-l-methionine-labelled crystals. The opportunistic bacterial pathogen Pseudomonas aeruginosa employs three transcriptional regulators, LasR, RhlR and PqsR, to control the transcription of a large subset of its genes in a cell-density-dependent process known as quorum sensing. Here, the recombinant production, crystallization and structure solution of the ligand-binding domain of PqsR (MvfR), the LysR-type transcription factor that responds to the Pseudomonas quinolone signal (PQS), a quinolone-based quorum-sensing signal that is unique to P. aeruginosa and possibly a small number of other bacteria, is reported. PqsR regulates the expression of many virulence genes and may therefore be an interesting drug target. The ligand-binding domain (residues 91–319) was produced as a fusion with SUMO, and hexagonal-shaped crystals of purified PqsR-91–319 were obtained using the vapour-diffusion method. Crystallization in the presence of a PQS precursor allowed data collection to 3.25 Å resolution on a synchrotron beamline, and initial phases have been obtained using single-wavelength anomalous diffraction data from seleno-l-methionine-labelled crystals, revealing the space group to be P6 5 22, with unit-cell parameters a = b = 116–120, c = 115–117 Å

  19. Spatial distribution of gamma-crystals in metallocene-made isotactic polypropylene crystallized under combined thermal and flow fields.

    Science.gov (United States)

    Wang, Yan; Pan, Ji-Lin; Mao, Yimin; Li, Zhong-Ming; Li, Liangbin; Hsiao, Benjamin S

    2010-05-27

    The present Article reports the relationships between molecular orientation, formation, and spatial distribution of gamma-crystals in metallocene-made isotactic polypropylene (m-iPP) samples prepared by two industrial processes: conventional injection molding (CIM) and oscillatory shear injection molding (OSIM), in which combined thermal and flow fields typically exist. In particular, spatial distributions of crystallinity, fraction of gamma-crystal (f(gamma)) with respect to alpha-crystal, and lamella-branched shish-kebab structure in the shaped samples were characterized by synchrotron two-dimensional (2D) wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. The results showed that the crystallinity in any given region of OSIM samples was always higher than that of CIM samples. The value of f(gamma) increased monotonously from skin to core in CIM samples, whereas the corresponding f(gamma) increased nonmonotonically in OSIM samples. The spatial distribution of gamma-crystal in OSIM samples can be explained by the epitaxial arrangement between gamma- and alpha-crystal in a lamella-branched shish-kebab structure. In the proposed model, the parent lamellae of alpha-crystal provide secondary nucleation sites for daughter lamellae of alpha-crystal and gamma-crystal, and the different content of parent lamellae results in varying amounts of gamma-crystal. In OSIM samples, the smallest parent-daughter ratio ([R]) = 1.38) in the core region led to the lowest fraction of gamma-crystal (0.57), but relatively higher gamma-crystal content (0.69) at 600 and 1200 mum depth of the samples (corresponding to [R] of 4.5 and 5.8, respectively). This is consistent with the proposed model where more parent lamellae provide more nucleation sites for crystallization, thus resulting in higher content of gamma-crystal. The melting behavior of CIM and OSIM samples was studied by differential scanning calorimetery (DSC). The observed double-melting peaks

  20. Spatial Distribution of -Crystals in Metallocene-Made Isotactic Polypropylene Crystallized under Combined Thermal and Flow Fields

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Y.; Pan, J; Mao, Y; Li, Z; Li, L; Hsiao, B

    2010-01-01

    The present Article reports the relationships between molecular orientation, formation, and spatial distribution of {gamma}-crystals in metallocene-made isotactic polypropylene (m-iPP) samples prepared by two industrial processes: conventional injection molding (CIM) and oscillatory shear injection molding (OSIM), in which combined thermal and flow fields typically exist. In particular, spatial distributions of crystallinity, fraction of {gamma}-crystal (f{gamma}) with respect to {alpha}-crystal, and lamella-branched shish-kebab structure in the shaped samples were characterized by synchrotron two-dimensional (2D) wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. The results showed that the crystallinity in any given region of OSIM samples was always higher than that of CIM samples. The value of f{gamma} increased monotonously from skin to core in CIM samples, whereas the corresponding f{gamma} increased nonmonotonically in OSIM samples. The spatial distribution of {gamma}-crystal in OSIM samples can be explained by the epitaxial arrangement between {gamma}- and {alpha}-crystal in a lamella-branched shish-kebab structure. In the proposed model, the parent lamellae of {alpha}-crystal provide secondary nucleation sites for daughter lamellae of {alpha}-crystal and {gamma}-crystal, and the different content of parent lamellae results in varying amounts of {gamma}-crystal. In OSIM samples, the smallest parent-daughter ratio ([R] = 1.38) in the core region led to the lowest fraction of {gamma}-crystal (0.57), but relatively higher {gamma}-crystal content (0.69) at 600 and 1200 {micro}m depth of the samples (corresponding to [R] of 4.5 and 5.8, respectively). This is consistent with the proposed model where more parent lamellae provide more nucleation sites for crystallization, thus resulting in higher content of {gamma}-crystal. The melting behavior of CIM and OSIM samples was studied by differential scanning calorimetery (DSC). The

  1. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  2. Field-Induced Co(II) Single-Ion Magnets with mer-Directing Ligands but Ambiguous Coordination Geometry.

    Science.gov (United States)

    Peng, Yan; Mereacre, Valeriu; Anson, Christopher E; Zhang, Yiquan; Bodenstein, Tilmann; Fink, Karin; Powell, Annie K

    2017-06-05

    Three air-stable Co(II) mononuclear complexes with different aromatic substituents have been prepared and structurally characterized by single-crystal X-ray diffraction. The mononuclear complexes [Co(H 2 L1) 2 ]·2THF (1), [Co(HL2) 2 ] (2), and [Co(H 2 L3) 2 ]·CH 2 Cl 2 (3) (where H 3 L1, H 2 L2, and H 3 L3 represent 3-hydroxy-naphthalene-2-carboxylic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, nicotinic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, and 2-hydroxy-benzoic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, respectively) feature a distorted mer octahedral coordination geometry. Detailed magnetic studies of 1-3 have been conducted using direct and alternating current magnetic susceptibility data. Field-induced slow magnetic relaxation was observed for these three complexes. There are few examples of such behavior in (distorted) octahedral coordination geometry (OC) Co(II) mononuclear complexes with uniaxial anisotropy. Analysis of the six-coordinate Co(II) mononuclear single-ion magnets (SIMs) in the literature using the SHAPE program revealed that they all show what is best described as distorted trigonal prismatic (TRP) coordination geometry, and in general, these show negative D zero-field splitting (ZFS) values. On the other hand, all the Co(II) mononuclear complexes displaying what is best approximated as distorted octahedral (OC) coordination geometry show positive D values. In the new Co(II) mononuclear complexes we describe here, there is an ambiguity, since the rigid tridentate ligands confer what is best described for an octahedral complex as a mer coordination geometry, but the actual shape of the first coordination sphere is between octahedral and trigonal prismatic. The negative D values observed experimentally and supported by high-level electronic structure calculations are thus in line with a trigonal prismatic geometry. However, a consideration of the rhombicity as indicated by the E value of the ZFS in

  3. The Symmetry of Optical Field in Photonic Crystal Fibre with Trigonal Symmetry

    Directory of Open Access Journals (Sweden)

    Ivan Turek

    2006-01-01

    Full Text Available Some photographs of intensity of optical field of a photonic crystal fibre are presented in the contribution. Presented photographs document that the symmetry of photonic crystal creating the cladding of fibre is manifested in the symmetry of distribution of the optical field intensity. In case when more modes are excited in the fibre the symmetry of the generated field can be different as the symmetry of the eventual modes. How the symmetry may be changed is illustrated by amodel example.

  4. Crystal structure prediction of flexible molecules using parallel genetic algorithms with a standard force field.

    Science.gov (United States)

    Kim, Seonah; Orendt, Anita M; Ferraro, Marta B; Facelli, Julio C

    2009-10-01

    This article describes the application of our distributed computing framework for crystal structure prediction (CSP) the modified genetic algorithms for crystal and cluster prediction (MGAC), to predict the crystal structure of flexible molecules using the general Amber force field (GAFF) and the CHARMM program. The MGAC distributed computing framework includes a series of tightly integrated computer programs for generating the molecule's force field, sampling crystal structures using a distributed parallel genetic algorithm and local energy minimization of the structures followed by the classifying, sorting, and archiving of the most relevant structures. Our results indicate that the method can consistently find the experimentally known crystal structures of flexible molecules, but the number of missing structures and poor ranking observed in some crystals show the need for further improvement of the potential. Copyright 2009 Wiley Periodicals, Inc.

  5. Effect of Ligand Field Tuning on the SMM Behavior for Three Related Alkoxide-Bridged Dysprosium Dimers.

    Science.gov (United States)

    Peng, Yan; Mereacre, Valeriu; Baniodeh, Amer; Lan, Yanhua; Schlageter, Martin; Kostakis, George E; Powell, Annie K

    2016-01-04

    The synthesis and characterization of three Dy2 compounds, [Dy2(HL1)2(NO3)4] (1), [Dy2(L2)2(NO3)4] (2), and [Dy2(HL3)2(NO3)4] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl and alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), and 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. The compounds are rare examples of alkoxide-bridged {Dy2} complexes and display capped square antiprism coordination geometry around each Dy(III) ion. Changes in the ligand field environment around the Dy(III) ions brought about through variations in the ligand donors can be gauged from the magnetic properties, with compounds 1 and 2 showing antiparallel coupling between the Dy(III) ions and 3 showing parallel coupling. Furthermore, slow relaxation of the magnetization typical of SMM behavior could be observed for compounds 2 and 3, suggesting that small variations in the ligand field can have a significant influence on the slow relaxation processes responsible for SMM behavior of Dy(III)-based systems.

  6. Synthesis, crystal structures, and thermal and spectroscopic properties of two Cd(II) metal-organic frameworks with a versatile ligand

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jia-Ming; He, Kun-Huan; Shi, Zhong-Feng [Qinzhou Univ. (China). Guangxi Colleges and Univs. Key Lab. of Beibu Gulf Oil and Natural Gas Resource Effective Utilization; Gao, Hui-Yuan; Jiang, Yi-Min [Guangxi Normal Univ., Guilin (China). Key Lab. for the Chemistry and Molecular Engineering of Medicinal Resources

    2016-11-01

    Two new metal-organic frameworks, namely, [Cd(L)(H{sub 2}O)]{sub n} (1) and {[Cd_0_._5(L)(4,4"'-bipy)_0_._5][Cd_0_._5(H_2O)(4,4"'-bipy)_0_._5].H_2O}{sub n} (2), where H{sub 2}L = N-pyrazinesulfonyl-glycine and 4,4{sup '}-bipy = 4,4{sup '}-bipyridine, have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental, thermogravimetric, and photoluminescent analysis. X-ray diffraction crystallographic analyses indicate that 1 displays a distorted octahedral metal coordination in a 3-connected (4, 8{sup 2}) topology, while the molecular structure of 2 has a 4-connected (4, 4) topology with two perfectly octahedrally coordinated Cd centers. The L{sup 2-} ligand serves as a N,N,O-tridentate, μ{sub 2}-pyrazine-bridging, and μ{sub 2}-carboxylate-bridging ligand in 1, and as a N,O-bidentate and μ{sub 2}-carboxylate-bridging ligand in 2. In the crystal, a 3D supramolecular architecture is formed by O-H..O hydrogen bond interactions in 1, but through O-H..O as well as π..π stacking in 2. The two compounds show intense fluorescence in the solid state at room temperature.

  7. Static magnetic susceptibility, crystal field and exchange interactions in rare earth titanate pyrochlores

    Energy Technology Data Exchange (ETDEWEB)

    Malkin, B Z; Zakirov, A R [Kazan State University, Kazan 420008 (Russian Federation); Lummen, T T A; Van Loosdrecht, P H M [Zernike Institute for Advanced Materials, University of Groningen, 9747 AG Groningen (Netherlands); Dhalenne, G, E-mail: boris.malkin@ksu.r [Laboratoire de Physico-Chimie de L' Etat Solide, ICMMO, UMR 8182, Universite Paris-Sud, 91405 Orsay (France)

    2010-07-14

    The experimental temperature dependence (T = 2-300 K) of single crystal bulk and site susceptibilities of rare earth titanate pyrochlores R{sub 2}Ti{sub 2}O{sub 7} (R = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) is analyzed in the framework of crystal field theory and a mean field approximation. Analytical expressions for the site and bulk susceptibilities of the pyrochlore lattice are derived taking into account long range dipole-dipole interactions and anisotropic exchange interactions between the nearest neighbor rare earth ions. The sets of crystal field parameters and anisotropic exchange coupling constants have been determined and their variations along the lanthanide series are discussed.

  8. The effect of magnetic field on the shape of etch pits of paracetamol crystals

    Energy Technology Data Exchange (ETDEWEB)

    Ivashchenko, V.E. [Kemerovo State University, Novosibirsk (Russian Federation); Research and Educational Center, Novosibirsk State University (Russian Federation); Boldyrev, V.V.; Shakhtshneider, T.P. [Institute of Solid State Chemistry and Mechanochemistry, RAS, Novosibirsk (Russian Federation); Zakharov, Yu.A.; Krasheninin, V.I. [Kemerovo State University, Novosibirsk (Russian Federation); Ermakov, A.E. [Institute of Physics of Metals, Ural Branch of RAS, Ekaterinburg (Russian Federation)

    2002-04-01

    In the present study we investigate the effect of magnetic field on the shape of etch pits of the crystals of p-hydroxyacetanilide (paracetamol), which is widely used in pharmacy as antipyretic, antiphlogistic medicine. It was discovered that the magnetic field (H=0.5 T, {tau}=15 min) changes the morphology of etch pits and shifts dislocations in paracetamol crystal. Activation energy of the changes induced by the action of the magnetic field was determined to be 63 kJ/mol, which is comparable with the energy of hydrogen bonds in crystal lattice. (orig.)

  9. Vitamin D Analogues with a p-Hydroxyphenyl Group at the C25 Position: Crystal Structure of Vitamin D Receptor Ligand-Binding Domain Complexed with the Ligand Explains the Mechanism Underlying Full Antagonistic Action.

    Science.gov (United States)

    Kato, Akira; Yamao, Makiko; Hashihara, Yuta; Ishida, Hiroaki; Itoh, Toshimasa; Yamamoto, Keiko

    2017-10-26

    Vitamin D receptor (VDR) antagonists can be classified into two categories: the first category of VDR antagonists, which do not stabilize the helix 11-12, and the second category of antagonists, which destabilize the helix 6-7 region. To elucidate the mechanism underlying the first category antagonists by using the crystal structure, we designed and synthesized several VDR ligands with a p-hydroxyphenyl group at the C25-position. Of these, 22S-butyl-25-carbonyl analogue 5b and 25-di-p-hydoroxyphenyl analogues 6a,b showed strong antagonistic activity. We succeeded in cocrystallizing the ligand-binding domain of VDR complexed with 5b and found that the structure showed an alternative conformation of the helix 11-12 that explained the mechanism of the first category antagonists. Taking the present and previous studies together, we could elucidate the mechanisms underlying first and second categories antagonists based on individual crystal structures. This study provides significant insights into antagonism against not only VDR but also nuclear receptors.

  10. Effects of Electronic Quantum Interference, Photonic-Crystal Cavity, Longitudinal Field and Surface-Plasmon- Polariton for Optical Amplification

    National Research Council Canada - National Science Library

    Cardimona, David A; Alsing, Paul M; Huang, Danhong

    2008-01-01

    ... by a coupling laser field in a three-level system, field enhancement through the cavity confinement of a radiation field in a photonic crystal and field concentration seen in a transmitted near field...

  11. Magnetic ions in crystals

    CERN Document Server

    Stevens, K W

    2014-01-01

    There have been many demonstrations, particularly for magnetic impurity ions in crystals, that spin-Hamiltonians are able to account for a wide range of experimental results in terms of much smaller numbers of parameters. Yet they were originally derived from crystal field theory, which contains a logical flaw; electrons on the magnetic ions are distinguished from those on the ligands. Thus there is a challenge: to replace crystal field theory with one of equal or greater predictive power that is based on a surer footing. The theory developed in this book begins with a generic Hamiltonian, on

  12. Time-dependent alignment of molecules trapped in octahedral crystal fields.

    Science.gov (United States)

    Kiljunen, Toni; Schmidt, Burkhard; Schwentner, Nikolaus

    2006-04-28

    The hindered rotational states of molecules confined in crystal fields of octahedral symmetry, and their time-dependent alignment obtained by pulsed nonresonant laser fields, are studied computationally. The control over the molecular axis direction is discussed based on the evolution of the rotational wave packet generated in the cubic crystal-field potential. The alignment degree obtained in a cooperative case, where the alignment field is applied in a favorable crystal-field direction, or in a competitive direction, where the crystal field has a saddle point, is presented. The investigation is divided into two time regimes where the pulse duration is either ultrashort, leading to nonadiabatic dynamics, or long with respect to period of molecular libration, which leads to synchronous alignment due to nearly adiabatic following. The results are contrasted to existing gas phase studies. In particular, the irregularity of the crystal-field energies leads to persistent interference patterns in the alignment signals. The use of nonadiabatic alignment for interrogation of crystal-field energetics and the use of adiabatic alignment for directional control of molecular dynamics in solids are proposed as practical applications.

  13. The Role of Coulomb Interactions for Spin Crossover Behaviors and Crystal Structural Transformation in Novel Anionic Fe(III Complexes from a π-Extended ONO Ligand

    Directory of Open Access Journals (Sweden)

    Suguru Murata

    2016-05-01

    Full Text Available To investigate the π-extension effect on an unusual negative-charged spin crossover (SCO FeIII complex with a weak N2O4 first coordination sphere, we designed and synthesized a series of anionic FeIII complexes from a π-extended naphthalene derivative ligand. Acetonitrile-solvate tetramethylammonium (TMA salt 1 exhibited an SCO conversion, while acetone-solvate TMA salt 2 was in a high-spin state. The crystal structural analysis for 2 revealed that two-leg ladder-like cation-anion arrays derived from π-stacking interactions between π-ligands of the FeIII complex anion and Coulomb interactions were found and the solvated acetone molecules were in one-dimensional channels between the cation-anion arrays. A desolvation-induced single-crystal-to-single-crystal transformation to desolvate compound 2’ may be driven by Coulomb energy gain. Furthermore, the structural comparison between quasi-polymorphic compounds 1 and 2 revealed that the synergy between Coulomb and π-stacking interactions induces a significant distortion of coordination structure of 2.

  14. Excess vibrational modes of a crystal in an external non-affine field

    Indian Academy of Sciences (India)

    Thermal displacement fluctuations in a crystal may be classified as either “affine” or “non-affine”. While the former couples to external stress with familiar consequences, the response of a crystal when nonaffine displacements are enhanced using the thermodynamically conjugate field, is relatively less studied. We examine ...

  15. Influence of Superconductivity on Crystal Electric Field Transitions in La1-xTbxAl2

    DEFF Research Database (Denmark)

    Feile, R.; Loewenhaupt, M.; Kjems, Jørgen

    1981-01-01

    Inelastic neutron scattering from the crystal electric field transitions in La1-xTbxAl2 single crystals has revealed an abrupt increase in the lifetimes of these transitions when the system becomes superconducting. An increase in the integrated intensities is also observed. The lifetime effects...

  16. Coligand-directed synthesis of five Co(II)/Ni(II) coordination polymers with a neutral tetradentate ligand: syntheses, crystal structures, and properties.

    Science.gov (United States)

    Qin, Ling; Wang, Zhong-Jie; Wang, Ting; Zheng, He-Gen; Chen, Jin-Xi

    2014-09-07

    The solvothermal reactions of 1,1'-oxybis[3,5-di-4-pyridine]-benzene (L) and transition metal cations (Co and Ni) afford five novel coordination polymers in the presence of flexible bridging ligands (4,4'-H2nba = 4,4'-dicarboxydiphenylamine, H2cam = d-camphoric acid, 4,4'-H2sdb = 4,4'-sulfonyldibenzoic acid, H2chdc = 1,4-trans-cyclohexanedicarboxylic acid), namely {[Co2L2(OH)2(nba)]·2DMF}n (), {[CoL(cam)(H2O)]}n (), {[Co3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), {[Ni3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), and {[Ni2L2(chdc)2(H2O)2]·(H2O)3}n () (DMF = N,N-dimethylformamide). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and powder X-ray diffraction. Complex reveals a 2-fold interpenetrating three-dimensional (3D) framework with the Schläfli symbol {4·8·10(4)}{4·8·10} topology. Compound crystallizes in the achiral space group with the d-camphorate ligand racemized. Compounds and reveal similar structure with the {3·4(4)·6}{3(2)·4(8)·5(9)·6(9)} topology based on a linear trinuclear building block M3(OOCR)6 (M = Co(ii) or Ni(ii)). Compound is a wavy sheet, where both carboxylate and L ligands act as bidentate ligands. Moreover, UV-Visible absorption spectra of complexes , and the magnetic properties of have been investigated.

  17. Absorption measurement s in InSe single crystal under an applied electric field

    International Nuclear Information System (INIS)

    Ates, A.; Guerbulak, B.; Guer, E.; Yildirim, T.; Yildirim, M.

    2002-01-01

    InSe single crystal was grown by Bridgman-Stockberger method. Electric field effect on the absorption measurements have been investigated as a function of temperature in InSe single crystal. The absorption edge shifted towards longer wavelengths and decreased of intensity in absorption spectra under an electric field. Using absorption measurements, Urbach energy was calculated under an electric field. Applied electric field caused a increasing in the Urbach energy. At 10 K and 320 K, the first exciton energies were calculated as 1.350 and 1.311 eV for zero voltage and 1.334 and 1.301 eV for electric field respectively

  18. Influence of initial seed distribution on the pattern formation of the phase field crystals

    Science.gov (United States)

    Starodumov, Ilya; Galenko, Peter; Kropotin, Nikolai; Alexandrov, Dmitri V.

    2017-11-01

    The process of crystal growth can be expressed as a transition of atomic structure to a finally stable state or to a metastable state. In the Phase Field Crystal Model (PFC-model) these states are described by regular distributions of the atomic density. Getting the system into any metastable condition may be caused by the peculiarities of the computational domain, initial and boundary conditions. However, an important factor in the formation of the crystal structure can be the initial disturbance. In the report we show how different types of initial disturbance can change the finally stable state of crystal structure in equilibrium.

  19. Mixed spin Ising model with four-spin interaction and random crystal field

    Energy Technology Data Exchange (ETDEWEB)

    Benayad, N., E-mail: n.benayad@fsac.ac.ma [Groupe de Mecanique Statistique, Laboratoire de physique theorique et appliquee, Faculte des sciences-Aien Chock, Universite Hassan II-Casablanca, B.P 5366 Maarif, Casablanca 20100 (Morocco); Laboratoire de physique des hautes energies et de la matiere condensee, Faculte des sciences-Aien Chock, Universite Hassan II-Casablanca, B.P 5366 Maarif, Casablanca 20100 (Morocco); Ghliyem, M. [Groupe de Mecanique Statistique, Laboratoire de physique theorique et appliquee, Faculte des sciences-Aien Chock, Universite Hassan II-Casablanca, B.P 5366 Maarif, Casablanca 20100 (Morocco); Laboratoire de physique des hautes energies et de la matiere condensee, Faculte des sciences-Aien Chock, Universite Hassan II-Casablanca, B.P 5366 Maarif, Casablanca 20100 (Morocco)

    2012-01-01

    The effects of fluctuations of the crystal field on the phase diagram of the mixed spin-1/2 and spin-1 Ising model with four-spin interactions are investigated within the finite cluster approximation based on a single-site cluster theory. The state equations are derived for the two-dimensional square lattice. It has been found that the system exhibits a variety of interesting features resulting from the fluctuation of the crystal field interactions. In particular, for low mean value D of the crystal field, the critical temperature is not very sensitive to fluctuations and all transitions are of second order for any value of the four-spin interactions. But for relatively high D, the transition temperature depends on the fluctuation of the crystal field, and the system undergoes tricritical behaviour for any strength of the four-spin interactions. We have also found that the model may exhibit reentrance for appropriate values of the system parameters.

  20. Spectroscopy of Charge Carriers and Traps in Field-Doped Single Crystal Organic Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaoyang [Columbia Univ., New York, NY (United States); Frisbie, Daniel [Univ. of Minnesota, Minneapolis, MN (United States)

    2017-03-31

    The proposed research aims to achieve quantitative, molecular level understanding of charge carriers and traps in field-doped crystalline organic semiconductors via in situ linear and nonlinear optical spectroscopy, in conjunction with transport measurements and molecular/crystal engineering.

  1. Photovoltaic Field-Induced Self-Phase Modulation in Liquid Crystal Cells (Preprint)

    National Research Council Canada - National Science Library

    Carns, Jennifer L; Cook, Gary; Saleh, Mohammad A; Serak, Svetlana V; Tabiryan, Nelson V; Basun, Sergei A; Evans, Dean R

    2006-01-01

    We show that photovoltaic fields generated internally in LiNbO3:Fe substrates are capable of efficiently reorienting liquid crystal molecules leading to new concepts of optically addressable light modulators...

  2. Crystal field of rare earth impurities in LaF.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Novák, Pavel; Kuneš, Jan; Knížek, Karel

    2014-01-01

    Roč. 37, NOV (2014), s. 414-418 ISSN 0925- 3467 Institutional support: RVO:68378271 Keywords : crystal field * rare earth * ab initio calculation Subject RIV: BE - Theoretical Physics Impact factor: 1.981, year: 2014

  3. Geometrical structure factors of the crystal-field coefficients in ionic and metallic cubic compounds

    International Nuclear Information System (INIS)

    Adam, S.; Adam, G.; Corciovei, A.

    1977-01-01

    The crystal-field Hamiltonian for cubic compounds is brought into the standard form of the crystal-field theory by a general symmetrization technique which uses point group considerations only. The obtained crystal-field coefficients are expressed as products between those given by Hutchings and some geometrical structure factors, which include the relative contribution of all the neighbouring ions to the crystal-field. Assuming point charges in vacuum, numerical values are reported for the geometrical structure factors of several cubic structures and significant departures from Hutchings' results are found in some cases. Then, the screening effect of the conduction electrons in cubic metallic structures is investigated supposing a screened Coulomb interionic potential. (author)

  4. Transverse magnetic field impact on waveguide modes of photonic crystals.

    Science.gov (United States)

    Sylgacheva, Daria; Khokhlov, Nikolai; Kalish, Andrey; Dagesyan, Sarkis; Prokopov, Anatoly; Shaposhnikov, Alexandr; Berzhansky, Vladimir; Nur-E-Alam, Mohammad; Vasiliev, Mikhail; Alameh, Kamal; Belotelov, Vladimir

    2016-08-15

    This Letter presents a theoretical and experimental study of waveguide modes of one-dimensional magneto-photonic crystals magnetized in the in-plane direction. It is shown that the propagation constants of the TM waveguide modes are sensitive to the transverse magnetization and the spectrum of the transverse magneto-optical Kerr effect has resonant features at mode excitation frequencies. Two types of structures are considered: a non-magnetic photonic crystal with an additional magnetic layer on top and a magneto-photonic crystal with a magnetic layer within each period. We found that the magneto-optical non-reciprocity effect is greater in the first case: it has a magnitude of δ∼10-4, while the second structure type demonstrates δ∼10-5 only, due to the higher asymmetry of the claddings of the magnetic layer. Experimental observations show resonant features in the optical and magneto-optical Kerr effect spectra. The measured dispersion properties are in good agreement with the theoretical predictions. An amplitude of light intensity modulation of up to 2.5% was observed for waveguide mode excitation within the magnetic top layer of the non-magnetic photonic crystal structure. The presented theoretical approach may be utilized for the design of magneto-optical sensors and modulators requiring pre-determined spectral features.

  5. Study of Fluid Flow Control in Protein Crystallization using Strong Magnetic Fields

    Science.gov (United States)

    Ramachandran, Narayanan; Leslie, Fred; Ciszak, Ewa

    2002-01-01

    An important component in biotechnology, particularly in the area of protein engineering and rational drug design is the knowledge of the precise three-dimensional molecular structure of proteins. The quality of structural information obtained from X-ray diffraction methods is directly dependent on the degree of perfection of the protein crystals. As a consequence, the growth of high quality macromolecular crystals for diffraction analyses has been the central focus for biochemists, biologists, and bioengineers. Macromolecular crystals are obtained from solutions that contain the crystallizing species in equilibrium with higher aggregates, ions, precipitants, other possible phases of the protein, foreign particles, the walls of the container, and a likely host of other impurities. By changing transport modes in general, i.e., reduction of convection and sedimentation, as is achieved in "microgravity", researchers have been able to dramatically affect the movement and distribution of macromolecules in the fluid, and thus their transport, formation of crystal nuclei, and adsorption to the crystal surface. While a limited number of high quality crystals from space flights have been obtained, as the recent National Research Council (NRC) review of the NASA microgravity crystallization program pointed out, the scientific approach and research in crystallization of proteins has been mainly empirical yielding inconclusive results. We postulate that we can reduce convection in ground-based experiments and we can understand the different aspects of convection control through the use of strong magnetic fields and field gradients. Whether this limited convection in a magnetic field will provide the environment for the growth of high quality crystals is still a matter of conjecture that our research will address. The approach exploits the variation of fluid magnetic susceptibility with concentration for this purpose and the convective damping is realized by appropriately

  6. Optical spectra and crystal field of Am{sup 3+} and Cm{sup 3+} in the cubic elpasolite crystals

    Energy Technology Data Exchange (ETDEWEB)

    Barbanel`, Yu.A.; Chudnovskaya, G.P.; Dushin, R.B.; Kolin, V.V.; Kotlin, V.P.; Nekhoroshkov, S.N.; Pen`kin, M.V. [Khlopin (V.G.) Radium Inst., St. Petersburg (Russian Federation)

    1997-12-31

    Absorption and luminescence spectra of the elpasolite (Fm3m) crystals Cs{sub 2}NaLnCl{sub 6}:An{sup 3+} (where Ln = Yb, Lu; An = Am, Cm) have been studied at room, liquid nitrogen and helium (4.2 or 12 K) temperatures. Some electronic sublevels have been localized based on the vibronic structure analysis and assigned as a result of the crystal-field (CF) calculations. Low-temperature phase transitions have been revealed in the Cs{sub 2}NaYbCl{sub 6} and Cs{sub 2}NaLuCl{sub 6} crystals within the 77-4.2 K range. The CF parameters have been estimated for the CmCl{sub 6}{sup 3-} complex and calculated (using both the relativistic and nonrelativistic versions of the CF theory) for the AmCl{sub 6}{sup 3-} complex. (orig.)

  7. Study on the temperature field of large-sized sapphire single crystal furnace

    Science.gov (United States)

    Zhai, J. P.; Jiang, J. W.; Liu, K. G.; Peng, X. B.; Jian, D. L.; Li, I. L.

    2018-01-01

    In this paper, the temperature field of large-sized (120kg, 200kg and 300kg grade) sapphire single crystal furnace was simulated. By keeping the crucible diameter ratio and the insulation system unchanged, the power consumption, axial and radial temperature gradient, solid-liquid surface shape, stress distribution and melt flow were studied. The simulation results showed that with the increase of the single crystal furnace size, the power consumption increased, the temperature field insulation effect became worse, the growth stress value increased and the stress concentration phenomenon occurred. To solve these problems, the middle and bottom insulation system should be enhanced during designing the large-sized sapphire single crystal furnace. The appropriate radial and axial temperature gradient was favorable to reduce the crystal stress and prevent the occurrence of cracking. Expanding the interface between the seed and crystal was propitious to avoid the stress accumulation phenomenon.

  8. A new approach to modeling liquid crystal elastomers using phase field methods

    International Nuclear Information System (INIS)

    Oates, W S; Wang, H

    2009-01-01

    A phase field modeling framework is developed to quantify domain structure evolution in nematic phase liquid crystal elastomers. A hyperelastic energy function is combined with liquid crystal energy relations to formulate a constitutive model for liquid crystal elastomers that undergo thermo-mechanical loads and finite deformation. A set of balance laws and constitutive relations are defined which lead to coupling behavior when finite deformation is introduced within the energy description. The theoretical framework is implemented numerically using a non-linear finite element phase field modeling approach which couples deformation of the elastomer network with microscopic liquid crystal domain structure evolution. A comparison of monodomain and polydomain behavior is analyzed to illustrate spontaneous deformation and polydomain evolution during heating and mechanical stretching. Many of the essential constitutive relations governing these materials are obtained without the use of explicit phenomenological coupling between the liquid crystals and the host elastomer

  9. Tricritical behavior in the diluted transverse spin-1 Ising model with a longitudinal crystal field

    International Nuclear Information System (INIS)

    Htoutou, K.; Oubelkacem, A.; Ainane, A.; Saber, M.

    2005-01-01

    The transverse spin-1 Ising model with a longitudinal crystal field exhibits a tricritical behavior. Within the effective field theory with a probability distribution technique that accounts for the self-spin correlations, we have studied the influence of site dilution on this behavior and have calculated the temperature-transverse field-longitudinal crystal field-concentration phase diagrams and determined, in particular, the influence of the concentration of magnetic atoms c on the tricritical behavior. We have found that the tricritical point appears for large values of the concentration c of magnetic atoms and disappears with the increase in dilution (small values of c). Results for square lattice are calculated numerically and some interesting results are obtained. In certain ranges of values of the strength of the longitudinal crystal field D/J when it becomes sufficiently negative, we found re-entrant phenomenon, which disappears with increase in the value of the strength of the transverse field

  10. Neutron study of crystal-field transitions in ErPO[sub 4

    Energy Technology Data Exchange (ETDEWEB)

    Loong, C.-K.; Soderholm, L.; Hammonds, J.P. (Argonne National Lab., IL (United States)); Abraham, M.M.; Boatner, L.A. (Oak Ridge National Lab., TN (United States)); Edelstein, N.M. (Lawrence Berkeley Lab., CA (United States))

    1992-01-01

    The crystal-field splitting of the Er[sup 3+] ground multiplet, [sup 4]I[sub 15/2], in ErPO[sub 4] is investigated by inelastic neutron scattering. Four excitations from the [Gamma][sub 7] ground state to the excited states and several transitions between the excited states have been identified. The observed transition energies and intensities are used to refine the parameters of the crystal-field potential. The calculated magnetic susceptibility, [chi](T), agrees well with experimental values from single-crystal measurements. A comparison of the neutron data with optical absorption and both nonresonance and resonance Raman scattering measurements has been made.

  11. Neutron study of crystal-field transitions in ErPO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Loong, C.-K.; Soderholm, L.; Hammonds, J.P. [Argonne National Lab., IL (United States); Abraham, M.M.; Boatner, L.A. [Oak Ridge National Lab., TN (United States); Edelstein, N.M. [Lawrence Berkeley Lab., CA (United States)

    1992-12-01

    The crystal-field splitting of the Er{sup 3+} ground multiplet, {sup 4}I{sub 15/2}, in ErPO{sub 4} is investigated by inelastic neutron scattering. Four excitations from the {Gamma}{sub 7} ground state to the excited states and several transitions between the excited states have been identified. The observed transition energies and intensities are used to refine the parameters of the crystal-field potential. The calculated magnetic susceptibility, {chi}(T), agrees well with experimental values from single-crystal measurements. A comparison of the neutron data with optical absorption and both nonresonance and resonance Raman scattering measurements has been made.

  12. A Navier-Stokes phase-field crystal model for colloidal suspensions.

    Science.gov (United States)

    Praetorius, Simon; Voigt, Axel

    2015-04-21

    We develop a fully continuous model for colloidal suspensions with hydrodynamic interactions. The Navier-Stokes Phase-Field Crystal model combines ideas of dynamic density functional theory with particulate flow approaches and is derived in detail and related to other dynamic density functional theory approaches with hydrodynamic interactions. The derived system is numerically solved using adaptive finite elements and is used to analyze colloidal crystallization in flowing environments demonstrating a strong coupling in both directions between the crystal shape and the flow field. We further validate the model against other computational approaches for particulate flow systems for various colloidal sedimentation problems.

  13. Synthesis, characterization, crystal structure, superoxide dismutase and biological activities of nickel (II) complexes with bidentate ligands possessing N and O donor atoms

    Science.gov (United States)

    Sangeeta, S.; Ahmad, K.; Noorussabah, N.; Bharti, S.; Mishra, M. K.; Sharma, S. R.; Choudhary, M.

    2017-12-01

    Two new Schiff bases 2-((E)-(4-bromo-2-chlorophenylimino)methyl)-4-bromophenol(HL1) and1-((E)-(4-bromo-2-chlorophenylimino)methyl)naphthalene-2-ol (HL2) and their new nickel (II) complexes [Ni(L1)2]·DMF(1) and [Ni(L2)2] (2) have been synthesized and characterized by various physico- chemical and spectroscopic methods. The solid-state structures of synthesized compounds were determined by single crystal X-ray crystallography, which revealed square planar geometry around Ni (II) ion. Infrared spectra, UV-Vis, thermal analysis and magnetic susceptibility measurements agreed with the observed crystal structures. The ligand (HL1) crystallized in the Orthorhombic system of the space group Pbca,a = 7.5485(4)Å, b = 11.5514(5) Å, c = 30.1370(14)Å, α = 90°, β = 90°, γ = 90°and Z = 8. Complex[Ni(L1)2]·DMF(1) crystallized in the Triclinic system of the space group P-1, a = 8.9954(3) Å, b = 9.4593(4) Å, c = 13.2657(5) Å, α = 101.478°, β = 99.595°, γ = 117.651°and Z = 2, whereas complex [Ni(L2)2]·(2) crystallized in the Monoclinic system of the space group P21/c, a = 9.301(9)Å, b = 12.149(8)Å, c = 13.792(10)Å, α = 90°, β = 106.35(4).°, γ = 90°and Z = 2. The Schiff bases (HL1and HL2) behaved as monobasic bidentate ligands possessing N and O donor atoms. The SOD activities of HL1 and its Ni (II) complex[Ni(L1)2]·DMF(1) have been measured using xanthine-xanthine oxidase as a source of superoxide radical and NBT assay as O2- scavenger. In vitro antimicrobial activities of the Ni(II) complexes (1) and (2)against Bacillus cereus and Staphylococcus aureus as Gram + ve and Salmonella typhi, Klebsiella pneumonia and Escherichia coli as Gram-ve species have been investigated comparing with the Schiff base ligands (HL1and HL2).

  14. Dependence of magnetization on crystal fields and exchange interactions in magnetite

    Energy Technology Data Exchange (ETDEWEB)

    Ouaissa, Mohamed, E-mail: m.ouaissa@yahoo.fr [Laboratoire de Génie Physique et Environnement, Faculté des Sciences, Université Ibn Tofail, Campus Universitaire BP 133, Kénitra 14000 (Morocco); Benyoussef, Abdelilah [Laboratory of Magnetism and Physics of High Energy, Faculty of Science, Mohammed V-Agdal University, Rabat (Morocco); Abo, Gavin S. [Department of Electrical and Computer Engineering and MINT Center, The University of Alabama, Tuscaloosa, AL 35487 (United States); Ouaissa, Samia; Hafid, Mustapha [Laboratoire de Génie Physique et Environnement, Faculté des Sciences, Université Ibn Tofail, Campus Universitaire BP 133, Kénitra 14000 (Morocco); Belaiche, Mohammed [Laboratoire de Magnétisme, Matériaux Magnétiques, Microonde et Céramique, Ecole Normale Supérieure, Université Mohammed V-Agdal, B.P. 9235, Océan, Rabat (Morocco)

    2015-11-15

    In this work, we study the magnetization of magnetite (Fe{sub 3}O{sub 4}) with different exchange interactions and crystal fields using variational method based on the Bogoliubov inequality for the Gibbs free energy within the mean field theory. The magnetic behavior was investigated in the absence and presence of crystal fields. The investigations also revealed that the transition temperature depends on the crystal fields of the octahedral and tetrahedral sites. Magnetite exhibits ferrimagnetic phase with second order transition to paramagnetic phase at 850 K. This result is confirmed using the mean field theory within the Heisenberg model. Important factors that can affect the magnetic behavior of the system are exchange interactions and crystal field. Indeed, a new magnetic behavior was observed depending on these parameters. A first order phase transition from ferrimagnetic to ferromagnetic was found at low temperature, and a second order transition from ferromagnetic to paramagnetic was observed at high temperature. - Highlights: • Magnetization of magnetite versus temperature was studied by mean field theory. • The critical temperature of magnetite (Fe{sub 3}O{sub 4}) was approximately obtained. • Effect of sublattice crystal fields on the magnetization of Fe{sub 3}O{sub 4} was investigated.

  15. A thermal model for czochralski silicon crystal growth with an axial magnetic field

    Science.gov (United States)

    Hjellming, L. N.

    1990-07-01

    This paper presents a thermal model for molten silicon in a Czochralski crystal puller system with an applied uniform axial magnetic field. The melt depth is treated as continually decreasing, which affects the thermal environment of the melt and crystal. The radiative heat loss and the input heat flux are treated as functions of time, with a constraint placed on the heat lost to the crystal from the melt. As the melt motion reaches a steady state rapidly, the temperature and flow fields are treated as instantaneously steady at each melt depth. The heat transport is a mixture of conduction and convection, and by considering the crystal and crucible to be rotating with the same angular velocity, the flows driven by buoyancy and thermocapillarity are isolated and provide the convective heat transport in the melt for the range of magnetic field strengths 0.2 ≤ B ≤ 1.0T.

  16. Effect of far-field flow on a columnar crystal in the convective undercooled melt

    Science.gov (United States)

    Ji, Xiao-Jian; Chen, Ming-Wen; Xu, Xiao-Hua; Wang, Zi-Dong

    2015-01-01

    The growth behavior of a columnar crystal in the convective undercooled melt affected by the far-field uniform flow is studied and the asymptotic solution for the interface evolution of the columnar crystal is derived by means of the asymptotic expansion method. The results obtained reveal that the far-field flow induces a significant change of the temperature around the columnar crystal and the convective flow caused by the far-field flow accelerates the growth velocity of the interface of the growing columnar crystal in the upstream direction and inhibits its growth velocity in the downstream direction. Our results are similar to the experimental data and numerical simulations. Project supported by the Overseas Distinguished Scholar Program by the Ministry of Education of China (Grant No. MS2010BJKJ005), the National Natural Science Foundation of China (Grant No. 10972030), and the Science and Technology Support Project of Jiangxi, China (Grant No. 20112BBE50006).

  17. Crystallization and preliminary X-ray crystallographic analysis of peptide deformylase (PDF) from Bacillus cereus in ligand-free and actinonin-bound forms.

    Science.gov (United States)

    Park, Joon Kyu; Moon, Jin Ho; Kim, Jae-Hong; Kim, Eunice EunKyeong

    2005-01-01

    In bacteria, protein expression initiates with an N-formyl group and this needs to be removed in order to ensure proper bacterial growth. These formylation and deformylation processes are unique to eubacteria; therefore, inhibition of these would provide a novel antibacterial therapy. Deformylation is carried out by peptide deformylase (PDF). PDF from Bacillus cereus, one of the major pathogenic bacteria, was cloned into expression plasmid pET-28a (Novagen), overexpressed in Escherichia coli BL21 (DE3) and purified to high quality. Crystals have been obtained of both ligand-free PDF and PDF to which actinonin, a highly potent naturally occurring inhibitor, is bound. Both crystals belong to space group P2(1)2(1)2(1), with unit-cell parameters a = 42.72, b = 44.04, c = 85.19 A and a = 41.31, b = 44.56, c = 84.47 A, respectively. Diffraction data were collected to 1.7 A resolution for the inhibitor-free crystals and to 2.0 A resolution for the actinonin-bound crystals.

  18. Colloidal Quantum Dot Inks for Single-Step-Fabricated Field-Effect Transistors: The Importance of Postdeposition Ligand Removal.

    Science.gov (United States)

    Balazs, Daniel M; Rizkia, Nisrina; Fang, Hong-Hua; Dirin, Dmitry N; Momand, Jamo; Kooi, Bart J; Kovalenko, Maksym V; Loi, Maria Antonietta

    2018-02-14

    Colloidal quantum dots are a class of solution-processed semiconductors with good prospects for photovoltaic and optoelectronic applications. Removal of the surfactant, so-called ligand exchange, is a crucial step in making the solid films conductive, but performing it in solid state introduces surface defects and cracks in the films. Hence, the formation of thick, device-grade films have only been possible through layer-by-layer processing, limiting the technological interest for quantum dot solids. Solution-phase ligand exchange before the deposition allows for the direct deposition of thick, homogeneous films suitable for device applications. In this work, fabrication of field-effect transistors in a single step is reported using blade-coating, an upscalable, industrially relevant technique. Most importantly, a postdeposition washing step results in device properties comparable to the best layer-by-layer processed devices, opening the way for large-scale fabrication and further interest from the research community.

  19. The role of halides on a chromium ligand field in lead borate glasses

    Science.gov (United States)

    Sekhar, K. Chandra; Srinivas, B.; Narsimlu, N.; Narasimha Chary, M.; Shareefuddin, Md

    2017-10-01

    Glasses with a composition of PbX–PbO–B2O3 (X  =  F2, Cl2 and Br2) containing Cr3+ ions were prepared by a melt quenching technique and investigated by using x-ray diffraction (XRD), optical absorption and electron paramagnetic resonance (EPR) studies. X-ray diffractograms revealed the amorphous nature of the glasses. The density and molar volume were determined. Density values increased for the PFPBCR glass system and decreased for the PCPBCR and PBPBCR glass systems with the composition. Optical absorption spectra were recorded at room temperature (RT) to evaluate the optical band gap E opt and Urbach energies. All the spectra showed characteristic peaks at around 450 nm, 600 nm and 690 nm, and they are assigned to 4 A 2g  →  4 T 1g, 4 A 2g  →  4 T 2g, 4 A 2g  →  2 E transitions respectively. From the optical absorption spectral data, the crystal field (D q ) and Racah parameters (B and C) have been evaluated. Variations in optical band gaps were explained using the electro negativity of halide ions. Electron paramagnetic resonance (EPR) studies were carried out by introducing Cr3+ as the spin probe. The EPR spectra of all the glass samples were recorded at X-band frequencies. The EPR spectra exhibit two resonance signals with effective g values at g  ≈  4.82 and g  ≈  1.99 and are attributed to isolated Cr3+ ions and exchange coupled Cr3+ pairs respectively. The number of spins along with susceptibility are also calculated from the EPR spectra.

  20. Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes.

    Science.gov (United States)

    Vadavi, Ramesh S; Shenoy, Rashmi V; Badiger, Dayananda S; Gudasi, Kalagouda B; Devi, L Gomathi; Nethaji, Munirathinam

    2011-07-01

    The coordinating behavior of a new dihydrazone ligand, 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with α=98.491(10)°, β=110.820(10)° and γ=92.228(10)°. The cell dimensions are a=10.196(7)Å, b=10.814(7)Å, c=10.017(7)Å, Z=2 and V=1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with g(iso)=2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Two crystal structures of dihydrofolate reductase-thymidylate synthase from Cryptosporidium hominis reveal protein–ligand interactions including a structural basis for observed antifolate resistance

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Amy C., E-mail: aca@dartmouth.edu [Dartmouth College, Department of Chemistry, Burke Laboratories, Hanover, NH 03755 (United States)

    2005-03-01

    An analysis of the protein–ligand interactions in two crystal structures of DHFR-TS from C. hominis reveals a possible structural basis for observed antifolate resistance in C. hominis DHFR. A comparison with the structure of human DHFR reveals residue substitutions that may be exploited for the design of species-selective inhibitors. Cryptosporidium hominis is a protozoan parasite that causes acute gastrointestinal illness. There are no effective therapies for cryptosporidiosis, highlighting the need for new drug-lead discovery. An analysis of the protein–ligand interactions in two crystal structures of dihydrofolate reductase-thymidylate synthase (DHFR-TS) from C. hominis, determined at 2.8 and 2.87 Å resolution, reveals that the interactions of residues Ile29, Thr58 and Cys113 in the active site of C. hominis DHFR provide a possible structural basis for the observed antifolate resistance. A comparison with the structure of human DHFR reveals active-site differences that may be exploited for the design of species-selective inhibitors.

  2. Magnetic properties and electronic structure of neptunyl(VI) complexes: wavefunctions, orbitals, and crystal-field models

    Energy Technology Data Exchange (ETDEWEB)

    Gendron, Frederic; Pritchard, Ben; Autschbach, Jochen [Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY (United States); Paez-Hernandez, Dayan; Bolvin, Helene [Laboratoire de Physique et de Chimie Quantiques, Universite Toulouse 3 (France); Notter, Francois-Paul [Laboratoire de Chimie Quantique, Universite de Strasbourg (France)

    2014-06-23

    The electronic structure and magnetic properties of neptunyl(VI), NpO{sub 2}{sup 2+}, and two neptunyl complexes, [NpO{sub 2}(NO{sub 3}){sub 3}]{sup -} and [NpO{sub 2}Cl{sub 4}]{sup 2-}, were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO{sub 2}Cl{sub 4}]{sup 2-}, a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Field-emission microscopy of initial stages of crystallization

    International Nuclear Information System (INIS)

    Shrednik, V.N.

    1976-01-01

    An overview of the investigations made by the methods of field ion and field emission microscopies during the last 5-7 years is given. Surface migrations and elementary associations studied at the level of the location of separate atoms by the field ion microscopy methods are discussed by the sections: surface migration of separate atoms, correlated migration of a pair of adatoms, formation of elementary surface dimers and polymers, formation of elementary surface compounds and initial stages of two-dimensional alloy formation, investigations of the interatomic interaction potential, structure of the elementary associations, and phase transformations in two-dimensional clusters. Problems of two-dimensional condensation/sublimation and initial stages of metal condensation under vacuum studied by the field emission microscopy methods, and three-dimensional knots investigated both by field ion microscopy methods and by field emission microscopy methods have been examined. A detailed treatment is accorded the importance of the field ion microscopy when studying knots occurring during self-diffusion in a strong electric field. In all the cases, the potentials of the methods of the field ion and field emission microscopies are analized

  4. Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes.

    Science.gov (United States)

    Jung, Julie; Atanasov, Mihail; Neese, Frank

    2017-08-07

    Actinide chemistry is gaining increased focus in modern research, particularly in the fields of energy research and molecular magnetism. However, the structure-function and structure-property relationships of actinides have still not been studied as intensely as those for transition metals. In this work, we report a detailed ab initio study of the spectroscopic, magnetic, and bonding properties of the trivalent actinide free ions and their associated hexachloride complexes in octahedral symmetry. The electronic structures of these systems are examined using complete active-space self-consistent-field calculations followed by second-order N-electron valence perturbation theory, including both scalar relativistic and spin-orbit-coupling effects. The computed energies and wave functions are further analyzed by means of ab initio ligand-field theory (AILFT) and finally chemically interpreted by means of the angular overlap model (AOM). The derived Slater-Condon and spin-orbit parameters have allowed us to systematically rationalize the spectroscopic and magnetic properties of the investigated free ions and complexes along the entire actinide series. Overall, the AILFT- and AOM-derived parameters accurately reproduce the multireference electronic structure calculations. The small observed discrepancies with respect to experimentally derived ligand-field parameters are essentially due to an underestimation of the electronic correlation, which arises from both the constrained size of the active space (restricted to the f orbitals) and the limit of the perturbation approach to account for dynamical correlation. Our analysis also provides insight into the metal-ligand covalency trends along the series. Consistent with natural population analysis, the nephelauxetic (Slater-Condon parameters) and relativistic nephelauxetic (spin-orbit-coupling) reductions determined for these complexes indicate a decrease in the covalency along the series. These trends also hold, to varying

  5. Reorientation of single-wall carbon nanotubes in negative anisotropy liquid crystals by an electric field.

    Science.gov (United States)

    García-García, Amanda; Vergaz, Ricardo; Algorri, José F; Zito, Gianluigi; Cacace, Teresa; Marino, Antigone; Otón, José M; Geday, Morten A

    2016-01-01

    Single-wall carbon nanotubes (SWCNT) are anisotropic nanoparticles that can cause modifications in the electrical and electro-optical properties of liquid crystals. The control of the SWCNT concentration, distribution and reorientation in such self-organized fluids allows for the possibility of tuning the liquid crystal properties. The alignment and reorientation of CNTs are studied in a system where the liquid crystal orientation effect has been isolated. Complementary studies including Raman spectroscopy, microscopic inspection and impedance studies were carried out. The results reveal an ordered reorientation of the CNTs induced by an electric field, which does not alter the orientation of the liquid crystal molecules. Moreover, impedance spectroscopy suggests a nonnegligible anchoring force between the CNTs and the liquid crystal molecules.

  6. Reorientation of single-wall carbon nanotubes in negative anisotropy liquid crystals by an electric field

    Directory of Open Access Journals (Sweden)

    Amanda García-García

    2016-06-01

    Full Text Available Single-wall carbon nanotubes (SWCNT are anisotropic nanoparticles that can cause modifications in the electrical and electro-optical properties of liquid crystals. The control of the SWCNT concentration, distribution and reorientation in such self-organized fluids allows for the possibility of tuning the liquid crystal properties. The alignment and reorientation of CNTs are studied in a system where the liquid crystal orientation effect has been isolated. Complementary studies including Raman spectroscopy, microscopic inspection and impedance studies were carried out. The results reveal an ordered reorientation of the CNTs induced by an electric field, which does not alter the orientation of the liquid crystal molecules. Moreover, impedance spectroscopy suggests a nonnegligible anchoring force between the CNTs and the liquid crystal molecules.

  7. Investigations of ultrafast ligand rebinding to heme and heme proteins using temperature and strong magnetic field perturbations

    Science.gov (United States)

    Zhang, Zhenyu

    This thesis is written to summarize investigations of the mechanisms that underlie the kinetics of diatomic ligand rebinding to the iron atom of the heme group, which is chelated inside heme proteins. The family of heme proteins is a major object of studies for several branches of scientific research activity. Understanding the ligand binding mechanisms and pathways is one of the major goals for biophysics. My interests mainly focus on the physics of this ligand binding process. Therefore, to investigate the problem, isolated from the influence of the protein matrix, Fe-protophorphyrin IX is chosen as the prototype system in my studies. Myoglobin, the most extensively and intensively studied protein, is another ideal system that allows coupling the protein polypeptide matrix into the investigation. A technique to synchro-lock two laser pulse trains electronically is applied to our pump-probe spectroscopic studies. Based on this technique, a two color, fs/ps pump-probe system is developed which extends the temporal window for our investigation to 13ns and fills a gap existing in previous pump-probe investigations. In order to apply this newly-developed pump-probe laser system to implement systematic studies on the kinetics of diatomic ligand (NO, CO, O2) rebinding to heme and heme proteins, several experimental setups are utilized. In Chapter 1, the essential background knowledge, which helps to understand the iron-ligand interaction, is briefly described. In Chapter 2, in addition to a description of the preparation protocols of protein samples and details of the method for data analysis, three home-made setups are described, which include: a picosecond laser regenerative amplifier, a pump-probe application along the bore (2-inch in diameter) of a superconducting magnet and a temperature-controllable cryostat for spinning sample cell. Chapter 3 presents high magnetic field studies of several heme-ligand or protein-ligand systems. Pump-probe spectroscopy is used to

  8. The influence of a high-frequency magnetic field on the neutron diffraction by perfect crystals

    International Nuclear Information System (INIS)

    Michalec, R.; Chalupa, B.; Vavra, J.

    1989-01-01

    Measurements of the influence of a high-frequency magnetic field on the neutron diffraction by perfect monocrystals of InSb were performed at a frequency of 25 MHz. The ratios of the integrated reflectivities with and without a magnetic field as a function of the output voltage from the amplifier are shown for different parts of the crystal. The time dependence of the integrated reflectivity after switching on and off the high-frequency field is given. Results may be interpreted on the basis of the dynamical theory of diffraction on elastically deformed crystals (caused by the temperature gradient). Similar phenomena were observed also with a perfect Si monocrystal

  9. The influence of a magnetic field on the microhardness of K, Rb, Cs, NH4, and Tl acid phthalate crystals

    Science.gov (United States)

    Koldaeva, M. V.; Turskaya, T. N.; Zakalyukin, R. M.; Darinskaya, E. V.

    2009-11-01

    The influence of a magnetic field on the microhardness of potassium acid phthalate has been studied for different magnetic inductions, exposure times, sample orientations in a magnetic field, and impurity compositions of the crystals. It was shown that the magnetic field effect is multiply repeated on the (010) face after relaxation. The influence of magnetic treatment on ammonium, rubidium, thallium, and cesium acid phthalate crystals is analyzed. The reasons for the observed changes in the crystal microhardness in the magnetic field are discussed.

  10. High-field magnetization of UCuGe single crystal

    Czech Academy of Sciences Publication Activity Database

    Andreev, Alexander V.; Mushnikov, N. V.; Gozo, T.; Honda, F.; Sechovský, V.; Prokeš, K.

    346-347, - (2004), s. 132-136 ISSN 0921-4526 R&D Projects: GA ČR GA202/02/0739 Institutional research plan: CEZ:AV0Z1010914 Keywords : uranium intermetallics * UCuGe * high fields * magnetic anisotropy * field-induced phase transition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.679, year: 2004

  11. High-field Solution NMR Spectroscopy as a Tool for Assessing Protein Interactions with Small Molecule Ligands

    Science.gov (United States)

    Skinner, Andria L.; Laurence, Jennifer S.

    2013-01-01

    The ability of a small molecule to bind and modify the activity of a protein target at a specific site greatly impacts the success of drugs in the pharmaceutical industry. One of the most important tools for evaluating these interactions has been high-field solution NMR because of its unique ability to examine even weak protein-drug interactions at high resolution. NMR can be used to evaluate the structural, thermodynamic and kinetic aspects of a binding reaction. The basis of NMR screening experiments is that binding causes a perturbation in the physical properties of both molecules. Unique properties of small and macromolecules allow selective detection of either the protein target or ligand, even in a mixture of compounds. This review outlines current methodologies for assessing protein-ligand interactions from the perspectives of the protein target and ligand and delineates the fundamental principles for understanding NMR approaches in drug research. Advances in instrumentation, pulse sequences, isotopic labeling strategies, and the development of competition experiments support the study of higher molecular weight protein targets, facilitate higher-throughput and expand the range of binding affinities that can be evaluated, enhancing the utility of NMR for identifying and characterizing potential therapeutics to druggable protein targets. PMID:18351634

  12. Functional clues from the crystal structure of an orphan periplasmic ligand-binding protein from Treponema pallidum.

    Science.gov (United States)

    Brautigam, Chad A; Deka, Ranjit K; Liu, Wei Z; Tomchick, Diana R; Norgard, Michael V

    2017-04-01

    The spirochete Treponema pallidum is the causative agent of syphilis, a sexually transmitted infection of major global importance. Other closely related subspecies of Treponema also are the etiological agents of the endemic treponematoses, such as yaws, pinta, and bejel. The inability of T. pallidum and its close relatives to be cultured in vitro has prompted efforts to characterize T. pallidum's proteins structurally and biophysically, particularly those potentially relevant to treponemal membrane biology, with the goal of possibly revealing the functions of those proteins. This report describes the structure of the treponemal protein Tp0737; this polypeptide has a fold characteristic of a class of periplasmic ligand-binding proteins associated with ABC-type transporters. Although no ligand for the protein was observed in electron-density maps, and thus the nature of the native ligand remains obscure, the structural data described herein provide a foundation for further efforts to elucidate the ligand and thus the function of this protein in T. pallidum. © 2017 The Protein Society.

  13. Large electric-field-induced strain in centrosymmetric crystals of a dipolar ruthenium alkynyl complex.

    Science.gov (United States)

    Lau, K; Barlow, A; Moxey, G J; Li, Q; Liu, Y; Humphrey, M G; Cifuentes, M P; Frankcombe, T J; Stranger, R

    2015-04-28

    Dipolar molecular crystals present different physical properties from traditionally strongly correlated ionic solid-state inorganic crystals due to the weak intermolecular bonding. Herein, centrosymmetric dipolar molecular crystals of the organoruthenium complex trans-[Ru(C≡CC6H4-4-NO2)(C≡CPh)(dppe)2] [dppe = 1,2-bis(diphenylphosphino)ethane] display a large electric-field-induced strain behaving differently from conventional piezoelectric materials that must, structurally, be noncentrosymmetric. Further studies of related systematically varied crystalline organoruthenium complexes reveal that the strong electromechanical coupling effect is not from classical ferroelectricity, electrostriction, flexoelectricity or electrochemical strain. It is, instead, attributed to the disorder in the molecular packing, which facilitates reorientation of the molecular dipoles under the action of an applied electric field. This provides a fresh insight into the design and development of new functional materials and a promising source of electromechanical coupling in organometallic, and more generally dipolar molecular, crystals.

  14. Light-induced electric field generated by photovoltaic substrates investigated through liquid crystal reorientation

    Science.gov (United States)

    Lucchetti, L.; Kushnir, K.; Reshetnyak, V.; Ciciulla, F.; Zaltron, A.; Sada, C.; Simoni, F.

    2017-11-01

    Liquid crystal reorientation is exploited to analyze the electric field generated by light irradiation in iron-doped lithium niobate crystals. The evaluation of the strength of this light-induced field is based on the measurement of the phase shift induced in a probe light beam by a liquid crystal cell built with two z-cut iron-doped lithium niobate crystals as substrates. Then, the field profile has been determined starting from a Gaussian-like surface charge density following the model described in the text. The director profile corresponding to the modelled electric field is in good agreement with the director reorientation evaluated experimentally by means of the light-induced phase shift. This investigation gives a new approach to study the effects based on the photovoltaic response of lithium niobate crystals. Moreover, the characterization of the electric field optically generated inside the LC layer is highly desirable in view of the realization of new all-optical devices to be integrated in optofluidic platforms.

  15. I. Enabling Single-Chain Surfactants to Form Vesicles by Nonamphiphilic Liquid Crystals in Water II. Controlling Attachment and Ligand-Mediated Adherence of Candida albicans on Monolayers

    Science.gov (United States)

    Varghese, Nisha

    This dissertation describes a fundamental study of weak noncovalent interactions and surface forces that exist at the interfaces of various interacting moieties (small molecules or microbes), and its relevance to colloidal and material chemistry. Chapter 1 presents an emulsion system that enables single-chain anionic or nonionic surfactants to sequester and encapsulate certain water-soluble organic salts, leading to the formation of vesicles in water. The water-soluble organic salt in the system comprises of disodium cromoglycate crystals that are emulsified by surfactants in water to form stable liquid crystal droplets. The work provides an exception to the rule of geometric packing factor that dictates formation of micelles by the surfactants in water. Chapter 2 shows that the odd or even number of carbon atoms present in the aliphatic chain of surfactants affect the ability of surfactants to emulsify aqueous-based liquid crystals of disodium cromoglycate. Such an odd-even effect is frequently observed for solid state properties like melting point, heat of fusion and refractive index but is rarely observed for molecules present in solution. When mixed in water, anionic single-chain surfactants with odd number of carbon atoms emulsifies disodium cromoglycate to form liquid crystal droplets, while surfactants with even number of carbon atoms fail to emulsify disodium cromoglycate. Chapter 3 Bolaamphiphiles usually form vesicles only in extreme conditions or in the presence of surfactants. Here, we explore the co-assembly system of synthesized bolaamphiphiles and disodium cromoglycate in water. The combination of the self-assembly forces of the bolaamphiphile and self-associating property of disodium cromoglycate liquid crystals act together at the interface form a unique microemulsion of liquid crystal droplets of disodium cromoglycate embedded in liquid crystal phase. Chapter 4 describes a key event (adhesion) that precedes infections caused by Candida albicans

  16. Ligands in PSI structures

    International Nuclear Information System (INIS)

    Kumar, Abhinav; Chiu, Hsiu-Ju; Axelrod, Herbert L.; Morse, Andrew; Elsliger, Marc-André; Wilson, Ian A.; Deacon, Ashley

    2010-01-01

    A survey of the types and frequency of ligands that are bound to PSI structures is analyzed as well as their utility in functional annotation of previously uncharacterized proteins. Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a survey of the types, variety and frequency of ligands that are observed in the PSI structures is also compiled and analyzed, including illustrations of how these bound ligands have provided functional clues for annotation of proteins with little or no previous experimental characterization. Furthermore, a web server was developed as a tool to mine and analyze the PSI structures for bound ligands and other identifying features

  17. Crystal structures of three mercury(II complexes [HgCl2L] where L is a bidentate chiral imine ligand

    Directory of Open Access Journals (Sweden)

    Guadalupe Hernández

    2015-12-01

    Full Text Available The crystal structures of three complexes [HgCl2L] were determined, namely, (S-(+-dichlorido[1-phenyl-N-(pyridin-2-ylmethylideneethylamine-κ2N,N′]mercury(II, [HgCl2(C14H14N2], (S-(+-dichlorido[1-(4-methylphenyl-N-(pyridin-2-ylmethylideneethylamine-κ2N,N′]mercury(II, [HgCl2(C15H16N2], and (1S,2S,3S,5R-(+-dichlorido[N-(pyridin-2-ylmethylideneisopinocampheylamine-κ2N,N′]mercury(II, [HgCl2(C16H22N2]. The complexes consist of a bidentate chiral imine ligand coordinating to HgCl2 and crystallize with four independent molecules in the first complex and two independent molecules in the other two. The coordination geometry of mercury is tetrahedral, with strong distortion towards a disphenoidal geometry, as a consequence of the imine bite angle being close to 70°. The Cl—Hg—Cl angles span a large range, 116.0 (2–138.3 (3°, which is related to the aggregation state in the crystals. For small Cl—Hg—Cl angles, complexes have a tendency to form dimers, via intermolecular Hg...Cl contacts. These contacts become less significant in the third complex, which features the largest intramolecular Cl—Hg—Cl angles.

  18. Coordination chemistry and bioactivity of Ni2+, Cu2+, and Zn2+ complexes containing a bidentate NS ligand, β-N-phenyldithiocarbazic acid, and the crystal structure of β-hydroxy-β-phenylmethylene α-phenylimine

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Ahmed Faizal Shamsuddin; Grouse, Karen A.; Yamin, B.M.; Ali, A.M.; Fun, H.-K.

    2003-07-01

    A bidentate ligand (PhDTCH) with NS donor sequence was prepared from the reaction between carbon disulfide and phenylhydrazine in ethanol. Complexes of this ligand with Ni(II), Cu(II) and Zn(II) were synthesized and characterized by elemental analyses, and various physicochemical techniques. The metal complexes were all four coordinated. In an attempt to resolve the crystal structure of PhDTCH, an ethanolic solution, after leaving for a few days gave bright crystals of PhD6, β-hydroxy-β-phenylmethylene α-phenylimine, the crystal structure of which has been resolved. The crystal packing indicated that it is monoclinic with a space group of P21/n. All of the compounds were tested against different bacteria and fungi, and also against leukemic cell lines. All of the compounds showed weak biological properties compared to standard drugs. (author)

  19. Crystal structure, conformational fixation and entry-related interactions of mature ligand-free HIV-1 Env.

    Science.gov (United States)

    Kwon, Young Do; Pancera, Marie; Acharya, Priyamvada; Georgiev, Ivelin S; Crooks, Emma T; Gorman, Jason; Joyce, M Gordon; Guttman, Miklos; Ma, Xiaochu; Narpala, Sandeep; Soto, Cinque; Terry, Daniel S; Yang, Yongping; Zhou, Tongqing; Ahlsen, Goran; Bailer, Robert T; Chambers, Michael; Chuang, Gwo-Yu; Doria-Rose, Nicole A; Druz, Aliaksandr; Hallen, Mark A; Harned, Adam; Kirys, Tatsiana; Louder, Mark K; O'Dell, Sijy; Ofek, Gilad; Osawa, Keiko; Prabhakaran, Madhu; Sastry, Mallika; Stewart-Jones, Guillaume B E; Stuckey, Jonathan; Thomas, Paul V; Tittley, Tishina; Williams, Constance; Zhang, Baoshan; Zhao, Hong; Zhou, Zhou; Donald, Bruce R; Lee, Lawrence K; Zolla-Pazner, Susan; Baxa, Ulrich; Schön, Arne; Freire, Ernesto; Shapiro, Lawrence; Lee, Kelly K; Arthos, James; Munro, James B; Blanchard, Scott C; Mothes, Walther; Binley, James M; McDermott, Adrian B; Mascola, John R; Kwong, Peter D

    2015-07-01

    As the sole viral antigen on the HIV-1-virion surface, trimeric Env is a focus of vaccine efforts. Here we present the structure of the ligand-free HIV-1-Env trimer, fix its conformation and determine its receptor interactions. Epitope analyses revealed trimeric ligand-free Env to be structurally compatible with broadly neutralizing antibodies but not poorly neutralizing ones. We coupled these compatibility considerations with binding antigenicity to engineer conformationally fixed Envs, including a 201C 433C (DS) variant specifically recognized by broadly neutralizing antibodies. DS-Env retained nanomolar affinity for the CD4 receptor, with which it formed an asymmetric intermediate: a closed trimer bound by a single CD4 without the typical antigenic hallmarks of CD4 induction. Antigenicity-guided structural design can thus be used both to delineate mechanism and to fix conformation, with DS-Env trimers in virus-like-particle and soluble formats providing a new generation of vaccine antigens.

  20. New grafted ferrite particles/liquid crystal composite under magnetic field

    Science.gov (United States)

    Manaila Maximean, D.

    2018-04-01

    A new colloidal composite formed by specially synthesized dimethylphenyl ferrite particles and a nematic liquid crystal (LC) is presented. By applying a small magnetic field during polarizing optical microscopy observations, it was found that the magnetic moment of the synthesized ferrite is perpendicular to the director of the LC. The optical transmission of laser light across the ferronematic was investigated under magnetic field. The critical magnetic field corresponding to the Freedericksz transition was obtained and discussed according to the Burylov and Raikher theory.

  1. Crystal fields of Pr sup 3 sup + in LiYF sub 4 under pressure

    CERN Document Server

    Tröster, T

    2003-01-01

    Fluorescence spectra of LiYF sub 4 :Pr sup 3 sup + have been measured between 12,000 and 22,000 cm sup - sup 1 under pressures up to 10 GPa. In total, 25 crystal field energy levels were obtained and used for the determination of free-ion and crystal field parameters under pressure. According to the nephelauxetic effect, the free-ion parameters decrease with increasing pressure. The relative decrease is larger for the Slater than for the spin-orbit coupling parameter. This behavior is consistent with former studies on Pr sup 3 sup + in different crystals and can be explained by a special covalency model. According to an effective D sub 2 sub d symmetry, five crystal field parameters B sub 0 sup 2 (f,f), B sub 0 sup 4 (f,f), B sub 4 sup 4 (f,f), B sub 0 sup 6 (f,f), and B sub 4 sup 6 (f,f) are non-zero. The pressure-induced changes of these parameters have been determined up to the maximum pressure of 10 GPa. In order to improve the calculation of the crystal field levels, the configuration interactions with t...

  2. Coordination of bis(pyrazol-1-ylamine to palladium(II: influence of the co-ligands and counter-ions on the molecular and crystal structures

    Directory of Open Access Journals (Sweden)

    María de los Angeles Mendoza

    2015-01-01

    Full Text Available The structures of a series of complexes with general formula n[Pd(pzaX]Y·mH2O (n = 1, 2; X = Cl, Br, I, N3, NCS; Y = NO3, I, N3, [Pd(SCN4]; m = 0, 0.5, 1 have been determined, where pza is the tridentate ligand bis[2-(3,5-dimethylpyrazol-1-ylethyl]amine, C14H23N5. In all complexes, {bis[2-(3,5-dimethylpyrazol-1-yl-κN2ethyl]amine-κN}chloridopalladium nitrate, [Pd(pzaCl]NO3, (1, {bis[2-(3,5-dimethylpyrazol-1-yl-κN2ethyl]amine-κN}bromidopalladium nitrate, [Pd(pzaBr]NO3, (2, {bis[2-(3,5-dimethylpyrazol-1-yl-κN2ethyl]amine-κN}iodidopalladium iodide hemihydrate, [Pd(pzaI]I·0.5H2O, (3, azido{bis[2-(3,5-dimethylpyrazol-1-yl-κN2ethyl]amine-κN}palladium azide monohydrate, [Pd(pzaN3]N3·H2O, (4, and bis[{bis[2-(3,5-dimethylpyrazol-1-yl-κN2ethyl]amine-κN}(thiocyanato-κNpalladium] tetrakis(thiocyanato-κSpalladate, [Pd(pzaNCS]2[Pd(SCN4], (5, the [Pd(pzaX]+ complex cation displays a square-planar coordination geometry, and the pza ligand is twisted, approximating twofold rotation symmetry. Although the pza ligand is found with the same conformation along the series, the dihedral angle between pyrazole rings depends on the co-ligand X. This angle span the range 79.0 (3–88.6 (1° for the studied complexes. In (3, two complex cations, two I− anions and one water molecule of crystallization are present in the asymmetric unit. In (5, the central amine group of pza is disordered over two positions [occupancy ratio 0.770 (18:0.230 (18]. The complex [Pd(SCN4]2− anion of this compound exhibits inversion symmetry and shows the Pd2+ transition metal cation likewise in a square-planar coordination environment. Compound (5 is also a rare occurrence of a non-polymeric compound in which the pseudohalide ligand NCS− behaves both as thiocyanate and isothiocyanate, i.e. is coordinating either through the N atom (in the cation or the S atom (in the anion.

  3. Novel CoIII complexes containing fluorescent coumarin-N-acylhydrazone hybrid ligands: Synthesis, crystal structures, solution studies and DFT calculations

    Science.gov (United States)

    Areas, Esther S.; Bronsato, Bruna Juliana da S.; Pereira, Thiago M.; Guedes, Guilherme P.; Miranda, Fábio da S.; Kümmerle, Arthur E.; da Cruz, Antônio G. B.; Neves, Amanda P.

    2017-12-01

    A series of new CoIII complexes of the type [Co(dien)(L1 -L3)]ClO4 (1-3), containing fluorescent coumarin-N-acylhydrazonate hybrid ligands, (E)-N‧-(1-(7-oxido-2-oxo-2H-chromen-3-yl)ethylidene)-4-R-benzohydrazonate [where R = H (L12 -), OCH3 (L22 -) or Cl (L32 -)], were obtained and isolated in the low spin CoIII configuration. Single-crystal X-ray diffraction showed that the coumarin-N-acylhydrazones act as tridentate ligands in their deprotonated form (L2 -). The cation (+ 1) complexes contain a diethylenetriamine (dien) as auxiliary ligand and their structures were calculated by DFT studies which were also performed for the CoII (S = 1/2 and S = 3/2) configurations. The LS CoII (S = 1/2) concentrated the spin density on the O-Co-O axis while the HS CoII (S = 3/2) exhibited a broad spin density distribution around the metallic center. Cyclic voltammetry studies showed that structural modifications made in the L2 - ligands caused a slight influence on the electronic density of the metal center, and the E1/2 values for the CoIII/CoII redox couple increased following the electronic effect of the R-substituent, in the order: 2 (R = OCH3) experimental values vs SHE (E°calc = - 0.37, - 0.36 and - 0.32 V vs E°exp. = - 0.371, - 0.406 and - 0.358 V, for 1-3 respectively). Complexes 1-3 exhibited a very intense absorption band around 470 nm, assigned by DFT calculations as π-π* transitions from the delocalized coumarin-N-acylhydrazone system. 1-3 were very stable in MeOH for several days. Likewise, 1-3 were stable in phosphate buffer containing sodium ascorbate after 15 h, which was attributed to the high chelate effect and σ-donor ability of the L2 - and dien ligands.

  4. Study of the crystal field in CeF3 and CeF3:Pr3+

    Directory of Open Access Journals (Sweden)

    Shafikov F.F., Savinkov A.V., Tagirov M.S.

    2016-12-01

    Full Text Available The crystal field analysis based on calculations in the framework of the semi phenomenological exchange charge model was carried out. The set of crystal field parameters for Ce3+ and Pr3+ ions in the matrix CeF3 related to the crystallographic system of coordinates has been obtained and used to reproduce satisfactory the crystal field energies of Ce3+ and Pr3+ ions.

  5. Flexible matching of test ligands to a 3D pharmacophore using a molecular superposition force field: Comparison of predicted and experimental conformations of inhibitors of three enzymes

    Science.gov (United States)

    McMartin, Colin; Bohacek, Regine S.

    1995-06-01

    A computer procedure TFIT, which uses a molecular superposition force field to flexibly match test compounds to a 3D pharmacophore, was evaluated to find out whether it could reliably predict the bioactive conformations of flexible ligands. The program superposition force field optimizes the overlap of those atoms of the test ligand and template that are of similar chemical type, by applying an attractive force between atoms of the test ligand and template which are close together and of similar type (hydrogen bonding, charge, hydrophobicity). A procedure involving Monte Carlo torsion perturbations, followed by torsional energy minimization, is used to find conformations of the test ligand which cominimize the internal energy of the ligand and the superposition energy of ligand and template. The procedure was tested by applying it to a series of flexible ligands for which the bioactive conformation was known experimentally. The 15 molecules tested were inhibitors of thermolysin, HIV-1 protease or endothiapepsin for which X-ray structures of the bioactive conformation were available. For each enzyme, one of the molecules served as a template and the others, after being conformationally randomized, were fitted. The fitted conformation was then compared to the known binding geometry. The matching procedure was successful in predicting the bioactive conformations of many of the structures tested. Significant deviation from experimental results was found only for parts of molecules where it was readily apparent that the template did not contain sufficient information to accurately determine the bioactive conformation.

  6. Transition metal complexes with thiosemicarbazide-based ligands. Part 45. Synthesis, crystal and molecular structure of [2,6-diacetylpyridine bis(S-methylisothiosemicarbazonato]diazide-iron(III

    Directory of Open Access Journals (Sweden)

    REFIK FAZLIC

    2003-05-01

    Full Text Available The template reaction of a warm methanolic solution of FeCl3.6H2O, S-methylisothiosemicarbazidehydroiodide and 2,6-diacetylpyridine in the presence of LiOAc and NaN3 yielded the high-spin complex [Fe(HL(N32], were HL is the monoanion of the ligand 2,6-diacetylpyridine bis(S-methylisothiosemicarbazone. X-Ray analysis of the complex showed its pentagonal-bipyramidal configuration, with pentadenate (N5 HL in the equatorial plane and two monodentate azide groups in the axial positions. Crystal data are: monoclinic, P21/c, a = 1.0263(2, b = 1.2525(2, c = 1.6660(3 nm, b = 98.94°, V = 2.1154 nm3, Z = 4, rx = 1.499 g cm-3, r0 = 1.48 g cm-3, F(000 = 984, m = 9.40 cm-3.

  7. Synthesis, crystal structures and properties of three coordination polymers based on semi-rigid bis(benzimidazole-1-ylmethyl)biphenyl ligand

    Science.gov (United States)

    Liang, Lili; Xue, Hongbao; Chen, Feijian; Zhang, Manli; Zhang, Bingyuan; Tao, Zhaolin

    2017-11-01

    Solvothermal reactions of three metal salts with a linear semi-rigid ligand 4,4‧-bis(benzimidazol-1-ylmethy1)biphenyl) (bbmb) and terephthalic acid (H2TA), lead to three metal-organic coordination polymers, namely, {[Co(bbmb)(TA)] 4H2O} 1, [Zn2(bbmb)2(TA)(NO2)2] 2 and [Cd(bbmb)(TA)(H2O)] 3. Single-crystal X-ray diffraction analyses reveal that compound 1 exhibits a zigzag-shaped 1-D chain, which extended into a three-dimensional supermolecular framework through π-π interactions, compound 2 exhibits a thick two-dimensional sheet, while compound 3 exhibits a unique 3D two-fold interpenetrated network of irl topology. Moreover, IR spectroscopy, powder X-ray diffraction, thermogravimetric analyses, and the properties of the three compounds were studied.

  8. Force Fields and Point Charges for Crystal Structure Modeling

    OpenAIRE

    Svärd, Michael; Rasmuson, Åke C.

    2009-01-01

    Molecular simulation is increasingly used by chemical engineers and industrial chemists in process and product development. In particular, the possibility to predict the structure and stability of potential polymorphs of a substance is of tremendous interest to the pharmaceutical and specialty chemicals industry. Molecular mechanics modeling relies on the use of parametrized force fields and methods of assigning point charges to the atoms in the molecules. In commercial molecular simulation s...

  9. Study of Fluid Flow Control in Protein Crystallization using Strong Magnetic Fields

    Science.gov (United States)

    Ramachandran, Narayanan; Leslie, Fred; Ciszak, Ewa

    2002-11-01

    An important component in biotechnology, particularly in the area of protein engineering and rational drug design is the knowledge of the precise three-dimensional molecular structure of proteins. The quality of structural information obtained from X-ray diffraction methods is directly dependent on the degree of perfection of the protein crystals. As a consequence, the growth of high quality macromolecular crystals for diffraction analyses has been the central focus for biochemists, biologists, and bioengineers. Macromolecular crystals are obtained from solutions that contain the crystallizing species in equilibrium with higher aggregates, ions, precipitants, other possible phases of the protein, foreign particles, the walls of the container, and a likely host of other impurities. By changing transport modes in general, i.e., reduction of convection and sedimentation, as is achieved in "microgravity", researchers have been able to dramatically affect the movement and distribution of macromolecules in the fluid, and thus their transport, formation of crystal nuclei, and adsorption to the crystal surface. While a limited number of high quality crystals from space flights have been obtained, as the recent National Research Council (NRC) review of the NASA microgravity crystallization program pointed out, the scientific approach and research in crystallization of proteins has been mainly empirical yielding inconclusive results. We postulate that we can reduce convection in ground-based experiments and we can understand the different aspects of convection control through the use of strong magnetic fields and field gradients. Whether this limited convection in a magnetic field will provide the environment for the growth of high quality crystals is still a matter of conjecture that our research will address. The approach exploits the variation of fluid magnetic susceptibility with concentration for this purpose and the convective damping is realized by appropriately

  10. Dark-field transmission electron microscopy of cortical bone reveals details of extrafibrillar crystals.

    Science.gov (United States)

    Schwarcz, Henry P; McNally, Elizabeth A; Botton, Gianluigi A

    2014-12-01

    In a previous study we showed that most of the mineral in bone is present in the form of "mineral structures", 5-6nm-thick, elongated plates which surround and are oriented parallel to collagen fibrils. Using dark-field transmission electron microscopy, we viewed mineral structures in ion-milled sections of cortical human bone cut parallel to the collagen fibrils. Within the mineral structures we observe single crystals of apatite averaging 5.8±2.7nm in width and 28±19nm in length, their long axes oriented parallel to the fibril axis. Some appear to be composite, co-aligned crystals as thin as 2nm. From their similarity to TEM images of crystals liberated from deproteinated bone we infer that we are viewing sections through platy crystals of apatite that are assembled together to form the mineral structures. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Damping of Solute Convection During Crystal Growth by Applying Magnetic Field Gradients

    Science.gov (United States)

    Wakayama, Nobuko I.

    2005-06-01

    One of the advantages of crystal growth under microgravity conditions is the damping of solute convection that affects crystal quality. The mechanism of the dampening effect of magnetic field gradients, B(dB/dz), on solute convection was studied, and the magnitude of B(dB/dz) required for dampening was calculated. When the absolute value of mass magnetic susceptibility, χg, of a solute is about 70% of that of a solvent (e.g., KCl crystal growth from an aqueous solution) and the weight ratio is 0.26, the gradient to damp convection considerably is estimated to be -3018 T2/m. On the other hand, when the χg of the solute is nearly equal to that of the solvent [protein crystal growth (lysozyme)], a gradient of -1394 T2/m damps convection completely on the earth.

  12. Electric-field-induced weakly chaotic transients in ferroelectric liquid crystals.

    Science.gov (United States)

    Śliwa, I; Jeżewski, W; Kuczyński, W

    2016-01-01

    Nonlinear dynamics induced in surface stabilized ferroelectric liquid crystals by strong alternating external electric fields is studied both theoretically and experimentally. As has already been shown, molecular reorientations induced by sufficiently strong fields of high-enough frequencies can reveal a long transient behavior that has a weakly chaotic character. The resulting complex dynamics of ferroelectric liquid crystals can be considered not only as a consequence of irregular motions of particular molecules but also as a repercussion of a surface-enforced partial decorrelation of nonlinear molecular motions within smectic layers. To achieve more insight into the nature of this phenomenon and to show that the underlying complex field-induced behavior of smectic liquid crystals is not exceptional, ranges of system parameters for which the chaotic behavior occurs are determined. It is proved that there exists a large enough set of initial phase trajectory points, for which weakly chaotic long-time transitory phenomena occur, and, thereby, it is demonstrated that such a chaotic behavior can be regarded as being typical for strongly field-driven thin liquid crystal systems. Additionally, the influence of low-amplitude random noise on the duration of the transient processes is numerically studied. The strongly nonlinear contribution to the electro-optic response, experimentally determined for liquid crystal samples at frequencies lower than the actual field frequency, is also analyzed for long-time signal sequences. Using a statistical approach to distinguish numerically response signals of samples from noise generated by measuring devices, it is shown that the distribution of sample signals distinctly differs from the device noise. This evidently corroborates the occurrence of the nonlinear low-frequency effect, found earlier for different surface stabilized liquid crystal samples.

  13. Ligand design for alkali-metal-templated self-assembly of unique high-nuclearity CuII aggregates with diverse coordination cage units: crystal structures and properties.

    Science.gov (United States)

    Du, Miao; Bu, Xian-He; Guo, Ya-Mei; Ribas, Joan

    2004-03-19

    The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, [(mu(3)-Cl)[Li subset Cu(4)(mu-L(1))(3)](3)](ClO(4))(8)(H(2)O)(4.5) (1) and [[Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)](ClO(4))(8)(H(2)O)(10)(H(3)O(+))(2)](infinity) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.

  14. Ruthenium(II) bipyridine complexes bearing quinoline-azoimine (NN'N″) tridentate ligands: synthesis, spectral characterization, electrochemical properties and single-crystal X-ray structure analysis.

    Science.gov (United States)

    Al-Noaimi, Mousa; Abdel-Rahman, Obadah S; Fasfous, Ismail I; El-khateeb, Mohammad; Awwadi, Firas F; Warad, Ismail

    2014-05-05

    Four octahedral ruthenium(II) azoimine-quinoline complexes having the general molecular formula [Ru(II)(L-Y)(bpy)Cl](PF6) {L-Y=YC6H4N=NC(COCH3)=NC9H6N, Y=H (1), CH3 (2), Br (3), NO2 (4) and bpy=2,2'-bipyrdine} were synthesized. The azoimine-quinoline based ligands behave as NN'N″ tridentate donors and coordinated to ruthenium via azo-N', imine-N' and quinolone-N″ nitrogen atoms. The composition of the complexes has been established by elemental analysis, spectral methods (FT-IR, electronic, (1)H NMR, UV/Vis and electrochemical (cyclic voltammetry) techniques. The crystal structure of complex 1 is reported. The Ru(II) oxidation state is greatly stabilized by the novel tridentate ligands, showing Ru(III/II) couples ranging from 0.93-1.27 V vs. Cp2Fe/Cp2Fe(+). The absorption spectrum of 1 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Four crystal structures of human LLT1, a ligand of human NKR-P1, in varied glycosylation and oligomerization states

    Energy Technology Data Exchange (ETDEWEB)

    Skálová, Tereza, E-mail: t.skalova@gmail.com [Academy of Sciences of the Czech Republic, v.v.i., Vídeňská 1083, 142 20 Praha 4 (Czech Republic); Bláha, Jan [Charles University Prague, Hlavova 8, 128 40 Praha (Czech Republic); Harlos, Karl [University of Oxford, Roosevelt Drive, Oxford OX3 7BN (United Kingdom); Dušková, Jarmila [Academy of Sciences of the Czech Republic, v.v.i., Vídeňská 1083, 142 20 Praha 4 (Czech Republic); Koval’, Tomáš [Academy of Sciences of the Czech Republic, v.v.i., Heyrovského nám. 2, 162 06 Praha 6 (Czech Republic); Stránský, Jan; Hašek, Jindřich [Academy of Sciences of the Czech Republic, v.v.i., Vídeňská 1083, 142 20 Praha 4 (Czech Republic); Vaněk, Ondřej [Charles University Prague, Hlavova 8, 128 40 Praha (Czech Republic); Dohnálek, Jan, E-mail: t.skalova@gmail.com [Academy of Sciences of the Czech Republic, v.v.i., Vídeňská 1083, 142 20 Praha 4 (Czech Republic); Academy of Sciences of the Czech Republic, v.v.i., Heyrovského nám. 2, 162 06 Praha 6 (Czech Republic)

    2015-03-01

    Four crystal structures of human LLT1, a ligand of human NKR-P1, are reported. Human LLT1 is a C-type lectin-like ligand of NKR-P1 (CD161, gene KLRB1), a C-type lectin-like receptor of natural killer cells. Using X-ray diffraction, the first experimental structures of human LLT1 were determined. Four structures of LLT1 under various conditions were determined: monomeric, dimeric deglycosylated after the first N-acetylglucosamine unit in two forms and hexameric with homogeneous GlcNAc{sub 2}Man{sub 5} glycosylation. The dimeric form follows the classical dimerization mode of human CD69. The monomeric form keeps the same fold with the exception of the position of an outer part of the long loop region. The hexamer of glycosylated LLT1 consists of three classical dimers. The hexameric packing may indicate a possible mode of interaction of C-type lectin-like proteins in the glycosylated form.

  16. Synthesis, crystal structures, and properties of two novel cadmium(II)-organic frameworks based on asymmetric dicarboxylate and N-donor ligands

    Science.gov (United States)

    Chen, Xiaoli; Gao, Loujun; Zhang, Xiaoge; Han, Xuhua; Wang, Yao; Sun, Rong

    2014-08-01

    Two novel cadmium(II)-organic frameworks with asymmetric dicarboxylate and N-donor ligands, namely [Cd(cpa)(phen)]n (1) and {[Cd2(cpa)2(bpy)1.5]·0.5H2O}n (2) (H2cpa = 3-(4-benzoic)propionic acid, phen = 1,10-phenanthroline, bpy = 4,4";-bipyridine) have been hydrothermally synthesized and characterized by elemental analyses, FT-IR spectra, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. 1 displays a double zigzag chain structure containing 8-number and 22-number circles. 2 Shows a 6-connected 3D polymer network based on tetranuclear cadmium cluster units. The most striking feature of 2 is that a pair of identical 3D networks are interlocked with each other to the form a 2-fold interpenetrated 3D α-Po structural topology. The diverse structures of two complexes indicate that the skeleton of N-donor ligands plays a great role in the assembly of such different frameworks. In addition, the thermal stabilities, XRD and photoluminescence properties of 1-2 were also studied.

  17. Dual gauge field theory of quantum liquid crystals in two dimensions

    Science.gov (United States)

    Beekman, Aron J.; Nissinen, Jaakko; Wu, Kai; Liu, Ke; Slager, Robert-Jan; Nussinov, Zohar; Cvetkovic, Vladimir; Zaanen, Jan

    2017-04-01

    We present a self-contained review of the theory of dislocation-mediated quantum melting at zero temperature in two spatial dimensions. The theory describes the liquid-crystalline phases with spatial symmetries in between a quantum crystalline solid and an isotropic superfluid: quantum nematics and smectics. It is based on an Abelian-Higgs-type duality mapping of phonons onto gauge bosons (;stress photons;), which encode for the capacity of the crystal to propagate stresses. Dislocations and disclinations, the topological defects of the crystal, are sources for the gauge fields and the melting of the crystal can be understood as the proliferation (condensation) of these defects, giving rise to the Anderson-Higgs mechanism on the dual side. For the liquid crystal phases, the shear sector of the gauge bosons becomes massive signaling that shear rigidity is lost. After providing the necessary background knowledge, including the order parameter theory of two-dimensional quantum liquid crystals and the dual theory of stress gauge bosons in bosonic crystals, the theory of melting is developed step-by-step via the disorder theory of dislocation-mediated melting. Resting on symmetry principles, we derive the phenomenological imaginary time actions of quantum nematics and smectics and analyze the full spectrum of collective modes. The quantum nematic is a superfluid having a true rotational Goldstone mode due to rotational symmetry breaking, and the origin of this 'deconfined' mode is traced back to the crystalline phase. The two-dimensional quantum smectic turns out to be a dizzyingly anisotropic phase with the collective modes interpolating between the solid and nematic in a non-trivial way. We also consider electrically charged bosonic crystals and liquid crystals, and carefully analyze the electromagnetic response of the quantum liquid crystal phases. In particular, the quantum nematic is a real superconductor and shows the Meissner effect. Their special properties

  18. Synthesis, crystal structure, and spectroscopic characterization of two new binuclear complexes of manganese(II) and vanadium(V) with dipicolinate ligands containing 2-aminopyrimidinium as a counter cation

    Czech Academy of Sciences Publication Activity Database

    Tabatabaee, M.; Mahmoodikhah, H.; Ahadiat, G.; Dušek, Michal; Pojarová, Michaela

    2013-01-01

    Roč. 144, č. 5 (2013), s. 621-626 ISSN 0026-9247 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : manganese complex * vanadium complex * dipicolinic ligand * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.347, year: 2013

  19. Crystal-field tuning of photoluminescence in two-dimensional materials with embedded lanthanide ions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ding; Chen, Weiyin; Zeng, Mengqi; Xue, Haifeng; Chen, Yunxu; Xiao, Yao; Zhang, Tao; Fu, Lei [College of Chemistry and Molecular Sciences, Institute for Advanced Studies, Wuhan University, Wuhan (China); Sang, Xiahan; Unocic, Raymond R.; Xiao, Kai [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2018-01-15

    Lanthanide (Ln) group elements have been attracting considerable attention owing to the distinct optical properties. The crystal-field surroundings of Ln ions in the host materials can determine their energy level splitting, which is of vital importance to tailor their optical properties. 2D MoS{sub 2} single crystals were utilized as the host material to embed Eu{sup 3+} and energy-level splitting was achieved for tuning its photoluminescence (PL). The high anisotropy of the 2D host materials makes them distort the degenerate orbitals of the Ln ions more efficiently than the symmetrical bulk host materials. A significant red-shift of the PL peak for Eu{sup 3+} was observed. The strategy for tailoring the energy level splitting of Ln ions by the highly designable 2D material crystal field provides a new method to extend their optical properties. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Waveguide modes of 1D photonic crystals in a transverse magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Sylgacheva, D. A., E-mail: sylgacheva.darjja@physics.msu.ru; Khokhlov, N. E.; Kalish, A. N.; Belotelov, V. I. [Moscow State University, Physics Department (Russian Federation)

    2016-11-15

    We analyze waveguide modes in 1D photonic crystals containing layers magnetized in the plane. It is shown that the magnetooptical nonreciprocity effect emerges in such structures during the propagation of waveguide modes along the layers and perpendicularly to the magnetization. This effect involves a change in the phase velocity of the mode upon reversal of the direction of magnetization. Comparison of the effects in a nonmagnetic photonic crystal with an additional magnetic layer and in a photonic crystal with magnetic layers shows that the magnitude of this effect is several times larger in the former case in spite of the fact that the electromagnetic field of the modes in the latter case is localized in magnetic regions more strongly. This is associated with asymmetry of the dielectric layers contacting with the magnetic layer in the former case. This effect is important for controlling waveguide structure modes with the help of an external magnetic field.

  1. Non-empirical Prediction of the Photophysical and Magnetic Properties of Systems with Open d- and f-Shells Based on Combined Ligand Field and Density Functional Theory (LFDFT).

    Science.gov (United States)

    Daul, Claude

    2014-09-01

    Despite the important growth of ab initio and computational techniques, ligand field theory in molecular science or crystal field theory in condensed matter offers the most intuitive way to calculate multiplet energy levels arising from systems with open shells d and/or f electrons. Over the past decade we have developed a ligand field treatment of inorganic molecular modelling taking advantage of the dominant localization of the frontier orbitals within the metal-sphere. This feature, which is observed in any inorganic coordination compound, especially if treated by Density Functional Theory calculation, allows the determination of the electronic structure and properties with a surprising good accuracy. In ligand field theory, the theoretical concepts consider only a single atom center; and treat its interaction with the chemical environment essentially as a perturbation. Therefore success in the simple ligand field theory is no longer questionable, while the more accurate molecular orbital theory does in general over-estimate the metal-ligand covalence, thus yields wave functions that are too delocalized. Although LF theory has always been popular as a semi-empirical method when dealing with molecules of high symmetry e.g. cubic symmetry where the number of parameters needed is reasonably small (3 or 5), this is no more the case for molecules without symmetry and involving both an open d- and f-shell (# parameters ∼90). However, the combination of LF theory and Density Functional (DF) theory that we introduced twenty years ago can easily deal with complex molecules of any symmetry with two and more open shells. The accuracy of these predictions from 1(st) principles achieves quite a high accuracy (<5%) in terms of states energies. Hence, this approach is well suited to predict the magnetic and photo-physical properties arbitrary molecules and materials prior to their synthesis, which is the ultimate goal of each computational chemist. We will illustrate the

  2. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Motamedi, Hossein [Department of Biology, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Mayer, Peter [LMU München Department Chemie, Butenandtstr 5-13, D-81377 München (Germany); Bruno, Giuseppe [Dipartimento di Chimica Inorganica, Università di Messina, Vill. S. Agata, Salita Sperone 31, 98166 Messina (Italy); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

    2017-05-15

    Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers

  3. Crystal structure of a samarium(III nitrate chain cross-linked by a bis-carbamoylmethylphosphine oxide ligand

    Directory of Open Access Journals (Sweden)

    Julie A. Stoscup

    2014-10-01

    Full Text Available In the title compound poly[aquabis(μ-nitrato-κ4O,O′:O,O′′tetrakis(nitrato-κ2O,O′{μ4-tetraethyl [(ethane-1,2-diylbis(azanediylbis(2-oxoethane-2,1-diyl]diphosphonate-κ2O,O′}disamarium(III], [Sm2(NO36(C14H30N2O8P2(H2O]n, a 12-coordinate SmIII and a nine-coordinate SmIII cation are alternately linked via shared bis-bidentate nitrate anions into a corrugated chain extending parallel to the a axis. The nine-coordinate SmIII atom of this chain is also chelated by a bidentate, yet flexible, carbamoylmethylphoshine oxide (CMPO ligand and bears one water molecule. This water molecule is hydrogen bonded to nitrate groups bonded to the 12-coordinate SmIII cation. The CMPO ligand, which lies about an inversion center, links neighboring chains along the c axis, forming sheets parallel to the ac plane. Hydrogen bonds between the amide NH group and metal-bound nitrate anions are also present in these sheets. The sheets are packed along the b axis through only van der Waals interactions.

  4. Ambipolar Cu- and Fe-phthalocyanine single-crystal field-effect transistors

    NARCIS (Netherlands)

    De Boer, R.W.I.; Stassen, A.F.; Craciun, M.F.; Mulder, C.L.; Molinari, A.; Rogge, S.; Morpurgo, A.F.

    2005-01-01

    We report the observation of ambipolar transport in field-effect transistors fabricated on single crystals of copper- and iron-phthalocyanine, using gold as a high work-function metal for the fabrication of source and drain electrodes. In these devices, the room-temperature mobility of holes reaches

  5. Crystal field and magnetism with Wannier functions: Orthorhombic rare-earth manganites

    Czech Academy of Sciences Publication Activity Database

    Novák, Pavel; Nekvasil, Vladimír; Knížek, Karel

    358-359, MAY (2014), s. 228-232 ISSN 0304-8853 R&D Projects: GA ČR GA13-25251S Institutional support: RVO:68378271 Keywords : crystal field * rare-earth magnetism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.970, year: 2014

  6. Crystal fields of dilute Tb, Dy, or Er in Sc obtained by magnetization measurements

    DEFF Research Database (Denmark)

    Høg, J.; Touborg, P.

    1976-01-01

    Crystal-field parameters for dilute Sc-Tb, Sc-Dy, and Sc-Er alloys have been obtained by fitting theoretical expressions to the experimentally measured paramagnetic susceptibility. The initial susceptibility was measured and corrected for the effects of ordering at the lowest temperatures...

  7. Random crystal field effect on the magnetic and hysteresis behaviors of a spin-1 cylindrical nanowire

    Energy Technology Data Exchange (ETDEWEB)

    Zaim, N.; Zaim, A., E-mail: ah_zaim@yahoo.fr; Kerouad, M., E-mail: kerouad@fs-umi.ac.ma

    2017-02-15

    In this work, the magnetic behavior of the cylindrical nanowire, consisting of a ferromagnetic core of spin-1 atoms surrounded by a ferromagnetic shell of spin-1 atoms is studied in the presence of a random crystal field interaction. Based on Metropolis algorithm, the Monte Carlo simulation has been used to investigate the effects of the concentration of the random crystal field p, the crystal field D and the shell exchange interaction J{sub s} on the phase diagrams and the hysteresis behavior of the system. Some characteristic behaviors have been found, such as the first and second-order phase transitions joined by tricritical point for appropriate values of the system parameters, triple and isolated critical points can be also found. Depending on the Hamiltonian parameters, single, double and para hysteresis regions are explicitly determined. - Highlights: • Phase diagrams of a ferromagnetic nanowire are examined by the Monte Carlo simulation. • Different types of the phase diagrams are obtained. • The effect of the random crystal field on the hysteresis loops is studied. • Single, double and para hysteresis regions are explicitly determined.

  8. Crystal electric field-phonon interaction in NdCu2

    International Nuclear Information System (INIS)

    Hense, K.; Gratz, E.; Nowotny, H.; Loewenhaupt, M.; Hoser, A.

    2004-01-01

    A comparison of the crystal electric field (CF)-level schema of NdCu 2 and its measured phonon dispersion relation suggests that some of the phonon branches should show a measurable coupling with the CF. The presented inelastic neutron scattering data obtained from triple axis spectrometer measurements confirm this interaction. In addition, a theoretical model describing the experimental data is presented

  9. Crystal field and magnetism with Wannier functions: rare-earth dopedaluminum garnets

    Czech Academy of Sciences Publication Activity Database

    Mihóková, Eva; Novák, Pavel; Laguta, Valentyn

    2015-01-01

    Roč. 33, č. 12 (2015), 1316-1323 ISSN 1002-0721 R&D Projects: GA ČR GA13-09876S Institutional support: RVO:68378271 Keywords : crystal field * ab initio calculations * garnets * rare earths Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.188, year: 2015

  10. Neutron Crystal-Field Spectroscopy and Susceptibility in ErcY1-cA1

    DEFF Research Database (Denmark)

    Heer, H.; Furrer, A.; Walker, E.

    1974-01-01

    Inelastic neutron scattering experiments and susceptibility measurements have been carried out on polycrystalline ErcY1-cAl2. A least-squares fitting procedure has been applied to the neutron data which favours four sets of crystal-field parameters. The results are compared with the measured...

  11. Ligand-field symmetry effects in Fe(ii) polypyridyl compounds probed by transient X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hana; Strader, Matthew L.; Hong, Kiryong; Jamula, Lindsey; Gullikson, Eric M.; Kim, Tae Kyu; de Groot, Frank M. F.; McCusker, James K.; Schoenlein, Robert W.; Huse, Nils

    2012-01-01

    Ultrafast excited-state evolution in polypyridyl FeII complexes are of fundamental interest for understanding the origins of the sub-ps spin-state changes that occur upon photoexcitation of this class of compounds as well as for the potential impact such ultrafast dynamics have on incorporation of these compounds in solar energy conversion schemes or switchable optical storage technologies. We have demonstrated that ground-state and, more importantly, ultrafast time-resolved x-ray absorption methods can offer unique insights into the interplay between electronic and geometric structure that underpin the photo-induced dynamics of this class of compounds. The present contribution examines in greater detail how the symmetry of the ligand field surrounding the metal ion can be probed using these x-ray techniques. In particular, we show that steady-state K-edge spectroscopy of the nearest-neighbour nitrogen atoms reveals the characteristic chemical environment of the respective ligands and suggests an interesting target for future charge-transfer femtosecond and attosecond spectroscopy in the x-ray water window.

  12. Redshift of A 1(longitudinal optical) mode for GaN crystals under strong electric field

    Science.gov (United States)

    Gu, Hong; Wu, Kaijie; Zheng, Shunan; Shi, Lin; Zhang, Min; Liu, Zhenghui; Liu, Xinke; Wang, Jianfeng; Zhou, Taofei; Xu, Ke

    2018-01-01

    We investigated the property of GaN crystals under a strong electric field. The Raman spectra of GaN were measured using an ultraviolet laser, and a remarkable redshift of the A 1(LO) mode was observed. The role of the surface depletion layer was discussed, and the interrelation between the electric field and phonons was revealed. First-principles calculations indicated that, in particular, the phonons that vibrate along the [0001] direction are strongly influenced by the electric field. This effect was confirmed by a surface photovoltage experiment. The results revealed the origin of the redshift and presented the phonon property of GaN under a strong electric field.

  13. First-order transition and tricritical behavior of the transverse crystal field spin-1 Ising model

    Science.gov (United States)

    Costabile, Emanuel; Viana, J. Roberto; de Sousa, J. Ricardo; de Arruda, Alberto S.

    2015-06-01

    The phase diagram of the spin-1 Ising model in the presence of a transverse crystal-field anisotropy (Dx) is studied within the framework of an effective-field theory with correlation. The effect of the coordination number (z) on the phase diagram in the T -Dx plane is investigated. We observe only second-order transitions for coordination number z Ricardo de Sousa and Branco, Phys. Rev. E 77 (2008) 012104] with a single tricritical point in the phase diagram.

  14. Effect of Bond-Diluted on Spin-32 Transverse Ising Model with Crystal Field

    Science.gov (United States)

    Jiang, Wei; Lu, Zhan-Hong; Wei, Guo-Zhu; Du, An

    2002-08-01

    The magnetic properties of the bond-diluted spin-3/2 transverse Ising model with the presence of a crystal field on the honeycomb lattice are studied within the framework of the effective field theory with correlations. The interactions Jij are assumed to be independent random variables with distribution P(Jij)=pδ(Jij-J)+(1-p)δ(Jij). The project supported by the Foundation of the Ministry of Education of China under Grant No. 99026

  15. Crystal structure, Hirshfeld surfaces and DNA cleavage investigation of two copper(II) complexes containing polypyridine and salicylide ligands.

    Science.gov (United States)

    Luo, Yang-Hui; Sun, Bai-Wang

    2014-05-21

    Two copper complexes 1 [Cu2(phen)2(salicylaldehyde)2(ClO4)2] and 2 [Cu2 (2,2'-dipyridyl)2(salicylaldehyde)2(ClO4)2] have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. These two complexes were display binuclear structure with Cu(II) ions in distorted octahedral environment but antipodal orientation of the binuclear units between them. Molecular Hirshfeld surfaces revealed that the crystal structures of 1 and 2 were supported mainly by H-H, C-H⋯π, π⋯π (C-C), and C-H⋯O intermolecular interactions. DNA cleavage experiments of complexes 1 and 2 revealed that these complexes can intercalation with DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Multiscale approach to nematic liquid crystals via statistical field theory.

    Science.gov (United States)

    Lu, Bing-Sui

    2017-08-01

    We propose an approach to a multiscale problem in the theory of thermotropic uniaxial nematics based on the method of statistical field theory. This approach enables us to relate the coefficients A, B, C, L_{1}, and L_{2} of the Landau-de Gennes free energy for the isotropic-nematic phase transition to the parameters of a molecular model of uniaxial nematics, which we take to be a lattice gas model of nematogenic molecules interacting via a short-ranged potential. We obtain general constraints on the temperature and volume fraction of nematogens for the Landau-de Gennes theory to be stable against molecular orientation fluctuations at quartic order. In particular, for the case of a fully occupied lattice, we compute the values of the isotropic-nematic transition temperature and the order parameter discontinuity predicted by (i) a continuum approximation of the nearest-neighbor Lebwohl-Lasher model and (ii) a Lebwohl-Lasher-type model with a nematogenic interaction of finite range. We find that the predictions of (i) are in reasonably good agreement with known results of Monte Carlo simulation.

  17. Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

    Science.gov (United States)

    Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

    2013-01-01

    We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

  18. Patterning technology for solution-processed organic crystal field-effect transistors

    Science.gov (United States)

    Li, Yun; Sun, Huabin; Shi, Yi; Tsukagoshi, Kazuhito

    2014-01-01

    Organic field-effect transistors (OFETs) are fundamental building blocks for various state-of-the-art electronic devices. Solution-processed organic crystals are appreciable materials for these applications because they facilitate large-scale, low-cost fabrication of devices with high performance. Patterning organic crystal transistors into well-defined geometric features is necessary to develop these crystals into practical semiconductors. This review provides an update on recentdevelopment in patterning technology for solution-processed organic crystals and their applications in field-effect transistors. Typical demonstrations are discussed and examined. In particular, our latest research progress on the spin-coating technique from mixture solutions is presented as a promising method to efficiently produce large organic semiconducting crystals on various substrates for high-performance OFETs. This solution-based process also has other excellent advantages, such as phase separation for self-assembled interfaces via one-step spin-coating, self-flattening of rough interfaces, and in situ purification that eliminates the impurity influences. Furthermore, recommendations for future perspectives are presented, and key issues for further development are discussed. PMID:27877656

  19. Patterning technology for solution-processed organic crystal field-effect transistors

    Directory of Open Access Journals (Sweden)

    Yun Li

    2014-04-01

    Full Text Available Organic field-effect transistors (OFETs are fundamental building blocks for various state-of-the-art electronic devices. Solution-processed organic crystals are appreciable materials for these applications because they facilitate large-scale, low-cost fabrication of devices with high performance. Patterning organic crystal transistors into well-defined geometric features is necessary to develop these crystals into practical semiconductors. This review provides an update on recent development in patterning technology for solution-processed organic crystals and their applications in field-effect transistors. Typical demonstrations are discussed and examined. In particular, our latest research progress on the spin-coating technique from mixture solutions is presented as a promising method to efficiently produce large organic semiconducting crystals on various substrates for high-performance OFETs. This solution-based process also has other excellent advantages, such as phase separation for self-assembled interfaces via one-step spin-coating, self-flattening of rough interfaces, and in situ purification that eliminates the impurity influences. Furthermore, recommendations for future perspectives are presented, and key issues for further development are discussed.

  20. Crystal structure, spectroscopy, DFT studies and thermal characterization of Cobalt(II) complex with 2-protonated aminopyridinium cation as ligand

    Science.gov (United States)

    Mhadhbi, Noureddine; Saïd, Salem; Elleuch, Slim; Naïli, Houcine

    2016-03-01

    Single crystals of a new organic-inorganic hybrid compound (2-HAMP)2[CoBr4], (2-HAMP = 2-protonated aminopyridinium cation) was synthesized and characterized by X-Ray diffraction at room temperature, DTA-TG measurement, FT-IR and FT-Raman spectroscopies and optical absorption. Its crystal structure is a packing of alternated organic and inorganic layers parallel to (a, b) plane. The different components are connected by a network of N/C-H⋯Br hydrogen bonds and halogen⋯halogen interactions. These hydrogen bonds give notable vibrational effects. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The simulated spectra satisfactorily coincide with the experimental UV-Visible spectrum. The results show good consistent with the experiment and confirm the contribution of metal orbital to the HOMO-LUMO boundary. Thermal analysis studies indicate the presence of three phase transitions at 68, 125 and 172 °C, which are confirmed by X-ray powder diffraction as a function of temperature.

  1. Rhenium complexes of chromophore-appended dipicolylamine ligands: syntheses, spectroscopic properties, DNA binding and X-ray crystal structure

    International Nuclear Information System (INIS)

    Mullice, L.A.; Buurma, N.J.; Pope, S.J.A.; Laye, R.H.; Harding, L.P.

    2008-01-01

    The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with penta-carbonyl-chloro-rhenium have been studied. The resultant complexes each possess the fac-Re(CO) 3 core. The ligands L 1 1-[bis(pyridine-2-yl-methyl)amino]methyl-pyrene and L 2 2-[bis(pyridine-2-yl-methyl)amino]methyl-quinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1 H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO) 3 (L 1 )}(BF 4 ), C 34 H 26 BF 4 N 4 O 3 Re: monoclinic, P2(1)/c, a 18.327(2) Angstroms, α = 90.00 degrees, b 14.1537(14) Angstroms, β96.263(6) degrees, c = 23.511(3) Angstroms, γ 90.00 Angstroms, 6062.4(11) (Angstroms) 3 , Z=8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO) 3 (L 1 )}(BF 4 ) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO) 3 (L 1 )}(BF 4 ) were undertaken and revealed that fac-{Re(CO) 3 (L 1 )}(BF 4 ) binding to fish sperm DNA (binding constant 1.5 ± 0.2 * 10 5 M -1 , binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (-14 ± 2 kcal mol -1 ) also agrees favourably with values as typically found for intercalators. (authors)

  2. Plasmodium falciparum field isolates from South America use an atypical red blood cell invasion pathway associated with invasion ligand polymorphisms.

    Directory of Open Access Journals (Sweden)

    Mary Lopez-Perez

    Full Text Available Studies of Plasmodium falciparum invasion pathways in field isolates have been limited. Red blood cell (RBC invasion is a complex process involving two invasion protein families; Erythrocyte Binding-Like (EBL and the Reticulocyte Binding-Like (PfRh proteins, which are polymorphic and not fully characterized in field isolates. To determine the various P. falciparum invasion pathways used by parasite isolates from South America, we studied the invasion phenotypes in three regions: Colombia, Peru and Brazil. Additionally, polymorphisms in three members of the EBL (EBA-181, EBA-175 and EBL-1 and five members of the PfRh (PfRh1, PfRh2a, PfRh2b, PfRh4, PfRh5 families were determined. We found that most P. falciparum field isolates from Colombia and Peru invade RBCs through an atypical invasion pathway phenotypically characterized as resistant to all enzyme treatments (NrTrCr. Moreover, the invasion pathways and the ligand polymorphisms differed substantially among the Colombian and Brazilian isolates while the Peruvian isolates represent an amalgam of those present in the Colombian and Brazilian field isolates. The NrTrCr invasion profile was associated with the presence of the PfRh2a pepC variant, the PfRh5 variant 1 and EBA-181 RVNKN variant. The ebl and Pfrh expression levels in a field isolate displaying the NrTrCr profile also pointed to PfRh2a, PfRh5 and EBA-181 as being possibly the major players in this invasion pathway. Notably, our studies demonstrate the uniqueness of the Peruvian P. falciparum field isolates in terms of their invasion profiles and ligand polymorphisms, and present a unique opportunity for studying the ability of P. falciparum parasites to expand their invasion repertoire after being reintroduced to human populations. The present study is directly relevant to asexual blood stage vaccine design focused on invasion pathway proteins, suggesting that regional invasion variants and global geographical variation are likely to

  3. crystal

    Science.gov (United States)

    Yu, Yi; Huang, Yisheng; Zhang, Lizhen; Lin, Zhoubin; Sun, Shijia; Wang, Guofu

    2014-07-01

    A Nd3+:Na2La4(WO4)7 crystal with dimensions of ϕ 17 × 30 mm3 was grown by the Czochralski method. The thermal expansion coefficients of Nd3+:Na2La4(WO4)7 crystal are 1.32 × 10-5 K-1 along c-axis and 1.23 × 10-5 K-1 along a-axis, respectively. The spectroscopic characteristics of Nd3+:Na2La4(WO4)7 crystal were investigated. The Judd-Ofelt theory was applied to calculate the spectral parameters. The absorption cross sections at 805 nm are 2.17 × 10-20 cm2 with a full width at half maximum (FWHM) of 15 nm for π-polarization, and 2.29 × 10-20 cm2 with a FWHM of 14 nm for σ-polarization. The emission cross sections are 3.19 × 10-20 cm2 for σ-polarization and 2.67 × 10-20 cm2 for π-polarization at 1,064 nm. The fluorescence quantum efficiency is 67 %. The quasi-cw laser of Nd3+:Na2La4(WO4)7 crystal was performed. The maximum output power is 80 mW. The slope efficiency is 7.12 %. The results suggest Nd3+:Na2La4(WO4)7 crystal as a promising laser crystal fit for laser diode pumping.

  4. An energy-stable convex splitting for the phase-field crystal equation

    KAUST Repository

    Vignal, P.

    2015-10-01

    Abstract The phase-field crystal equation, a parabolic, sixth-order and nonlinear partial differential equation, has generated considerable interest as a possible solution to problems arising in molecular dynamics. Nonetheless, solving this equation is not a trivial task, as energy dissipation and mass conservation need to be verified for the numerical solution to be valid. This work addresses these issues, and proposes a novel algorithm that guarantees mass conservation, unconditional energy stability and second-order accuracy in time. Numerical results validating our proofs are presented, and two and three dimensional simulations involving crystal growth are shown, highlighting the robustness of the method. © 2015 Elsevier Ltd.

  5. Lattice distortion under an electric field in BaTiO3 piezoelectric single crystal

    International Nuclear Information System (INIS)

    Tazaki, Ryoko; Fu Desheng; Daimon, Masahiro; Koshihara, Shin-ya; Itoh, Mitsuru

    2009-01-01

    Lattice distortions under an electric field in a mono-domain of BaTiO 3 ferroelectric crystal have been detected with synchrotron x-ray radiation. The variation of the lattice constant with an electric field observed with high angle diffraction shows a linear response nature of the piezoelectric effect. When an electric field is applied along the spontaneous polarization direction, the c-axis of the lattice elongates and the a-axis of the lattice shrinks at a rate of d 33 = 149 ± 54 pm V -1 and d 31 = -82 ± 61 pm V -1 ; these represent the longitudinal and transverse piezoelectric coefficients of BaTiO 3 crystal, respectively. These results give an insight into the intrinsic piezoelectric response on the lattice scale in BaTiO 3 that has been widely used to explore high performance lead-free piezoelectric alloys.

  6. Creating physically-based three-dimensional microstructures: Bridging phase-field and crystal plasticity models.

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Hojun [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Owen, Steven J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Abdeljawad, Fadi F. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Hanks, Byron [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Battaile, Corbett Chandler [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    In order to better incorporate microstructures in continuum scale models, we use a novel finite element (FE) meshing technique to generate three-dimensional polycrystalline aggregates from a phase field grain growth model of grain microstructures. The proposed meshing technique creates hexahedral FE meshes that capture smooth interfaces between adjacent grains. Three dimensional realizations of grain microstructures from the phase field model are used in crystal plasticity-finite element (CP-FE) simulations of polycrystalline a -iron. We show that the interface conformal meshes significantly reduce artificial stress localizations in voxelated meshes that exhibit the so-called "wedding cake" interfaces. This framework provides a direct link between two mesoscale models - phase field and crystal plasticity - and for the first time allows mechanics simulations of polycrystalline materials using three-dimensional hexahedral finite element meshes with realistic topological features.

  7. Neutron investigations of magnetic properties of crystal substances with use of a pulsed magnetic field

    CERN Document Server

    Nitts, V V

    2001-01-01

    Bases for neutron researches of magnetic properties of crystal substances with use of a pulsed magnetic field and analysis of possible application of various neutron sources in this area are submitted. The review of the most interesting physical results is presented. Main investigations on pulsed reactors of JINR are researches on kinetics of the first order reorientational phase transitions induced in single crystals, and also measurements of antiferromagnetic ordering induced by an external magnetic field. Magnetic phase transitions, induced by a field up to 160 kOe in several magnetic ordering substances, were studied in KEK (Japan). Experiment on observation of spin-flop transition in MnF sub 2 was carried out on TRIGA-reactor in a mode of single flashes of power

  8. Crystal field in ErGa sub 3 - a neutron spectroscopy study

    CERN Document Server

    Murasik, A; Clementyev, E; Schefer, J

    2000-01-01

    The splitting of the J=15/2 multiplet of Er sup 3 sup + in a cubic crystal field has been determined by inelastic scattering from a polycrystalline sample of ErGa sub 3. On the basis of the observed intensities and their temperature variation we have been able to determine two crystal electric field (CEF) parameters required for cubic symmetry. Least-squares fits applied to the observed spectra taken at various temperatures gave crystal field parameters: B sub 4 =(7.15+-0.05)x10 sup - sup 5 and B sub 6 =(1.28+-0.05)x10 sup - sup 6 meV yielding the GAMMA sub 7 doublet as a ground level with the overall splitting of 10.92 meV. The results are used to calculate the temperature-dependant zero-field magnetisation, the Schottky anomaly of the specific heat associated with the CEF splitting of Er sup 3 sup + in ErGa sub 3 , and the high-field magnetisation.

  9. The influence of strong crystalline fields on QED-processes investigated using diamond crystals to crystals in $\\gamma, \\gamma$ colliders

    CERN Document Server

    Uggerhøj, Erik

    2002-01-01

    The very recent indications of Higgs-candidates at CERN have led to a strong interest in new types of facilities like high-energy photon colliders. This again leads to a search for strong high-energy gamma sources. In the present paper it is shown that single crystals are unique radiators due to the strong crystalline fields of 10/sup 12/ V /cm or more, in which incident particles move over very large distances (~100 mu m). Along axes, radiation emission and energy loss is enhanced more than two orders of magnitude. This dramatic effect loads to radiation cooling followed by capture to high-lying channeling states. The radiation is emitted in the forward angular cone of 40 mu rad or less. In the planar cases certain incident directions give hard photons with an intensity ~10 times the normal coherent bremsstrahlung. Therefore, in general, crystals turn out to be very interesting gamma -sources for photo production and coming gamma , gamma colliders. (10 refs).

  10. Crystal field distortion of La3+ ion-doped Mn-Cr ferrite

    Science.gov (United States)

    Abdellatif, M. H.; El-Komy, G. M.; Azab, A. A.; Salerno, M.

    2018-02-01

    Ion doping in crystals can result in lattice modifications triggering interesting magnetic and optical properties of the material, understood as a compensation of the crystal deformation and microstrain. We investigated the spinel structure of Mn-Cr ferrite after doping with La3+ ions. The structure was first characterized by X-ray diffraction and high-resolution transmission electron microscopy. Raman scattering spectra were taken that could also be interpreted in terms of crystal field distortion due to La3+ ion doping. On assessing the magneto-impedance of the doped ferrite, it showed giant magneto-impedance behavior, with a strong drop of over 50%. The saturation magnetization was characterised by vibrating sample magnetometer and was found to be 20.25 emu/g with remnant magnetization of 1.47 emu/g.

  11. A Hirshfeld surface analysis, crystal structure and spectroscopic properties of new Zn(II) complex with N-aminoethylpiperazine ligand

    Science.gov (United States)

    El Glaoui, Maroua; El Glaoui, Maher; Jelsch, Christian; Aubert, Emmanuel; Lefebvre, Frédéric; Ben Nasr, Chérif

    2017-04-01

    A new organic-inorganic hybrid material, 1-amonioethylpiperazine-1, 4-diium tetrachloridozincate(II) chloride, (C6H18N3)[ZnCl4]Cl, has been synthesized and characterized by various physicochemical techniques including UV-visible absorption, Infra-Red (IR), Raman and NMR spectroscopies. The compound crystallizes in the monoclinic system and P21 space group with Z = 2 and the following unit cell dimensions: a = 7.1728 (6), b = 12.4160 (11), c = 8.0278 (7) Å, β = 97.513 (1)°, V = 708.80 (11) Å3. In this structure, the Zn2+ ion, surrounded by four chlorides, adopts a distorted tetrahedral coordination geometry. The structure of this compound consists of monomeric 1-amonioethylpiperazine-1, 4-diium trications and monomeric [ZnCl4]2- and Cl- anions. These entities are interconnected by means of hydrogen bonding contacts [Nsbnd H⋯Cl, Csbnd H⋯Cl], forming a three-dimensional network. Intermolecular interactions were investigated by Hirshfeld surfaces. More than three quarters of the interaction surface in the crystal packing is constituted by attractive and favored H⋯Cl hydrogen bonds. The 13C and 15N CP-MAS NMR spectra are discussed and the vibrational absorption bands were identified by infrared and Raman spectroscopy.

  12. Crystal structure, molecular docking, and biological activity of the zinc complexes with 2-thenoyltrifluoroacetone and N-donor heterocyclic ligands

    Science.gov (United States)

    Eshaghi Malekshah, Rahime; Salehi, Mehdi; Kubicki, Maciej; Khaleghian, Ali

    2017-12-01

    Two novel mononuclear complexes, [Zn (TTA) (bipy)Cl] (1) and [Zn (TTA) (phen)Cl] (2) (TTA = 4,4,4-Trifluoro-1-(2-furyl)-1,3-butanedione, phen = 1,10-phenanthroline and bipy 2, 2ʹ-bipyridine), were synthesized and fully characterized by elemental analyses, 1H NMR, UV-Vis, FTIR spectroscopy, and conductivity measurements. The crystal structures of these two mono-nuclear zinc (II) complexes were determined by X-ray single-crystal diffraction. The result of X-ray diffraction analyses revealed that both complexes have distorted tetragonal-pyramid structures. In MTT cytotoxicity studies, these Zn (II) complexes exhibited antitumor activity against MCF-7 and MKN-45 cell lines. It was also found that the proliferation rate of MCF-7 and MKN-45 cells decreased after treatment with the above-mentioned complexes. In addition, the apoptosis-inducing activity was assessed by AO/EB (Acridine Orange/Ethidium bromide) staining assay and found that they have the potential to act as effective metal-based anticancer drugs. Finally, the molecular docking studies showed that complex 2 strongly binds through minor groove with DNA by relative binding energy -7.33 kcal mol-1.

  13. Near-field characterization of low-loss photonic crystal waveguides

    DEFF Research Database (Denmark)

    Volkov, V. S.; Bozhevolnyi, S. I.; Borel, Peter Ingo

    2005-01-01

    A scanning near-field optical microscope is used to directly map the propagation of light in the wavelength range of 1500-1630 nm along straight photonic crystal waveguides (PCWs) fabricated on silicon-on-insulator wafers. The PVWs were formed by removing a single row of holes in the triangular 428......-nm-period lattices with different filling factors (0.76 and 0.82) and connected to access ridge waveguides. Using the near-field optical images we investigate the light propagation along PCWs for TM and TE polarization (the electric field is perpendicular/parallel to the sample surface). Efficient...

  14. Molecular Field Calculation of Magnetization on NdRh2Ge2 Single Crystal

    Directory of Open Access Journals (Sweden)

    A. Himori

    2008-01-01

    Full Text Available Calculation of magnetization of the ternary single crystal compound NdRh2Ge2 has been carried out by using the wave-like molecular field model to explain the complex magnetic behavior. The field-induced magnetic structures having the propagation vectors, 2=(0,0,39/40, 3=(0,0,35/40, 4=(0,0,31/40, and 5=(0,0,0/40 (= the field-induced ferromagnetic phase were proposed. Calculation on the basis of these structures and the antiferromagnetic phase with 1=(0,0,1 well reproduces the experimental magnetization processes and - magnetic phase diagram.

  15. Light scattering from liquid crystal director fluctuations in steady magnetic fields up to 25 tesla.

    Science.gov (United States)

    Challa, Pavan K; Curtiss, O; Williams, J C; Twieg, R; Toth, J; McGill, S; Jákli, A; Gleeson, J T; Sprunt, S N

    2012-07-01

    We report on homodyne dynamic light scattering measurements of orientational fluctuation modes in both calamitic and bent-core nematic liquid crystals, carried out in the new split-helix resistive magnet at the National High Magnetic Field Laboratory. The relaxation rate and inverse scattered intensity of director fluctuations exhibit a linear dependence on field-squared up to 25 tesla, which is consistent with strictly lowest order coupling of the tensor order parameter Q to field (Q(αβ)B(α)B(β)) in the nematic free energy. However, we also observe evidence of field dependence of certain nematic material parameters, an effect which may be expected from the mean field scaling of these quantities with the magnitude of Q and the predicted variation of Q with field.

  16. Phase field model of the nanoscale evolution during the explosive crystallization phenomenon

    Science.gov (United States)

    Lombardo, S. F.; Boninelli, S.; Cristiano, F.; Deretzis, I.; Grimaldi, M. G.; Huet, K.; Napolitani, E.; La Magna, A.

    2018-03-01

    Explosive crystallization is a well known phenomenon occurring due to the thermodynamic instability of strongly under-cooled liquids, which is particularly relevant in pulsed laser annealing processes of amorphous semiconductor materials due to the globally exothermic amorphous-to-liquid-to-crystal transition pathway. In spite of the assessed understanding of this phenomenon, quantitative predictions of the material kinetics promoted by explosive crystallization are hardly achieved due to the lack of a consistent model able to simulate the concurrent kinetics of the amorphous-liquid and liquid-crystal interfaces. Here, we propose a multi-well phase-field model specifically suited for the simulation of explosive crystallization induced by pulsed laser irradiation in the nanosecond time scale. The numerical implementation of the model is robust despite the discontinuous jumps of the interface speed induced by the phenomenon. The predictive potential of the simulations is demonstrated by means of comparisons of the modelling predictions with experimental data in terms of in situ reflectivity measurements and ex-situ micro-structural and chemical characterization.

  17. Nano structure zinc (II) Schiff base complexes of a N3-tridentate ligand as new biological active agents: spectral, thermal behaviors and crystal structure of zinc azide complex.

    Science.gov (United States)

    Montazerozohori, M; Mojahedi Jahromi, S; Masoudiasl, A; McArdle, P

    2015-03-05

    In this work, synthesis of some new five coordinated zinc halide/pseudo-halide complexes of a N3-tridentate ligand is presented. All complexes were subjected to spectroscopic and physical methods such as FT-IR, UV-visible, (1)H and (13)C NMR spectra, thermal analyses and conductivity measurements for identification. Based on spectral data, the general formula of ZnLX2 (X=Cl(-), Br(-), I(-), SCN(-) and N3(-)) was proposed for the zinc complexes. Zinc complexes have been also prepared in nano-structure sizes under ultrasonic irradiation. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied for confirmation of nano-structure character for the complexes. Among the complexes, zinc azide complex structure was analyzed by X-ray crystallography. This complex crystallizes as a triplet in trigonal system with space group of P31. The coordination sphere around the zinc center is well shown as a distorted trigonal bipyramidal with three nitrogen atoms from Schiff base ligand and two terminal azide nitrogen atoms attached to zinc ion. Various intermolecular interactions such as NH⋯N, CH⋯N and CH⋯π hydrogen bonding interactions stabilize crystalline lattice so that they causes a three dimensional supramolecular structure for the complex. In vitro screening of the compounds for their antimicrobial activities showed that ZnLI2, ZnL(N3)2, ZnLCl2 and ZnL(NCS)2 were found as the most effective compound against bacteria of Bacillus subtilis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli respectively. Also ZnLI2 and ZnLCl2 complexes were found more effective against two selected fungi than others. Finally, thermal behaviors of the zinc complexes showed that they are decomposed via 2-4 thermal steps from room temperature up to 1000°C. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Effect of magnetic field on the wave dispersion relation in three-dimensional dusty plasma crystals

    Energy Technology Data Exchange (ETDEWEB)

    Yang Xuefeng [School of Mathematical Sciences, Dalian University of Technology, Dalian 116024 (China); Wang Zhengxiong [School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024 (China)

    2012-07-15

    Three-dimensional plasma crystals under microgravity condition are investigated by taking into account an external magnetic field. The wave dispersion relations of dust lattice modes in the body centered cubic (bcc) and the face centered cubic (fcc) plasma crystals are obtained explicitly when the magnetic field is perpendicular to the wave motion. The wave dispersion relations of dust lattice modes in the bcc and fcc plasma crystals are calculated numerically when the magnetic field is in an arbitrary direction. The numerical results show that one longitudinal mode and two transverse modes are coupled due to the Lorentz force in the magnetic field. Moreover, three wave modes, i.e., the high frequency phonon mode, the low frequency phonon mode, and the optical mode, are obtained. The optical mode and at least one phonon mode are hybrid modes. When the magnetic field is neither parallel nor perpendicular to the primitive wave motion, all the three wave modes are hybrid modes and do not have any intersection points. It is also found that with increasing the magnetic field strength, the frequency of the optical mode increases and has a cutoff at the cyclotron frequency of the dust particles in the limit of long wavelength, and the mode mixings for both the optical mode and the high frequency phonon mode increase. The acoustic velocity of the low frequency phonon mode is zero. In addition, the acoustic velocity of the high frequency phonon mode depends on the angle of the magnetic field and the wave motion but does not depend on the magnetic field strength.

  19. Synthesis, crystal structures and antitumor activities of copper(II) complexes with a 2-acetylpyrazine isonicotinoyl hydrazone ligand

    Science.gov (United States)

    Xu, Jun; Zhou, Tao; Xu, Zhou-Qing; Gu, Xin-Nan; Wu, Wei-Na; Chen, Hong; Wang, Yuan; Jia, Lei; Zhu, Tao-Feng; Chen, Ru-Hua

    2017-01-01

    Five complexes, [Cu(L)2]·4.5H2O (1), [Cu(HL)2](NO3)2·CH3OH (2) {[Cu2(L)2(NO3)(H2O)2]·(NO3)}n (3), [Cu2(HL)2(SO4)2]·2CH3OH (4) and [Cu4(L)4Cl4]·5H2O (5) based on HL (where HL = 2-acetylpyrazine isonicotinoyl hydrazone) have been synthesized and characterized by X-ray diffraction analyses. The counter anion and organic base during the synthesis procedure influence the structures of the complexes efficiently, which generate five complexes as mono-, bi-, tetra-nuclear and one-dimensional structures. The antitumor activities of the complexes 1-5 (except for complex 3 with the poor solubility) against the Patu8988 human pancreatic cancer, ECA109 human esophagus cancer and SGC7901 human gastric cancer cell lines are screened by MTT assay. The results indicate that the chelation of Cu(II) with the ligand is responsible for the observed high cytotoxicity of the copper(II) complexes and the 1:2 copper species 1 and 2 demonstrate lower antitumor activities than that of the 1:1 copper species 4 and 5. In addition, the in vitro apoptosis inducing activity of the copper(II) complex 5 against SGC7901 cell line is determined. And the results show that the complex can bring about apoptosis of the cancerous cells in vitro.

  20. Recent developments in Liquid Phase Electroepitaxial growth of bulk crystals under magnetic field

    Science.gov (United States)

    Dost, Sadik; Lent, Brian; Sheibani, Hamdi; Liu, Yongcai

    2004-05-01

    This review article presents recent developments in Liquid Phase Electroepitaxial (LPEE) growth of bulk single crystals of alloy semiconductors under an applied static magnetic field. The growth rate in LPEE is proportional to the applied electric current. However, at higher electric current levels the growth becomes unstable due to the strong convection occurring in the liquid zone. In order to address this problem, a significant body of research has been performed in recent years to suppress and control the natural convection for the purpose of prolonging the growth process to grow larger crystals. LPEE growth experiments show that the growth rate under an applied static magnetic field is also proportional and increases with the field intensity level. The modeling of LPEE growth under magnetic field was also the subject of interest. Two-dimensional mathematical models developed for the LPEE growth process predicted that the natural convection in the liquid zone would be suppressed almost completely with increasing the magnetic field level. However, experiments and also three-dimensional models have shown that there is an optimum magnetic field level below which the growth process is stable and the convection in the liquid zone is suppressed, but above such a field level the convective flow becomes very strong and leads to unstable growth with unstable interfaces. To cite this article: S. Dost et al., C. R. Mecanique 332 (2004).

  1. The use of single-crystal iron frames in transient field measurements, ch. 3

    International Nuclear Information System (INIS)

    Zalm, P.C.

    1977-01-01

    An experimental technique for measuring g-factors of short-lived states (tausub(m)=0.1-10 ps) is discussed. In this method, one uses the strong hyperfine interaction caused by the transient magnetic field. The transient field method dates from 1967. A gain in measuring time of at least a factor of four is shown to be obtained by the use of a single crystal iron frame as a ferromagnetic target backing in which the excited nuclei, formed in a nuclear reaction, recoil. Such frames can be fully magnetized with low external fields as shown by magneto-optical Kerr-effect measurements. The important improvement is that the associated magnetic fringing field near the target is negligible. This is in contrast to the conventional set-up in which strong external fields, with corresponding large disturbing fringing fields, were necessary. The single-crystal set-up is compared to the conventional set-up in several transient field experiments and proves to be successful

  2. Phase field modeling of rapid crystallization in the phase-change material AIST

    Science.gov (United States)

    Tabatabaei, Fatemeh; Boussinot, Guillaume; Spatschek, Robert; Brener, Efim A.; Apel, Markus

    2017-07-01

    We carry out phase field modeling as a continuum simulation technique in order to study rapid crystallization processes in the phase-change material AIST (Ag4In3Sb67Te26). In particular, we simulate the spatio-temporal evolution of the crystallization of a molten area of the phase-change material embedded in a layer stack. The simulation model is adapted to the experimental conditions used for recent measurements of crystallization rates by a laser pulse technique. Simulations are performed for substrate temperatures close to the melting temperature of AIST down to low temperatures when an amorphous state is involved. The design of the phase field model using the thin interface limit allows us to retrieve the two limiting regimes of interface controlled (low temperatures) and thermal transport controlled (high temperatures) dynamics. Our simulations show that, generically, the crystallization velocity presents a maximum in the intermediate regime where both the interface mobility and the thermal transport, through the molten area as well as through the layer stack, are important. Simulations reveal the complex interplay of all different contributions. This suggests that the maximum switching velocity depends not only on material properties but also on the precise design of the thin film structure into which the phase-change material is embedded.

  3. Structural and EPR studies on single-crystal and polycrystalline samples of copper(II) and cobalt(II) complexes with N2S2-based macrocyclic ligands.

    Science.gov (United States)

    Tamayo, Abel; Casabó, Jaume; Escriche, Lluís; González, Pablo; Lodeiro, Carlos; Rizzi, Alberto C; Brondino, Carlos D; Passeggi, M C G; Kivekäs, Raikko; Sillanpää, Reijo

    2007-07-09

    The properties of Cu(II) and Co(II) complexes with oxygen- or nitrogen-containing macrocycles have been extensively studied; however, less attention has been paid to the study of complexes containing sulfur atoms in the first coordination sphere. Herein we present the interaction between these two metal ions and two macrocyclic ligands with N2S2 donor sets. Cu(II) and Co(II) complexes with the pyridine-containing 14-membered macrocycles 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L) and 7-(9-anthracenylmethyl)-3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) have been synthesized. The X-ray structural analysis of {[Co(ClO4)(H2O)(L)][Co(H2O)2(L)]}(ClO4)3 shows two different metal sites in octahedral coordination. The EPR spectra of powdered samples of this compound are typical of distorted six-coordinated Co(II) ions in a high-spin (S=3/2) configuration, with the ground state being S=1/2 (g1=5.20, g2=3.20, g3=1.95). The EPR spectrum of [Cu(ClO4)(L)](ClO4) was simulated assuming an axial g tensor (g1=g2=2.043, g3=2.145), while that of [Cu(ClO4)(L1)](ClO4) slightly differs from an axial symmetry (g1=2.025, g2=2.060, g3=2.155). These results are compatible with a Cu(II) ion in square-pyramidal coordination with N2S2 as basal ligands. Single-crystal EPR experiment performed on [Cu(ClO4)(L1)](ClO4) allowed determining the eigenvalues of the molecular g tensor associated with the copper site, as well as the two possible orientations for the tensor. On the basis of symmetry arguments, an assignment in which the eigenvectors are nearly along the Cu(II)-ligand bonds is chosen.

  4. Synthesis, crystal structures, luminescence properties of two metal coordination polymers derived from 5-substituted isophthalate and flexible bis (triazole) ligands.

    Science.gov (United States)

    Ming, Chun-lun; Wang, Li-na; Van Hecke, Kristof; Cui, Guang-hua

    2014-08-14

    Two new metal complexes, [Ni(btx)(nip)(H2O)]n (1), {[Cd(btx)(mip)(H2O)]·H2O}n (2) (btx=1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, H2nip=5-nitroisophthalic acid, H2mip=5-methyisophthalic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA and elemental analysis. Complex 1 features a 3D metal-organic framework with three-fold interpenetrating CdSO4-type topology. Complex 2 exhibits a 2D network with square grid units, which is further extended into a rare 3,5T1 three-dimensional supramolecular network via three modes of classical OH⋯O hydrogen bonds. In addition, luminescence properties of 1 and 2 have also been investigated in the solid state. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Crystal-field investigations of rare-earth-doped wide band gap semiconductors

    CERN Multimedia

    Muller, S; Wahl, U

    Crystal field investigations play a central role in the studies of rare earth doped semiconductors. Optical stark level spectroscopy and lattice location studies of radioactive rare earth isotopes implanted at ISOLDE have provided important insight into these systems during the last years. It has been shown that despite a major site preference of the probe atoms in the lattice, several defect configurations do exist. These sites are visible in the optical spectra but their origin and nature aren't deducible from these spectra alone. Hyperfine measurements on the other hand should reveal these defect configurations and yield the parameters necessary for a description of the optical properties at the atomic scale. In order to study the crystal field with this alternative approach, we propose a new concept for perturbed $\\gamma\\gamma$-angular correlation (PAC) experiments at ISOLDE based on digital signal processing in contrast to earlier analog setups. The general functionality of the spectrometer is explained ...

  6. CALIBRE and CRYSTAL: Near-field and geosphere models for Project-90

    International Nuclear Information System (INIS)

    Robinson, P.C.; Worgan, K.J.; Shaw, W.T.; Wingefors, S.

    1991-01-01

    A new near-field model (CALIBRE) and a fractured geosphere model (CRYSTAL) have been developed in support of the Swedish Nuclear Power Inspectorate's Project-90 safety assessment of a reference repository for spent nuclear fuel. CALIBRE calculates in two dimensions the twin problems of oxidant and radionuclide migration through a bentonite buffer and fractured host rock, with redox front formation and precipitation of nuclides at the redox front. The output from CALIBRE can be input directly to the CRYSTAL code, which is a fast, one-dimensional contaminant transport model of a fractured rock geosphere. This paper describes the main features of the models and illustrates how certain processes can have a significant impact on the flux of radionuclides emerging from the near field to the geosphere, and from the geosphere to the biosphere

  7. Sensitized charge carrier injection into organic crystals studied by isotope effects in weak magnetic fields

    International Nuclear Information System (INIS)

    Bube, W.; Michel-Beyerle, M.E.; Haberkorn, R.; Steffens, E.

    1977-01-01

    The magnetic field (H approximately 50 Oe) dependence of the rhodamine sensitized triplet exciton density in anthracene crystals is influenced by isotopic substitution. This confirms the hyperfine interaction as mechanism explaining the change of the spin multiplicity in the initially formed singlet state of the radical pair. The isotope effect occurs in the sensitizing dye ( 14 N/ 15 N) rather than at the molecular site of the injected charge within the crystal. This can be understood in terms of the high hopping frequency of the charge carriers as compared to the time constant of the hyperfine induced singlet-triplet transition. Since the dye molecules adsorb in an oriented fashion, the angular dependence of the magnetic field modulation of the triplet exciton density can be interpreted without assuming any additional interactions. (Auth.)

  8. Synthetic routes to mixed-ligand cobalt(III) dithiocarbamato complexes containing imidazole, amine and pyridine donors and the X-ray crystal structure of a cobalt(III) bis(dithiocarbamato) histamine complex.

    Science.gov (United States)

    Hodgson, Michael C; Brothers, Penelope J; Clark, George R; Ware, David C

    2008-04-01

    The binuclear cobalt complex [Co(2)(Me(2)dtc)(5)](+) reacts with a range of nitrogen donor ligands L' or L'' to form an equimolar mixture of Co(Me(2)dtc)(3) and the mixed-ligand complexes [Co(Me(2)dtc)(2)(L')(2)](+) or [Co(Me(2)dtc)(2)(L'')](+), where (L')(2) is two monodentate ligands and (L'') is one bidentate ligand. The complexes prepared by this route contain the monodentate ligands L'=1-methyl-imidazole, 1-methyl-5-nitro-imidazole and benzimidazole, all of which coordinate to cobalt through an imidazole nitrogen atom. Symmetrical bidentate ligand complexes contain the bisimidazole L''=2,2'-bis(4,5-dimethylimidazole), the diamine L''=1,2-diaminobenzene and the pyridine donors L''=2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine and 1,10-phenanthroline. Two examples of complexes with unsymmetrical bidentate imidazole-amine donors were prepared in which L''=4-(2-aminoethyl)imidazole (histamine) and 2-aminomethylbenzimidazole. All new complexes were fully characterised, and the X-ray crystal structure of the histamine complex [Co(Me(2)dtc)(2)(hist)]ClO(4) is also reported.

  9. Crystal field parameters with Wannier functions: application to rare-earth aluminates

    Czech Academy of Sciences Publication Activity Database

    Novák, Pavel; Knížek, Karel; Kuneš, Jan

    2013-01-01

    Roč. 87, č. 20 (2013), "205139-1"-"205139-7" ISSN 1098-0121 R&D Projects: GA ČR(CZ) GAP204/11/0713 Institutional support: RVO:68378271 Keywords : crystal-field * rare earths * Wannier functions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.664, year: 2013 http://link.aps.org/doi/10.1103/PhysRevB.87.205139

  10. Electric field influence on exciton absorption of Er doped and undoped InSe single crystals

    International Nuclear Information System (INIS)

    Guerbulak, B; Kundakci, M; Ates, A; Yildirim, M

    2007-01-01

    Undoped InSe and Er doped InSe (InSe:Er) single crystals were grown by using the Stockbarger method. Ingots had no cracks and voids on the surface. The absorption measurements were carried out in InSe and InSe:Er samples for U=0 and U=30 V in the temperature range 10-320 K with a step of 10 K. Electric field effects on excitons are observed in InSe and InSe:Er single crystals. The absorption edge shifted towards longer wavelengths and decreased intensity in absorption spectra under an electric field E≅5.9 kV cm -1 . The applied electric field caused a shifting and a decreasing of intensity in the absorption spectra. The shifting of the absorption edge can be explained on the basis of the Franz-Keldysh effect (FKE) or thermal heating of the sample under the electric field. At 10 and 320 K, the first exciton energies for InSe were calculated as 1.336 and 1.291 eV for zero voltage and 1.331 and 1.280 eV for electric field and InSe:Er as 1.329 and 1.251 eV for zero voltage and 1.318 and 1.248 eV for electric field, respectively

  11. Crystal Growth of High-Quality Protein Crystals under the Presence of an Alternant Electric Field in Pulse-Wave Mode, and a Strong Magnetic Field with Radio Frequency Pulses Characterized by X-ray Diffraction

    Directory of Open Access Journals (Sweden)

    Adela Rodríguez-Romero

    2017-06-01

    Full Text Available The first part of this research was devoted to investigating the effect of alternate current (AC using four different types of wave modes (pulse-wave at 2 Hz on the crystal growth of lysozyme in solution. The best results, in terms of size and crystal quality, were obtained when protein crystals were grown under the influence of electric fields in a very specific wave mode (“breathing” wave, giving the highest resolution up to 1.34 Å in X-ray diffraction analysis compared with controls and with those crystals grown in gel. In the second part, we evaluated the effect of a strong magnetic field of 16.5 Tesla combined with radiofrequency pulses of 0.43 μs on the crystal growth in gels of tetragonal hen egg white (HEW lysozyme. The lysozyme crystals grown, both in solution applying breathing-wave and in gel under the influence of this strong magnetic field with pulses of radio frequencies, produced the larger-in-size crystals and the highest resolution structures. Data processing and refinement statistics are very good in terms of the resolution, mosaicity and Wilson B factor obtained for each crystal. Besides, electron density maps show well-defined and distinctly separated atoms at several selected tryptophan residues for the crystal grown using the “breathing wave pulses”.

  12. Using a Combination of Experimental and Computational Methods to Explore the Impact of Metal Identity and Ligand Field Strength on the Electronic Structure of Metal Ions

    Science.gov (United States)

    Pernicone, Naomi C.; Geri, Jacob B.; York, John T.

    2011-01-01

    In this exercise, students apply a combination of techniques to investigate the impact of metal identity and ligand field strength on the spin states of three d[superscript 5] transition-metal complexes: Fe(acac)[subscript 3], K[subscript 3][Fe(CN)[subscript 6

  13. Origin of the Anomalous Color of Egyptian and Han Blue Historical Pigments: Going beyond the Complex Approximation in Ligand Field Theory

    Science.gov (United States)

    García-Fernandez, Pablo; Moreno, Miguel; Aramburu, José Antonio

    2016-01-01

    The complex approximation is widely used in the framework of the Ligand Field Theory for explaining the optical properties of crystalline coordination compounds. Here, we show that there are essential features of these systems that cannot be understood with the usual approximation that only considers an isolated complex at the correct equilibrium…

  14. Synthesis, Crystal Structure, Luminescence and Magnetism of Three Novel Coordination Polymers Based on Flexible Multicarboxylate Zwitterionic Ligand

    Directory of Open Access Journals (Sweden)

    Yulu Ma

    2017-01-01

    Full Text Available Three novel zwitterionic coordination polymers, namely, {[Zn(HCbdcp2]·H2O} (1, {[Mn(Cbdcp]·3H2O} (2 and {[Cu2(Cbdcp(HCbdcpCl·H2O]·2H2O} (3, Cbdcp = 3,5-dicarboxy-1-(4-carboxybenzylpyridin-1-ium, have been prepared by a hydrothermal method and characterized by X-ray single crystal diffraction analysis, powder X-ray diffraction analysis, IR spectroscopy, and thermogravimetric analysis. With the changing of metal centers, these complexes show distinct structures: a mononuclear 2D 44-sql network for 1, a 3D 6,6-connected-type topology for 2 and a novel dinuclear 2D layer for 3. These diverse architectures prove that coordination geometry of metal ions, coordination modes of carboxylate groups and the rotationally flexible CH2 linker played significant roles in the construction of CPs; moreover, they also indicated that H3CbdcpCl is an ideal organic candidate for the building of novel structures. The solid-state luminescent properties of complexes 1–3 were investigated, respectively. In addition, the magnetic properties of 2 and 3 were studied and both of them exhibit antiferromagnetic behaviors.

  15. Dicynamide bridged two new zig-zag 1-D Zn(II) coordination polymers of pyrimidine derived Schiff base ligands: Synthesis, crystal structures and fluorescence studies

    Science.gov (United States)

    Konar, Saugata

    2015-07-01

    Two new zigzag 1-D polymeric Zn(II) coordination polymers {[Zn(L1)(μ1,5-dca)](H2O)}n (1), {[Zn(L2)(μ1,5-dca)](ClO4)}n (2) of two potentially tridentate NNO-, NNN-, donor Schiff base ligands [2-(2-(4,6-dimethylpyrimidin-2-yl)hydrazono)methyl)phenol] (L1), [1-(4,6-dimethylpyrimidin-2-yl)-2-(dipyridin-2ylmethylene)hydrazine] (L2) have been synthesized and characterized by elemental analyses, IR and 1H NMR, fluorescence spectroscopy and single crystal X-ray crystallography. The dicyanamide ions act as linkers (μ1,5 mode) in the formation of these coordination polymers. Both the complexes 1 and 2 have same distorted square pyramidal geometry around the Zn(II) centres. The weak forces like π⋯π, Csbnd H⋯π, anion⋯π interactions lead to various supramolecular architectures. Complex 1 shows high chelation enhanced fluorescence compared to that of 2. The fluorescence spectral changes observed high selectivity towards Zn(II) over other metal ions such as Mn(II), Co(II), Ni(II), Cu(II).

  16. Field-controllable Spin-Hall Effect of Light in Optical Crystals: A Conoscopic Mueller Matrix Analysis

    OpenAIRE

    Samlan, C. T.; Viswanathan, Nirmal K.

    2018-01-01

    Electric-field applied perpendicular to the direction of propagation of paraxial beam through an optical crystal dynamically modifies the spin-orbit interaction (SOI), leading to the demonstration of controllable spin-Hall effect of light (SHEL). The electro- and piezo-optic effects of the crystal modifies the radially symmetric spatial variation in the fast-axis orientation of the crystal, resulting in a complex pattern with different topologies due to the symmetry-breaking effect of the app...

  17. Slave Boson Theory of Orbital Differentiation with Crystal Field Effects: Application to UO2

    Science.gov (United States)

    Lanatà, Nicola; Yao, Yongxin; Deng, Xiaoyu; Dobrosavljević, Vladimir; Kotliar, Gabriel

    2017-03-01

    We derive an exact operatorial reformulation of the rotational invariant slave boson method, and we apply it to describe the orbital differentiation in strongly correlated electron systems starting from first principles. The approach enables us to treat strong electron correlations, spin-orbit coupling, and crystal field splittings on the same footing by exploiting the gauge invariance of the mean-field equations. We apply our theory to the archetypical nuclear fuel UO2 and show that the ground state of this system displays a pronounced orbital differentiation within the 5 f manifold, with Mott-localized Γ8 and extended Γ7 electrons.

  18. Slave Boson Theory of Orbital Differentiation with Crystal Field Effects: Application to UO_{2}.

    Science.gov (United States)

    Lanatà, Nicola; Yao, Yongxin; Deng, Xiaoyu; Dobrosavljević, Vladimir; Kotliar, Gabriel

    2017-03-24

    We derive an exact operatorial reformulation of the rotational invariant slave boson method, and we apply it to describe the orbital differentiation in strongly correlated electron systems starting from first principles. The approach enables us to treat strong electron correlations, spin-orbit coupling, and crystal field splittings on the same footing by exploiting the gauge invariance of the mean-field equations. We apply our theory to the archetypical nuclear fuel UO_{2} and show that the ground state of this system displays a pronounced orbital differentiation within the 5f manifold, with Mott-localized Γ_{8} and extended Γ_{7} electrons.

  19. Dynamic behaviors of ferroelectric liquid crystal molecules under an applied electric field

    Science.gov (United States)

    Kawaguchi, Masato; Takei, Misaki; Yamashita, Masafumi

    2009-03-01

    The dynamic changes in ferroelectric liquid crystal (FLC) molecular alignments under an applied electric field are examined by observing the formation of conoscopic figures with a time resolution of 0.1 ms. Close agreements between observed and simulated conoscopic figures under low voltage (30 V) were obtained. Under high voltage (120 V), however, the observed conoscopic figures became blurred between 0.8 ms and 1.1 ms after reversal of the electric field. The light scattering producing the blurriness occurred due to the development of fast transient molecular alignments during the switching transition above the applied voltage 70 V.

  20. Novel colloidal system: Magnetite-polymer particles/lyotropic liquid crystal under magnetic field

    Science.gov (United States)

    Mănăilă-Maximean, D.; Cîrtoaje, C.; Dănilă, O.; Donescu, D.

    2017-09-01

    We obtained a new highly ordered colloidal composite using specially manufactured magnetite-polymer nanoparticles and lyotropic liquid crystal. A good compatibility between the components was ensured by the functionalization of the particles during their synthesis. We studied the laser light transmission for the mixtures filled in sandwich-glass cells with homeotropic and planar treatment of the surfaces under external magnetic field. The Fréedericksz transition critical field was estimated, and its' behavior was compared to our new theoretical model based on the Brochard-de Gennes one.

  1. Algorithm for the propagation of electromagnetic fields through etalons and crystals.

    Science.gov (United States)

    Zhang, Site; Hellmann, Christian; Wyrowski, Frank

    2017-05-20

    We investigate the propagation of general electromagnetic fields through optical layer structures made of either isotropic or anisotropic media, by using the spectrum-of-plane-waves analysis together with the S-matrix method. We also develop an algorithm based on the fast Fourier transform technique, with a numerically efficient sampling rule. By using this algorithm in combination with other system modeling techniques, we present a few simulation examples, such as field propagation through an isotropic Fabry-Perot etalon, as well as uniaxial crystal slabs with arbitrary orientation and optic axis direction.

  2. Theoretically informed Monte Carlo simulation of liquid crystals by sampling of alignment-tensor fields

    Energy Technology Data Exchange (ETDEWEB)

    Armas-Pérez, Julio C.; Londono-Hurtado, Alejandro [Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Guzmán, Orlando [Departamento de Física, Universidad Autónoma Metropolitana, Iztapalapa, DF 09340, México (Mexico); Hernández-Ortiz, Juan P. [Departamento de Materiales y Minerales, Universidad Nacional de Colombia, Sede Medellín, Medellín (Colombia); Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Pablo, Juan J. de, E-mail: depablo@uchicago.edu [Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2015-07-28

    A theoretically informed coarse-grained Monte Carlo method is proposed for studying liquid crystals. The free energy functional of the system is described in the framework of the Landau-de Gennes formalism. The alignment field and its gradients are approximated by finite differences, and the free energy is minimized through a stochastic sampling technique. The validity of the proposed method is established by comparing the results of the proposed approach to those of traditional free energy minimization techniques. Its usefulness is illustrated in the context of three systems, namely, a nematic liquid crystal confined in a slit channel, a nematic liquid crystal droplet, and a chiral liquid crystal in the bulk. It is found that for systems that exhibit multiple metastable morphologies, the proposed Monte Carlo method is generally able to identify lower free energy states that are often missed by traditional approaches. Importantly, the Monte Carlo method identifies such states from random initial configurations, thereby obviating the need for educated initial guesses that can be difficult to formulate.

  3. Theoretically informed Monte Carlo simulation of liquid crystals by sampling of alignment-tensor fields.

    Energy Technology Data Exchange (ETDEWEB)

    Armas-Perez, Julio C.; Londono-Hurtado, Alejandro; Guzman, Orlando; Hernandez-Ortiz, Juan P.; de Pablo, Juan J.

    2015-07-27

    A theoretically informed coarse-grained Monte Carlo method is proposed for studying liquid crystals. The free energy functional of the system is described in the framework of the Landau-de Gennes formalism. The alignment field and its gradients are approximated by finite differences, and the free energy is minimized through a stochastic sampling technique. The validity of the proposed method is established by comparing the results of the proposed approach to those of traditional free energy minimization techniques. Its usefulness is illustrated in the context of three systems, namely, a nematic liquid crystal confined in a slit channel, a nematic liquid crystal droplet, and a chiral liquid crystal in the bulk. It is found that for systems that exhibit multiple metastable morphologies, the proposed Monte Carlo method is generally able to identify lower free energy states that are often missed by traditional approaches. Importantly, the Monte Carlo method identifies such states from random initial configurations, thereby obviating the need for educated initial guesses that can be difficult to formulate.

  4. Synthesis, Characterization, Crystal Structure, and Biological Studies of a Cadmium(II) Complex with a Tridentate Ligand 4′-Chloro-2,2′:6′,2′′-Terpyridine

    Science.gov (United States)

    Saghatforoush, L. A.; Valencia, L.; Chalabian, F.; Ghammamy, Sh.

    2011-01-01

    A new Cd(II) complex with the ligand 4′-chloro-2,2′6′,2′′-terpyridine (Cltpy), [Cd(Cltpy)(I)2], has been synthesized and characterized by CHN elemental analysis, 1H-NMR, 13C-NMR, and IR spectroscopy and structurally analyzed by X-ray single-crystal diffraction. The single-crystal X-ray analyses show that the coordination number in complex is five with three terpyridine (Cltpy) N-donor atoms and two iodine atoms. The antibacterial activities of Cltpy and its Cd(II) complex are tested against different bacteria. PMID:21738495

  5. Properties of the localized field emitted from degenerate Λ-type atoms in photonic crystals

    International Nuclear Information System (INIS)

    Foroozani, N.; Golshan, M. M.; Mahjoei, M.

    2007-01-01

    The spontaneous emission from a degenerate Λ-type three-level atom, embedded in a photonic crystal, is studied. The emitted field, as a function of time and position, is calculated by solving the three coupled differential equations governing the amplitudes. We show that the spontaneously emitted field is characterized by three components (as in the case of two-level and V-type atoms): a localized part, a traveling part, and a t -3/2 decaying part. Our calculations indicate that under specific conditions the atoms do not emit propagating fields, while the localized field, having shorter localization length and time, is intensified. As a consequence, the population of the upper level, after a short period of oscillations, approaches a constant value. It is also shown that this steady value, under the same conditions, is much larger than its counterpart in V-type atoms

  6. Self-assembly of one Ag(I) 2D metallacrown polymer with bis-bidentate Schiff-base ligand N,N‧-bis(furan-2-ylmethylene)hydrazine: Synthesis, crystal structures and luminescent properties

    Science.gov (United States)

    Dang, Dongbin; Gao, Hui; Bai, Yan; Pan, Xiaojing; Shang, Weili

    2010-04-01

    One new coordination polymer, [{Ag 2L 3(BF 4) 2}H 2O] n ( 1), has been generated via self-assembly from the ligand LN, N'-bis(furan-2-ylmethylene)hydrazine and AgBF 4. The complex 1 and ligand L are characterized by single-crystal X-ray diffraction analysis. Crystal structure analyses show that the complex 1 belongs to the rhombohedral space group R3¯ with a = 9.8999(6) Å, b = 9.8999(6) Å, c = 34.208(4) Å, V = 2903.5(4) Å 3 and the ligand L belongs to the orthorhombic space group Pbca with a = 6.9014(12) Å, b = 9.0215(16) Å, c = 15.235(3) Å, V = 948.5(3) Å 3. The structure of 1 exhibits a 2D layer hexagonal network with 18-Mc-6 [Ag 6L 6] metallacrowns as building blocks and every two adjacent silver atoms are bridged through the two nitrogen atoms of N-N bridge of a ligand. Luminescence studies revealed that L and complex 1 exhibit fluorescent emissions in the solid state at room temperature at λmax = 348 and 506 nm, respectively.

  7. Crystal field excitations of YbMn{sub 2}Si{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Mole, R.A. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW 2234 (Australia); School of Physical, Environmental and Mathematical Sciences, The University of New South Wales at the Australian Defence Force Academy, Canberra, ACT 2600 (Australia); Hofmann, M. [School of Physical, Environmental and Mathematical Sciences, The University of New South Wales at the Australian Defence Force Academy, Canberra, ACT 2600 (Australia); Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München, 85747 Garching (Germany); Adroja, D.T. [ISIS Facility, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Didcot, OX11 OQX (United Kingdom); Moze, O. [Dipartimento di Fisica, Università degli Studi di Modena e Reggio Emilia, Modena (Italy); Campbell, S.J., E-mail: stewart.campbell@adfa.edu.au [School of Physical, Environmental and Mathematical Sciences, The University of New South Wales at the Australian Defence Force Academy, Canberra, ACT 2600 (Australia)

    2013-12-15

    The crystal field excitations of the rare earth intermetallic compound YbMn{sub 2}Si{sub 2} have been measured by inelastic neutron scattering over the temperature range 2.5–50 K. The YbMn{sub 2}Si{sub 2} spectra exhibit three low energy excitations (∼3–7 meV) in the antiferromagnetic AFil region above the magnetic phase transition at T{sub N2} = 30(5) K. The crystal field parameters have been determined for YbMn{sub 2}Si{sub 2} in the antiferromagnetic AFil region. A further two inelastic excitations (∼9 meV, 17 meV) are observed below T{sub N2}=30(5) K, the temperature at which the high temperature antiferromagnetic structure is reported to exhibit doubling of the magnetic cell. Energy level diagrams have been determined for Yb{sup 3+} ions in the different sites above (single site) and below the magnetic transition temperature (two sites). The excitation energies for both sites are shown to be temperature independent with the temperature dependences of the transition intensities for the two sites described well by a simple Boltzmann model. The spectra below T{sub N2} cannot be described fully in terms of molecular field models based on either a single Yb{sup 3+} site or two Yb{sup 3+} sites. This indicates that the magnetic behaviour of YbMn{sub 2}Si{sub 2} is more complicated than previously considered. The inability to account fully for excitations below the magnetic phase transition may be due to an, as yet, unresolved structural transition associated with the magnetic transition. - Highlights: • The inelastic neutron scattering from YbMn{sub 2}Si{sub 2} has been investigated over the temperature range 2.5–50 K. • The crystal field splitting has been monitored through the magnetic transition at 30(5) K. • We have determined the crystal field parameters for the antiferromagnetic AFil region. • The transition intensities are described well by Boltzmann occupancy models. • The spectra below the magnetic transition have been analysed by

  8. Direct current electric field assembly of colloidal crystals displaying reversible structural color.

    Science.gov (United States)

    Shah, Aayush A; Ganesan, Mahesh; Jocz, Jennifer; Solomon, Michael J

    2014-08-26

    We report the application of low-voltage direct current (dc) electric fields to self-assemble close-packed colloidal crystals in nonaqueous solvents from colloidal spheres that vary in size from as large as 1.2 μm to as small as 0.1 μm. The assemblies are created rapidly (∼2 min) from an initially low volume fraction colloidal particle suspension using a simple capacitor-like electric field device that applies a steady dc electric voltage. Confocal microscopy is used to observe the ordering that is produced by the assembly method. This spatial evidence for ordering is consistent with the 6-fold diffraction patterns identified by light scattering. Red, green, and blue structural color is observed for the ordered assemblies of colloids with diameters of 0.50, 0.40, and 0.29 μm, respectively, consistent with spectroscopic measurements of reflectance. The diffraction and spectrophotometry results were found to be consistent with the theoretical Bragg's scattering expected for closed-packed crystals. By switching the dc electric field from on to off, we demonstrate reversibility of the structural color response on times scales ∼60 s. The dc electric field assembly method therefore represents a simple method to produce reversible structural color in colloidal soft matter.

  9. Crystallization and preliminary X-ray diffraction analysis of the wild-type haloalkane dehalogenase DhaA and its variant DhaA13 complexed with different ligands.

    Science.gov (United States)

    Stsiapanava, Alena; Chaloupkova, Radka; Fortova, Andrea; Brynda, Jiri; Weiss, Manfred S; Damborsky, Jiri; Smatanova, Ivana Kuta

    2011-02-01

    Haloalkane dehalogenases make up an important class of hydrolytic enzymes which catalyse the cleavage of carbon-halogen bonds in halogenated aliphatic compounds. There is growing interest in these enzymes owing to their potential use in environmental and industrial applications. The haloalkane dehalogenase DhaA from Rhodococcus rhodochrous NCIMB 13064 can slowly detoxify the industrial pollutant 1,2,3-trichloropropane (TCP). Structural analysis of this enzyme complexed with target ligands was conducted in order to obtain detailed information about the structural limitations of its catalytic properties. In this study, the crystallization and preliminary X-ray analysis of complexes of wild-type DhaA with 2-propanol and with TCP and of complexes of the catalytically inactive variant DhaA13 with the dye coumarin and with TCP are described. The crystals of wild-type DhaA were plate-shaped and belonged to the triclinic space group P1, while the variant DhaA13 can form prism-shaped crystals belonging to the orthorhombic space group P2(1)2(1)2(1) as well as plate-shaped crystals belonging to the triclinic space group P1. Diffraction data for crystals of wild-type DhaA grown from crystallization solutions with different concentrations of 2-propanol were collected to 1.70 and 1.26 Å resolution, respectively. A prism-shaped crystal of DhaA13 complexed with TCP and a plate-shaped crystal of the same variant complexed with the dye coumarin diffracted X-rays to 1.60 and 1.33 Å resolution, respectively. A crystal of wild-type DhaA and a plate-shaped crystal of DhaA13, both complexed with TCP, diffracted to atomic resolutions of 1.04 and 0.97 Å, respectively.

  10. Effect of an external magnetic field on polytypism of CdI2 crystals grown from solutions

    International Nuclear Information System (INIS)

    Palosz, B.; Przedmojski, J.

    1982-01-01

    The effect of growth conditions on the polytypic structure of crystals of CdI 2 was analyzed for crystallization from solutions. Three solvents were used: H 2 O, 3 H 2 O + 1 C 2 H 5 OH and 1 H 2 O + 1 C 2 H 5 OH. Crystals were grown at two temperatures: 5 and 25 0 C with low and high growth rates; an external magnetic field of about 0.25 tesla was used. The effect of the above three parameters on the formation of the basic polytypes 2H and 4H and on the ordering of faults in disordered structures and in polytype cells was studied by X-ray analysis of crystal surfaces. Some distinct relations between the polytypic structure of crystals of CdI 2 and the magnetic field were found. (author)

  11. Effects of a High Magnetic Field on the Microstructure of Ni-Based Single-Crystal Superalloys During Directional Solidification

    Science.gov (United States)

    Xuan, Weidong; Lan, Jian; Liu, Huan; Li, Chuanjun; Wang, Jiang; Ren, Weili; Zhong, Yunbo; Li, Xi; Ren, Zhongming

    2017-08-01

    High magnetic fields are widely used to improve the microstructure and properties of materials during the solidification process. During the preparation of single-crystal turbine blades, the microstructure of the superalloy is the main factor that determines its mechanical properties. In this work, the effects of a high magnetic field on the microstructure of Ni-based single-crystal superalloys PWA1483 and CMSX-4 during directional solidification were investigated experimentally. The results showed that the magnetic field modified the primary dendrite arm spacing, γ' phase size, and microsegregation of the superalloys. In addition, the size and volume fractions of γ/ γ' eutectic and the microporosity were decreased in a high magnetic field. Analysis of variance (ANOVA) results showed that the effect of a high magnetic field on the microstructure during directional solidification was significant ( p Ni-based single-crystal superalloy blades by applying a high magnetic field.

  12. Field analysis of TE and TM modes in photonic crystal Bragg fibers by transmission matrix method

    Directory of Open Access Journals (Sweden)

    M Hosseini Farzad

    2010-03-01

    Full Text Available In this article, we considered the field analysis in photonic crystal Bragg fibers. We apply the method of transmission matrix to calculater the dispersion curves, the longitudinal wave number over wave number versus incident wavelength, and the field distributions of TE and TM modes in the Bragg fiber. Our analysis shows that the field of guided modes is confined in the core and can exist only in particular wavelength bands corresponding to the band-gap of the periodic structure of the clad. From another point of view, light confinement is due to Bragg reflection from high-and low-refractive index layers of the clad. Also, the diagram of average angular frequency with respect to average longitudinal wave number is plotted so that the band gap regions of the clad are clearly observed.

  13. Melt Motion Due to Peltier Marking During Bridgman Crystal Growth with an Axial Magnetic Field

    Science.gov (United States)

    Sellers, C. C.; Walker, John S.; Szofran, Frank R.; Motakef, Shariar

    2000-01-01

    This paper treats a liquid-metal flow inside an electrically insulating cylinder with electrically conducting solids above and below the liquid region. There is a uniform axial magnetic field, and there is an electric current through the liquid and both solids. Since the lower liquid-solid interface is concave into the solid and since the liquid is a better electrical conductor than the adjacent solid, the electric current is locally concentrated near the centerline. The return to a uniform current distribution involves a radial electric current which interacts with the axial magnetic field to drive an azimuthal flow. The axial variation of the centrifugal force due to the azimuthal velocity drives a meridional circulation with radial and axial velocities. This problem models the effects of Peltier marking during the vertical Bridgman growth of semiconductor crystals with an externally applied magnetic field, where the meridional circulation due to the Peltier Current may produce important mixing in the molten semiconductor.

  14. Bifurcation properties of nematic liquid crystals exposed to an electric field: Switchability, bistability, and multistability

    KAUST Repository

    Cummings, L. J.

    2013-07-01

    Bistable liquid crystal displays (LCDs) offer the potential for considerable power savings compared with conventional (monostable) LCDs. The existence of two (or more) stable field-free states that are optically distinct means that contrast can be maintained in a display without an externally applied electric field. An applied field is required only to switch the device from one state to the other, as needed. In this paper we examine the basic physical principles involved in generating multiple stable states and the switching between these states. We consider a two-dimensional geometry in which variable surface anchoring conditions are used to control the steady-state solutions and explore how different anchoring conditions can influence the number and type of solutions and whether or not switching is possible between the states. We find a wide range of possible behaviors, including bistability, tristability, and tetrastability, and investigate how the solution landscape changes as the boundary conditions are tuned. © 2013 American Physical Society.

  15. Crystallization and preliminary X-ray diffraction analysis of the wild-type haloalkane dehalogenase DhaA and its variant DhaA13 complexed with different ligands

    International Nuclear Information System (INIS)

    Stsiapanava, Alena; Chaloupkova, Radka; Fortova, Andrea; Brynda, Jiri; Weiss, Manfred S.; Damborsky, Jiri; Kuta Smatanova, Ivana

    2011-01-01

    Crystals of the wild-type haloalkane dehalogenase DhaA derived from R. rhodochrous NCIMB 13064 and of its catalytically inactive variant DhaA13 were grown in the presence of various ligands and diffraction data were collected to high and atomic resolution. Haloalkane dehalogenases make up an important class of hydrolytic enzymes which catalyse the cleavage of carbon–halogen bonds in halogenated aliphatic compounds. There is growing interest in these enzymes owing to their potential use in environmental and industrial applications. The haloalkane dehalogenase DhaA from Rhodococcus rhodochrous NCIMB 13064 can slowly detoxify the industrial pollutant 1,2,3-trichloropropane (TCP). Structural analysis of this enzyme complexed with target ligands was conducted in order to obtain detailed information about the structural limitations of its catalytic properties. In this study, the crystallization and preliminary X-ray analysis of complexes of wild-type DhaA with 2-propanol and with TCP and of complexes of the catalytically inactive variant DhaA13 with the dye coumarin and with TCP are described. The crystals of wild-type DhaA were plate-shaped and belonged to the triclinic space group P1, while the variant DhaA13 can form prism-shaped crystals belonging to the orthorhombic space group P2 1 2 1 2 1 as well as plate-shaped crystals belonging to the triclinic space group P1. Diffraction data for crystals of wild-type DhaA grown from crystallization solutions with different concentrations of 2-propanol were collected to 1.70 and 1.26 Å resolution, respectively. A prism-shaped crystal of DhaA13 complexed with TCP and a plate-shaped crystal of the same variant complexed with the dye coumarin diffracted X-rays to 1.60 and 1.33 Å resolution, respectively. A crystal of wild-type DhaA and a plate-shaped crystal of DhaA13, both complexed with TCP, diffracted to atomic resolutions of 1.04 and 0.97 Å, respectively

  16. AC electric field assisted orientational photorefractive effect in C60-doped nematic liquid crystal

    International Nuclear Information System (INIS)

    Sun Xiudong; Pei Yanbo; Yao Fengfeng; Zhang Jianlong; Hou Chunfeng

    2007-01-01

    Photorefractive gratings were produced in a C 60 -doped nematic liquid crystal cell under the application of two coherent beams and a nonbiased sinusoidal ac electric field. The beam coupling and diffraction of the ac electric field assisted gratings were studied systematically. A stable asymmetric energy transference was obtained. Diffraction was observed when the angle (between the normal of the cell and the bisector of the writing beams) was 0 0 , and the dependence of diffraction efficiency on the peak-to-peak value of the ac voltage was similar to that at an incidence angle of 45 0 , suggesting that the role of the ac field was to facilitate the charge separation, and the space-charge field (SCF) originated predominantly from the diffusion of the ac electric field assisted photo-induced carriers under the application of nonuniform illumination and an applied ac field. The grating was produced by director reorientation induced by the cooperation of the SCF and the applied ac electric field. A self-erasing phenomenon was observed in this cell. An explanation in terms of the movement of two kinds of carriers with opposite signs was proposed

  17. Crystal growth of pure substances: Phase-field simulations in comparison with analytical and experimental results

    Science.gov (United States)

    Nestler, B.; Danilov, D.; Galenko, P.

    2005-07-01

    A phase-field model for non-isothermal solidification in multicomponent systems [SIAM J. Appl. Math. 64 (3) (2004) 775-799] consistent with the formalism of classic irreversible thermodynamics is used for numerical simulations of crystal growth in a pure material. The relation of this approach to the phase-field model by Bragard et al. [Interface Science 10 (2-3) (2002) 121-136] is discussed. 2D and 3D simulations of dendritic structures are compared with the analytical predictions of the Brener theory [Journal of Crystal Growth 99 (1990) 165-170] and with recent experimental measurements of solidification in pure nickel [Proceedings of the TMS Annual Meeting, March 14-18, 2004, pp. 277-288; European Physical Journal B, submitted for publication]. 3D morphology transitions are obtained for variations in surface energy and kinetic anisotropies at different undercoolings. In computations, we investigate the convergence behaviour of a standard phase-field model and of its thin interface extension at different undercoolings and at different ratios between the diffuse interface thickness and the atomistic capillary length. The influence of the grid anisotropy is accurately analyzed for a finite difference method and for an adaptive finite element method in comparison.

  18. Field-induced non-linear optical features of p-aminoazobenzene crystals

    Science.gov (United States)

    Krishnakumar, V.; Eazhilarasi, G.; Nagalakshmi, R.; Piasecki, M.; Kityk, I. V.; Bragiel, P.

    2008-06-01

    Using ethanol as a solvent p-aminoazobenzene (p-AAZB), an organic nonlinear optical crystal having good optical quality was grown by slow evaporation solution technique. Structural and optical properties were studied by applying XRD and UV-Vis spectroscopy. The measurement of the second harmonic generation was performed using the fundamental Nd:YAG 10 ns laser beam with wavelength 1.064 μm. Dependence of the second order susceptibilities for the two principal second order susceptibility tensor components d14 and d25 with the simultaneously applied dc- and UV-laser fields were investigated and discussed.

  19. Near-field imaging of out-of-plane light scattering in photonic crystal slabs

    DEFF Research Database (Denmark)

    Volkov, Valentyn; Bozhevolnyi, Sergey; Taillaert, Dirk

    2003-01-01

    A collection scanning near-field optical microscope (SNOM) is used to image the propagating of light at telecommunication wavelengths (1520-1570 nm) along photonic crystal (PC) slabs, which combine slab waveguides with in-plane PCs consisting of one- and two-dimensional gratings. The efficient out......-of-plane light scattering is directly observed for both 1D and 2D gratings (period 590 nm) fabricated on silicon-on-insulator wafers and the corresponding SNOM images are presented. Using the obtained SNOM images, we analyze light intensity distributions along PC gratings measured at different wavelengths and...

  20. Steady state bifurcations for phase field crystal equations with underlying two dimensional kernel

    Directory of Open Access Journals (Sweden)

    Appolinaire Abourou Ella

    2015-10-01

    Full Text Available This paper is concerned with the study of some properties of stationary solutions to phase field crystal equations bifurcating from a trivial solution. It is assumed that at this trivial solution, the kernel of the underlying linearized operator has dimension two. By means of the multiparameter method, we give a second order approximation of these bifurcating solutions and analyse their stability properties. The main result states that the stability of these solutions can be described by the variation of a certain angle in a two dimensional parameter space. The behaviour of the parameter curve is also investigated.

  1. Calculation of crystal-field parameters for rare-earth noble metal alloys

    Energy Technology Data Exchange (ETDEWEB)

    Steinbeck, L. [MPG Research Group `Electron Systems`, Department of Physics, University of Technology, Mommsenstr. 13, D-01062, Dresden (Germany); Richter, M. [MPG Research Group `Electron Systems`, Department of Physics, University of Technology, Mommsenstr. 13, D-01062, Dresden (Germany); Eschrig, H. [MPG Research Group `Electron Systems`, Department of Physics, University of Technology, Mommsenstr. 13, D-01062, Dresden (Germany); Nitzsche, U. [MPG Research Group `Electron Systems`, Department of Physics, University of Technology, Mommsenstr. 13, D-01062, Dresden (Germany)

    1995-02-09

    The crystal-field (CF) parameters for 4f electrons of a series of rare-earth impurities in Ag and Au have been evaluated from first-principles density functional calculations of the charge distribution which are based on an optimized LCAO scheme. The localized 4f states are treated as `open core shell`. By including the self-interaction correction for the 4f states, artificial constraints on the 4f charge density employed in earlier density functional CF calculations are avoided. The calculated parameters are compared with recent neutron scattering data. ((orig.)).

  2. On-fiber 3D printing of photonic crystal fiber tapers for mode field diameter conversion

    KAUST Repository

    Bertoncini, Andrea

    2017-11-02

    The large mismatch between the Mode Field Diameter (MFD) of conventional single-mode fibers (SMFs) and the MFD of highly nonlinear Photonic Crystal Fibers (PCFs), that can be down to 1.5 μm, or Large Mode Area PCF, that can be up to 25 μm, would require a substantial fiber mode size rescaling in order to allow an efficient direct coupling between PCFs and SMFs. Over the years different solutions have been proposed, as fiber splicing of SMF to PCF. However these procedures are not straightforward, as they involve developing special splicing recipes, and can affect PCF optical properties at the splice interface [1].

  3. Magnetocrystalline anisotropy of cementite pseudo single crystal fabricated under a rotating magnetic field

    Science.gov (United States)

    Yamamoto, Sukeyoshi; Terai, Tomoyuki; Fukuda, Takashi; Sato, Kazunori; Kakeshita, Tomoyuki; Horii, Shigeru; Ito, Mikio; Yonemura, Mitsuharu

    2018-04-01

    We have fabricated a pseudo single crystal of cementite under a rotating magnetic field and investigated its easy and hard axes of magnetization, and determined its magnetocrystalline anisotropy energy. The obtained results are as follows: the hard and easy axes of cementite are the a- and c-axes of the orthorhombic structure with the space group Pnma, respectively. The hard axis observed experimentally was in good agreement with that obtained by an ab initio calculation; however, such consistency was not observed for the easy axis. The magnetocrystalline anisotropy energy was determined as 334 ± 20 kJ/m3 at 5 K.

  4. Why zinc fingers prefer zinc: ligand-field symmetry and the hidden thermodynamics of metal ion selectivity.

    Science.gov (United States)

    Lachenmann, Marcel J; Ladbury, John E; Dong, Jian; Huang, Kun; Carey, Paul; Weiss, Michael A

    2004-11-09

    The zinc finger, a motif of protein-nucleic acid recognition broadly conserved among eukaryotes, is a globular minidomain containing a tetrahedral metal-binding site. Preferential coordination of Zn(2+) (relative to Co(2+)) is proposed to reflect differences in ligand-field stabilization energies (LFSEs) due to complete or incomplete occupancy of d orbitals. LFSE predicts that the preference for Zn(2+) should be purely enthalpic in accord with calorimetric studies of a high-affinity consensus peptide (CP-1; Blasie, C. A., and Berg, J. (2002) Biochemistry 41, 15068-73). Despite its elegance, the general predominance of LFSE is unclear as (i) the magnitude by which CP-1 prefers Zn(2+) is greater than that expected and (ii) the analogous metal ion selectivity of a zinc metalloenzyme (carbonic anhydrase) is driven by changes in entropy rather than enthalpy. Because CP-1 was designed to optimize zinc binding, we have investigated the NMR structure and metal ion selectivity of a natural finger of lower stability derived from human tumor-suppressor protein WT1. Raman spectroscopy suggests that the structure of the WT1 domain is unaffected by interchange of Zn(2+) and Co(2+). As in CP-1, preferential binding of Zn(2+) (relative to Co(2+)) is driven predominantly by differences in enthalpy, but in this case the enthalpic advantage is less than that predicted by LFSE. A theoretical framework is presented to define the relationship between LFSE and other thermodynamic factors, such as metal ion electroaffinities, enthalpies of hydration, and the topography of the underlying folding landscape. The contribution of environmental coupling to entropy-enthalpy compensation is delineated in a formal thermodynamic cycle. Together, these considerations indicate that LFSE provides an important but incomplete description of the stringency and thermodynamic origin of metal-ion selectivity.

  5. A Phase Field Technique for Modeling and Predicting Flow Induced Crystallization Morphology of Semi-Crystalline Polymers

    Directory of Open Access Journals (Sweden)

    Xiaodong Wang

    2016-06-01

    Full Text Available Flow induced crystallization of semi-crystalline polymers is an important issue in polymer science and engineering because the changes in morphology strongly affect the properties of polymer materials. In this study, a phase field technique considering polymer characteristics was established for modeling and predicting the resulting morphologies. The considered crystallization process can be divided into two stages, which are nucleation upon the flow induced structures and subsequent crystal growth after the cessation of flow. Accordingly, the proposed technique consists of two parts which are a flow induced nucleation model based on the calculated information of molecular orientation and stretch, and a phase field crystal growth model upon the oriented nuclei. Two-dimensional simulations are carried out to predict the crystallization morphology of isotactic polystyrene under an injection molding process. The results of these simulations demonstrate that flow affects crystallization morphology mainly by producing oriented nuclei. Specifically, the typical skin-core structures along the thickness direction can be successfully predicted. More importantly, the results reveal that flow plays a dominant part in generating oriented crystal morphologies compared to other parameters, such as anisotropy strength, crystallization temperature, and physical noise.

  6. The effect of stationary and sweeping frequency AC electric fields on frost crystal removal on a cold plate

    Energy Technology Data Exchange (ETDEWEB)

    Tudor, V. [US Naval Academy, Annapolis, MD (United States). Advanced Thermal Systems Laboratory, Mechanical Engineering Department; Ohadi, M. [University of Maryland, College Park, MD (United States). Smart and Small Thermal Systems Laboratory, Mechanical Engineering Department

    2006-06-15

    The effect of stationary and sweeping frequency AC electric fields on frost crystals growth and frost control/removal on a cold plate was studied for the first time in this paper. The main results of this study showed that the presence of AC electric fields can greatly affect both the frost crystals growth pattern and mass accumulation on cold surfaces. The ice surface electrical properties and basic electrostatics were used to explain the main findings in this paper. Up to 46% frost reduction was obtained when the electric field frequency spanned 370Hz to 7.5kHz while the applied voltage was 14.5kV. Two different sets of environmental conditions were tested, which showed that the plate temperature placed an important effect on frost crystals growth under electric fields. An optimum application time of the AC electric fields was found based on least frost mass accumulation on the cold plate. (author)

  7. Copper in the terrestrial environment: Verification of a laboratory-derived terrestrial biotic ligand model to predict earthworm mortality with toxicity observed in field soils

    OpenAIRE

    Koster, Marijke; Groot, Arthur de; Vijver, Martina G; Peijnenburg, Willie J G M

    2006-01-01

    This study was set up for validation of a regression model to predict mortality in the terrestrial earthworm Aporrectodea caliginosa following exposure to copper. This model was derived from a terrestrial biotic ligand model and incorporates the protective effects of H+ and Na+ on copper toxicity. Three soil sets were used for the experiments, all of which had a different copper contamination history over more than 20 years and were considered to be aged field soils. The soils were characteri...

  8. Thermal field emission observation of single-crystal LaB6

    International Nuclear Information System (INIS)

    Nagata, H.; Harada, K.; Shimizu, R.

    1990-01-01

    TFE (thermal field emission) properties of LaB 6 left-angle 100 right-angle and left-angle 310 right-angle single crystals were investigated by emission pattern observation. It was found that field evaporation with the tip temperature held at ∼1500 degree C is very useful to get a clean pattern of fourfold symmetry. Each of four bright spots in the clean pattern was presumed to correspond to left-angle 310 right-angle emission. It is proposed, as the most appropriate operating condition, to use the left-angle 310 right-angle LaB 6 tip at a temperature ∼1000 degree C in vacuum of 10 -9 Torr region, promising a new TF emitter of high brightness and stability for practical use

  9. Response of Ferroelectric Molecules in Liquid Crystal Display under an Applied Electric Field

    Science.gov (United States)

    Takei, Misaki; Shirochi, Hideki; Yamashita, Masafumi

    2007-09-01

    The dynamic changes of ferroelectric liquid crystal (FLC) molecular alignments under the applied electric field were examined by observing the formation of conoscopic figures with a time resolution of 0.1 ms, which reflect the temporal and spatial dependences of the LC molecular alignments on the azimuthal angle. By a detailed comparison of the experimental conoscopic figures with simulated figures, the molecules began to shift from the central portion of the helix to the outer ends within 0.1 ms following application of the electric field. The positions of molecular layers having the fastest moving velocity (Δφ/Δ t) corresponded to the positions with the azimuthal angles of π/2 and 3π/2rad.

  10. Extensional flow of nematic liquid crystal with an applied electric field

    KAUST Repository

    CUMMINGS, L. J.

    2013-10-17

    Systematic asymptotic methods are used to formulate a model for the extensional flow of a thin sheet of nematic liquid crystal. With no external body forces applied, the model is found to be equivalent to the so-called Trouton model for Newtonian sheets (and fibres), albeit with a modified \\'Trouton ratio\\'. However, with a symmetry-breaking electric field gradient applied, behaviour deviates from the Newtonian case, and the sheet can undergo finite-time breakup if a suitable destabilizing field is applied. Some simple exact solutions are presented to illustrate the results in certain idealized limits, as well as sample numerical results to the full model equations. Copyright © Cambridge University Press 2013.

  11. Precise Patterning of Organic Single Crystals via Capillary-Assisted Alternating-Electric Field.

    Science.gov (United States)

    Zhang, Yedong; Jie, Jiansheng; Sun, Yuning; Jeon, Seok-Gy; Zhang, Xiujuan; Dai, Gaole; Lee, Cheol Jin; Zhang, Xiaohong

    2017-07-01

    Owing to the extraordinary properties, organic micro/nanocrystals are important building blocks for future low-cost and high-performance organic electronic devices. However, integrated device application of the organic micro/nanocrystals is hampered by the difficulty in high-throughput, high-precision patterning of the micro/nanocrystals. In this study, the authors demonstrate, for the first time, a facile capillary-assisted alternating-electric field method for the large-scale assembling and patterning of both 0D and 1D organic crystals. These crystals can be precisely patterned at the photolithography defined holes/channels at the substrate with the yield up to 95% in 1 mm 2 . The mechanism of assembly kinetics is systematically studied by the electric field distribution simulation and experimental investigations. By using the strategy, various organic micro/nanocrystal patterns are obtained by simply altering the geometries of the photoresist patterns on substrates. Moreover, ultraviolet photodetectors based on the patterned Alq3 micro/nanocrystals exhibit visible-blind photoresponse with high sensitivity as well as excellent stability and reproducibility. This work paves the way toward high-integration, high-performance organic electronic, and optoelectronic devices from the organic micro/nanocrystals. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. EPR studies of excited state exchange and crystal-field effects in rare earth compounds

    International Nuclear Information System (INIS)

    Huang, C.Y.; Sugawara, K.; Cooper, B.R.

    1976-01-01

    EPR in excited crystal-field states of Tm 3+ , Pr 3+ , and Tb 3+ in singlet-ground-state systems and in the excited state of Ce 3+ in CeP are reviewed. Because one is looking at a crystal-field excited state resonance, the exchange, even if isotropic, does not act as a secular perturbation. This means that one obtains different effects and has access to more information about the dynamic effects of exchange than in conventional paramagnetic resonance experiments. The Tm and Pr monopnictides studied are paramagnetic at all temperatures. The most striking feature of the behavior of the GAMMA 5 /sup (2)/ EPR in the Tm compounds is the presence of an anomalous maximum in the temperature dependence of the g-factor. The relationship of this effect to anisotropic exchange is discussed. The results of the EPR of the excited GAMMA 5 /sup (2)/ level of Tb 3 + (g-factor becomes very large at T/sub N/ in antiferromagnetic TbX (X = P, As, Sb) and that of the excited GAMMA 8 level of Ce 3+ in antiferromagnetic CeP will also be reported. For sufficient dilution of the Tb 3+ in the terbium monopnictides, the systems become paramagnetic (Van Vleck paramagnets) down to 0 0 K. The Tb 3+ excited state resonance EPR in Tb/sub 0.1/ La/sub 0.9/P was studied as an example of behavior in such systems. 10 fig

  13. From ligand fields to molecular orbitals: probing the local valence electronic structure of Ni(2+) in aqueous solution with resonant inelastic X-ray scattering.

    Science.gov (United States)

    Kunnus, Kristjan; Josefsson, Ida; Schreck, Simon; Quevedo, Wilson; Miedema, Piter S; Techert, Simone; de Groot, Frank M F; Odelius, Michael; Wernet, Philippe; Föhlisch, Alexander

    2013-12-27

    Bonding of the Ni(2+)(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d-3d electron correlation interactions in the Ni(2+)(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d-3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV-vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.

  14. Confined photovoltaic fields in a photo-responsive liquid crystal test cell

    Science.gov (United States)

    Habibpourmoghadam, Atefeh; Jiao, Lin; Omairat, Faissal; Evans, Dean R.; Lucchetti, Liana; Reshetnyak, Viktor; Lorenz, Alexander

    2017-08-01

    Exciting experimental results on the response properties of hybridized photo responsive liquid crystal test cells are reported, where iron doped lithium niobate substrates were used to photo generate electric fields and indium tin oxide coated cover glasses were used to confine these photo generated fields in a liquid crystal layer. Samples were investigated in a modified inverted optical polarizing microscope with white probe light (crossed polarizers) and exposed with a Gaussian laser beam focused to a small spot (14 μm FWHM). Test cells filled with nematic LC showed homeotropic director alignment. Upon exposure, this alignment was maintained at the exposure spot center and the LC director was selectively realigned in a surrounding single ring. This ring had a thickness of a few microns and its diameter increased with increasing exposure intensity (112 μm at 0.7 mW, 204 μm at 1.1 mW). This characteristic director realignment was traced back to the optically generated electric field distributions by simulations. In samples filled with chiral nematic LC, uniformly standing helix alignment was found. Textural transitions were induced at the focus position, which again led to the formation of well-defined circular defects. We could show that these defects can be permanently stored within the chiral nematic LC. Polarized optical microscopy of a rotated sample revealed that a point like defect with +1 topological charge was enclosed in each of these defects. Photovoltaic fields generated in small lithium niobate particles dispersed in a LC were found to cause promising optical responses and particle movement.

  15. New Mn(II, Ni(II, Cd(II, Pb(II complexes with 2-methylbenzimidazole and other ligands. Synthesis, spectroscopic characterization, crystal structure, magnetic susceptibility and biological activity studies

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker

    2016-11-01

    Full Text Available Synthesis and characterization of Mn(II, Ni(II, Cd(II and Pb(II mixed ligand complexes of 2-methylbenzimidazole with other ligands have been reported. The structure of the ligands and their complexes was investigated using elemental analysis, IR, UV–Vis, (1H, 13C NMR spectroscopy, molar conductivity and magnetic susceptibility measurements. In all the studies of complexes, the 2-methylbenzimidazole behaves as a neutral monodentate ligand which is coordinated with the metal ions through the N atom. While benzotriazole behaves as a neutral bidentate ligand which is coordinated with the Ni(II ion through the two N atoms. Moreover, the N-acetylglycine behaves as a bidentate ligand which is coordinated with the Mn(II, Ni(II and Pb(II ions through the N atom and the terminal carboxyl oxygen atom. The magnetic and spectral data indicate the tetrahedral geometry for Mn(II complex, irregular tetrahedral geometry for Pb(II complex and octahedral geometry for Ni(II complex. The X-ray single crystal diffraction method was used to confirm a centrosymmetric dinuclear Cd(II complex as each two metal ions are linked by a pair of thiocyanate N = S bridge. Two 2-methylbenzimidazole N-atom donors and one terminal thiocyanate N atom complete a highly distorted square pyramid geometry around the Cd atom. Besides, different cell types were used to determine the inhibitory effect of Mn(II, Ni(II, Cd(II and Pb(II complexes on cell growth using MTT assay. Cd(II complex showed cytotoxic effect on various types of cancer cell lines with different EC50 values.

  16. A new 1D manganese(II) coordination polymer with end-to-end azide bridge and isonicotinoylhydrazone Schiff base ligand: Crystal structure, Hirshfeld surface, NBO and thermal analyses

    Science.gov (United States)

    Khani, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

    2018-02-01

    A new manganese (II) coordination polymer, [MnL2 (μ-1,3-N3)2]n, with co-ligands including azide anion and Schiff base based on isonicotinoylhydrazone has been synthesized and characterized. The crystal structure determination shows that the azide ligand acts as end-to-end (EE) bridging ligand and generates a one-dimensional coordination polymer. In this compound, each manganes (II) metal center is hexa-coordinated by four azide nitrogens and two pyridinic nitrogens for the formation of octahedral geometry. The analysis of crystal packing indicates that the 1D chain of [MnL2 (μ-1,3-N3)2]n, is stabilized as a 3D supramolecular network by intra- and inter-chain intermolecular interactions of X-H···Y (X = N and C, Y = O and N). Hirshfeld surface analysis and 2D fingerprint plots have been used for a more detailed investigation of intermolecular interactions. Also, natural bond orbital (NBO) analysis was performed to get information about atomic charge distributions, hybridizations and the strength of interactions. Finally, thermal analysis of compound showed its complete decomposition during three thermal steps.

  17. Crystal structure of a helical silver(I coordination polymer based on an unsymmetrical dipyridyl ligand: catena-poly[[silver(I-μ-N-(pyridin-4-ylmethylpyridine-3-amine-κ2N:N′] tetrafluoridoborate methanol hemisolvate

    Directory of Open Access Journals (Sweden)

    Suk-Hee Moon

    2015-11-01

    Full Text Available The asymmetric unit of the title compound, {[AgL]·BF4·0.5CH3OH}n, L = N-(pyridin-4-ylmethylpyridine-3-amine, C11H11N3, contains one AgI ion, one ligand L, one tetrafluoridoborate anion disordered over two orientations in a 0.669 (13:0.331 (13 ratio and one half of a methanol solvent molecule situated on an inversion center. Each AgI ion is coordinated by two N atoms from two L ligands in a distorted linear geometry [N—Ag—N = 174.70 (19°]. Each L ligand bridges two AgI ions, thus forming polymeric helical chains propagating in [010]. In the crystal, Ag...Ag [3.3369 (10 Å] and π–π interactions between the aromatic rings [centroid-to-centroid distance = 3.676 (4 Å] link these chains into layers parallel to (10-1. Ag...F and weak N(C—H...F interactions further consolidate the crystal packing.

  18. Crystal structure of di-μ-chlorido-bis[dichloridobis(methanol-κOiridium(III] dihydrate: a surprisingly simple chloridoiridium(III dinuclear complex with methanol ligands

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola

    2015-05-01

    Full Text Available The reaction between IrCl3·xH2O in methanol led to the formation of small amounts of the title compound, [Ir2Cl6(CH3OH4]·2H2O, which consists of two IrCl4O2 octahedra sharing an edge via chloride bridges. The molecule lies across an inversion center. Each octahedron can be envisioned as being comprised of four chloride ligands in the equatorial plane with methanol ligands in the axial positions. A lattice water molecule is strongly hydrogen-bonded to the coordinating methanol ligands and weak interactions with coordinating chloride ligands lead to the formation of a three-dimensional network. This is a surprising structure given that, while many reactions of iridium chloride hydrate are carried out in alcoholic solvents, especially methanol and ethanol, this is the first structure of a chloridoiridium compound with only methanol ligands.

  19. Phase Transition for a Mixed Spin-1/2 and Spin-SB System with a Transverse Crystal Field

    Science.gov (United States)

    Jiang, Wei; Xiao, Gui-Bin; Wei, Guo-Zhu; Du, An; Zhang, Qi

    2004-01-01

    The critical behaviors of a mixed spin-1/2 and spin-sB Ising system with a transverse crystal field are studied by use of the effective-field theory with correlations. The effect of the transverse crystal field on transition temperatures is investigated numerically for the honeycomb (z = 3) and square (z = 4) lattices. The results show that there is no tricritical point for the system. The project supported by Science Foundation of the Ministry of Education of China under Grant No. 99026

  20. Viewing angle switching of liquid crystal display using fringe-field switching to control off-axis phase retardation

    International Nuclear Information System (INIS)

    Lim, Young Jin; Kim, Jin Ho; Her, Jung Hwa; Lee, Seung Hee; Park, Kyoung Ho; Lee, Joun Ho; Kim, Byeong Koo; Kang, Wan-Seok; Lee, Gi-Dong

    2010-01-01

    A viewing angle switchable liquid crystal display associated with fringe-field switching mode is proposed. In the device, one pixel is composed of a main pixel and a sub-pixel, in which both pixels are formed to generate a fringe electric field. However, the field directions are different from each other so that in the main pixel, the fringe field rotates the liquid crystal for displaying the main image, whereas it controls only the tilt angle of the liquid crystal without rotating in the sub-pixel region. In this way, phase retardation to cause leakage of light at the off-normal axis can be generated in the sub-pixel, and by utilizing the light, the main displayed image in the normal direction can be blocked in the oblique viewing direction.

  1. Viewing angle switching of liquid crystal display using fringe-field switching to control off-axis phase retardation

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Young Jin; Kim, Jin Ho; Her, Jung Hwa; Lee, Seung Hee [Polymer BIN Fusion Research Center, Department of Polymer Nano-Science and Technology, Chonbuk National University, Chonju, Chonbuk 561-756 (Korea, Republic of); Park, Kyoung Ho; Lee, Joun Ho; Kim, Byeong Koo [Mobile Product Development Department, LG Display Company, Ltd, Gumi, Gyungbuk 730-350 (Korea, Republic of); Kang, Wan-Seok; Lee, Gi-Dong, E-mail: gdlee@dau.ac.k, E-mail: lsh1@chonbuk.ac.k [Department of Electronics Engineering, Dong-A University, Pusan 604-714 (Korea, Republic of)

    2010-03-03

    A viewing angle switchable liquid crystal display associated with fringe-field switching mode is proposed. In the device, one pixel is composed of a main pixel and a sub-pixel, in which both pixels are formed to generate a fringe electric field. However, the field directions are different from each other so that in the main pixel, the fringe field rotates the liquid crystal for displaying the main image, whereas it controls only the tilt angle of the liquid crystal without rotating in the sub-pixel region. In this way, phase retardation to cause leakage of light at the off-normal axis can be generated in the sub-pixel, and by utilizing the light, the main displayed image in the normal direction can be blocked in the oblique viewing direction.

  2. Synthesis and crystal structure of a copper complex with (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one ligand

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shu-Wen, E-mail: sunsw0819@163.com [Yuncheng University, Department of Applied Chemistry (China); Zhang, Xiao, E-mail: zhangx@hit.edu.cn [Harbin Institute of Technology, Academy of Fundamental and Interdisciplinary Science (China); Wang, Gao-Feng [Yuncheng University, Department of Applied Chemistry (China)

    2015-12-15

    The title compound, C{sub 35}H{sub 23}CuF{sub 6}N{sub 3}O{sub 5}S{sub 2} (1), was synthesized by the reaction of Cu(tta){sub 2} and L{sup 1}, (L{sup 1} = (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one) in the dichloromethane solution. It crystallizes in the monoclinic, space group P2{sub 1}/c with a = 33.8388(5), b = 9.3874(2), c = 21.8194(4) Å, β = 95.522(2), V = 6898.9(2) Å{sup 3}, Z = 8, D{sub x} = 1.554 Mg/m{sup 3}, F(000) = 3272, µ = 0.834 mm{sup –1}, R{sub 1} = 0.0639, wR{sub 2} = 0.1637. The copper(II) ion of 1 is in a distorted square-pyramidal environment with four O atoms of the two tta ligands and one N atom of triazole ligand L{sup 1}. Single-crystal X-ray diffraction data revealed that the hydrogen bonds, weak C–H···π and π···π interactions in the crystals link the coordination units to form 3D supramolecular structures.

  3. Synthesis and crystal structure of a copper complex with (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one ligand

    International Nuclear Information System (INIS)

    Sun, Shu-Wen; Zhang, Xiao; Wang, Gao-Feng

    2015-01-01

    The title compound, C 35 H 23 CuF 6 N 3 O 5 S 2 (1), was synthesized by the reaction of Cu(tta) 2 and L 1 , (L 1 = (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one) in the dichloromethane solution. It crystallizes in the monoclinic, space group P2 1 /c with a = 33.8388(5), b = 9.3874(2), c = 21.8194(4) Å, β = 95.522(2), V = 6898.9(2) Å 3 , Z = 8, D x = 1.554 Mg/m 3 , F(000) = 3272, µ = 0.834 mm –1 , R 1 = 0.0639, wR 2 = 0.1637. The copper(II) ion of 1 is in a distorted square-pyramidal environment with four O atoms of the two tta ligands and one N atom of triazole ligand L 1 . Single-crystal X-ray diffraction data revealed that the hydrogen bonds, weak C–H···π and π···π interactions in the crystals link the coordination units to form 3D supramolecular structures

  4. Liquid crystal tunable photonic crystal dye laser

    DEFF Research Database (Denmark)

    Buss, Thomas; Christiansen, Mads Brøkner; Smith, Cameron

    2010-01-01

    We present a dye-doped liquid crystal laser using a photonic crystal cavity. An applied electric field to the liquid crystal provides wavelength tunability. The photonic crystal enhances resonant interaction with the gain medium.......We present a dye-doped liquid crystal laser using a photonic crystal cavity. An applied electric field to the liquid crystal provides wavelength tunability. The photonic crystal enhances resonant interaction with the gain medium....

  5. Efficient hydrolytic cleavage of plasmid DNA by chloro-cobalt(II) complexes based on sterically hindered pyridyl tripod tetraamine ligands: synthesis, crystal structure and DNA cleavage.

    Science.gov (United States)

    Massoud, Salah S; Perkins, Richard S; Louka, Febee R; Xu, Wu; Le Roux, Anne; Dutercq, Quentin; Fischer, Roland C; Mautner, Franz A; Handa, Makoto; Hiraoka, Yuya; Kreft, Gabriel L; Bortolotto, Tiago; Terenzi, Hernán

    2014-07-14

    Four new cobalt(ii) complexes [Co(6-MeTPA)Cl]ClO4/PF6 (2/2a), [Co(6-Me2TPA)Cl]ClO4/PF6 (3/3a), [Co(BPQA)Cl]ClO4/PF6 (4/4a) and [Co(BQPA)Cl]ClO4/PF6 (5/5a) as well as [Co(TPA)Cl]ClO4 (1) where TPA = tris(2-pyridylmethyl)amine, 6-MeTPA = ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine, 6-Me2TPA = bis(6-methyl-2-pyridyl)methyl)-(2-pyridylmethyl)amine, BPQA = bis(2-pyridylmethyl)-(2-quinolylmethyl)-amine and BQPA = bis(2-quinolylmethyl)-(2-pyridylmethyl)amine were synthesized and structurally characterized. Single crystal X-ray crystallography confirmed the distorted trigonal bipyramidal geometries of complexes 2a-5a. Spectrophotometric titrations and conductivity measurements of the complexes in the CH3CN-H2O mixture showed that the chloro complexes exist in equilibrium with the corresponding hydrolyzed aqua species, [Co(L)(H2O)](2+). The pKa values of the coordinated H2O in aqua complexes vary from 8.4 to 8.7 (37 °C). The interactions of the complexes (1-5) with DNA have been investigated at pH = 7.0 and 9.0 (10 mM Tris-HCl buffer) and 37 °C where very high catalytic cleavage was observed. Under pseudo Michaelis-Menten kinetic conditions, the catalytic rate constants, kcat, decrease in the order 4>2>5>1>3. At pH 7.0 (10 mM Tris-HCl buffer) and 37 °C, the kcat value for complex 4 (6.02 h(-1)), where [Co(BPQA)(H2O)](2+) is the major species, corresponds to 170 million rate enhancement over the non-catalyzed DNA. Electrophoretic experiments conducted in the presence and absence of radical scavengers (DMSO, KI, NaN3) ruled out the oxidative mechanistic pathway of the reaction and suggested that the hydrolytic mechanism is the preferred one. This finding was in agreement with the observed increase in the kcat values at pH 9.0 compared to the corresponding values at pH 7.0 as a result of the increased concentration of the reactive hydroxo species, [Co(L)(OH)](+). The reactivity of the synthesized complexes in catalyzing the DNA cleavage is discussed in relation to

  6. Field-controllable Spin-Hall Effect of Light in Optical Crystals: A Conoscopic Mueller Matrix Analysis.

    Science.gov (United States)

    Samlan, C T; Viswanathan, Nirmal K

    2018-01-31

    Electric-field applied perpendicular to the direction of propagation of paraxial beam through an optical crystal dynamically modifies the spin-orbit interaction (SOI), leading to the demonstration of controllable spin-Hall effect of light (SHEL). The electro- and piezo-optic effects of the crystal modifies the radially symmetric spatial variation in the fast-axis orientation of the crystal, resulting in a complex pattern with different topologies due to the symmetry-breaking effect of the applied field. This introduces spatially-varying Pancharatnam-Berry type geometric phase on to the paraxial beam of light, leading to the observation of SHEL in addition to the spin-to-vortex conversion. A wave-vector resolved conoscopic Mueller matrix measurement and analysis provides a first glimpse of the SHEL in the biaxial crystal, identified via the appearance of weak circular birefringence. The emergence of field-controllable fast-axis orientation of the crystal and the resulting SHEL provides a new degree of freedom for affecting and controlling the spin and orbital angular momentum of photons to unravel the rich underlying physics of optical crystals and aid in the development of active photonic spin-Hall devices.

  7. Syntheses, characterization, superoxide dismutase, antimicrobial, crystal structure and molecular studies of copper (II) and nickel (II) complexes with 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol as Schiff base ligand

    Science.gov (United States)

    Bharti, Sulakshna; Choudhary, Mukesh; Mohan, Bharti; Rawat, S. P.; Sharma, S. R.; Ahmad, Khursheed

    2017-12-01

    Three new copper (II) and nickel (II) complexes viz. [Cu(L)2](1a), [Cu(L)2](1b) and [Ni(L)2].DMF(2), where HL = 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol, have been synthesized and characterized by using various physico-chemical and spectroscopic techniques. The crystal structures of Schiff base (HL) and their metal complexes (1a), (1b) and (2) were determined by single crystal X-ray diffraction. IR and UV-Vis spectra and magnetic susceptibility measurements agree with the observed crystal structures. The crystallographic and spectroscopic studies confirmed four coordinate environments around the metal (II) ions. The synthesized Schiff base ligand (HL) crystallizes in the orthorhombic system of the space group Pbca. Complex (1a) of HL was crystallized in the monoclinic system of the space group P21/c, a = 10.1712(9) Å, b = 10.9299(10) Å,c = 12.7684(11) Å,α = 90̊,β = 104.649(2)̊, γ = 90̊ and Z = 2 whereas complex (1b) and (2) crystallized in the triclinic system of the space group P-1, a = 11.499(5)Å, b = 11.598(5)Å, c = 12.211(5)Å, α = 98.860(5), β = 115.653(5),γ = 100.906(5) and Z = 2 for (1b), a = 9.080(6) Å, b = 9.545(8)Å, c = 9.545(8)Å, α = 101.43(4)º,β = 99.63(3)̊, γ = 117.71(2)º and Z = 1 for (2). The synthesized ligand (HL) was behaved as monobasic bidentate Schiff base ligand having N and O donor sites. The electron paramagnetic resonance spectra indicate a dx2-y2ground state (g|| > g⊥> 2.0023) for (1a) and (1b). Copper (II) complexes display X-band EPR spectra in 100% DMSO and 77 K, giving indicating dx2-y2ground state. Superoxide dismutase-like activities of HL and its complexes were investigated by nitrobluetetrazolium chloride-DMSO assay and IC50 values were evaluated. These complexes were also tested for their in vitro antimicrobial activities against two bacteria (E. coli and Salmonella typhi) and two fungi (Pencillium, Aspergillus sp.) comparing with the Schiff base. The antimicrobial results showed that the

  8. Scanning near-field optical microscopy-based study of local dynamics of receptor-ligand interactions at the single molecule level

    Science.gov (United States)

    Mensi, M.; Dukenbayev, K.; Sekatskii, S. K.; Dietler, G.

    2010-01-01

    A scanning near-field optical microscope (SNOM)—based modification of the method to study the dynamics of single molecule receptor—ligand interactions exploiting the fluorescence imaging by total internal reflection fluorescence microscopy is introduced. The main advantage of this approach consists in the possibility to study the single molecule interaction dynamics with a subwavelength spatial resolution and a submillisecond time resolution. Additionally, due to the much smaller irradiation area and some other technical features, such a modification enables to enlarge the scope of the receptor—ligand pairs to be investigated and to improve the temporal resolution. We briefly discuss corresponding experimental set up with a special accent on the SNOM operation in liquid and present some preliminary results of related investigations.

  9. Electric-field gradient characterization at 181Ta impurities in sapphire single crystals

    International Nuclear Information System (INIS)

    Renteria, M.; Darriba, G.N.; Errico, L.A.; Munoz, E.L.; Eversheim, P.D.

    2005-01-01

    We report Perturbed-Angular-Correlation (PAC) experiments on corundum Al 2 O 3 single crystals implanted with 181 Hf/ 181 Ta ions at the ISKP at Bonn and measured at La Plata with high efficiency and time-resolution. The magnitude, asymmetry, and orientation (with respect to the crystalline axes) of the electric-field gradient (EFG) tensor were determined measuring the spin-rotation curves as a function of different orientations of the single crystals relative to the detector system. These results are analyzed in the framework of point-charge model and ab initio Full-Potential Linearized-Augmented Plane Wave calculations, and compared with EFG results coming from PAC experiments with 111 In/ 111 Cd impurities. This combined study enables the determination of lattice relaxations induced by the presence of the impurity and the state of charge of a deep impurity donor level in the band gap of the semiconductor. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  10. Electric-field gradient characterization at {sup 181}Ta impurities in sapphire single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Renteria, M.; Darriba, G.N.; Errico, L.A.; Munoz, E.L. [Departamento de Fisica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CC 67, 1900 La Plata (Argentina); Eversheim, P.D. [Helmholtz-Institut fuer Strahlen-und Kernphysik (ISKP), Universitaet Bonn, Nussallee 14-16, 53115 Bonn (Germany)

    2005-07-01

    We report Perturbed-Angular-Correlation (PAC) experiments on corundum Al{sub 2}O{sub 3} single crystals implanted with {sup 181}Hf/{sup 181}Ta ions at the ISKP at Bonn and measured at La Plata with high efficiency and time-resolution. The magnitude, asymmetry, and orientation (with respect to the crystalline axes) of the electric-field gradient (EFG) tensor were determined measuring the spin-rotation curves as a function of different orientations of the single crystals relative to the detector system. These results are analyzed in the framework of point-charge model and ab initio Full-Potential Linearized-Augmented Plane Wave calculations, and compared with EFG results coming from PAC experiments with {sup 111}In/{sup 111}Cd impurities. This combined study enables the determination of lattice relaxations induced by the presence of the impurity and the state of charge of a deep impurity donor level in the band gap of the semiconductor. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Evidence of two-dimensional quantum Wigner Crystal in a zero magnetic field

    Science.gov (United States)

    Huang, Jian; Pfeiffer, Loren; West, Ken

    2014-03-01

    In disorder-dominated cases, Anderson localization occurs as a result of destructive interference effects caused by (short-ranged) random disorders. On the other hand, in interaction-dominated scenarios, striking manifestations of quantum physics emerge in response to strong inter-particle Coulomb energy (EC). The most prominent interaction-driven effect is the Wigner crystallization (WC) of electrons, an electron solid made up with spatially separated charges settling in a form of a lattice. The classical version of the crystallization, with the Debye temperature ΘD desired quantum version with the Fermi energy EF <field. We present a transport study of ultra-high quality dilute two-dimensional hole (2DH) systems in a genuine interaction-driven regime. A high resolution dc VI measurement reveals a pA level threshold transport accompanied by resistivity oscillations, indicating the coexistence of a pinned quantum WC with discrete edge filaments of unpinned carriers. NSF DMR 1105183

  12. Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

    Science.gov (United States)

    Gaudet, J.; Hallas, A. M.; Kolesnikov, A. I.; Gaulin, B. D.

    2018-01-01

    We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er2B2O7 with B =Ge , Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4 f11Er3 + and nonmagnetic B4 +. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er2B2O7 pyrochlores. The different ionic sizes associated with different nonmagnetic B4 + cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise to different local environments at the Er3 + site. Our results show that the g -tensor components are X Y -like for all four members of the Er2B2O7 series. However, the X Y anisotropy is much stronger for Er2Pt2O7 and Er2Sn2O7(g⊥/gz>25 ) than for Er2Ge2O7 and Er2Ti2O7(g⊥/gz<4 ) . The variation in the nature of the X Y anisotropy in these systems correlates strongly with their ground states as Er2Ge2O7 and Er2Ti2O7 order into Γ5 magnetic structures, whereas Er2Pt2O7 and Er2Sn2O7 order in the Γ7 Palmer-Chalker structure.

  13. A statistical analysis of the elastic distortion and dislocation density fields in deformed crystals

    KAUST Repository

    Mohamed, Mamdouh S.

    2015-05-18

    The statistical properties of the elastic distortion fields of dislocations in deforming crystals are investigated using the method of discrete dislocation dynamics to simulate dislocation structures and dislocation density evolution under tensile loading. Probability distribution functions (PDF) and pair correlation functions (PCF) of the simulated internal elastic strains and lattice rotations are generated for tensile strain levels up to 0.85%. The PDFs of simulated lattice rotation are compared with sub-micrometer resolution three-dimensional X-ray microscopy measurements of rotation magnitudes and deformation length scales in 1.0% and 2.3% compression strained Cu single crystals to explore the linkage between experiment and the theoretical analysis. The statistical properties of the deformation simulations are analyzed through determinations of the Nye and Kröner dislocation density tensors. The significance of the magnitudes and the length scales of the elastic strain and the rotation parts of dislocation density tensors are demonstrated, and their relevance to understanding the fundamental aspects of deformation is discussed.

  14. Soaking suggests "alternative facts": Only co-crystallization discloses major ligand-induced interface rearrangements of a homodimeric tRNA-binding protein indicating a novel mode-of-inhibition.

    Directory of Open Access Journals (Sweden)

    Frederik Rainer Ehrmann

    Full Text Available For the efficient pathogenesis of Shigella, the causative agent of bacillary dysentery, full functionality of tRNA-guanine transglycosylase (TGT is mandatory. TGT performs post-transcriptional modifications of tRNAs in the anticodon loop taking impact on virulence development. This suggests TGT as a putative target for selective anti-shigellosis drug therapy. Since bacterial TGT is only functional as homodimer, its activity can be inhibited either by blocking its active site or by preventing dimerization. Recently, we discovered that in some crystal structures obtained by soaking the full conformational adaptation most likely induced in solution upon ligand binding is not displayed. Thus, soaked structures may be misleading and suggest irrelevant binding modes. Accordingly, we re-investigated these complexes by co-crystallization. The obtained structures revealed large conformational rearrangements not visible in the soaked complexes. They result from spatial perturbations in the ribose-34/phosphate-35 recognition pocket and, consequently, an extended loop-helix motif required to prevent access of water molecules into the dimer interface loses its geometric integrity. Thermodynamic profiles of ligand binding in solution indicate favorable entropic contributions to complex formation when large conformational adaptations in the dimer interface are involved. Native MS titration experiments reveal the extent to which the homodimer is destabilized in the presence of each inhibitor. Unexpectedly, one ligand causes a complete rearrangement of subunit packing within the homodimer, never observed in any other TGT crystal structure before. Likely, this novel twisted dimer is catalytically inactive and, therefore, suggests that stabilizing this non-productive subunit arrangement may be used as a further strategy for TGT inhibition.

  15. Rosetta Ligand docking with flexible XML protocols.

    Science.gov (United States)

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol.

  16. Ligand-biased ensemble receptor docking (LigBEnD): a hybrid ligand/receptor structure-based approach

    Science.gov (United States)

    Lam, Polo C.-H.; Abagyan, Ruben; Totrov, Maxim

    2018-01-01

    Ligand docking to flexible protein molecules can be efficiently carried out through ensemble docking to multiple protein conformations, either from experimental X-ray structures or from in silico simulations. The success of ensemble docking often requires the careful selection of complementary protein conformations, through docking and scoring of known co-crystallized ligands. False positives, in which a ligand in a wrong pose achieves a better docking score than that of native pose, arise as additional protein conformations are added. In the current study, we developed a new ligand-biased ensemble receptor docking method and composite scoring function which combine the use of ligand-based atomic property field (APF) method with receptor structure-based docking. This method helps us to correctly dock 30 out of 36 ligands presented by the D3R docking challenge. For the six mis-docked ligands, the cognate receptor structures prove to be too different from the 40 available experimental Pocketome conformations used for docking and could be identified only by receptor sampling beyond experimentally explored conformational subspace.

  17. Large field enhancement obtained by combining Fabry-Perot resonance and Rayleigh anomaly in photonic crystal slabs

    Science.gov (United States)

    Dossou, Kokou B.

    2017-04-01

    By applying the properties of Fabry-Perot resonance and Rayleigh anomaly, we have shown that a photonic crystal slab can scatter the light from an incident plane wave into a diffracted light with a very large reflection or transmission coefficient. The enhanced field is either a propagating diffracted wave (with a grazing angle of diffraction) or a weakly evanescent diffracted wave, so it can be particularly useful for applications requiring an enhanced propagating field (or an enhanced field with a low attenuation). An efficient effective medium technique is developed for the design of the resonant photonic crystal slabs. Numerical simulations have shown that photonic crystal slabs with low index contrast, such as the ones found in the cell wall of diatoms, can enhance the intensity of the incident light by four orders of magnitude.

  18. Exchange and crystal field effects in the ESR spectra of Eu2+ in LaB6

    Science.gov (United States)

    Duque, J. G. S.; Urbano, R. R.; Venegas, P. A.; Pagliuso, P. G.; Rettori, C.; Fisk, Z.; Oseroff, S. B.

    2007-09-01

    Electron spin resonance of Eu2+ ( 4f7 , S=7/2 ) in a La hexaboride (LaB6) single crystal shows a single anisotropic Dysonian resonance. From the observed negative g shift of the resonance, it is inferred that the Eu2+ ions are covalent exchange coupled to the B2p -like host conduction electrons. From the anisotropy of the spectra (linewidth and field for resonance), we found that the S ground state of Eu2+ ions experience a cubic crystal field of a negative fourth order crystal field parameter (CFP), b4=-11.5(2.0)Oe , in agreement with the negative fourth order CFP, A4 , found for the non- S ground state R hexaborides. These results support covalency as the dominant contribution to the fourth order CFP for the whole R hexaboride family.

  19. Calcium-containing crystals enhance receptor activator of nuclear factor κB ligand/macrophage colony-stimulating factor-mediated osteoclastogenesis via extracellular-signal-regulated kinase and p38 pathways.

    Science.gov (United States)

    Chang, Chi-Ching; Tsai, Yu-Hui; Liu, Yu; Lin, Shyr-Yi; Liang, Yu-Chih

    2015-10-01

    Diseases associated with calcium-containing crystal deposition can lead to local bone erosion. We aimed to determine whether calcium-containing crystal-hydroxyapatite, β-tricalcium phosphate and CPPD enhanced osteoclastogenesis and to define underlying mechanisms of action. Osteoclastogenesis was studied by culturing murine RAW 264.7 osteoclast precursor cells with RANK ligand (RANKL)/ M-CSF and/or calcium-containing crystals, and observing the tartrate-resistant acid phosphatase (TRAP)-positive multinucleated cells and TRAP activity. Resorption pit formation was used to evaluate osteoclast activity. Real-time RT-PCR analysis revealed osteoclast marker genes, including TRAP, cathepsin K and calcitonin receptor (CTR). Western blotting was used to analyse the phosphorylation levels of signal transduction molecules. Three kinds of calcium-containing crystal significantly enhanced RANKL/M-CSF-induced osteoclastogenesis in RAW 264.7 cells, as evidenced by the increased number of TRAP-positive multinucleated cells, TRAP activity and resorption pit formation in a dose-dependent manner. Hydroxyapatite, β-tricalcium phosphate and CPPD treatments significantly enhanced RANKL/M-CSF-induced mRNA expression of TRAP, cathepsin K and CTR. Moreover, the three kinds of calcium-containing crystal enhanced the phosphorylation of extracellular-signal-regulated kinase and p38 in RANKL/M-CSF-treated cells. We concluded that calcium-containing crystals can promote osteoclastogenesis and bone resorption through the extracellular-signal-regulated kinase and p38 pathways. Together with synovial activation, this mechanism may be important in the pathogenesis of destructive arthropathies triggered by calcium-containing crystals. © The Author 2015. Published by Oxford University Press on behalf of the British Society for Rheumatology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  20. Vectorial near-field imaging of a GaN based photonic crystal cavity

    International Nuclear Information System (INIS)

    La China, F.; Intonti, F.; Caselli, N.; Lotti, F.; Vinattieri, A.; Gurioli, M.; Vico Triviño, N.; Carlin, J.-F.; Butté, R.; Grandjean, N.

    2015-01-01

    We report a full optical deep sub-wavelength imaging of the vectorial components of the electric local density of states for the confined modes of a modified GaN L3 photonic crystal nanocavity. The mode mapping is obtained with a scanning near-field optical microscope operating in a resonant forward scattering configuration, allowing the vectorial characterization of optical passive samples. The optical modes of the investigated cavity emerge as Fano resonances and can be probed without the need of embedded light emitters or evanescent light coupling into the nanocavity. The experimental maps, independently measured in the two in-plane polarizations, turn out to be in excellent agreement with numerical predictions

  1. Phase-field study of crystal growth in three-dimensional capillaries: Effects of crystalline anisotropy

    Science.gov (United States)

    Debierre, Jean-Marc; Guérin, Rahma; Kassner, Klaus

    2016-07-01

    Phase-field simulations are performed to explore the thermal solidification of a pure melt in three-dimensional capillaries. Motivated by our previous work for isotropic or slightly anisotropic materials, we focus here on the more general case of anisotropic materials. Different channel cross sections are compared (square, hexagonal, circular) to reveal the influence of geometry and the effects of a competition between the crystal and the channel symmetries. In particular, a compass effect toward growth directions favored by the surface energy is identified. At given undercooling and anisotropy, the simulations generally show the coexistence of several growth modes. The relative stability of these growth modes is tested by submitting them to a strong spatiotemporal noise for a short time, which reveals a subtle hierarchy between them. Similarities and differences with experimental growth modes in confined geometry are discussed qualitatively.

  2. Inductive crystal field control in layered metal oxides with correlated electrons

    Energy Technology Data Exchange (ETDEWEB)

    Balachandran, P. V.; Cammarata, A.; Rondinelli, J. M., E-mail: jrondinelli@nortwestern.edu [Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104 (United States); Nelson-Cheeseman, B. B. [School of Engineering, University of St. Thomas, St. Paul, Minnesota 55105 (United States); Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Bhattacharya, A. [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2014-07-01

    We show that the NiO{sub 6} crystal field energies can be tailored indirectly via heterovalent A cation ordering in layered (La,A)NiO{sub 4} Ruddlesden–Popper (RP) oxides, where A = Sr, Ca, or Ba, using density functional calculations. We leverage as a driving force the electrostatic interactions between charged [LaO]{sup 1+} and neutral [AO]{sup 0} planes to inductively tune the Ni–O bond distortions, without intentional doping or epitaxial strain, altering the correlated d-orbital energies. We use this strategy to design cation ordered LaCaNiO{sub 4} and LaBaNiO{sub 4} with distortions favoring enhanced Ni e{sub g} orbital polarization, and find local electronic structure signatures analogous to those in RP La-cuprates, i.e., parent phases of the high-temperature superconducting oxides.

  3. Crystal field symmetry and magnetic interactions in rare earth-silver amorphous alloys

    International Nuclear Information System (INIS)

    Pappa, Catherine.

    1979-01-01

    A study has been made of the following rare earth based amorphous alloys: Ndsub(x)Agsub(100-x), Prsub(x)Agsub(100-x), Gdsub(x)Agsub(100-x), Tlsub(x)Agsub(100-x). In rare earth based amorphous alloys, the symmetrical distribution of the crystal field is very wide and hence not very sensitive to the content of the alloys. The existence of preponderant negative magnetic interactions leads to an upset magnetic order, the magnetization of a small volume not being nil. The magnetic behaviour of alloys with a small concentration of rare earths is governed by the existence of clusters of statistical origin, within which a rare earth ion has at least one other rare earth ion in the position of first neighbour. The presence of a high anisotropy at low temperatures make the magnetic interactions between clusters inoperative [fr

  4. Synthesis, crystal structure, antimicrobial activity and electrochemistry study of chromium(III) and copper(II) complexes based on semicarbazone Schiff base and azide ligands

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Mahmoudi, F.

    2013-01-01

    Roč. 394, JAN (2013), s. 563-568 ISSN 0020-1693 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:68378271 Keywords : antimicrobial activity * azide ligand * metal complex * Schiff base ligand * X-ray structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.041, year: 2013

  5. Crystal structure of thioflavin T bound to the peripheral site of Torpedo californica acetylcholinesterase reveals how thioflavin T acts as a sensitive fluorescent reporter of ligand binding to the acylation site.

    Science.gov (United States)

    Harel, Michal; Sonoda, Leilani K; Silman, Israel; Sussman, Joel L; Rosenberry, Terrone L

    2008-06-25

    Acetylcholinesterase plays a key role in cholinergic synaptic transmission by hydrolyzing the neurotransmitter acetylcholine with one of the highest known catalytic rate constants. Hydrolysis occurs in a narrow and deep gorge that contains two sites of ligand binding: A peripheral site, or P-site, near the gorge entrance that contributes to catalytic efficiency both by transiently trapping substrate molecules as they enter the gorge and by allosterically accelerating the transfer of the substrate acyl group to a serine hydroxyl in an acylation site or A-site at the base of the gorge. Thioflavin T is a useful reporter of ligand interactions with the A-site. It binds specifically to the P-site with fluorescence that is enhanced approximately 1000-fold over that of unbound thioflavin T, and the enhanced fluorescence is quenched 1.5- to 4-fold when another ligand binds to the A-site in a ternary complex. To clarify the structural basis of this advantageous signal change, we here report the X-ray structure of the complex of thioflavin T with Torpedo californica acetylcholinesterase. The two aromatic rings in thioflavin T are coplanar and are packed snugly parallel to the aromatic side chains of Trp279, Tyr334, and Phe330. Overlays of this structure with the crystal structures of Torpedo californica acetylcholinesterase complexes with either edrophonium or m-( N, N, N-trimethylammonio)-2,2,2-trifluoroacetophenone, two small aromatic ligands that bind specifically to the A-site, indicate that the phenyl side chain of Phe330 must rotate to sterically accommodate both thioflavin T and the A-site ligand in the ternary complex. This rotation may allow some relaxation of the strict coplanarity of the aromatic rings in the bound thioflavin T and result in partial quenching of its fluorescence.

  6. Spectroscopy of Charge Carriers and Traps in Field-Doped Single Crystal Organic Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaoyang

    2014-12-10

    The proposed research aims to achieve quantitative, molecular level understanding of charge carriers and traps in field-doped crystalline organic semiconductors via in situ linear and nonlinear optical spectroscopy, in conjunction with transport measurements and molecular/crystal engineering. Organic semiconductors are emerging as viable materials for low-cost electronics and optoelectronics, such as organic photovoltaics (OPV), organic field effect transistors (OFETs), and organic light emitting diodes (OLEDs). Despite extensive studies spanning many decades, a clear understanding of the nature of charge carriers in organic semiconductors is still lacking. It is generally appreciated that polaron formation and charge carrier trapping are two hallmarks associated with electrical transport in organic semiconductors; the former results from the low dielectric constants and weak intermolecular electronic overlap while the latter can be attributed to the prevalence of structural disorder. These properties have lead to the common observation of low charge carrier mobilities, e.g., in the range of 10-5 - 10-3 cm2/Vs, particularly at low carrier concentrations. However, there is also growing evidence that charge carrier mobility approaching those of inorganic semiconductors and metals can exist in some crystalline organic semiconductors, such as pentacene, tetracene and rubrene. A particularly striking example is single crystal rubrene (Figure 1), in which hole mobilities well above 10 cm2/Vs have been observed in OFETs operating at room temperature. Temperature dependent transport and spectroscopic measurements both revealed evidence of free carriers in rubrene. Outstanding questions are: what are the structural features and physical properties that make rubrene so unique? How do we establish fundamental design principles for the development of other organic semiconductors of high mobility? These questions are critically important but not comprehensive, as the nature of

  7. Travelling-wave amplitudes as solutions of the phase-field crystal equation

    Science.gov (United States)

    Nizovtseva, I. G.; Galenko, P. K.

    2018-01-01

    The dynamics of the diffuse interface between liquid and solid states is analysed. The diffuse interface is considered as an envelope of atomic density amplitudes as predicted by the phase-field crystal model (Elder et al. 2004 Phys. Rev. E 70, 051605 (doi:10.1103/PhysRevE.70.051605); Elder et al. 2007 Phys. Rev. B 75, 064107 (doi:10.1103/PhysRevB.75.064107)). The propagation of crystalline amplitudes into metastable liquid is described by the hyperbolic equation of an extended Allen-Cahn type (Galenko & Jou 2005 Phys. Rev. E 71, 046125 (doi:10.1103/PhysRevE.71.046125)) for which the complete set of analytical travelling-wave solutions is obtained by the method (Malfliet & Hereman 1996 Phys. Scr. 15, 563-568 (doi:10.1088/0031-8949/54/6/003); Wazwaz 2004 Appl. Math. Comput. 154, 713-723 (doi:10.1016/S0096-3003(03)00745-8)). The general solution of travelling waves is based on the function of hyperbolic tangent. Together with its set of particular solutions, the general solution is analysed within an example of specific task about the crystal front invading metastable liquid (Galenko et al. 2015 Phys. D 308, 1-10 (doi:10.1016/j.physd.2015.06.002)). The influence of the driving force on the phase-field profile, amplitude velocity and correlation length is investigated for various relaxation times of the gradient flow. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

  8. Nanomechanical control of optical field and quality factor in photonic crystal structures

    Science.gov (United States)

    Cotrufo, Michele; Midolo, Leonardo; Zobenica, Žarko; Petruzzella, Maurangelo; van Otten, Frank W. M.; Fiore, Andrea

    2018-03-01

    Actively controlling the properties of localized optical modes is crucial for cavity quantum electrodynamics experiments. While several methods to tune the optical frequency have been demonstrated, the possibility of controlling the shape of the modes has scarcely been investigated. Yet an active manipulation of the mode pattern would allow direct control of the mode volume and the quality factor and therefore of the radiative processes. In this work, we propose and demonstrate a nano-optoelectromechanical device in which a mechanical displacement affects the spatial pattern of the electromagnetic field. The device is based on a double-membrane photonic crystal waveguide which, upon bending, creates a spatial modulation of the effective refractive index, resulting in an effective potential well or antiwell for the optical modes. The change in the field pattern drastically affects the optical losses: large modulations of the quality factors and dissipative coupling rates larger than 1 GHz/nm are predicted by calculations and confirmed by experiments. This concept opens new avenues in solid-state cavity quantum electrodynamics in which the field, instead of the frequency, is coupled to the mechanical motion.

  9. Ultrasound studies of single crystal thulium in an applied magnetic field

    International Nuclear Information System (INIS)

    Lim, C.M.; Edwards, C.; Dixon, S.; Palmer, S.B.

    2001-01-01

    The paper reports the first measurements of the single crystal elastic constants of the heavy rare earth metal thulium as a function of temperature and magnetic field. The constants were obtained from ultrasonic velocity measurements over a temperature range of 4.2-296 K and in applied magnetic fields of up to 5 T. The elastic constants; C 11 , C 33 , C 44 and C 66 =(C 11 -C 12 )/2 were determined from the ultrasonic velocities. Anomalies in the elastic constants were observed at 58 K from the c-axis propagated shear wave measurements and at 55 K from the c-axis propagated longitudinal wave measurements. Significant softening of the elastic constants C 33 and C 44 was observed close to T N . Application of a magnetic field (>2 T) along the c-axis direction induced further softening of the material. Electromagnetic acoustic transducers (EMATs) were also employed in addition to conventional piezoelectric quartz transducers. A marked increase in the EMATs acoustic coupling efficiency (generation and detection efficiency) occurred close to T N

  10. Meshed doped silicon photonic crystals for manipulating near-field thermal radiation

    Science.gov (United States)

    Elzouka, Mahmoud; Ndao, Sidy

    2018-01-01

    The ability to control and manipulate heat flow is of great interest to thermal management and thermal logic and memory devices. Particularly, near-field thermal radiation presents a unique opportunity to enhance heat transfer while being able to tailor its characteristics (e.g., spectral selectivity). However, achieving nanometric gaps, necessary for near-field, has been and remains a formidable challenge. Here, we demonstrate significant enhancement of the near-field heat transfer through meshed photonic crystals with separation gaps above 0.5 μm. Using a first-principle method, we investigate the meshed photonic structures numerically via finite-difference time-domain technique (FDTD) along with the Langevin approach. Results for doped-silicon meshed structures show significant enhancement in heat transfer; 26 times over the non-meshed corrugated structures. This is especially important for thermal management and thermal rectification applications. The results also support the premise that thermal radiation at micro scale is a bulk (rather than a surface) phenomenon; the increase in heat transfer between two meshed-corrugated surfaces compared to the flat surface (8.2) wasn't proportional to the increase in the surface area due to the corrugations (9). Results were further validated through good agreements between the resonant modes predicted from the dispersion relation (calculated using a finite-element method), and transmission factors (calculated from FDTD).

  11. High Magnetic Field Dependence of Magnetodielectric Properties in Sr2CoSi2O7 Crystal

    Science.gov (United States)

    Akaki, M.; Tadokoro, T.; Kihara, T.; Tokunaga, M.; Kuwahara, H.

    2013-03-01

    We have investigated magnetic and dielectric properties of åkermanite Sr2CoSi2O7 single crystal in which the orbital hybridization is controllable by external magnetic fields. Sr2CoSi2O7 shows the electric polarization that is originated from asymmetric orbital hybridization induced by magnetic field. This induced electric polarization was observed even at temperatures considerably higher than the magnetic transition temperature. The polarization data obtained for the paramagnetic phase are scaled with the square of the induced magnetization. By the discussion of the crystal symmetry, the space group of a polar state of åkermanite materials is probably Cmm2.

  12. Terminological confusions and problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians—Survey of the CF=ZFS confusion in recent literature

    Energy Technology Data Exchange (ETDEWEB)

    Rudowicz, Czesław, E-mail: crudowicz@zut.edu.pl [Institute of Physics, West Pomeranian University of Technology, Al. Piastów 17, 70-310 Szczecin (Poland); Karbowiak, Mirosław [Faculty of Chemistry, University of Wrocław, ul. F. Joliot-Curie 14, 50-383 Wrocław (Poland)

    2014-10-15

    The single transition ions in various crystals or molecules as well as the exchange coupled systems (ECS) of transition ions, especially the single molecule magnets (SMM) or molecular nanomagnets (MNM), have been extensively studied in recent decades using electron magnetic resonance (EMR), optical spectroscopy, and magnetic measurements. Interpretation of magnetic and spectroscopic properties of transition ions is based on two physically distinct types of Hamiltonians: the physical crystal field (CF), or equivalently ligand field (LF), Hamiltonians and the effective spin Hamiltonians (SH), which include the zero-field splitting (ZFS) Hamiltonians. Survey of recent literature has revealed a number of terminological confusions and specific problems occurring at the interface between these Hamiltonians (denoted CF (LF)↔SH (ZFS)). Elucidation of sloppy or incorrect usage of crucial notions, especially those describing or parameterizing crystal fields and zero field splittings, is a very challenging task that requires several reviews. Here we focus on the prevailing confusion between the CF (LF) and SH (ZFS) quantities, denoted as the CF=ZFS confusion, which consists in referring to the parameters (or Hamiltonians), which are the true ZFS (or SH) quantities, as purportedly the CF (LF) quantities. The inverse ZFS=CF confusion, which pertains to the cases of labeling the true CF (LF) quantities as purportedly the ZFS quantities, is considered in a follow-up paper. The two reviews prepare grounds for a systematization of nomenclature aimed at bringing order to the zoo of different Hamiltonians. Specific cases of the CF=ZFS confusion identified in the recent textbooks, review articles, and SMM (MNM)- and EMR-related papers are surveyed and the pertinent misconceptions are outlined. The consequences of the terminological confusions go far beyond simple semantic issues or misleading keyword classifications of papers in journals and scientific databases. Serious

  13. Liquid crystal designs for high-contrast field sequential color liquid crystal on silicon (LCoS) microdisplays (Invited Paper)

    Science.gov (United States)

    Anderson, James; Chen, Cheng; Bos, Philip J.

    2005-04-01

    Single or dual panel microdisplay systems are becoming more popular in the marketplace. Consequently, Liquid Crystal on Silicon (LCoS) microdisplays are constantly being pushed to achieve faster switching times as well as higher contrast, while becoming simpler and allowing simpler optics engine design. Currently, most products use a Twisted Nematic (TN) mode with a retardation film. The most promising solution in research now is the Vertically Aligned Nematic (VAN) mode, which does not require a retarder.

  14. Spin-glass polyamorphism induced by a magnetic field in LaMnO3 single crystal

    Science.gov (United States)

    Eremenko, V. V.; Sirenko, V. A.; Baran, A.; Čižmár, E.; Feher, A.

    2018-05-01

    We present experimental evidence of field-driven transition in spin-glass state, similar to pressure-induced transition between amorphous phases in structural and metallic glasses, attributed to the polyamorphism phenomena. Cusp in temperature dependences of ac magnetic susceptibility of weakly disordered LaMnO3 single crystal is registered below the temperature of magnetic ordering. Frequency dependence of the cusp temperature proves its spin-glass origin. The transition induced by a magnetic field in spin-glass state, is manifested by peculiarity in dependence of cusp temperature on applied magnetic field. Field dependent maximum of heat capacity is observed in the same magnetic field and temperature range.

  15. Multi-modes interferometer for magnetic field and temperature measurement using Photonic crystal fiber filled with magnetic fluid

    Science.gov (United States)

    Li, Xue-gang; Zhou, Xue; Zhao, Yong; Lv, Ri-Qing

    2018-03-01

    An in-line modal Mach-Zehnder interferometer (MZI) based on a magnetic fluid-filled photonic crystal fiber (PCF) was proposed in this paper. The Mach-Zehnder interference was induced by the single mode fiber (SMF)-photonic crystal fiber (PCF)-single mode fiber (SMF) structure. And the photonic crystal fiber was filled with magnetic fluid to measure the magnetic field and temperature. There are multiple cladding modes are involved into the interference. Hence simultaneous measurement of temperature and refractive index can be achieved by simultaneously monitoring the two different modes interference spectra. The sensitivities of magnetic field and temperature can reach up to 0.072 nm/Gs and -0.080 nm/°C, respectively.

  16. Stress field of a near-surface basal screw dislocation in elastically anisotropic hexagonal crystals

    Directory of Open Access Journals (Sweden)

    Valeri S. Harutyunyan

    2017-11-01

    Full Text Available In this study, we derive and analyze the analytical expressions for stress components of the dislocation elastic field induced by a near-surface basal screw dislocation in a semi-infinite elastically anisotropic material with hexagonal crystal lattice. The variation of above stress components depending on “free surface–dislocation” distance (i.e., free surface effect is studied by means of plotting the stress distribution maps for elastically anisotropic crystals of GaN and TiB2 that exhibit different degrees of elastic anisotropy. The dependence both of the image force on a screw dislocation and the force of interaction between two neighboring basal screw dislocations on the “free surface–dislocation” distance is analyzed as well. The influence of elastic anisotropy on the latter force is numerically analyzed for GaN and TiB2 and also for crystals of such highly elastically-anisotropic materials as Ti, Zn, Cd, and graphite. The comparatively stronger effect of the elastic anisotropy on dislocation-induced stress distribution quantified for TiB2 is attributed to the higher degree of elastic anisotropy of this compound in comparison to that of the GaN. For GaN and TiB2, the dislocation stress distribution maps are highly influenced by the free surface effect at “free surface–dislocation” distances roughly smaller than ≈15 and ≈50 nm, respectively. It is found that, for above indicated materials, the relative decrease of the force of interaction between near-surface screw dislocations due to free surface effect is in the order Ti > GaN > TiB2 > Zn > Cd > Graphite that results from increase of the specific shear anisotropy parameter in the reverse order Ti < GaN < TiB2 < Zn < Cd < Graphite. The results obtained in this study are also applicable to the case when a screw dislocation is situated in the “thin film–substrate” system at a (0001 basal interface between the film and substrate provided that the elastic constants

  17. Two new coordination polymers with flexible alicyclic carboxylate and bipyridyl co-ligands bearing trinuclear [Ni3(COO)6] SBUs: Synthesis, crystal structures, and magnetic properties

    Science.gov (United States)

    Zhu, Xian-Dong; Li, Yong; Gao, Jian-Gang; Wang, Fen-Hua; Li, Qing-Hai; Yang, Hong-Xun; Chen, Lei

    2017-02-01

    Two new coordination polymers generally formulated as [Ni3(Hchda)2(chda)2(bpy)2(H2O)2]n (1) and [Ni3(Hchda)2(chda)2(bpp)2(H2O)2]n (2) [H2chda = 1,1'-cyclohexanediacetic acid, bpy = 4,4'-bipyridine and bpp = 1,3-bis(4-pyridyl)propane], have been successfully assembled through mixed-ligands synthetic strategy with flexible alicyclic carboxylate and bipyridyl ligands. There structures feature trinuclear nickel secondary building units connected via the bridging bipyridyl spacers to form two-dimensional (4,4) grid layer. The nature of the different N-donor auxiliary ligands leads to the discrepancy in supramolecular structure of the two compounds. Magnetic studies indicate the ferromagnetic intra-complex magnetic interaction in the molecule for 1 and 2.

  18. The effect of uniaxial crystal-field anisotropy on magnetic properties of the superexchange antiferromagnetic Ising model

    Directory of Open Access Journals (Sweden)

    L.Canová

    2006-01-01

    Full Text Available The generalized Fisher super-exchange antiferromagnetic model with uniaxial crystal-field anisotropy is exactly investigated using an extended mapping technique. An exact relation between partition function of the studied system and that of the standard zero-field spin-1/2 Ising model on the corresponding lattice is obtained applying the decoration-iteration transformation. Consequently, exact results for all physical quantities are derived for arbitrary spin values S of decorating atoms. Particular attention is paid to the investigation of the effect of crystal-field anisotropy and external longitudinal magnetic field on magnetic properties of the system under investigation. The most interesting numerical results for ground-state and finite-temperature phase diagrams, thermal dependences of the sublattice magnetization and other thermodynamic quantities are discussed.

  19. Coupling between crystal field transitions and phonons in the 4f-electron system CeCu2

    Czech Academy of Sciences Publication Activity Database

    Schedler, R.; Witte, U.; Loewenhaupt, M.; Kulda, Jiří

    2003-01-01

    Roč. 335, 1, 2, 3, 4 (2003), s. 41-43 ISSN 0921-4526 R&D Projects: GA AV ČR KSK1048102 Keywords : crystal field phonon coupling Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 0.908, year: 2003

  20. Crystal-field excitations in the visible spectrum of Nd.sub.2./sub.CuO.sub.4./sub..

    Czech Academy of Sciences Publication Activity Database

    Richard, P.; Jandl, S.; Hölsä, J.; Nekvasil, Vladimír

    2004-01-01

    Roč. 374, - (2004), s. 14-17 ISSN 0925-8388 R&D Projects: GA ČR GA202/03/0552 Institutional research plan: CEZ:AV0Z1010914 Keywords : crystal-field excitation * optical absorption * cuprate superconductors Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.562, year: 2004

  1. Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets

    DEFF Research Database (Denmark)

    Johnson, Phillip S.; García Lastra, Juan Maria; Kennedy, Colton K.

    2014-01-01

    Polarization-dependent X-ray absorption spectroscopy is combined with density functional calculations and atomic multiplet calculations to determine the crystal field parameters 10Dq, Ds, and Dt of transition metal phthalocyanines and octaethylporphyrins (Mn, Fe, Co, Ni). The polarization depende...

  2. Study of crystal-field excitations and Raman active phonons in o-DyMnO.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Jandl, S.; Mansouri, S.; Mukhin, A.A.; Ivanov, V.Yu.; Balbashov, A.; Gospodino, M.M.; Nekvasil, Vladimír; Orlita, Milan

    2011-01-01

    Roč. 323, č. 8 (2011), s. 1104-1108 ISSN 0304-8853 R&D Projects: GA AV ČR IAA100100803 Institutional research plan: CEZ:AV0Z10100521 Keywords : manganite * multiferroic * Raman active phonons * crystal fields Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.780, year: 2011

  3. Optical spectroscopy and crystal-field analysis of YAl sub 3 (BO sub 3) sub 4 single crystals doped with dysprosium

    CERN Document Server

    Cavalli, E; Magnani, N; Ramirez, M O; Speghini, A; Bettinelli, M

    2003-01-01

    YAl sub 3 (BO sub 3) sub 4 crystals doped with Dy sup 3 sup + were grown from a potassium trimolybdate flux. Their absorption and visible emission spectra and decay curves were measured at temperatures ranging from 10 to 298 K. The complete energy level scheme has been deduced from the low temperature measurements and reproduced by theoretical calculations based on a parametric Hamiltonian including coulombic, spin-orbit and crystal-field terms. The Judd-Ofelt parametrization scheme has been applied to the analysis of the room temperature absorption spectra. The calculated radiative lifetime of the sup 4 F sub 9 sub / sub 2 state is 344 mu s; this value is reasonably consistent with the experimental data.

  4. Crystallization of a 2:2 complex of granulocyte-colony stimulating factor (GCSF) with the ligand-binding region of the GCSF receptor

    Science.gov (United States)

    Honjo, Eijiro; Tamada, Taro; Maeda, Yoshitake; Koshiba, Takumi; Matsukura, Yasuko; Okamoto, Tomoyuki; Ishibashi, Matsujiro; Tokunaga, Masao; Kuroki, Ryota

    2005-01-01

    The granulocyte-colony stimulating factor (GCSF) receptor receives signals for regulating the maturation, proliferation and differentiation of the precursor cells of neutrophilic granulocytes. The signalling complex composed of two GCSFs (GCSF, 19 kDa) and two GCSF receptors (GCSFR, 34 kDa) consisting of an Ig-like domain and a cytokine-receptor homologous (CRH) domain was crystallized. A crystal of the complex was grown in 1.0 M sodium formate and 0.1 M sodium acetate pH 4.6 and belongs to space group P41212 (or its enantiomorph P43212), with unit-cell parameters a = b = 110.1, c = 331.8 Å. Unfortunately, this crystal form did not diffract beyond 5 Å resolution. Since the heterogeneity of GCSF receptor appeared to prevent the growth of good-quality crystals, the GCSF receptor was fractionated by anion-exchange chromatography. Crystals of the GCSF–fractionated GCSF receptor complex were grown as a new crystal form in 0.2 M ammonium phosphate. This new crystal form diffracted to beyond 3.0 Å resolution and belonged to space group P3121 (or its enantiomorph P3221), with unit-cell parameters a = b = 134.8, c = 105.7 Å. PMID:16511159

  5. Quinoxaline-2-carboxamide as a carrier ligand in two new platinum(ii) compounds: Synthesis, crystal structure, cytotoxic activity and DNA interaction

    NARCIS (Netherlands)

    Marques Gallego, P.; Amparo Gamiz-Gonzalez, M.; Fortea-Pérez, F. R.; Lutz, M.; Spek, A.L.; Pevec, A.; Kozlevar, B.; Reedijk, J.

    2010-01-01

    The search for platinum compounds structurally different from cisplatin has led to two new platinum(II) compounds containing quinoxaline-2-carboxamide as a carrier ligand, i.e. cis-[Pt(qnxca)(MeCN)Cl2] (1) and the [Pt(qnxca−H)(dmso)Cl] (2). Both compounds have been synthesized and characterized

  6. Syntheses, crystal structures and antimicrobial activities of 6-coordinate antimony(III) complexes with tridentate 2-acetylpyridine thiosemicarbazone, bis(thiosemicarbazone) and semicarbazone ligands.

    Science.gov (United States)

    Kasuga, Noriko Chikaraishi; Onodera, Kuniaki; Nakano, Saori; Hayashi, Kunihiko; Nomiya, Kenji

    2006-07-01

    Five novel antimony(III) complexes with the mono- and bis(thiosemicarbazone) ligands of 2N1S or 4N2S donor atoms, N'-[1-(2-pyridyl)ethylidene]morpholine-4-carbothiohydrazide (Hmtsc, L1) and bis[N'-[1-(2-pyridyl)ethylidene

  7. Synthesis, Crystal Structure, and Luminescent Properties of New Zinc(II and Cadmium(II Metal-Organic Frameworks Based on Flexible Bis(imidazol-1-ylalkane Ligands

    Directory of Open Access Journals (Sweden)

    Marina Barsukova

    2016-10-01

    Full Text Available New metal-organic frameworks (MOFs based on zinc and cadmium ions, terephthalic acid, and flexible ligands 1,5-bis(imidazol-1-ylpentane or 1,6-bis(imidazol-1-ylhexane were prepared and characterized by X-ray diffraction, thermorgavimetric analysis and IR spectroscopy. The imidazolyl ligands were prepared by a new robust procedure involving the reaction between imidazole and 1,5-dibromopentane or 1,6-dibromohexane in a superbasic medium (KOH in DMSO. MOFs based on 1,5-bis(imidazol-1-ylpentane had diamond topology (dia and are triply interpenetrated. Ligands with longer spacer 1,6-bis(imidazol-1-ylhexane, terephthalate ions and zinc(II ions formed five-fold interpenetrated metal-organic framework also with dia topology, while cadmium(II ions with the same ligands formed eight-connected uninodal net with a very rare self-penetrated topological type ilc and a point symbol 424.5.63. The influence of the chemical composition of MOFs on their photoluminescent properties is investigated and discussed in detail.

  8. Crystal structure of a mixed-ligand silver(I complex of the non-steroidal anti-inflammatory drug diclofenac and pyrimidine

    Directory of Open Access Journals (Sweden)

    Sevim Hamamci Alisir

    2016-10-01

    Full Text Available In the title mixed-ligand silver(I coordination polymeric complex with the non-steroidal anti-inflammatory drug diclofenac (C14H11Cl2NO2 (diclH and pyrimidine (pym, namely poly[{μ2-2-[2-(2,6-dichloroanilinophenyl]acetato-κ2O:O′}(μ2-pyrimidine-κ2N1:N3silver(I], [Ag(C14H10Cl2NO2(C4H4N2]n or [Ag(μ-dicl(μ-pym]n, the very distorted tetrahedral AgN2O2 coordination centres comprise two N-atom donors from bridging pym ligands [Ag—N = 2.381 (3 and 2.412 (3 Å] and two carboxylate O-atom donors from dicl ligands [Ag—O = 2.279 (2 and 2.280 (2 Å], which bridge Ag atoms, giving a centrosymmetric dinuclear units with a short Ag...Ag separation [2.8931 (5 Å]. Within the units are short intraligand C—Cl...π(pym interactions [3.6409 (15 Å]. The units are linked through the bridging N atoms of the pym ligand into a two-dimensional sheet–polymer structure lying parallel to (100 and stabilized by inter-ring π–π interactions between the pym ligands [Cg...Cg = 3.4199 (17 Å]. Additional inter-unit C—H...O and C—H...Cg hydrogen-bonding interactions between the sheets give an overall three-dimensional structure.

  9. Collective classical and quantum fields in plasmas, superconductors, superfluid $^{3}$He, and liquid crystals

    CERN Document Server

    Hagen Kleinert

    2018-01-01

    This is an introductory book dealing with collective phenomena in many-body systems. A gas of bosons or fermions can show oscillations of various types of density. These are described by different combinations of field variables. Especially delicate is the competition of these variables. In superfluid 3He, for example, the atoms can be attracted to each other by molecular forces, whereas they are repelled from each other at short distance due to a hardcore repulsion. The attraction gives rise to Cooper pairs, and the repulsion is overcome by paramagnon oscillations. The combination is what finally led to the discovery of superfluidity in 3He. In general, the competition between various channels can most efficiently be studied by means of a classical version of the Hubbard-Stratonovich transformation. A gas of electrons is controlled by the interplay of plasma oscillations and pair formation. In a system of rod- or disc-like molecules, liquid crystals are observed with directional orientations that behave in ...

  10. Low-Voltage Organic Single-Crystal Field-Effect Transistor with Steep Subthreshold Slope.

    Science.gov (United States)

    Yang, Fangxu; Sun, Lingjie; Han, Jiangli; Li, Baili; Yu, Xi; Zhang, Xiaotao; Ren, Xiaochen; Hu, Wenping

    2018-03-06

    Anodization is a promising technique to form high- k dielectrics for low-power organic field-effect transistor (OFET) applications. However, the surface quality of the dielectric, which is mainly inherited from the metal electrode, can be improved further than other fabrication techniques, such as sol-gel. In this study, we applied the template stripping method to fabricate a low-power single-crystalline OFET based on the anodized AlO x dielectric. We found that the template stripping method largely improves the surface roughness of the deposited Al and allows for the formation of a high-quality AlO x high- k dielectric by anodization. The ultraflat AlO x /SAM dielectric combined with a single-crystal 2,6-diphenylanthracene (DPA) semiconductor produced a nearly defect-free interface with a steep subthreshold swing (SS) of 66 mV/decade. The current device is a promising candidate for future ultralow-power applications. Other than metal deposition, template stripping could provide a general approach to improve thin-film quality for many other types of materials and processes.

  11. Touch sensors based on planar liquid crystal-gated-organic field-effect transistors

    International Nuclear Information System (INIS)

    Seo, Jooyeok; Lee, Chulyeon; Han, Hyemi; Lee, Sooyong; Nam, Sungho; Kim, Youngkyoo; Kim, Hwajeong; Lee, Joon-Hyung; Park, Soo-Young; Kang, Inn-Kyu

    2014-01-01

    We report a tactile touch sensor based on a planar liquid crystal-gated-organic field-effect transistor (LC-g-OFET) structure. The LC-g-OFET touch sensors were fabricated by forming the 10 μm thick LC layer (4-cyano-4 ′ -pentylbiphenyl - 5CB) on top of the 50 nm thick channel layer (poly(3-hexylthiophene) - P3HT) that is coated on the in-plane aligned drain/source/gate electrodes (indium-tin oxide - ITO). As an external physical stimulation to examine the tactile touch performance, a weak nitrogen flow (83.3 μl/s) was employed to stimulate the LC layer of the touch device. The LC-g-OFET device exhibited p-type transistor characteristics with a hole mobility of 1.5 cm 2 /Vs, but no sensing current by the nitrogen flow touch was measured at sufficiently high drain (V D ) and gate (V G ) voltages. However, a clear sensing current signal was detected at lower voltages, which was quite sensitive to the combination of V D and V G . The best voltage combination was V D = −0.2 V and V G = −1 V for the highest ratio of signal currents to base currents (i.e., signal-to-noise ratio). The change in the LC alignment upon the nitrogen flow touch was assigned as the mechanism for the present LC-g-OFET touch sensors

  12. Pressure dependence of crystal field splitting in Pr pnictides and chalcogenides

    International Nuclear Information System (INIS)

    Schirber, J.E.; Weaver, H.T.; Ginley, D.S.

    1978-01-01

    We have measured the pressure dependence of the Pr nuclear magnetic resonance shift in PrN, PrP, PrSb, PrAs, PrS and PrSe. The shifts in all the pnictides increase while in the chalcogenides the shifts decrease with pressure. The rare earth frequency shift is inversely proportional to the crystal field splitting in the context of the point charge model (PCM) so a decrease would be expected for all of these materials at a rate of 5/3 the volume compressibility. Our values for the pnictides tend to be considerably larger than the PCM value as well as the wrong sign. The chalcogenide values are much nearer in magnitude and are of the right sign for the PCM. Contrary to the report of Guertin et al. we see no anomaly in the pressure dependence of the susceptibility of PrS. The fact that PrN which is reported to be non-metallic also shows the wrong sign for the PCM presents difficulties for various conduction electron explanations for this unexpected behavior of the pnictides

  13. Crystal-field analysis of Eu sup 3 sup + in Lu sub 2 O sub 3

    CERN Document Server

    Karbowiak, M; Hoelsae, J

    2003-01-01

    Low temperature (7 K) absorption spectra of polycrystalline sintered ceramic Lu sub 2 O sub 3 :Eu sup 3 sup + were recorded between 3950 and 50000 cm sup - sup 1. There are two different intrinsic Eu sup 3 sup + sites, C sub 2 and S sub 6 (C sub 3 sub i), in this host. A total of 105 crystal-field (CF) energy levels were assigned and fitted to a semiempirical Hamiltonian representing the combined free-ion (FI) and CF interactions for a 4f sup 6 ion in the C sub 2 symmetry site. 10 FI and 14 CF parameters were varied simultaneously in the least square adjustments yielding an rms deviation between the calculated and experimental levels of 15 cm sup - sup 1. The CF strength parameter, S, obtained from calculated B sub q sup k parameters is larger for Lu sub 2 O sub 3 when compared to the Y sub 2 O sub 3 host, which is in accordance with the smaller ionic radius of the Lu sup 3 sup + ion. The CF splittings of the sup 7 F sub 1 and sup 5 D sub 1 levels were also determined experimentally for the Eu sup 3 sup + ion...

  14. High temperature grain shrinkage under different pre-strains: a phase-field-crystal study

    Science.gov (United States)

    Hu, Shi; Wang, Song; Chen, Zheng; Xi, Wen; Zhang, Ting-Hui

    2018-01-01

    In this work, we use the phase-field-crystal method to study high temperature grain shrinkage. A circular grain embedded in a symmetric tilt planar grain boundary (GB) is constructed as the simulation system. Misorientation angle of the circular GB has influence on the specific evolution process. Difference between low and high misorientation angle systems is explored. In low misorientation angle system, grain shrinkage is first enabled by dislocation migration. Then dislocation rearrangement process in trijunction areas triggers the further shrinkage of inner grain. The free energy density (FED) curve has a rising stage during the overall decline process. For high misorientation angle system, dissociation and recombination reaction of dislocations is the primary way to shrink inner grain. The FED curve monotonically declines. Additionally, we apply pre-strain to simulation system. The influence of pre-strain on grain shrinkage in low and high misorientation angle systems is also investigated. When pre-strain is relatively small, the evolution process has no difference with unstrained situation, but grain shrinkage is impeded. Further increasing pre-strain, dislocations are emitted from circular GB. Grain shrinkage is accelerated and the inner grain eventually disappears prior to the grain disappearance in unstrained system. There exists a critical pre-strain to control the emission of dislocations.

  15. Crystal field splitting in CePt{sub 5}. Magnetic analysis and Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zinner, Martin; Praetorius, Christian; Fauth, Kai [Universitaet Wuerzburg, Experimentelle Physik II, 97074 Wuerzburg (Germany); Halbig, Benedikt; Bass, Utz; Geurts, Jean [Universitaet Wuerzburg, Experimentelle Physik III, 97074 Wuerzburg (Germany)

    2015-07-01

    The crystal electric field (CF) is an essential factor determining the paramagnetic response of rare earth ions in solids. In Ce intermetallics, Kondo screening can additionally modify the magnetic behavior and it may then prove difficult to disentangle the two. In the hexagonal surface intermetallic CePt{sub 5}, grown on Pt(111), we find two distinct sets of CF parameters which both account rather well for the anisotropic magnetic susceptibility and its temperature dependence. Different strengths of Kondo screening have to be assumed in the two cases in order to obtain quantitative agreement with experimental results. Discriminating between the two solutions requires an independent determination of the CF splitting. We shall report on our attempts to obtain this information from electronic Raman scattering. Raman signal is indeed even obtained from CePt{sub 5} specimens with a thickness of just two unit cells. We shall discuss the identification of electronic Raman losses by comparison with LaPt{sub 5} as well as the dependence of the Raman features on temperature and thickness of the intermetallic film.

  16. Crystal Field Parameters and Optical Parameters of Nd3+ in Sodium Bismuth Silicate Glass

    Directory of Open Access Journals (Sweden)

    Vinoy Thomas

    2015-06-01

    Full Text Available Neodymium doped sodium bismuth silicate glasses were prepared by the melt quench technique. Optical absorption spectra of the Nd3+ion in the present glassy systems were recorded in the UV-Vis-NIR region. Taylor series expansion method was adopted for theoretical evaluation of various crystal field parameters such as the Slater-Condon (F2,F4,F6, spin orbit and Racah parameters (E1,E2,E3. Oscillator strength and electric dipole line strength of the observed transitions were evaluated with the help of Judd-Ofelt (JO theory. Radiative transition probability (A, total radiative transition probability (At, radiative life time (trad, branching ratios (b and integrated absorption (sa cross section for stimulated emission between the meta stable state 4F3/2 and 4IJ ( J= 15/2,13/2,11/2 and 9/2 levels were calculated using JO parameters. Optical basicity of the glass was found to increase with the addition of  bismuth.

  17. Interband coherence response to electric fields in crystals: Berry-phase contributions and disorder effects

    Science.gov (United States)

    Culcer, Dimitrie; Sekine, Akihiko; MacDonald, Allan H.

    2017-07-01

    by scattering that is sensitive to the presence of the Fermi surface. To demonstrate the rich physics captured by our theory, we explicitly solve for some electric-field response properties of simple model systems that are known to be dominated by interband coherence contributions. At the same time we discuss an extensive list of complicated problems that cannot be solved analytically. Our goal is to stimulate progress in computational transport theory for electrons in crystals.

  18. Direct Writing and Aligning of Small-Molecule Organic Semiconductor Crystals via "Dragging Mode" Electrohydrodynamic Jet Printing for Flexible Organic Field-Effect Transistor Arrays.

    Science.gov (United States)

    Kim, Kyunghun; Bae, Jaehyun; Noh, Sung Hoon; Jang, Jaeyoung; Kim, Se Hyun; Park, Chan Eon

    2017-11-16

    Patterning and aligning of organic small-molecule semiconductor crystals over large areas is an important issue for their commercialization and practical device applications. This Letter reports "dragging mode" electrohydrodynamic jet printing that can simultaneously achieve direct writing and aligning of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) crystals. Dragging mode provides favorable conditions for crystal growth with efficient controls over supply voltages and nozzle-to-substrate distances. Optimal printing speed produces millimeter-long TIPS-PEN crystals with unidirectional alignment along the printing direction. These crystals are highly crystalline with a uniform packing structure that favors lateral charge transport. Organic field-effect transistors (OFETs) based on the optimally printed TIPS-PEN crystals exhibit high field-effect mobilities up to 1.65 cm 2 /(V·s). We also demonstrate the feasibility of controlling pattern shapes of the crystals as well as the fabrication of printed flexible OFET arrays.

  19. Low-dimensional compounds containing cyanido groups. XXVI. Crystal structure, spectroscopic and magnetic properties of Co(II) complexes with non-linear pseudohalide ligands

    Czech Academy of Sciences Publication Activity Database

    Váhovská, L.; Potočňák, I.; Vitushkina, S.; Dušek, Michal; Titiš, J.; Boča, R.

    2014-01-01

    Roč. 81, Oct (2014), s. 396-408 ISSN 0277-5387 Institutional support: RVO:68378271 Keywords : cobalt * dicyanamide * tricyanomethanide * crystal structure * magnetism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.011, year: 2014

  20. Broken symmetry phase transition in solid p-H 2, o-D 2 and HD: crystal field effects

    Science.gov (United States)

    Freiman, Yu. A.; Hemley, R. J.; Jezowski, A.; Tretyak, S. M.

    1999-04-01

    We report the effect of the crystal field (CF) on the broken symmetry phase transition (BSP) in solid parahydrogen, orthodeuterium, and hydrogen deuteride. The CF was calculated taking into account a distortion from the ideal HCP structure. We find that, in addition to the molecular field generated by the coupling terms in the intermolecular potential, the Hamiltonian of the system contains a crystal-field term, originating from single-molecular terms in the intermolecular potential. Ignoring the CF is the main cause of the systematic underestimation of the transition pressure, characteristic of published theories of the BSP transition. The distortion of the lattice that gives rise to the negative CF in response to the applied pressure is in accord with the general Le Chatelier-Braun principle.

  1. Effect of elastic deformation and the magnetic field on the electrical conductivity of p-Si crystals

    Science.gov (United States)

    Lys, R.; Pavlyk, B.; Didyk, R.; Shykorjak, J.; Karbovnyk, I.

    2018-03-01

    It is shown that at a deformation rate of 0.41 kg/min, the characteristic feature of the dependence of the surface resistance of the p-Si sample on the magnitude of its elastic deformation (R(σ)) is the reduction of the resistance during compression and unclamping. With the increase in the number of "compression-unclamping" cycles, the difference between the positions of the compression and unclamping curves decreases. The transformation of two types of magnetically sensitive defects occurs under the impact of a magnetic field on p-Si crystals. The defects are interrelated with two factors that cause the mutually opposite influence on the conductivity of the crystal. The first factor is that the action of the magnetic field decreases the activation energy of the dislocation holders, which leads to an increase in the electrical conductivity of the sample. The second factor is that due to the decay of molecules of oxygen-containing impurities in the magnetic field, the stable chemisorption bonds appear in the crystal that leads to a decrease in its conductivity. If the sample stays in the magnetic field for a long time, the one or the other mechanism predominates, causing a slow growth or decrease in resistance around a certain (averaged) value. Moreover, the frequency of such changes is greater in the deformed sample. The value of the surface resistance of p-Si samples does not change for a long time without the influence of the magnetic field.

  2. Thermal characterization, crystal field analysis and in-band pumped laser performance of Er doped NaY(WO(4(2 disordered laser crystals.

    Directory of Open Access Journals (Sweden)

    María Dolores Serrano

    Full Text Available Undoped and Er-doped NaY(WO42 disordered single crystals have been grown by the Czochralski technique. The specific heat and thermal conductivity (κ of these crystals have been characterized from T = 4 K to 700 K and 360 K, respectively. It is shown that κ exhibits anisotropy characteristic of single crystals as well as a κ(T behavior observed in glasses, with a saturation mean free phonon path of 3.6 Å and 4.5 Å for propagation along a and c crystal axes, respectively. The relative energy positions and irreducible representations of Stark Er(3+ levels up to (4G(7/2 multiplet have been determined by the combination of experimental low (<10 K temperature optical absorption and photoluminescence measurements and simulations with a single-electron Hamiltonian including both free-ion and crystal field interactions. Absorption, emission and gain cross sections of the (4I(13/2↔(4I(15/2 laser related transition have been determined at 77 K. The (4I(13/2 Er(3+ lifetime (τ was measured in the temperature range of 77-300 K, and was found to change from τ (77K ≈ 4.5 ms to τ (300K ≈ 3.5 ms. Laser operation is demonstrated at 77 K and 300 K by resonantly pumping the (4I(13/2 multiplet at λ≈1500 nm with a broadband (FWHM≈20 nm diode laser source perfectly matching the 77 K crystal (4I(15/2 → (4I(13/2 absorption profile. At 77 K as much as 5.5 W of output power were obtained in π-polarized configuration with a slope efficiency versus absorbed pump power of 57%, the free running laser wavelength in air was λ≈1611 nm with the laser output bandwidth of 3.5 nm. The laser emission was tunable over 30.7 nm, from 1590.7 nm to 1621.4 nm, for the same π-polarized configuration.

  3. Dielectric properties of layered FeGaInS{sub 4} single crystals in an alternating electric field

    Energy Technology Data Exchange (ETDEWEB)

    Mammadov, F. M. [Azerbaijan National Academy of Sciences, Nagiyev Institute of Catalysis and Inorganic Chemistry (Azerbaijan); Niftiyev, N. N., E-mail: namiq7@bk.ru [Azerbaijan State Pedagogical University (Azerbaijan)

    2016-09-15

    The results of investigations of the frequency and temperature dependences of dielectric losses and the imaginary part of the dielectric permittivity in FeGaInS{sub 4} single crystals are presented. Their experimental values are determined. It is established that the loss tangent and the imaginary part of the permittivity of FeGaInS{sub 4} single crystals in a field with frequencies of 10{sup 4}–10{sup 6} Hz decrease inversely proportional to the frequency (tanδ ~ 1/ω), and the conductivity is characterized by the band–hopping mechanism. For FeGaInS{sub 4}, the relaxation time is calculated, and it is established that there is a mechanism of electron polarization caused by thermal motion in this crystal.

  4. On beam shaping of the field radiated by a line source coupled to finite or infinite photonic crystals.

    Science.gov (United States)

    Ceccuzzi, Silvio; Jandieri, Vakhtang; Baccarelli, Paolo; Ponti, Cristina; Schettini, Giuseppe

    2016-04-01

    Comparison of the beam-shaping effect of a field radiated by a line source, when an ideal infinite structure constituted by two photonic crystals and an actual finite one are considered, has been carried out by means of two different methods. The lattice sums technique combined with the generalized reflection matrix method is used to rigorously investigate the radiation from the infinite photonic crystals, whereas radiation from crystals composed of a finite number of rods along the layers is analyzed using the cylindrical-wave approach. A directive radiation is observed with the line source embedded in the structure. With an increased separation distance between the crystals, a significant edge diffraction appears that provides the main radiation mechanism in the finite layout. Suitable absorbers are implemented to reduce the above-mentioned diffraction and the reflections at the boundaries, thus obtaining good agreement between radiation patterns of a localized line source coupled to finite and infinite photonic crystals, when the number of periods of the finite structure is properly chosen.

  5. Syntheses, crystal structures and characterizations of three new copper(II) azide coordination polymers with 1,2,4-triazole ligands

    Science.gov (United States)

    Liu, Jing-Jing; He, Xiang; Shao, Min; Li, Ming-Xing

    2009-02-01

    Three new copper(II) azide coordination polymers with derivatives of 1,2,4-triazole as bridging coligands, namely [Cu 2(admtrz) 2(N 3) 4] n ( 1) (admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole), [Cu(4-abpt)(N 3) 2] n·2 nH 2O ( 2) (4-abpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole) and [Cu 3(2-ptrz) 2(N 3) 6] n ( 3) (2-ptrz = 4-(2-pyridyl)-1,2,4-triazole), were prepared and characterized by elemental analyses, IR spectra and X-ray structural analyses. Compound 1 has a 1D chain structure in which Cu(II) ions are bridged by end-on (EO) azides and admtrz ligands. This compound contains three kinds of coordination modes for Cu(II) ions, including tetrahedral, square pyramidal and octahedral geometries. Compound 2 displays an interesting 3D framework structure, in which the azide ligands link Cu(II) ions in end-to-end (EE) mode affording a 2D square layer. This 2D layers are further bridged by bent 4-abpt ligands to form an interesting 3D framework. Furthermore, this structure also exhibits an alpha-Po net topology. Compound 3 displays a 1D rectangle-like chain structure linked by azides adopting end-on (EO) and end-to-end (EE) modes and 2-ptrz ligands. The IR and thermal stabilities of these coordination polymers 1-3 have also been studied.

  6. Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

    NARCIS (Netherlands)

    Matovic, Zoran D.; Meetsma, Auke; Miletic, Vesna D.; van Koningsbruggen, Petra J.; Matović, Zoran D.; Miletić, Vesna D.; D. Matović, Z.; D. Miletić, V.

    2007-01-01

    The O-O-N-N-O-type pentadentate ligands H(3)ed3a, H(3)pd3a and H(3)pd3p (H(3)ed3a stands ethylenediamine-N,N,N'-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N'-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N'-tri-3-propionic acid) and the corresponding novel octahedral or

  7. Electric field induced structural colour tuning of a silver/titanium dioxide nanoparticle one-dimensional photonic crystal

    Directory of Open Access Journals (Sweden)

    Eduardo Aluicio-Sarduy

    2016-10-01

    Full Text Available An electric field is employed for the active tuning of the structural colour in photonic crystals, which acts as an effective external stimulus with an impact on light transmission manipulation. In this work, we demonstrate structural colour in a photonic crystal device comprised of alternating layers of silver nanoparticles and titanium dioxide nanoparticles, exhibiting spectral shifts of around 10 nm for an applied voltage of only 10 V. The accumulation of charge at the metal/dielectric interface with an applied electric field leads to an effective increase of the charges contributing to the plasma frequency in silver. This initiates a blue shift of the silver plasmon band with a simultaneous blue shift of the photonic band gap as a result of the change in the silver dielectric function (i.e. decrease of the effective refractive index. These results are the first demonstration of active colour tuning in silver/titanium dioxide nanoparticle-based photonic crystals and open the route to metal/dielectric-based photonic crystals as electro-optic switches.

  8. Particles at fluid-fluid interfaces: A new Navier-Stokes-Cahn-Hilliard surface- phase-field-crystal model

    Science.gov (United States)

    Aland, Sebastian; Lowengrub, John; Voigt, Axel

    2012-10-01

    Colloid particles that are partially wetted by two immiscible fluids can become confined to fluid-fluid interfaces. At sufficiently high volume fractions, the colloids may jam and the interface may crystallize. The fluids together with the interfacial colloids form an emulsion with interesting material properties and offer an important route to new soft materials. A promising approach to simulate these emulsions was presented in Aland [Phys. FluidsPHFLE61070-663110.1063/1.3584815 23, 062103 (2011)], where a Navier-Stokes-Cahn-Hilliard model for the macroscopic two-phase fluid system was combined with a surface phase-field-crystal model for the microscopic colloidal particles along the interface. Unfortunately this model leads to spurious velocities which require very fine spatial and temporal resolutions to accurately and stably simulate. In this paper we develop an improved Navier-Stokes-Cahn-Hilliard-surface phase-field-crystal model based on the principles of mass conservation and thermodynamic consistency. To validate our approach, we derive a sharp interface model and show agreement with the improved diffuse interface model. Using simple flow configurations, we show that the new model has much better properties and does not lead to spurious velocities. Finally, we demonstrate the solid-like behavior of the crystallized interface by simulating the fall of a solid ball through a colloid-laden multiphase fluid.

  9. Particles at fluid-fluid interfaces: A new Navier-Stokes-Cahn-Hilliard surface- phase-field-crystal model.

    Science.gov (United States)

    Aland, Sebastian; Lowengrub, John; Voigt, Axel

    2012-10-01

    Colloid particles that are partially wetted by two immiscible fluids can become confined to fluid-fluid interfaces. At sufficiently high volume fractions, the colloids may jam and the interface may crystallize. The fluids together with the interfacial colloids form an emulsion with interesting material properties and offer an important route to new soft materials. A promising approach to simulate these emulsions was presented in Aland et al. [Phys. Fluids 23, 062103 (2011)], where a Navier-Stokes-Cahn-Hilliard model for the macroscopic two-phase fluid system was combined with a surface phase-field-crystal model for the microscopic colloidal particles along the interface. Unfortunately this model leads to spurious velocities which require very fine spatial and temporal resolutions to accurately and stably simulate. In this paper we develop an improved Navier-Stokes-Cahn-Hilliard-surface phase-field-crystal model based on the principles of mass conservation and thermodynamic consistency. To validate our approach, we derive a sharp interface model and show agreement with the improved diffuse interface model. Using simple flow configurations, we show that the new model has much better properties and does not lead to spurious velocities. Finally, we demonstrate the solid-like behavior of the crystallized interface by simulating the fall of a solid ball through a colloid-laden multiphase fluid.

  10. Substituted biurets as uranophilic ligands: A facile DMSO-induced conversion of a 1:1 into a 2:1 uranyl-ligand complex

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.; O' Brien, J.J.; Tham, F.S. (Rensselaer Polytechnic Inst., Troy, NY (United States))

    1990-01-01

    1,5-Bis(6-(1-ethoxycarbonyl-3-thioureido)-2-pyridindiyl)biuret and uranyl acetate gave a crystalline 1:1 uranyl-ligand complex which, on crystallization from DMSO, underwent rearrangement to a crystalline 2:1 uranyl-ligand complex and a stoichiometric amount of the uncomplexed ligand. Spectral characteristics of these ligands and their uranyl complexes together with single crystal x-ray data for the uranyl-ligand complexes are described.

  11. Complexes of biuret with Cr(III), Ag(II), Cu(III) mixed ligand and UO2(II)

    International Nuclear Information System (INIS)

    Sanyal, R.M.; Ansari, B.J.; Srivastava, P.C.; Banerjee, B.K.; Chakraburtty

    1979-01-01

    The methods of preparation of some new complexes of Cr(III), Ag(III), Cu(II) mixed ligand and UO 2 (II) and their characterisation from their electronic, infrared and ESR spectra as well as from their magnetic susceptibility values are described. Crystal field parameters of some of the complexes have been calculated. (auth.)

  12. Evaluation of the novel algorithm of flexible ligand docking with moveable target-protein atoms.

    Science.gov (United States)

    Sulimov, Alexey V; Zheltkov, Dmitry A; Oferkin, Igor V; Kutov, Danil C; Katkova, Ekaterina V; Tyrtyshnikov, Eugene E; Sulimov, Vladimir B

    2017-01-01

    We present the novel docking algorithm based on the Tensor Train decomposition and the TT-Cross global optimization. The algorithm is applied to the docking problem with flexible ligand and moveable protein atoms. The energy of the protein-ligand complex is calculated in the frame of the MMFF94 force field in vacuum. The grid of precalculated energy potentials of probe ligand atoms in the field of the target protein atoms is not used. The energy of the protein-ligand complex for any given configuration is computed directly with the MMFF94 force field without any fitting parameters. The conformation space of the system coordinates is formed by translations and rotations of the ligand as a whole, by the ligand torsions and also by Cartesian coordinates of the selected target protein atoms. Mobility of protein and ligand atoms is taken into account in the docking process simultaneously and equally. The algorithm is realized in the novel parallel docking SOL-P program and results of its performance for a set of 30 protein-ligand complexes are presented. Dependence of the docking positioning accuracy is investigated as a function of parameters of the docking algorithm and the number of protein moveable atoms. It is shown that mobility of the protein atoms improves docking positioning accuracy. The SOL-P program is able to perform docking of a flexible ligand into the active site of the target protein with several dozens of protein moveable atoms: the native crystallized ligand pose is correctly found as the global energy minimum in the search space with 157 dimensions using 4700 CPU ∗ h at the Lomonosov supercomputer.

  13. 1.2.4. Synthesis, crystal structure and thermal stability property of Ni(aze(4,4′ –bipy(H2O based on longer-spanning azelaic acid and 4,4′ -bipyridine ligands

    Directory of Open Access Journals (Sweden)

    Ge Song, Feng Ying Bai*, Yan Xie, Yong Heng Xing.

    2014-04-01

    Full Text Available Abstract: One new three-dimensional (3D supramolecular longer-spanning azelaic acid (H2aze complex: Ni(aze(4,4′– bipy(H2O (4,4′-bipy = 4,4′-bipyridine has been synthesized using hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, UV spectrum, powder X-ray diffraction, TG analysis and single crystal X–ray diffraction. Structural analysis reveals that the title complex is six-coordinate and connected by the azelaic acid and 4,4′-bipy ligands to generate a 2D planar structure, further linked through the interaction of hydrogen bond of C–H···O to form a 3D supramolecular structure . Supporting information: FT-IR, UV-Vis, X-Ray, Cif file

  14. Synthesis and crystal structure of copper (II) uracil ternary polymeric complex with 1,10-phenanthroline along with the Hirshfeld surface analysis of the metal binding sites for the uracil ligand

    Science.gov (United States)

    Patil, Yogesh Prakash; Nethaji, Munirathinam

    2015-02-01

    The study of models for "metal-enzyme-substrate" interaction has been a proactive area of research owing to its biological and pharmacological importance. In this regard the ternary copper uracil complex with 1,10-phenanthroline represents metal-enzyme-substrate system for DNA binding enzymes. The synthesis of the complex, followed by slow evaporation of the reaction mixture forms two concomitant solvatomorph crystals viz., {[Cu(phen)(μ-ura)(H2O)]n·H2O (1a)} and {[Cu(phen)(μ-ura)(H2O)]n·CH3OH (1b)}. Both complexes are structurally characterized, while elemental analysis, IR and EPR spectra were recorded for 1b (major product). In both complexes, uracil coordinates uniquely via N1 and N3 nitrogen atom acting as a bidentate bridging ligand forming a 1-D polymer. The two solvatomorphs were quantitatively analyzed for the differences with the aid of Hirshfeld surface analysis.

  15. Synthesis, Crystal Structure, Gas Absorption, and Separation Properties of a Novel Complex Based on Pr and a Three-Connected Ligand

    Directory of Open Access Journals (Sweden)

    Jie Sun

    2017-12-01

    Full Text Available A novel Pr complex, constructed from a rigid three-connected H3TMTA and praseodymium(III ion, has been synthesized in a mixed solvent system and characterized by X-ray single crystal diffraction, infrared spectroscopy, a thermogravimetric analysis, an element analysis, and powder X-ray diffraction, which reveals that complex 1 crystallizes in a three-dimensional porous framework. Moreover, the thermal stabilities and the fluorescent and gas adsorption and separation properties of complex 1 were investigated systematically.

  16. Crystal orientation effects on the piezoelectric field of strained zinc-blende quantum-well structures

    DEFF Research Database (Denmark)

    Duggen, Lars; Willatzen, Morten; Lassen, Benny

    2008-01-01

    A three-layered zinc-blende quantum-well structure is analyzed subject to both static and dynamic conditions for different crystal growth directions taking into account piezoelectric effects and lattice mismatch. It is found that the strain component Szz in the quantum-well region strongly depends...... on the crystal growth direction and that a piezoelectric strain contribution exists in zinc blende as in wurtzite, albeit smaller. It is also found in the absence of loss effects that resonance frequencies, giving large strains in the structure, depend strongly on the crystal growth direction. Due to the higher...... symmetry of the zinc-blende structure, we find in a one-dimensional model that piezoelectric effects do not affect strain values for zinc-blende structures grown along the [001] direction in contrast to the corresponding wurtzite result. However, zinc-blende structures grown along a general crystal...

  17. Mapping the field distribution of a photonic crystal resonator, using transmission SNOM

    NARCIS (Netherlands)

    Hopman, W.C.L.; van der Werf, Kees; de Ridder, R.M.

    We show that transmission SNOM (T-SNOM) can be used for imaging optical intensity distributions in a photonic crystal resonator with a resolution better than 100 nm. Two alternatives are explored: contact and tapping mode operation.

  18. High-frequency electromagnetic radiation of germanium crystals in magnetic fields

    Directory of Open Access Journals (Sweden)

    G.V. Milenin

    2017-07-01

    Full Text Available The cyclotron radiation of plasma of thermal carriers of germanium crystals, which is not in the state of thermodynamic equilibrium with semiconductor, has been experimentally confirmed.

  19. Crystal Plasticity Modeling of Microstructure Evolution and Mechanical Fields During Processing of Metals Using Spectral Databases

    Science.gov (United States)

    Knezevic, Marko; Kalidindi, Surya R.

    2017-05-01

    This article reviews the advances made in the development and implementation of a novel approach to speeding up crystal plasticity simulations of metal processing by one to three orders of magnitude when compared with the conventional approaches, depending on the specific details of implementation. This is mainly accomplished through the use of spectral crystal plasticity (SCP) databases grounded in the compact representation of the functions central to crystal plasticity computations. A key benefit of the databases is that they allow for a noniterative retrieval of constitutive solutions for any arbitrary plastic stretching tensor (i.e., deformation mode) imposed on a crystal of arbitrary orientation. The article emphasizes the latest developments in terms of embedding SCP databases within implicit finite elements. To illustrate the potential of these novel implementations, the results from several process modeling applications including equichannel angular extrusion and rolling are presented and compared with experimental measurements and predictions from other models.

  20. Light- and electric-field-induced first-order orientation transitions in a dendrimer-doped nematic liquid crystal.

    Science.gov (United States)

    Babayan, E A; Budagovsky, I A; Shvetsov, S A; Smayev, M P; Zolot'ko, A S; Boiko, N I; Barnik, M I

    2010-12-01

    Interaction of light and ac electric fields with a nematic liquid crystal (NLC) doped with nanosized second-generation carbosilane codendrimers containing terminal azobenzene fragments has been studied. A first-order Freedericksz transition in the linearly polarized light, accompanied by an intrinsic bistability in a wide region, was observed. An additional ac electric field decreases the light-induced Freedericksz transition threshold and narrows the bistability region. Light illumination transforms the second-order electric-field-induced Freedericksz transition to a first-order one. The width of the bistability region increases with the light wave intensity. The theory of the interaction of light and ac electric fields with the dendrimer-doped NLCs is developed taking into account an additional (with respect to the undoped nematic host) dependence of the optical torque on the angle between the director and the light field.

  1. Crystal field and magnetism of Pr.sup.3+./sup. and Nd.sup.3+./sup. ions in orthorhombic perovskites

    Czech Academy of Sciences Publication Activity Database

    Novák, Pavel; Knížek, Karel; Maryško, Miroslav; Jirák, Zdeněk; Kuneš, Jan

    2013-01-01

    Roč. 25, č. 44 (2013), s. 1-8 ISSN 0953-8984 R&D Projects: GA ČR GA13-25251S; GA ČR GAP204/10/0284; GA ČR(CZ) GAP204/11/0713 Institutional support: RVO:68378271 Keywords : crystal field * rare earth * ab initio method Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.223, year: 2013

  2. Tunable photonic crystal for THz radiation in layered superconductors: Strong magnetic-field dependence of the transmission coefficient

    International Nuclear Information System (INIS)

    Savel'ev, Sergey; Rakhmanov, A.L.; Nori, Franco

    2006-01-01

    Josephson plasma waves are scattered by the Josephson vortex lattice. This scattering results in a strong dependence, on the in-plane magnetic-field H ab , of the reflection and transmission of THz radiation propagating in layered superconductors. In particular, a tunable band-gap structure (THz photonic crystal) occurs in such a medium. These effects can be used, by varying H ab , for the selective frequency-filtering of THz radiation

  3. Crystal-field study of Yb.sup.3+./sup. doped LuVO.sub.4./sub..

    Czech Academy of Sciences Publication Activity Database

    Jandl, S.; Lévesque, Y.; Nekvasil, Vladimír; Bettinelli, M.

    2008-01-01

    Roč. 103, č. 11 (2008), 113102/1-113102/4 ISSN 0021-8979 R&D Projects: GA AV ČR IAA100100627 Institutional research plan: CEZ:AV0Z10100521 Keywords : crystal field interactions * doping profiles * infrared spectra * luminescence * lutetium compounds phonons * vibronic states * ytterbium Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.201, year: 2008

  4. Influence of the magnetic and laser fields on the director structures of a ferrocholesteric liquid crystal in homeotropic cells

    International Nuclear Information System (INIS)

    Petrescu, Emil; Bena, Eleonora-Rodica

    2008-01-01

    We study the influence of the magnetic and laser fields on the director structures of a ferrocholesteric liquid crystal in homeotropic cells. Using the analytical method based on the Euler-Lagrange equations, we find a correlation between the fields intensities and the confinement ratio r=d/p, (d is the cell thickness and p is the cholesteric pitch) at the limit of the transition from the homeotropic alignment to the translationally invariant configuration (TIC) with uniform in plane twist. We discuss this correlation as a function of the sign of the magnetic and dielectric anisotropies. If both anisotropies are positive and the magnetic field and the laser beam are perpendicular to the cell walls, the magnetic field preserves the homeotropic alignment while the laser beam pushes the system towards the TIC. The control parameters of the transition are the laser beam intensity and the confinement ratio. If the magnetic anisotropy is negative and the dielectric one is positive both fields concur in driving the system towards the TIC. The spinodal surface separating the metastable homeotropic configuration from the instable TIC is an ellipsoid whose halfaxes are smaller that in the case of a pure liquid crystal by a factor depending on the material constants and the cell thickness. We find also the total twist angle across the sample witch can be varied between a lower and an upper limit by changing the light intensity or the magnetic field strength. Our results can be useful in designing magneto-optical devices

  5. Numerical model of protein crystal growth in a diffusive field such as the microgravity environment

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Hiroaki, E-mail: tanakah@confsci.co.jp [Confocal Science Inc., Hayakawa 2nd Building 7F, 2-12-2 Iwamoto-cho, Chiyoda-ku, Tokyo 101-0032 (Japan); Sasaki, Susumu [Neo Force, 5-9-14-403 Tsurumaki, Setagaya-ku, Tokyo 154-0016 (Japan); Takahashi, Sachiko [Confocal Science Inc., Hayakawa 2nd Building 7F, 2-12-2 Iwamoto-cho, Chiyoda-ku, Tokyo 101-0032 (Japan); Inaka, Koji [Maruwa Foods and Biosciences Inc., 170-1 Tsutsui-cho, Yamatokoriyama, Nara 639-1123 (Japan); Wada, Yoshio; Yamada, Mitsugu; Ohta, Kazunori; Miyoshi, Hiroshi; Kobayashi, Tomoyuki; Kamigaichi, Shigeki [Japan Aerospace Exploration Agency, 2-1-1 Sengen, Tsukuba, Ibaraki 305-8505 (Japan)

    2013-11-01

    Numerical analysis of the concentration depletion zones in a transient state suggested that, in microgravity, protein crystals grow in a lower supersaturation and the impurity ratio decreases in the centre of the crystal. It is said that the microgravity environment positively affects the quality of protein crystal growth. The formation of a protein depletion zone and an impurity depletion zone due to the suppression of convection flow were thought to be the major reasons. In microgravity, the incorporation of molecules into a crystal largely depends on diffusive transport, so the incorporated molecules will be allocated in an orderly manner and the impurity uptake will be suppressed, resulting in highly ordered crystals. Previously, these effects were numerically studied in a steady state using a simplified model and it was determined that the combination of the diffusion coefficient of the protein molecule (D) and the kinetic constant for the protein molecule (β) could be used as an index of the extent of these depletion zones. In this report, numerical analysis of these depletion zones around a growing crystal in a non-steady (i.e. transient) state is introduced, suggesting that this model may be used for the quantitative analysis of these depletion zones in the microgravity environment.

  6. [Mo2(CN)11]:5- A detailed description of ligand-field spectra and magnetic properties by first-principles calculations.

    Science.gov (United States)

    Hendrickx, Marc F A; Clima, S; Chibotaru, L F; Ceulemans, A

    2005-10-06

    An ab initio multiconfigurational approach has been used to calculate the ligand-field spectrum and magnetic properties of the title cyano-bridged dinuclear molybdenum complex. The rather large magnetic coupling parameter J for a single cyano bridge, as derived experimentally for this complex by susceptibility measurements, is confirmed to a high degree of accuracy by our CASPT2 calculations. Its electronic structure is rationalized in terms of spin-spin coupling between the two constituent hexacyano-monomolybdate complexes. An in-depth analysis on the basis of Anderson's kinetic exchange theory provides a qualitative picture of the calculated CASSCF antiferromagnetic ground-state eigenvector in the Mo dimer. Dynamic electron correlations as incorporated into our first-principles calculations by means of the CASPT2 method are essential to obtain quantitative agreement between theory and experiment.

  7. A new oxidovanadium(IV) Schiff base complex containing asymmetric tetradentate ONN′O′ Schiff base ligand: synthesis, characterization, crystal structure determination, thermal study and catalytic activity

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Ghavami, A.; Eigner, Václav; Dušek, Michal; Khalaji, A.D.

    2015-01-01

    Roč. 26, č. 6 (2015), s. 779-784 ISSN 1001-8417 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : oxidovanadium(IV) * Schiff base * crystal structure * nanoparticle * epoxidation Subject RIV: CC - Organic Chemistry Impact factor: 1.947, year: 2015

  8. Synthesis, characterization, crystal structure, catalytic activity in oxidative bromination, and thermal study of a new oxidovanadium Schiff base complex containing O, N-bidentate Schiff base ligand

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Tahmasebi, V.; Khalaji, A.D.; Eigner, Václav; Dušek, Michal

    2014-01-01

    Roč. 67, č. 22 (2014), s. 3664-3677 ISSN 0095-8972 Institutional support: RVO:68378271 Keywords : oxidovanadium(IV) * Schiff base * single crystal * oxidative bromination Subject RIV: CA - Inorganic Chemistry Impact factor: 2.012, year: 2014

  9. Anisotropy of the upper critical fields and the paramagnetic Meissner effect in La1.85Sr0.15CuO4 single crystals

    Science.gov (United States)

    Felner, I.; Tsindlekht, M. I.; Drachuck, G.; Keren, A.

    2013-02-01

    Optimally doped La1.85Sr0.15CuO4 single crystals have been investigated by dc and ac magnetic measurements. These crystals have rectangular needle-like shapes with the long needle axis parallel to the crystallographic c axis (c-crystal) or parallel to the basal planes (a-crystal). In both crystals, the temperature dependence of the upper critical fields (HC2) and the surface critical field (HC3) were measured. The H-T phase diagram is presented. Close to TC = 35 K, for the c-crystal, {\\boldsymbol{\\gamma}}^{c}={H}_{{C3}}^{c}/{H}_{{C2}}^{c}=1.8 0(2), whereas for the a-crystal the {\\boldsymbol{\\gamma}}^{a}={H}_{{C3}}^{a}/{H}_{{C2}}^{a}=4.0(2) obtained is much higher than 1.69, predicted by the ideal mathematical model. At low applied dc fields, positive field-cooled branches known as the ‘paramagnetic Meissner effect’ (PME) are observed; their magnitude is inversely proportional to H. The anisotropic PME is observed in both a- and c-crystals, only when the applied field is along the basal planes. It is speculated that the high γa and the PME are connected to each other.

  10. Crystal Structure and Band-Gap Engineering of a Semiconducting Coordination Polymer Consisting of Copper(I) Bromide and a Bridging Acceptor Ligand.

    Science.gov (United States)

    Okubo, Takashi; Himoto, Kento; Tanishima, Koki; Fukuda, Sanshiro; Noda, Yusuke; Nakayama, Masanobu; Sugimoto, Kunihisa; Maekawa, Masahiko; Kuroda-Sowa, Takayoshi

    2018-03-05

    A new semiconducting 3D coordination polymer, [Cu 2 Br 2 (ttz)] n (1), with an acceptor bridging ligand, 1,2,4,5-tetrazine (ttz), was synthesized. The complex shows large absorption bands extending to the near-IR region, indicating a small band gap in the coordination polymer. This complex shows higher conductivity than those of [CuBr(pyz)] n (2), including pyrazine (pyz) with a higher lowest unoccupied molecular orbital level. We performed density functional theory band calculations using the VASP program to understand the electronic states and conducting paths of the coordination polymer.

  11. Four crystal structures of human LLT1, a ligand of human NKR-P1, in varied glycosylation and oligomerization states

    Czech Academy of Sciences Publication Activity Database

    Skálová, Tereza; Bláha, J.; Harlos, K.; Dušková, Jarmila; Koval, Tomáš; Stránský, Jan; Hašek, Jindřich; Vaněk, O.; Dohnálek, Jan

    2015-01-01

    Roč. 71, č. 3 (2015), s. 578-591 ISSN 1399-0047 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0109; GA ČR GAP302/11/0855; GA ČR(CZ) GA15-15181S; GA MŠk LG14009; GA MŠk(CZ) EE2.3.30.0029 Institutional support: RVO:86652036 ; RVO:61389013 Keywords : LLT1 * C-type lectin -like ligand * NATURAL-KILLER-CELLS Subject RIV: EB - Genetics ; Molecular Biology; EB - Genetics ; Molecular Biology (UMCH-V) Impact factor: 2.674, year: 2014

  12. Crystal structure, configurational and DFT-NEDA analysis of nickel(II) complexes with pentadentate ed3a-type ligands

    NARCIS (Netherlands)

    Belosevic, Svetlana; Cendic, Marina; Meetsma, Auke; Matovic, Zoran D.

    2013-01-01

    The O-O-N-N-O-type pentadentate ligands H(3)ed3a, H(3)1,2-pd3a, H(3)eda2p and H(3)ed3p (H(3)ed3a stands for ethylenediamine-N,N,N'-triacetic acid; H(3)1,2-pd3a stands for 1,2-propanediamine-N,N,N'-triacetic acid; H(3)eda2p stands for ethylenediamine-N-acetato-N,N'-di-3-propionic acid and H(3)ed3p

  13. Structural color tuning in a Ag/TiO2 nanoparticle one-dimensional photonic crystal induced by electric field

    Science.gov (United States)

    Aluicio-Sarduy, Eduardo; Callegari, Simone; Figueroa del Valle, Diana Gisell; Desii, Andrea; Kriegel, Ilka; Scotognella, Francesco

    2017-02-01

    We present the electric field-induced tuning of the light transmission in a photonic crystal device. The device, with alternating layers of Silver and Titanium dioxide nanoparticles, shows a shift of around 10 nm for an applied voltage of 10 V. An accumulation of charges at the Silver/TiO2 interface due to electric field leads to an increase of the number of charges contributing to the plasma frequency in Silver. This results in a blue shift of the Silver plasmon band, with concomitant blue shift of the photonic band gap as a result of the decrease in the Silver dielectric function.

  14. Crystal structures of a copper(II and the isotypic nickel(II and palladium(II complexes of the ligand (E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-ol

    Directory of Open Access Journals (Sweden)

    Souheyla Chetioui

    2016-08-01

    Full Text Available In the copper(II complex, bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}copper(II, [Cu(C16H8Br3N2O2], (I, the metal cation is coordinated by two N atoms and two O atoms from two bidentate (E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olate ligands, forming a slightly distorted square-planar environment. In one of the ligands, the tribromobenzene ring is inclined to the naphthalene ring system by 37.4 (5°, creating a weak intramolecular Cu...Br interaction [3.134 (2 Å], while in the other ligand, the tribromobenzene ring is inclined to the naphthalene ring system by 72.1 (6°. In the isotypic nickel(II and palladium(II complexes, namely bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}nickel(II, [Ni(C16H8Br3N2O2], (II, and bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}palladium(II, [Pd(C16H8Br3N2O2], (III, respectively, the metal atoms are located on centres of inversion, hence the metal coordination spheres have perfect square-planar geometries. The tribromobenzene rings are inclined to the naphthalene ring systems by 80.79 (18° in (II and by 80.8 (3° in (III. In the crystal of (I, molecules are linked by C—H...Br hydrogen bonds, forming chains along [010]. The chains are linked by C—H...π interactions, forming sheets parallel to (011. In the crystals of (II and (III, molecules are linked by C—H...π interactions, forming slabs parallel to (10-1. For the copper(II complex (I, a region of disordered electron density was corrected for using the SQUEEZE routine in PLATON [Spek (2015. Acta Cryst. C71, 9–18]. The formula mass and unit-cell characteristics of the disordered solvent molecules were not taken into account during refinement.

  15. Synthesis, X-ray crystal structure, photo luminescent property, antimicrobial activities and DFT computational study of Zn(II) coordination polymer derived from multisite N,O donor Schiff base ligand (H2L1)

    Science.gov (United States)

    Majumdar, Dhrubajyoti; Surendra Babu, M. S.; Das, Sourav; Biswas, Jayanta Kumar; Mondal, Monojit; Hazra, Suman

    2017-06-01

    A unique thiocyanato linked 1D chain of Zn(II) coordination polymer [Zn2L1(μ1,3-SCN)(η1SCN)]n (1) has been synthesized using potential multisite compartmental N,O donor Schiff base blocker ligand (L1H2) in presence of Zn(OAc)2 and KSCN. The Schiff base ligand [N, N‧-bis(3-methoxysalicylidenimino)-1,3-daminopropane] (L1H2) is 2:1 M ratio condensation product of O-vaniline and 1,3-diaminopropane in methanol medium. The characterization of Complex 1 was accomplished by means of different micro analytical techniques like elemental analyses, IR, UV-Vis, 1H NMR, emission spectroscopy and Single X-ray crystallographic study. Complex 1 crystallizes in Orthorhombic system, space group Pbca, with values a = 11.579(2), b = 18.538(3), and c = 22.160(4) Å; α = β = γ = 90.00°; V = 4756.6(14) and Z = 8. The single crystal X-ray revealed that the one dimensional chain system with the repeating unit [Zn2(μ1,3-SCN)(η1SCN)(L1)]n bridge by an end to end μ1,3 thiocyanate anion. Within each repeating unit two different types of Zn(II) ions are present. One of these is five-coordinate in a square pyramidal geometry while the other is six-coordinate in an octahedral geometry. A brief but lucid comparative approach has been demonstrated in between Schiff base (L1H2) and complex 1 with respect to their photoluminescence activities. Active luminescence behavior of complex 1 in presence of ligand (L1H2) is due to quenching of PET process which is mediated by 'chelating effect'. Complex 1 exhibits strong antimicrobial efficacy against some important Gram + ve and Gram -ve bacteria. Apart from antimicrobial potential, a combined experimental and theoretical investigation has been performed via DFT on molecular structure of complex 1 with respect to Hirshfeld surface analysis.

  16. End-to-end single cyanato and thiocyanato bridged Cu(II) polymers with a new tridentate Schiff base ligand: crystal structure and magnetic properties.

    Science.gov (United States)

    Talukder, Pritha; Datta, Amitabha; Mitra, Samiran; Rosair, Georgina; El Fallah, M Salah; Ribas, Joan

    2004-12-21

    A new tridentate Schiff base ligand HL (L = C14H19N2O), derived from the condensation of benzoylacetone and 2-dimethylaminoethylamine in a 1:1 ratio, reacts with copper(ii) acetate and cyanate, thiocyanate or azide, to give rise to several end-to-end polymeric complexes of formulae [CuL(mu(1,3)-NCO)]n 1, [CuL(mu(1,3)-NCS)]n 2 and the complex 3 has two crystallographically independent units of formula [CuL(N3)] in the asymmetric unit cell. Complex 3 exists in dimeric form rather than as a polymeric chain. Compound 1 is the first report of a singly end-to-end cyanate bridged polymeric chain of Cu(II) with a Schiff base as a co-ligand. There are many examples of double NCS bridged polymeric chains, but fewer singly bridged ones such as compound 2. We have characterized these complexes by analytical, spectroscopic, structural and variable temperature magnetic susceptibility measurements. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2 and square planar for complex 3. The magnetic susceptibility data show slight antiferromagnetic coupling for the polymers having J values -0.19 and -0.57 cm(-1) for complexes 1 and 2 respectively. The low values of J are consistent with the equatorial-axial disposition of the bridges in the polymers.

  17. Four unprecedented cobalt(II) and cadmium(II) metal-organic frameworks based on a rigid tricarboxylate ligand: Synthesis, crystal structures, magnetic and fluorescence properties

    Science.gov (United States)

    Liu, Yaru; Liu, Lan; Zhang, Xiao; Wu, Jie

    2018-03-01

    A Co(II) MOF {[Co3(L)2(H2O)4](DMF)2}n (1) and three Cd(II) MOFs [Cd3(L)2(H2O)7]n (2), [Cd3(L)2(H2O)11]n (3) and [Cd3(L)2(DMF)2(H2O)]n (4) are synthesized based on the promising multifunctional tricarboxylate ligand 6-(3, 5-dicarboxyl phenyl) nicotinic acid (H3L). 1 exhibits a 3D framework with 1D channels which contains opposite-handedness helical chains based on the trinuclear Co(II) clusters. 2-4 are obtained depend on different reaction conditions. 2 displays a 3D framework, which is composed of two kinds of 2D layers linked with each other. 3 shows a rare tongue-and-groove-type bilayer structure. And 4 is an interesting 3D framework containing infinite 1D inorganic Cdsbnd Osbnd Cd chains. In these MOFs, the H3L ligand shows the versatile coordination modes and strong coordination ability. Furthermore, the magnetic and solid-state luminescent properties of the MOFs have been investigated.

  18. Negative Differential Velocity in Artificial Crystals Probed by High Magnetic Fields

    Science.gov (United States)

    Patanè, A.

    -level, where they become spatially localized.7-10 This Resonant Electron Localization in Electric Field, to which we give the acronym RELIEF, leads to NDV and strongly non-linear current-voltage characteristics. We envisage that the RELIEF-effect could be observed in other III-N-V alloys, such as InP1-xNx and InAs1-xNx. In these compounds the nature of the resonant interaction between the N-level and the conduction band states of the host-crystal is still relatively unexplored. However, it is clear that the different energy positions of the N-level relative to the conduction band minimum of different materials could offer new degrees of freedom in the design of the electronic band structure and electron dynamics. The RELIEF-effect may open up prospects for future applications in fast electronics. We have shown that the maximum response frequency, fmax, of a RELIEF-diode can be tuned by the applied electric field in the THz frequency range.7 This is of potential technological significance for the development of detectors/sources in the 0.6-1 THz region, which is not currently attainable using conventional Transferred Electron Devices and Quantum Cascade Lasers. Our recent studies of GaAs1-xNx have also shown a fast response of the current in the sub-T

  19. Far-field and Fresnel Liquid Crystal Geometric Phase Holograms via Direct-Write Photo-Alignment

    Directory of Open Access Journals (Sweden)

    Xiao Xiang

    2017-12-01

    Full Text Available We study computer-generated geometric-phase holograms (GPHs realized by photo-aligned liquid crystals, in both simulation and experiment. We demonstrate both far-field and Fresnel holograms capable of producing far-field and near-field images with preserved fidelity for all wavelengths. The GPHs are fabricated by patterning a photo-alignment layer (PAL using a direct-write laser scanner and coating the surface with a polymerizable liquid crystal (i.e., a reactive mesogen. We study various recording pixel sizes, down to 3 μm, that are easily recorded in the PAL. We characterize the fabricated elements and find good agreement with theory and numerical simulation. Because of the wavelength independent geometric phase, the (phase fidelity of the replay images is preserved for all wavelengths, unlike conventional dynamic phase holograms. However, governed by the diffraction equation, the size and location of a reconstructed image depends on the replay wavelength for far-field and near-field GPHs, respectively. These offer interesting opportunities for white-light holography.

  20. Polarization-Dependent Photoinduced Bias-Stress Effect in Single-Crystal Organic Field-Effect Transistors.

    Science.gov (United States)

    Choi, Hyun Ho; Najafov, Hikmet; Kharlamov, Nikolai; Kuznetsov, Denis V; Didenko, Sergei I; Cho, Kilwon; Briseno, Alejandro L; Podzorov, Vitaly

    2017-10-04

    Photoinduced charge transfer between semiconductors and gate dielectrics can occur in organic field-effect transistors (OFETs) operating under illumination, leading to a pronounced bias-stress effect in devices that are normally stable while operating in the dark. Here, we report an observation of a polarization-dependent photoinduced bias-stress effect in two prototypical single-crystal OFETs, based on rubrene and tetraphenylbis(indolo{1,2-a})quinolin. We find that the decay rate of the source-drain current in these OFETs under illumination is a periodic function of the polarization angle of incident photoexcitation with respect to the crystal axes, with a periodicity of π. The angular positions of maxima and minima of the bias-stress rate match those of the optical absorption coefficient of the corresponding crystals. The analysis of the effect shows that it stems from a charge transfer of "hot" holes, photogenerated in the crystal within a very short thermalization length (≪μm) from the semiconductor-dielectric interface. The observed phenomenon is a type of intrinsic structure-property relationship, revealing how molecular packing affects parameter drift in organic transistors under illumination. We also demonstrate that a photoinduced charge transfer in OFETs can be used for recording rewritable accumulation channels with an optically defined geometry and resolution, which can be used in a number of potential applications.

  1. Propagation characteristics of a focused laser beam in a strontium barium niobate photorefractive crystal under reverse external electric field.

    Science.gov (United States)

    Guo, Q L; Liang, B L; Wang, Y; Deng, G Y; Jiang, Y H; Zhang, S H; Fu, G S; Simmonds, P J

    2014-10-01

    The propagation characteristics of a focused laser beam in a SBN:75 photorefractive crystal strongly depend on the signal-to-background intensity ratio (R=Is/Ib) under reverse external electric field. In the range 20>R>0.05, the laser beam shows enhanced self-defocusing behavior with increasing external electric field, while it shows self-focusing in the range 0.03>R>0.01. Spatial solitons are observed under a suitable reverse external electric field for R=0.025. A theoretical model is proposed to explain the experimental observations, which suggest a new type of soliton formation due to "enhancement" not "screening" of the external electrical field.

  2. In-situ temperature field measurements and direct observation of crystal/melt at vertical Bridgman growth of lead chloride under stationary and dynamic arrangement

    Czech Academy of Sciences Publication Activity Database

    Král, Robert; Nitsch, Karel

    2015-01-01

    Roč. 427, Oct (2015), 7-15 ISSN 0022-0248 R&D Projects: GA MŠk(CZ) LH14266 Institutional support: RVO:68378271 Keywords : single crystal growth * temperature field measurements * crystal/melt interface * lead chloride * vertical Bridgman method Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.462, year: 2015

  3. Highly Sensitive Ammonia Gas Sensor Based on Single-Crystal Poly(3-hexylthiophene) (P3HT) Organic Field Effect Transistor.

    Science.gov (United States)

    Mun, Seohyun; Park, Yoonkyung; Lee, Yong-Eun Koo; Sung, Myung Mo

    2017-11-28

    A highly sensitive organic field-effect transistor (OFET)-based sensor for ammonia in the range of 0.01 to 25 ppm was developed. The sensor was fabricated by employing an array of single-crystal poly(3-hexylthiophene) (P3HT) nanowires as the organic semiconductor (OSC) layer of an OFET with a top-contact geometry. The electrical characteristics (field-effect mobility, on/off current ratio) of the single-crystal P3HT nanowire OFET were about 2 orders of magnitude larger than those of the P3HT thin film OFET with the same geometry. The P3HT nanowire OFET showed excellent sensitivity to ammonia, about 3 times higher than that of the P3HT thin film OFET at 25 ppm ammonia. The ammonia response of the OFET was reversible and was not affected by changes in relative humidity from 45 to 100%. The high ammonia sensitivity of the P3HT nanowire OFET is believed to result from the single crystal nature and high surface/volume ratio of the P3HT nanowire used in the OSC layer.

  4. Raman study of crystal-field excitations in Pr{sub 2}CuO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Jandl, S. [Centre de Recherche en Physique du Solide, Departement de Physique, Universite de Sherbrooke, Sherbrooke, Quebec, J1K2R1 (CANADA); Strach, T.; Ruf, T.; Cardona, M. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, D-70569 Stuttgart (Germany); Nekvasil, V. [Institute of Physics, Czech Academy of Sciences, Cukrovarnicka 10, 162 00 Prague 6 (Czech Republic); Iliev, M. [Faculty of Physics, University of Sofia, BG-1126 Sofia (Bulgaria); Zhigunov, D.I.; Barilo, S.N.; Shiryaev, S.V. [Institute of Physics of Solids and Semiconductors, Academy Science Belarus, Tolstoi street 4, 220072 Minsk (Belarus)

    1997-09-01

    Raman measurements in a Pr{sub 2}CuO{sub 4} single crystal show structures related to nine crystal-field (CF) excitations. They correspond to transitions within the {sup 3}H{sub 4}, {sup 3}H{sub 5}, and {sup 3}H{sub 6} multiplets of Pr{sup 3+} ions in C{sub 4v} site symmetry. Satellites to these CF excitations are also observed and associated with the presence of an inequivalent Pr{sup 3+} site of lower symmetry. A set of CF parameters which describes the observed energy spectra is derived and compared to previous calculations. {copyright} {ital 1997} {ital The American Physical Society}

  5. Quasi-static crack tip fields in rate-sensitive FCC single crystals

    Indian Academy of Sciences (India)

    gle crystals are now well-understood. On the other hand, there has been no investigation on the effect of strain rate sensitivity and loading rate on the stress and plastic slip distribution as well as constraint levels near a tip. Thus, the objective of this work is to examine the general structure of these distributions and the plastic ...

  6. Structure fits the purpose: photonic crystal fibers for evanescent-field surface-enhanced Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Oo, M. K .K.; Han, Y.; Kaňka, Jiří; Sukhishvili, S.; Du, H.

    2010-01-01

    Roč. 35, č. 4 (2010), s. 466-468 ISSN 0146-9592 R&D Projects: GA ČR GA102/08/1719 Institutional research plan: CEZ:AV0Z20670512 Keywords : Photonic crystal fiber * Raman spectroscopy * Fiber - optic evanescent sensor Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 3.316, year: 2010

  7. Determination of crystal and molecular structures of two complexes resulting from the reaction between bis (diethyl muconate) monocarbonyliron and monodentate nitrogenated heterocyclic ligands, by X-ray diffractometry

    International Nuclear Information System (INIS)

    Inumaru, A.T.

    1983-01-01

    The crystal structures of (diethylmuconate) (quinoline) dicarbonyliron and (diethyl muconate) (pyrazine) dicarbonyliron have been determined from diffractometric X-ray data using the heavy atom method. (Diethyl muconate) (quinoline) dicarbonyliron. C 21 H 21 O 6 NFe. Crystal system: triclinic; space group P1 sup(-); a=7.766(2), b=9.664(2), c=14.917(2)A sup(o), α=84.12(2), β=74.99(2), γ=76.54(2) sup(o), V=1050.6(5)A sup(o) 3 , Z=2, D sub(c)=1.382 Mg m -3 , lambda(M sub(o) K sub(α))=0.71073A sup(o), μ(M sub(o) K sub(α))=0.78mm -1 . The final R-factor was 0.058 for 1589 reflections with I>3σ(I). (Diethyl muconate) (pyrazine) dicarbonyliron. C 16 H 18 O 6 N 2 Fe. Crystal system: monoclinic; space group P2 1 /C; a=10.390(2), b=19.754(4), c=9.051(2)A sup(o), β=108.27(2) sup(o), V=1764(1)A sup(o) 3 , Z=4, D sub(c)=1.469 Mg m -3 , lambda(M sub(o) K sub(α))=0.71073A sup(o), μ(M sub(o) K sub(α))=0.98mm -1 . The final R-factor was 0.066 for 967 reflections with I>3σ(I). In both compunds the Fe sup(o) atom is penta coordinated in the form of a quadrangular pyramid, being that the nitrogen atom occupies the apical position in the pyrazine complex and one of the basal positions in the quinolinecase. (Author) [pt

  8. Plasmodium falciparum field isolates from South America use an atypical red blood cell invasion pathway associated with invasion ligand polymorphisms

    DEFF Research Database (Denmark)

    Lopez-Perez, Mary; Villasis, Elizabeth; Machado, Ricardo L D

    2012-01-01

    members of the PfRh (PfRh1, PfRh2a, PfRh2b, PfRh4, PfRh5) families were determined. We found that most P. falciparum field isolates from Colombia and Peru invade RBCs through an atypical invasion pathway phenotypically characterized as resistant to all enzyme treatments (NrTrCr). Moreover, the invasion...... blood stage vaccine design focused on invasion pathway proteins, suggesting that regional invasion variants and global geographical variation are likely to preclude a simple one size fits all type of vaccine....

  9. Intensifying the density of a horizontal electric field to improve light efficiency in a fringe-field switching liquid crystal display

    Energy Technology Data Exchange (ETDEWEB)

    Yu, In Ho; Song, Il Sub; Lee, Ji Youn; Lee, Seung Hee [Research Center of Advanced Material Development, School of Advanced Materials Engineering, Chonbuk National University, Chonju, Chonbuk 561-756 (Korea, Republic of)

    2006-06-07

    The transmittance in fringe-field switching liquid crystal (LC) displays, which show a wide viewing angle, is dependent on the position along the electrode position. The reason for this is that the dielectric torque (and hence the twist angle) varies with position. This effect depends on the type of LC: a display using an LC with positive dielectric anisotropy has less transmittance than one with negative dielectric anisotropy. Furthermore, the transmittance decreases with decreasing cell gap. The difference between the LC types can be reduced and the transmittance can be improved greatly even for a low cell gap by optimizing the electrode structure to enhance the region of in-plane twist.

  10. Vectorial magnetic field sensing with a dual-core photonic-crystal fiber: Toward fiber-optic stereomagnetometry

    Science.gov (United States)

    Blakley, S.; Becker, J.; Fedotov, I. V.; Kilin, S. Ya.; Sakoda, K.; Zheltikov, A. M.

    2018-02-01

    A monolithic, ultra-compact fiber probe integrating a nitrogen-vacancy diamond microcrystal, a dual-core photonic-crystal fiber (PCF), and a microwave transmission line is shown to enable a highly sensitive dual-channel vectorial magnetic field measurements by means of simultaneous optical detection of magnetic resonances through the two fiber cores. A reliable detection of microscale magnetic-field variations as low as ˜10 µT/(Hz)1/2 is demonstrated using a dual-core PCF with a core-to-core separation of 6 µm. Such a fiber probe is shown to provide a unique tool for a vectorial three-dimensional mapping of weak magnetic fields induced by microscale objects.

  11. Transferable force field for crystal structure predictions, investigation of performance and exploration of different rescoring strategies using DFT-D methods.

    Science.gov (United States)

    Broo, Anders; Nilsson Lill, Sten O

    2016-08-01

    A new force field, here called AZ-FF, aimed at being used for crystal structure predictions, has been developed. The force field is transferable to a new type of chemistry without additional training or modifications. This makes the force field very useful in the prediction of crystal structures of new drug molecules since the time-consuming step of developing a new force field for each new molecule is circumvented. The accuracy of the force field was tested on a set of 40 drug-like molecules and found to be very good where observed crystal structures are found at the top of the ranked list of tentative crystal structures. Re-ranking with dispersion-corrected density functional theory (DFT-D) methods further improves the scoring. After DFT-D geometry optimization the observed crystal structure is found at the leading top of the ranking list. DFT-D methods and force field methods have been evaluated for use in predicting properties such as phase transitions upon heating, mechanical properties or intrinsic crystalline solubility. The utility of using crystal structure predictions and the associated material properties in risk assessment in connection with form selection in the drug development process is discussed.

  12. Study of crystal-field excitations and Raman active phonons in o-DyMnO3

    International Nuclear Information System (INIS)

    Jandl, S.; Mansouri, S.; Mukhin, A.A.; Yu Ivanov, V.; Balbashov, A.; Gospodino, M.M.; Nekvasil, V.; Orlita, M.

    2011-01-01

    In DyMnO 3 orthorhombic single crystals, the weak Raman active phonon softening below T=100 K is correlated with the study of infrared active Dy 3+ CF excitations as a function of temperature and under applied magnetic field. We detect five H 13/2 CF transitions that we predict with appropriate CF Hamiltonian and we confirm that the magnetic easy axis lies in the ab plane. While the CF energy level shifts below T=100 K reflect different displacements of the oxygen ions that contribute to the phonon softening, lifting of the ground state Kramers doublet degeneracy (∼30 cm -1 ) is observed below T N =39 K due to the anisotropic Mn 3+ -Dy 3+ interaction, which could be responsible for the stability of the bc-cycloid ferroelectric phase. - Research highlights: → Origin of Raman active phonon softening in the multiferroic o-DyMnO 3 . → A crystal-field study under magnetic field of Dy 3+ in o-DyMnO 3 . → Location of the magnetic easy axis in o-DyMnO 3 . → Lifting of Kramers doublet degeneracy in o-DyMnO 3 .

  13. On the neutron diffraction in crystals in the field of a standing sound wave

    International Nuclear Information System (INIS)

    Grigoryan, K.K.; Hayrapetyan, A.G.; Petrosyan, R.G.

    2010-01-01

    The diffraction of neutrons is considered in crystals under the influence of a standing sound wave. The scattering probability is calculated for the elastic neutron-crystal interaction, whereas the neutron-standing sound wave interaction can be either elastic and inelastic. The possibility of short-wave (high-energy) neutrons diffraction is illustrated. It is shown that the Debye-Waller factor can be changed and tuned. The analysis of conservation laws are adduced both for thermal and short-wave neutrons. The formation of a 'sublattice' is shown in the process of neutrons elastic diffraction with respect to standing sound wave. The analogous to the Kapitza-Dirac effect is considered for neutrons. The problem is solved within the frame of non-stationary S-matrix theory, where the neutron-phonon interaction is described by the Fermi pseudopotential, which is considered as a perturbation.

  14. Te inclusion-induced electrical field perturbation in CdZnTe single crystals revealed by Kelvin probe force microscopy.

    Science.gov (United States)

    Gu, Yaxu; Jie, Wanqi; Li, Linglong; Xu, Yadong; Yang, Yaodong; Ren, Jie; Zha, Gangqiang; Wang, Tao; Xu, Lingyan; He, Yihui; Xi, Shouzhi

    2016-09-01

    To understand the effects of tellurium (Te) inclusions on the device performance of CdZnTe radiation detectors, the perturbation of the electrical field in and around Te inclusions was studied in CdZnTe single crystals via Kelvin probe force microscopy (KPFM). Te inclusions were proved to act as lower potential centers with respect to surrounding CdZnTe matrix. Based on the KPFM results, the energy band diagram at the Te/CdZnTe interface was established, and the bias-dependent effects of Te inclusion on carrier transportation is discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Noninvasive Vibrational Mode Spectroscopy of Ion Coulomb Crystals through Resonant Collective Coupling to an Optical Cavity Field

    DEFF Research Database (Denmark)

    Dantan, Aurélien; Marler, Joan; Albert, Magnus

    2010-01-01

    We report on a novel noninvasive method to determine the normal mode frequencies of ion Coulomb crystals in traps based on the resonance enhanced collective coupling between the electronic states of the ions and an optical cavity field at the single photon level. Excitations of the normal modes...... are observed through a Doppler broadening of the resonance. An excellent agreement with the predictions of a zero-temperature uniformly charged liquid plasma model is found. The technique opens up for investigations of the heating and damping of cold plasma modes, as well as the coupling between them....

  16. Determination of the spin orbit coupling and crystal field splitting in wurtzite InP by polarization resolved photoluminescence

    Science.gov (United States)

    Chauvin, Nicolas; Mavel, Amaury; Jaffal, Ali; Patriarche, Gilles; Gendry, Michel

    2018-02-01

    Excitation photoluminescence spectroscopy is usually used to extract the crystal field splitting (ΔCR) and spin orbit coupling (ΔSO) parameters of wurtzite (Wz) InP nanowires (NWs). However, the equations expressing the valence band splitting are symmetric with respect to these two parameters, and a choice ΔCR > ΔSO or ΔCR silicon. The experimental results combined with a theoretical model and finite difference time domain calculations allow us to conclude that ΔCR > ΔSO in Wz InP.

  17. Synthesis and physicochemical characterization of two lead(II) complexes with O-, N-donor ligands. Lone pair functionality and crystal structure

    Science.gov (United States)

    Masternak, Joanna; Barszcz, Barbara; Hodorowicz, Maciej; Khavryuchenko, Oleksiy V.; Majka, Alina

    2015-02-01

    A dinuclear [Pb2(4-CHO-5-MeIm)6(NO3)2](NO3)2 (1) and a polynuclear [Pb(2-pzc)2(H2O)]n (2) complexes (where 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm) and pyrazine-2-carboxylic acid (2-pzcH)) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Structural determination for complex 1 reveals a cationic species [Pb(4-CHO-5-MeIm)3]2+ connected through bridging nitrate(V) ions. There are also an uncoordinated nitrate ions as counterions. Complex 2 is a three-dimensional architecture consisting of Pb6O12 building units. The pyrazine-2-carboxylato ligand behaves as a chelating agent and a bi-connective bridge. The coordination polyhedra around lead(II) ion could be described as a distorted docecahedron (1) or monocapped trigonal prism (2). The luminescent properties of 1 and 2 investigated in the solid state at room temperature indicate structure-dependent photoluminescent properties. The DFT calculations and the X-ray structural data point on rather hemidirected type of coordination around Pb(II) ions of 1 and 2.

  18. Dependence of Internal Crystal Structures of InAs Nanowires on Electrical Characteristics of Field Effect Transistors

    Science.gov (United States)

    Han, Sangmoon; Choi, Ilgyu; Lee, Kwanjae; Lee, Cheul-Ro; Lee, Seoung-Ki; Hwang, Jeongwoo; Chung, Dong Chul; Kim, Jin Soo

    2018-02-01

    We report on the dependence of internal crystal structures on the electrical properties of a catalyst-free and undoped InAs nanowire (NW) formed on a Si(111) substrate by metal-organic chemical vapor deposition. Cross-sectional transmission electron microscopy images, obtained from four different positions of a single InAs NW, indicated that the wurtzite (WZ) structure with stacking faults was observed mostly in the bottom region of the NW. Vertically along the InAs NW, the amount of stacking faults decreased and a zinc-blende (ZB) structure was observed. At the top of the NW, the ZB structure was prominently observed. The resistance and resistivity of the top region of the undoped InAs NW with the ZB structure were measured to be 121.5 kΩ and 0.19 Ω cm, respectively, which are smaller than those of the bottom region with the WZ structure, i.e., 251.8 kΩ and 0.39 Ω cm, respectively. The reduction in the resistance of the top region of the NW is attributed to the improvement in the crystal quality and the change in the ZB crystal structure. For a field effect transistor with an undoped InAs NW channel, the drain current versus drain-source voltage characteristic curves under various negative gate-source voltages were successfully observed at room temperature.

  19. Application of the anisotropic phase-field crystal model to investigate the lattice systems of different anisotropic parameters and orientations

    Science.gov (United States)

    Kundin, Julia; Ajmal Choudhary, Muhammad

    2017-07-01

    In this article, we present the recent advances in the development of the anisotropic phase-field crystal (APFC) model. These advances are important in basic researches for multiferroic and thermoelectric materials with anisotropic crystal lattices and in thin-film applications. We start by providing a general description of the model derived in our previous studies based on the crystal symmetry and the microscopic dynamical density functional theory for anisotropic interactions and show that there exist only two possible degrees of freedom for the anisotropic lattices which are described by two independent parameters. New findings concerning the applications of the APFC model for the estimation of the elastic modules of anisotropic systems including sheared and stretched lattices as well as for the investigation of the heterogeneous thin film growth are described. The simulation results demonstrate the strong dependency of the misfit dislocation formation during the film growth on the anisotropy and reveal the asymmetric behavior in the cases of positive and negative misfits. We also present the development of the amplitude representation for the full APFC model of two orientation variants and show the relationship between the wave vectors and the base angles of the anisotropic lattices.

  20. Copper and manganese complexes based on 1,4-naphthalene dicarboxylic acid ligand and its derivative: Syntheses, crystal structures, and magnetic properties

    Science.gov (United States)

    Xing, Yubo; Liu, Yuqi; Xue, Xiaofei; Wang, Xinying; Li, Wei

    2018-02-01

    Three new metal-organic coordination polymers, {[Mn2(1,4-NDC)2 (C2H5OH) (DMF) (H2O)]·CH3OH}n(1), {[Mn(III)(1,4-NDC)(C2H5O)][Mn(II)(1,4-NDC)(DMF)(H2O)]}n(2) and {[Cu2(C13H9O4)4(H2O)2]}n(3) based on1,4-H2NDC and its derivative were hydrothermally synthesized (1,4-H2NDC = 1,4-naphthalene-dicarboxylic acid, C13H10O4 = 4-methyl formate-1-naphthalenecarboxylic acid), and characterized by techniques of single crystal X-ray diffraction, infrared spectra (IR), elemental analysis, powder X-ray diffraction(PXRD) and variable-temperature magnetic susceptibility measurements. X-ray crystal structure analyses reveal that complexes 1 and 2 show a same 3,5-connected fsc 3D topology network with the Schlȁfli symbol of {4·6·8}{4·66·83}. But, the valence of some Mn atom in complex 2 take place transition from the +II oxidation state to the +III oxidation state, which may be the effect of the different solvent ratio. In complex 3, the Cu⋯Cu distance of 2.620(13) Å is significantly shorter than the sum of the van der Waals radii of Cu (1.40 Å), resulting in a strong ferromagnetic interaction between the Cu(II) centers. Furthermore, the temperature-dependent magnetic susceptibility measurements exhibit overall antiferromagnetic interactions between manganese ions for complexes 1 and 2, and a strong ferromagnetic interaction between the Cu(II) centers for complex 3.

  1. Prediction of Flow Effect on Crystal Growth of Semi-Crystalline Polymers Using a Multi-Scale Phase-Field Approach

    Directory of Open Access Journals (Sweden)

    Xiaodong Wang

    2017-11-01

    Full Text Available A multi-scale phase-field approach, which couples the mesoscopic crystallization with the microscopic orientation of chain segments and macroscopic viscoelastic melt flow, is proposed to study how the crystal growth of semi-crystalline polymers is affected by flows. To make the simulation feasible, we divide the problem into three parts. In the first part, a finitely extensible nonlinear elastic (FENE dumbbell model is used to simulate the flow induced molecular structure. In the second part, formulas for estimating the density, orientation and aspect ratio of nuclei upon the oriented molecular structure are derived. Finally, in the third part, a massive mathematical model that couples the phase-field, temperature field, flow field and orientation field is established to model the crystal growth with melt flow. Two-dimensional simulations are carried out for predicting the flow effect on the crystal growth of isotactic polystyrene under a plane Poiseuille flow. In solving the model, a semi-analytical method is adopted to avoid the numerical difficult of a “high Weissenberg number problem” in the first part, and an efficient fractional step method is used to reduce the computing complexity in the third part. The simulation results demonstrate that flow strongly affects the morphology of single crystal but does not bring a significant influence on the holistic morphology of bulk crystallization.

  2. Prospecting Lighting Applications with Ligand Field Tools and Density Functional Theory: A First-Principles Account of the 4f(7)-4f(6)5d(1) Luminescence of CsMgBr3:Eu(2+).

    Science.gov (United States)

    Ramanantoanina, Harry; Cimpoesu, Fanica; Göttel, Christian; Sahnoun, Mohammed; Herden, Benjamin; Suta, Markus; Wickleder, Claudia; Urland, Werner; Daul, Claude

    2015-09-08

    The most efficient way to provide domestic lighting nowadays is by light-emitting diodes (LEDs) technology combined with phosphors shifting the blue and UV emission toward a desirable sunlight spectrum. A route in the quest for warm-white light goes toward the discovery and tuning of the lanthanide-based phosphors, a difficult task, in experimental and technical respects. A proper theoretical approach, which is also complicated at the conceptual level and in computing efforts, is however a profitable complement, offering valuable structure-property rationale as a guideline in the search of the best materials. The Eu(2+)-based systems are the prototypes for ideal phosphors, exhibiting a wide range of visible light emission. Using the ligand field concepts in conjunction with density functional theory (DFT), conducted in nonroutine manner, we develop a nonempirical procedure to investigate the 4f(7)-4f(6)5d(1) luminescence of Eu(2+) in the environment of arbitrary ligands, applied here on the CsMgBr3:Eu(2+)-doped material. Providing a salient methodology for the extraction of the relevant ligand field and related parameters from DFT calculations and encompassing the bottleneck of handling large matrices in a model Hamiltonian based on the whole set of 33,462 states, we obtained an excellent match with the experimental spectrum, from first-principles, without any fit or adjustment. This proves that the ligand field density functional theory methodology can be used in the assessment of new materials and rational property design.

  3. Heteronuclear, mixed-metal Ag(I)-Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties.

    Science.gov (United States)

    Bikas, Rahman; Hosseini-Monfared, Hassan; Vasylyeva, Vera; Sanchiz, Joaquín; Alonso, Javier; Barandiaran, Jose Manuel; Janiak, Christoph

    2014-08-21

    Mixed-metal dicyanoargentate-bridged coordination polymers of Ag(i)-Mn(ii) have been prepared and their structure and magnetic properties were determined. Reaction of manganese(ii) chloride and potassium dicyanoargentate(i) with (X)(pyridin-2-ylmethylene)isonicotinohydrazide ligands (HL(1) X = Ph, HL(2) X = Me, HL(3) X = H) produced the coordination polymer 2D-[Mn(μ-L(1))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n (), 1D-{[Mn(L(2))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]CH3OH}n () and [Mn(L(3))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n () in good yields. Trinuclear {Mn(μ-L(1))Mn(μ-L(1))Mn} and [Ag(CN)2](-) building units form a two-dimensional slab in and 1D strands in . Variable temperature magnetic susceptibility measurements showed that despite the long distance among the high spin Mn(ii) ions [10.4676(12) Å and 10.522(1) Å, for and , respectively], weak antiferromagnetic coupling takes place through the long NC-Ag-CN bridge. The best fit parameters to the model led to the magnetic coupling constant of J = -0.1 and J = -0.47 cm(-1) for and , respectively. The photoluminescence behaviour of compounds and was studied. The spectrum of compound shows a broad emission centered at about 450 nm and two excitation maxima at 270 and 310 nm.

  4. Dynamics of ligand exchange mechanism at Cu(II) in water: An ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region

    International Nuclear Information System (INIS)

    Moin, Syed Tarique; Hofer, Thomas S.; Weiss, Alexander K. H.; Rode, Bernd M.

    2013-01-01

    Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment

  5. Investigation of fringing electric field effect on high-resolution blue phase liquid crystal spatial light modulator.

    Science.gov (United States)

    Yan, Jing; Guo, Zhengbo; Xing, Yufei; Li, Qing

    2015-08-20

    The fringing electric field effect which determines the performance of a high-resolution blue phase liquid crystal spatial light modulator (BPLC-SLM) is investigated by numerical modeling. The BPLC-SLM is polarization-dependent due to the transverse electric field component. The physical mechanism of the phase profile properties for different polarization states is analyzed. General design issues related to the BPLC-SLM configuration and phase profile properties are discussed. Notably, the material parameters and cell gap thickness are both optimized to obtain a low operation voltage (V2π=26.07  V). This work provides fundamental understanding for the feasibility of low operation voltage and high spatial resolution BPLC-SLM.

  6. Energy stable and efficient finite-difference nonlinear multigrid schemes for the modified phase field crystal equation

    Science.gov (United States)

    Baskaran, Arvind; Hu, Zhengzheng; Lowengrub, John S.; Wang, Cheng; Wise, Steven M.; Zhou, Peng

    2013-10-01

    In this paper we present two unconditionally energy stable finite difference schemes for the modified phase field crystal (MPFC) equation, a sixth-order nonlinear damped wave equation, of which the purely parabolic phase field crystal (PFC) model can be viewed as a special case. The first is a convex splitting scheme based on an appropriate decomposition of the discrete energy and is first order accurate in time and second order accurate in space. The second is a new, fully second-order scheme that also respects the convex splitting of the energy. Both schemes are nonlinear but may be formulated from the gradients of strictly convex, coercive functionals. Thus, both are uniquely solvable regardless of the time and space step sizes. The schemes are solved by efficient nonlinear multigrid methods. Numerical results are presented demonstrating the accuracy, energy stability, efficiency, and practical utility of the schemes. In particular, we show that our multigrid solvers enjoy optimal, or nearly optimal complexity in the solution of the nonlinear schemes.

  7. Tracing crystal-field splittings in the rare-earth-based intermetallic CeIrIn5

    Science.gov (United States)

    Chen, Q. Y.; Wen, C. H. P.; Yao, Q.; Huang, K.; Ding, Z. F.; Shu, L.; Niu, X. H.; Zhang, Y.; Lai, X. C.; Huang, Y. B.; Zhang, G. B.; Kirchner, S.; Feng, D. L.

    2018-02-01

    Crystal electric field states in rare earth intermetallics show an intricate entanglement with the many-body physics that occurs in these systems and that is known to lead to a plethora of electronic phases. Here we attempt to trace different contributions to the crystal electric field (CEF) splittings in CeIrIn5, a heavy-fermion compound and member of the Ce M In5 (M = Co, Rh, Ir) family. To this end, we utilize high-resolution resonant angle-resolved photoemission spectroscopy (ARPES) and present a spectroscopic study of the electronic structure of this unconventional superconductor over a wide temperature range. As a result, we show how ARPES can be used in combination with thermodynamic measurements or neutron scattering to disentangle different contributions to the CEF splitting in rare earth intermetallics. We also find that the hybridization is stronger in CeIrIn5 than CeCoIn5 and the effects of the hybridization on the Fermi volume increase is much smaller than predicted. By providing experimental evidence for 4 f7/2 1 splittings which, in CeIrIn5, split the octet into four doublets, we clearly demonstrate the many-body origin of the so-called 4 f7/2 1 state.

  8. Crystal field interactions in DyFe2Si2 and DyFe2Ge2

    Science.gov (United States)

    Chatterji, A.; Saha, D. P.; Chatterjee, Reba; Mitra, S.

    2009-11-01

    Two sets of crystal field (CF) parameters have been proposed for DyFe2Si2, none of which could provide a simultaneous explanation of the available experimental data, particularly at low temperatures (below 100 K). The set derived from magnetic studies could not even explain the thermal variation of the magnetic specific heat reported in the same work. Although the set of CF parameters, obtained from a fit to the Mossbauer spectra, could provide a fairly good explanation of the thermal variation of the magnetic susceptibilities along the c-axis, it could not explain the observed thermal variation of other reported experimental findings. In the present work, an appraisal of the CF parameters proposed earlier has been done and a set of CF parameters has been derived, which provide a simultaneous explanation of all the available experimental data. The effect of substitution of Ge for Si on the magnetic properties and the magnetic specific heat of DyFe2Si2 has been studied in the framework of one electron crystal field model. The inelastic neutron scattering studies and EPR measurements are required to check the predicted Stark energies and the paramagnetic resonance g-values.

  9. Tunable, multiwavelength-swept fiber laser based on nematic liquid crystal device for fiber-optic electric-field sensor

    Science.gov (United States)

    Lee, Hyun Ji; Kim, Sung-Jo; Ko, Myeong Ock; Kim, Jong-Hyun; Jeon, Min Yong

    2018-03-01

    We propose a tunable multiwavelength-swept laser based on a nematic liquid crystal (NLC) Fabry-Perot (FP) etalon, which is embedded in the resonator of a wavelength-swept laser. We achieve the continuous wavelength tuning of the multiwavelength-swept laser by applying the electric field to the NLC FP etalon. The free spectral range of the fabricated NLC FP etalon is approximately 7.9 nm. When the electric field applied to the NLC FP etalon exceeds the threshold value (Fréedericksz threshold voltage), the output of the multiwavelength-swept laser can be tuned continuously. The tuning range of the multiwavelength-swept laser can be achieved at a value greater than 75 nm, which has a considerably wider tunable range than a conventional multiwavelength laser based on an NLC FP etalon. The slope efficiencies in the spectral and temporal domains for the tunable multiwavelength-swept laser are 22.2 nm/(mVrms / μm) and 0.17 ms/(mVrms / μm), respectively in the linear region. Therefore, the developed multiwavelength-swept laser based on the NLC FP etalon can be applied to an electric-field sensor. Because the wavelength measurement and time measurement have a linear relationship, the electric-field sensor can detect a rapid change in the electric-field intensity by measuring the peak change of the pulse in the temporal domain using the NLC FP etalon-based multiwavelength-swept laser.

  10. X-ray diffraction study of KTP (KTiOPO4) crystals under a static electric field

    International Nuclear Information System (INIS)

    Sebastian, M.T.; Klapper, H.; Bolt, R.J.

    1992-01-01

    X-ray diffraction studies are made on ion-conducting potassium titanyl phosphate (KTP) crystals with in situ DC electric field along different crystallographic directions. The X-ray rocking curves recorded with an electric field along the polar b axis (which is the direction of ion conduction) show a strong enhancement of the 040 reflection intensity (reflecting planes normal to the b axis) whereas the h0l reflections (reflecting planes parallel to the polar axis) do not show any intensity change. For an electric field normal to the polar axis no intensity change, either in 040 or in h0l reflections occurs. This observation is supplemented by X-ray topography. The 040 X-ray topographs recorded with in situ electric field along b exhibit strong extinction contrast in the form of striations parallel to the polar (ion-conduction) axis. The 040 intensity increase and the striation contrast are attributed to lattice deformation by the space-charge polarization due to the movement of the K + ions under the influence of the electric field. (orig.)

  11. Magnetic properties of a diluted transverse spin-1 Ising nanocube with a longitudinal crystal-field

    Science.gov (United States)

    El Hamri, M.; Bouhou, S.; Essaoudi, I.; Ainane, A.; Ahuja, R.

    2016-12-01

    In the present work, the effective field theory with correlations based on the probability distribution technique has been used to investigate the effect of the surface shell longitudinal cristal field on the magnetic properties of a diluted antiferromagnetic spin-1 Ising nanocube particle. This effect has also been studied on the hysteresis loops of the system. It is found that this parameter has a strong effect on the magnetization profiles, compensation temperature, coercive field and remanent magnetization.

  12. Electric-field-tunable mechanical properties of relaxor ferroelectric single crystal measured by nanoindentation

    OpenAIRE

    Zhou, Hao; Pei, Yongmao; Li, Faxin; Luo, Haosu; Fang, Daining

    2014-01-01

    Electric field dependent mechanical properties of relaxor ferroelectric material Pb(Mn1/3Nb2/3)O3-PbTiO3 are investigated with the nanoindentation technique. Giant electric-field-tunable apparent elastic modulus (up to -39%), hardness (-9% to 20%) and energy dissipation (up to -13%) are reported. Based on experimental data, a characterization method of electromechanical coupled nanoindentation is proposed. In this method, an electric field tunable scaling relationship among elastic modulus, h...

  13. Late First-Row Transition-Metal Complexes Containing a 2-Pyridylmethyl Pendant-Armed 15-Membered Macrocyclic Ligand. Field-Induced Slow Magnetic Relaxation in a Seven-Coordinate Cobalt(II) Compound.

    Science.gov (United States)

    Antal, Peter; Drahoš, Bohuslav; Herchel, Radovan; Trávníček, Zdeněk

    2016-06-20

    The 2-pyridylmethyl N-pendant-armed heptadentate macrocyclic ligand {3,12-bis(2-methylpyridine)-3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1,14,16-triene = L} and [M(L)](ClO4)2 complexes, where M = Mn(II) (1), Fe(II) (2), Co(II) (3), Ni(II) (4), and Cu(II) (5), were prepared and thoroughly characterized, including elucidation of X-ray structures of all the compounds studied. The complexes 1-5 crystallize in non-centrosymmetric Sohncke space groups as racemic compounds. The coordination numbers of 7, 6 + 1, and 5 were found in complexes 1-3, 4, and 5, respectively, with a distorted pentagonal bipyramidal (1-4) or square pyramidal (5) geometry. On the basis of the magnetic susceptibility experiments, a large axial zero-field splitting (ZFS) was found for 2, 3, and 4 (D(Fe) = -7.4(2) cm(-1), D(Co) = 34(1) cm(-1), and D(Ni) = -12.8(1) cm(-1), respectively) together with a rhombic ZFS (E/D = 0.136(3)) for 4. Despite the easy plane anisotropy (D > 0, E/D = 0) in 3, the slow relaxation of the magnetization below 8 K was observed and analyzed either with Orbach relaxation mechanism (the relaxation time τ0 = 9.90 × 10(-10) s and spin reversal barrier Ueff = 24.3 K (16.9 cm(-1))) or with Raman relaxation mechanism (C = 2.12 × 10(-5) and n = 2.84). Therefore, compound 3 enlarges the small family of field-induced single-molecule magnets with pentagonal-bipyramidal chromophore. The cyclic voltammetry in acetonitrile revealed reversible redox processes in 1-3 and 5, except for the Ni(II) complex 4, where a quasi-reversible process was dominantly observed. Presence of the two 2-pyridylmethyl pendant arms in L with a stronger σ-donor/π-acceptor ability had a great impact on the properties of all the complexes (1-5), concretely: (i) strong pyridine-metal bonds provided slight axial compression of the coordination sphere, (ii) substantial changes in magnetic anisotropy, and (iii) stabilization of lower oxidation states.

  14. Two novel 2D coordination polymers constructed from 5-aminoisophthalic acid and 4,4‧-bipyridyl ligands: Syntheses, crystal structure, and photocatalytic performance

    Science.gov (United States)

    Xu, Dao-Xin; Wang, Chong-Chen; Wang, Peng; Li, Jin; Guo, Xin-Xing; Gao, Shi-Jie

    2017-05-01

    Two coordination polymers, [Zn(5-aip)(bpy)0.5]·H2O (1), and [Ni(5-aip)(bpy)0.5(H2O)]·2H2O (2), constructed by 5-aminoisophthalic acid (5-H2aip), 4,4'-bipyridine (bpy), and corresponding ions, have been synthesized under hydrothermal conditions, and characterized by single crystal X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), CHN elemental analysis and UV-Visible diffuse reflectance spectra (UV-Vis DRS). Both 1 and 2 were built up of two-dimensional [Zn(5-aip)(bpy)0.5] and [Ni(5-aip)(bpy)0.5(H2O)] sheets, respectively. The UV-Vis DRS results revealed that the Eg values of 1 and 2 are 3.4 and 2.4 eV, respectively. The photocatalytic activities of degradation of methyl orange (MO), methylene blue (MB) and MO&MB mixture over 1 and degradation of MB over 2 under UV light irradiation were investigated. The results revealed that 1 exhibited good performance to photocatalytically decompose MB, MO and MB&MO mixture, while 2 can only degrade MB efficiently.

  15. Enhancing the Antibacterial Activity of Light-Activated Surfaces Containing Crystal Violet and ZnO Nanoparticles: Investigation of Nanoparticle Size, Capping Ligand, and Dopants.

    Science.gov (United States)

    Sehmi, Sandeep K; Noimark, Sacha; Pike, Sebastian D; Bear, Joseph C; Peveler, William J; Williams, Charlotte K; Shaffer, Milo S P; Allan, Elaine; Parkin, Ivan P; MacRobert, Alexander J

    2016-09-30

    Healthcare-associated infections pose a serious risk for patients, staff, and visitors and are a severe burden on the National Health Service, costing at least £1 billion annually. Antimicrobial surfaces significantly contribute toward reducing the incidence of infections as they prevent bacterial adhesion and cause bacterial cell death. Using a simple, easily upscalable swell-encapsulation-shrink method, novel antimicrobial surfaces have been developed by incorporating metal oxide nanoparticles (NPs) and crystal violet (CV) dye into medical-grade polyurethane sheets. This study compares the bactericidal effects of polyurethane incorporating ZnO, Mg-doped ZnO, and MgO. All metal oxide NPs are well defined, with average diameters ranging from 2 to 18 nm. These materials demonstrate potent bactericidal activity when tested against clinically relevant bacteria such as Escherichia coli and Staphylococcus aureus . Additionally, these composites are tested against an epidemic strain of methicillin-resistant Staphylococcus aureus (MRSA) that is rife in hospitals throughout the UK. Furthermore, we have tested these materials using a low light intensity (∼500 lx), similar to that present in many clinical environments. The highest activity is achieved from polymer composites incorporating CV and ∼3 nm ZnO NPs, and the different performances of the metal oxides have been discussed.

  16. Synthesis, Crystal Structure and Characterization of Cu(II) and Cd(II) Coordination Compounds Based on Ligand 2-(3-(Pyridin-2-yl)-1H-pyrazol-1-yl)acetic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yajun; Wang, Cuijuan; Mao, Kaili; Liu, Xiaolei; Huang, Shuai; Tong, Yan; Zhou, Xianli [Southwest Jiaotong Univ., Chengdu (China)

    2014-07-15

    Two novel coordination compounds [Cu{sub 2}(pypya){sub 3}(H{sub 2}O){sub 2}]·Cl·(H{sub 2}O){sub 5} and {[Cd(pypya)(ta)1/2]·H_2O}n (Hpypya=2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid, H{sub 2}ta=terephthalic acid) were synthesized and characterized by single X-ray diffraction. Structure determination reveals that complex and complex crystallize in the triclinic system, with the P-1 space group. The asymmetric unit of contains two Cu(II) ions, and their coordination modes are different. These units of complex are linked together via hydrogen bonds and π-π interactions, and the 3D structure of complex was formed. Complex, a mononuclear Cd(II) coordination compound, has a 2D structure which was constructed via coordination bonds. TGA and fluorescence spectra analysis of complex and complex have also been studied. In addition, the geometry parameters of complex have been optimized with the B3LYP method of density functional theory (DFT) to explain its coordination behavior. The electronic properties of the complex and ligand Hpypya have been investigated based on the nature bond orbital (NBO) analysis at the B3LYP level of theory. The result verifies that the synergistic effect have occurred in the compound.

  17. Electric-field-tunable mechanical properties of relaxor ferroelectric single crystal measured by nanoindentation

    Science.gov (United States)

    Zhou, Hao; Pei, Yongmao; Li, Faxin; Luo, Haosu; Fang, Daining

    2014-02-01

    Electric field dependent mechanical properties of relaxor ferroelectric material Pb(Mn1/3Nb2/3)O3-PbTiO3 are investigated with the nanoindentation technique. Giant electric-field-tunable apparent elastic modulus (up to -39%), hardness (-9% to 20%), and energy dissipation (up to -13%) are reported. Based on experimental data, a characterization method of electromechanical coupled nanoindentation is proposed. In this method, an electric field tunable scaling relationship among elastic modulus, hardness, and indentation work for ferroelectric materials can be determined. In addition, this method can be used to obtain the electric-field-dependent elastic modulus and hardness, and avoid the estimate of contact area in the Oliver-Pharr method. Finally, the different effects on elastic modulus between positive and negative electric fields can be explained by the flexoelectric effect.

  18. Photonic time crystals.

    Science.gov (United States)

    Zeng, Lunwu; Xu, Jin; Wang, Chengen; Zhang, Jianhua; Zhao, Yuting; Zeng, Jing; Song, Runxia

    2017-12-07

    When space (time) translation symmetry is spontaneously broken, the space crystal (time crystal) forms; when permittivity and permeability periodically vary with space (time), the photonic crystal (photonic time crystal) forms. We proposed the concept of photonic time crystal and rewritten the Maxwell's equations. Utilizing Finite Difference Time Domain (FDTD) method, we simulated electromagnetic wave propagation in photonic time crystal and photonic space-time crystal, the simulation results show that more intensive scatter fields can obtained in photonic time crystal and photonic space-time crystal.

  19. RNA Crystallization

    Science.gov (United States)

    Golden, Barbara L.; Kundrot, Craig E.

    2003-01-01

    RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

  20. Nd(III) and Dy(III) coordination compounds based on 1H-tetrazolate-5-acetic acid ligands: Synthesis, crystal structures and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Li Qiaoyun; Chen Dianyu; He Minghua [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China); Yang Gaowen, E-mail: ygwsx@126.com [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China); Shen Lei; Zhai Chun; Shen Wei; Gu Kun; Zhao Jingjing [Jiangsu Laboratory of Advanced Functional Materials, Department of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu 215500, Jiangsu (China)

    2012-06-15

    Reactions of 1H-tetrazolate-5-acetic acid(H{sub 2}tza) with Nd(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O or Dy(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O with the presence of KOH under solvothermal conditions, produced two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)]. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 reveal 1D structures via bridging tza as linker. Furthermore, the compounds 1 and 2 showed a specific and good catalytic behavior for the polymerization of styrene, and the polymerization showed controlled characteristics. - Graphical Abstract: Two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)] have been synthesis. 1 and 2 reveal 1D structures via bridging tza as linker, and showed a specific and good catalytic behavior for the polymerization of styrene. Highlights: Black-Right-Pointing-Pointer we have reported two novel compounds formed by H{sub 2}tza and Nd(III) or Dy(III). Black-Right-Pointing-Pointer Compounds 1 and 2 were found to have catalysis property for the photo-polymerization of styrene. Black-Right-Pointing-Pointer The high molecular weight polymers with narrow molecular weight distributions were obtained.

  1. Molecular dynamics modeling self-organization of pyramid-like structures after crystallization of nanodrops in the field of solid surface

    International Nuclear Information System (INIS)

    Samsonov, V.M.; Murav'ev, S.D.; Pushkar', M.Yu.

    2005-01-01

    The process of nanodrop crystallization in the field of solid surface was investigated on the basis of the isothermal molecular dynamics. The initial stage of the process corresponds to the spreading under a constant cooling rate. The crystallization resulted in the formation of layered pyramid-like structures. A comparative analysis of forms and conditions was made, which yielded the pyramid-like structure formation in molecular dynamics simulation and in the experiments with Ge/Si systems [ru

  2. Narrowing the Zero-Field Tunneling Resonance by Decreasing the Crystal Symmetry of Mn12 Acetate.

    Science.gov (United States)

    Espín, Jordi; Zarzuela, Ricardo; Statuto, Nahuel; Juanhuix, Jordi; Maspoch, Daniel; Imaz, Inhar; Chudnovsky, Eugene; Tejada, Javier

    2016-07-27

    We report the discovery of a less symmetric crystalline phase of Mn12 acetate, a triclinic phase, resulting from recrystallizing the original tetragonal phase reported by Lis in acetonitrile and toluene. This new phase exhibits the same structure of Mn12 acetate clusters and the same positions of tunneling resonances on the magnetic field as the conventional tetragonal phase. However, the width of the zero-field resonance is at least 1 order of magnitude smaller-can be as low as 50 Oe-indicating very small inhomogeneous broadening due to dipolar and nuclear fields.

  3. Control of coercive field in lithium niobate crystals with repeated polarization reversal

    International Nuclear Information System (INIS)

    Ro, Jung Hoon; Jeong, Doun; Park, Taeyong; Kim, Chulhan; Kwon, Soon-Bok; Cha, Myoungsik; Choi, Byeong Cheol; Yu, Nanei; Kurimura, Sunao; Jeon, Gyerok

    2005-01-01

    In this study, the amount of decrease in coercive field of congruent lithium niobate during repeated poling and back-poling was measured. The polarization is reversed in 300 ms and then back-poled during the rest period. The coercive field can be decreased around 1 kV/mm with a repeated poling interval of 5 s. As the interval prolonged, the poling field decrease became smaller, and a stretched exponential function is suggested for the experimental fitting resulting in a set of meaningful parameters. These values are essential for the design of high quality domain engineering

  4. Colloidal Stability and Magnetic Field-Induced Ordering of Magnetorheological Fluids Studied with a Quartz Crystal Microbalance.

    Science.gov (United States)

    Rodriguez-López, Jaime; Castro, Pedro; de Vicente, Juan; Johannsmann, Diethelm; Elvira, Luis; Morillas, Jose R; Montero de Espinosa, Francisco

    2015-12-04

    This work proposes the use of quartz crystal microbalances (QCMs) as a method to analyze and characterize magnetorheological (MR) fluids. QCM devices are sensitive to changes in mass, surface interactions, and viscoelastic properties of the medium contacting its surface. These features make the QCM suitable to study MR fluids and their response to variable environmental conditions. MR fluids change their structure and viscoelastic properties under the action of an external magnetic field, this change being determined by the particle volume fraction, the magnetic field strength, and the presence of thixotropic agents among other factors. In this work, the measurement of the resonance parameters (resonance frequency and dissipation factor) of a QCM are used to analyze the behavior of MR fluids in static conditions (that is, in the absence of external mechanical stresses). The influence of sedimentation under gravity and the application of magnetic fields on the shifts of resonance frequency and dissipation factor were measured and discussed in the frame of the coupled resonance produced by particles touching the QCM surface. Furthermore, the MR-fluid/QCM system has a great potential for the study of high-frequency contact mechanics because the translational and rotational stiffness of the link between the surface and the particles can be tuned by the magnetic field.

  5. Colloidal Stability and Magnetic Field-Induced Ordering of Magnetorheological Fluids Studied with a Quartz Crystal Microbalance

    Directory of Open Access Journals (Sweden)

    Jaime Rodriguez-López

    2015-12-01

    Full Text Available This work proposes the use of quartz crystal microbalances (QCMs as a method to analyze and characterize magnetorheological (MR fluids. QCM devices are sensitive to changes in mass, surface interactions, and viscoelastic properties of the medium contacting its surface. These features make the QCM suitable to study MR fluids and their response to variable environmental conditions. MR fluids change their structure and viscoelastic properties under the action of an external magnetic field, this change being determined by the particle volume fraction, the magnetic field strength, and the presence of thixotropic agents among other factors. In this work, the measurement of the resonance parameters (resonance frequency and dissipation factor of a QCM are used to analyze the behavior of MR fluids in static conditions (that is, in the absence of external mechanical stresses. The influence of sedimentation under gravity and the application of magnetic fields on the shifts of resonance frequency and dissipation factor were measured and discussed in the frame of the coupled resonance produced by particles touching the QCM surface. Furthermore, the MR-fluid/QCM system has a great potential for the study of high-frequency contact mechanics because the translational and rotational stiffness of the link between the surface and the particles can be tuned by the magnetic field.

  6. D3R Grand Challenge 2: blind prediction of protein-ligand poses, affinity rankings, and relative binding free energies

    Science.gov (United States)

    Gaieb, Zied; Liu, Shuai; Gathiaka, Symon; Chiu, Michael; Yang, Huanwang; Shao, Chenghua; Feher, Victoria A.; Walters, W. Patrick; Kuhn, Bernd; Rudolph, Markus G.; Burley, Stephen K.; Gilson, Michael K.; Amaro, Rommie E.

    2018-01-01

    The Drug Design Data Resource (D3R) ran Grand Challenge 2 (GC2) from September 2016 through February 2017. This challenge was based on a dataset of structures and affinities for the nuclear receptor farnesoid X receptor (FXR), contributed by F. Hoffmann-La Roche. The dataset contained 102 IC50 values, spanning six orders of magnitude, and 36 high-resolution co-crystal structures with representatives of four major ligand classes. Strong global participation was evident, with 49 participants submitting 262 prediction submission packages in total. Procedurally, GC2 mimicked Grand Challenge 2015 (GC2015), with a Stage 1 subchallenge testing ligand pose prediction methods and ranking and scoring methods, and a Stage 2 subchallenge testing only ligand ranking and scoring methods after the release of all blinded co-crystal structures. Two smaller curated sets of 18 and 15 ligands were developed to test alchemical free energy methods. This overview summarizes all aspects of GC2, including the dataset details, challenge procedures, and participant results. We also consider implications for progress in the field, while highlighting methodological areas that merit continued development. Similar to GC2015, the outcome of GC2 underscores the pressing need for methods development in pose prediction, particularly for ligand scaffolds not currently represented in the Protein Data Bank (http://www.pdb.org), and in affinity ranking and scoring of bound ligands.

  7. Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity

    KAUST Repository

    Kuhn, Paul-Steffen

    2015-08-10

    A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by 13C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)]2− are coordinated to YIII and DyIII, respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4]5− (Ln=Y, Dy). While YIII is eight-coordinate in 2, DyIII is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N+ ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells.

  8. N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Zhi-Hang [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Han, Min-Le [College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471022 (China); Wu, Ya-Pan; Dong, Wen-Wen [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Lu, Jack Y., E-mail: lu@uhcl.edu [Department of Chemistry, University of Houstons-Clear Lake, Houston, TX 77058 (United States)

    2016-10-15

    Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.

  9. Investigation of thermoluminescent response of K2YF5:Dy3+ crystals for gamma and X radiation fields

    International Nuclear Information System (INIS)

    Silva, E.C.; Nogueira, M.S.; Faria, L.O.; Khaidukov, N.M.

    2005-01-01

    K 2 YF 5 crystals doped with rare earths have been synthesized with 0 to 100% of Dy 3+ ions optically active ions and an investigation was conducted to test its thermoluminescent (TL) response due to function of Dy 3+ concentration and their response in energy. After being irradiated with gamma and X-rays, it was observed that crystals doped with 1.0% of Dy 3+ feature the best response TL. The main dosimetric peak can be decomposed into three secondary TL peaks, centered in 96.4, 104.9 and 130.7 deg C, respectively, showing a good linearity and reproducibility of the dose measurements. The sensitization process seems to improve response TL and TL peak sensitivity increase to 130, 7 deg C at the expense of TL peak to 104, 9 deg C. The linear coefficient sign TL for K 2 Y 0.09 Dy 0.01 F5 is comparable to that of the dosemeter CaSO 4 : Mn, irradiated with gamma radiation source ( 137 Cs) under the same conditions. Energy dependence measurements show that the answer for X-rays with energy of 41.1 keV is more than 30 times the response to Cs-137, when exposed to the same dose. Due to the main peak in low temperature and the TL high reply to low energy fields, the results reported indicate that the K 2 YF 5 crystals doped with Dy 3+ present great potential for radiation dosimetry in X-rays therapy, clinical dosimetry and also for applications in digital thermoluminescent images

  10. Crystal fields in Sc, Y, and the heavy-rare-earth metals Tb, Dy, Ho, Er, Tm, and Lu

    International Nuclear Information System (INIS)

    Touborg, P.

    1977-01-01

    Experimental investigations of the magnetic poperties of dilute alloys of the rare-earth solutes Tb, Dy, Ho, Er, and Tm in the nonmagnetic hosts Lu, Y, and Sc have been performed. These measurements, which include and supplement earlier published results, have been analyzed and crystal-field parameters for all these 15 alloy systems deduced. The consistency of the parameters was confirmed by a variety of magnetic measurements, including neutron spectroscopy. Crystal-field parameters have also been derived for the ions in pure magnetic rare-earth metals and their alloys using the results for the dilute alloys supplemented with paramagnetic measurements up to high temperatures on the concentrated systems. Mean values and standard deviations of the higher-order crystal-field parameters for all Y and Lu alloys are B 40 /β = 6.8 +- 0.9 K, B 60 /γ = 13.6 +- 0.7 K, and B 66 /γ = (9.7 +- 1.1) B 60 /γ. These values: with the inaccuracies somewhat increased: are expected to be representative also for the magnetic rare-earth metals. For rare-earth ions in the Sc host the values B 40 /β = 9.9 +- 1.9 K, B 60 /γ = 19.8 +- 1.5 K, and B 66 /γ = (9.4 +- 0.9) B 60 /γ were deduced. B 20 /α is a host-sensitive parameter which has the average values of -102.7, -53.4, and 29.5 K for rare-earth ions in Y, Lu, and Sc, respectively. There is also evidence that this parameter varies with the solute. B 20 /α for ions in the pure magnetic rare-earth metals and their alloys shows a linear variation with c/a ratio characteristic of each ion. The results indicate a contribution from anisotropic exchange to the high-temperature paramagnetic anisotropy of approximately 20% for Tb, Dy, Ho, and Er, and approximately 10% for Tm

  11. Numerical Investigation of the Effect of Bottom Shape on the Flow Field and Particle Suspension in a DTB Crystallizer

    Directory of Open Access Journals (Sweden)

    Hao Pan

    2016-01-01

    Full Text Available The influence of the bottom shape on the flow field distribution and particle suspension in a DTB crystallizer was investigated by Computational Fluid Dynamics (CFD coupled with Two-Fluid Model (Eulerian model. Volume fractions of three sections were monitored on time, and effect on particle suspension could be obtained by analyzing the variation tendency of volume fraction. The results showed that the protruding part of a W type bottom could make the eddies smaller, leading to the increase of velocity in the vortex. Modulating the detailed structure of the W type bottom to make the bottom surface conform to the streamlines can reduce the loss of the kinetic energy of the flow fluid and obtain a larger flow velocity, which made it possible for the particles in the bottom to reach a better suspension state. Suitable shape parameters were also obtained; the concave and protruding surface diameter are 0.32 and 0.373 times of the cylindrical shell diameter, respectively. It is helpful to provide a theoretical guidance for optimization of DTB crystallizer.

  12. Interaction of phonons with intraband electronic excitations and crystal field transitions in Raman spectra of (Nd,Eu,Gd)Ba.sub.2./sub.Cu.sub.3./sub.O.sub.y./sub. crystals

    Czech Academy of Sciences Publication Activity Database

    Rameš, Michal; Železný, Vladimír; Gregora, Ivan; Wolf, T.; Jirsa, Miloš

    2015-01-01

    Roč. 197, Jul (2015), 10-17 ISSN 0921-5107 R&D Projects: GA MŠk(CZ) ME10069 Institutional support: RVO:68378271 Keywords : cuprate superconductors * phonons * crystal field * vortex pinning Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.331, year: 2015

  13. Mononuclear Ni(II) complexes of Schiff base ligands formed from unsymmetrical tripodal amines of differing arm lengths: Spectral, X-ray crystal structural, antimicrobial and DNA cleavage activity

    Science.gov (United States)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Dhers, Sébastien; Küp, Fatma Öztürk; Güllü, Mithat; Ng, Seikweng

    2017-11-01

    The synthesis of two unsymmetrical N-capped tripodal amines, 2-((4-aminobutyl)(pyridin-2-ylmethyl)amino)ethanol (3) and 3-((2-aminoethyl)(pyridin-2-ylmethyl)amino)propan-1-ol (4) is reported. They feature a longer, 3-hydroxypropyl or butylamino arm than that in the analogues previously employed. All four tripodal amines, 1-4, are equipped with a 2-methylpyridyl-arm, and either an ethylamino-arm (1 and 4), propylamino-arm (2) or butylamino-arm (3). The amines, 3 and 4, have been employed in one pot condensation reactions with salicylaldehyde and its derivatives in the presence of Ni(II) metal ion. A series of new mononuclear complexes, [NiIILaldi](ClO4) or [NiIILaldi(solvent)](ClO4) with different geometry, of Schiff base ligands were generated. X-ray crystal structure determinations of [NiIILOMe3(H2O)](ClO4)·2H2O and [NiIILOMe4](ClO4) revealed them to be mononuclear. The Ni(II) ion in [NiIILOMe4](ClO4) complex is in a distorted square-planar environment whilst this ion is in distorted octahedral environment in [NiIILOMe3(H2O)](ClO4)·2H2O complex despite the longer arm length of L3. While, in related systems in our previous work, they had led to dimeric complexes. These results clearly showed that the variation of the arm lengths of the ligands and metal ions has a remarkable impact on the formation and structure of the complexes. The cleavage of DNA by all synthesised complexes was examined using gel electrophoresis experiments. Also, the antibacterial effects of components were determined against the three Gram-positive bacteria, and against the three Gram-negative bacteria and against the three yeast Candida albicans ATCC 10231, Candida krusei ATCC 1424 and Candida tropicalis ATCC 13803.

  14. Effect of electrode design on crosstalk between neighboring organic field-effect transistors based on one single crystal

    Science.gov (United States)

    Li, Mengjie; Tang, Qingxin; Tong, Yanhong; Zhao, Xiaoli; Zhou, Shujun; Liu, Yichun

    2018-03-01

    The design of high-integration organic circuits must be such that the interference between neighboring devices is eliminated. Here, rubrene crystals were used to study the effect of the electrode design on crosstalk between neighboring organic field-effect transistors (OFETs). Results show that a decreased source/drain interval and gate electrode width can decrease the diffraction distance of the current, and therefore can weaken the crosstalk. In addition, the inherent low carrier concentration in organic semiconductors can create a high-resistance barrier at the space between gate electrodes of neighboring devices, limiting or even eliminating the crosstalk as a result of the gate electrode width being smaller than the source/drain electrode width.

  15. Elastic softening in HoFe2Al10 due to the quadrupole interaction under an orthorhombic crystal electric field

    International Nuclear Information System (INIS)

    Kamikawa, Shuhei; Ishii, Isao; Noguchi, Yoshihito; Goto, Hiroki; Fujita, Takahiro K.; Nakagawa, Fumiya; Tanida, Hiroshi; Sera, Masafumi; Suzuki, Takashi

    2016-01-01

    To investigate 4f electronic states in HoFe 2 Al 10 under an orthorhombic crystal electric field (CEF), we measured the specific heat, magnetic susceptibility, magnetization, and elastic modulus of single-crystalline samples. We found elastic softening of the transverse elastic moduli C 55 and C 66 below 20 and 130 K, respectively. With further decreasing temperature, C 66 shows further elastic softening below 5 K. We observed two Schottky peaks in the specific heat at 2.2 and 20 K and small anisotropy of the magnetic susceptibility and magnetization in the paramagnetic region. By analyzing these experimental data, we obtained the CEF parameters of HoFe 2 Al 10 . From the analysis, we clarified that the softening of C 55 and C 66 originates from indirect quadrupole interactions of O zx and O xy , and propose that the overall CEF splitting is about 85 K. (author)

  16. The influence of an external electric field on the propagation of light waves in cholesteric liquid crystal cells

    Science.gov (United States)

    Aksenova, E. V.; Karetnikov, A. A.; Kovshik, A. P.; Krainyukov, E. S.; Svanidze, A. V.

    2017-05-01

    The specific features of light transmission in a cholesteric liquid crystal (LC) cell with a director rotated by 90° have been investigated. In this structure, where a light wave is incident at a large angle with respect to the LC surface, the light is reflected (refracted) in the LC layer near the opposite boundary. It is shown that the application of an electric field changes the character of extraordinary wave refraction, as a result of which light starts passing through a cell. The transmission threshold voltage is determined, and its dependence on the angle of incidence of light is obtained. The dependence of the transmitted-light intensity on the voltage across the cell is obtained as well. The same dependences are also derived by numerical calculations with allowance for the turning points and extinction.

  17. Effects of deformation on the crystal field parameter of the Nd ions in Nd2Fe14B

    Science.gov (United States)

    Suzuki, Tsuneaki; Toga, Yuta; Sakuma, Akimasa

    2014-05-01

    Recently, the reduced coercivity of sintered Nd-Fe-B magnets was explained by distortion of the Nd-Fe-B region at the grain boundaries using classical molecular dynamics and phenomenological theory regarding magnetoelastic anisotropy. In this paper, we investigate how the deformation of Nd2Fe14B affects the crystal field parameter A20 of the Nd ions using first-principles calculations. By examining some cases of crystalline deformation, we confirm that the compressive deformation of Nd ions within the c-plane forces A20 to negative values. This is qualitatively consistent with the results of a previous study. However, quantitatively, the first-principles calculation shows that the magnetic anisotropy constant Ku is less sensitive to the distortion of Nd2Fe14B than suggested from the results obtained using classical and phenomenological theories.

  18. Contribution to the study of the crystal field in rare earth alloys. Moessbauer effect on 161Dy

    International Nuclear Information System (INIS)

    Iraldi, Renato.

    1974-01-01

    Hyperfine interactions in Dy-Y and Dy-Sc alloys were studied using Moessbauer effect on 161 Dy. It was shown that all RE-RE and RE-Y alloys are equivalents systems as for the conduction electron structure and magnetic properties, when crystal fields and anisotropy effects are taken into account. On the other hand, quadrupolar interaction studies in Dy-Sc alloys showed that in these alloys electronic properties vary considerably with the concentration of Sc. These results are interpreted as being due to pressure effect that changes the properties of conduction electrons. A high charge density at the nucleus in Dy-Sc was observed. This phenomenon is also interpreted as being due to a pressure effect on dysprosium external shells [fr

  19. Core electron excitations in U(4+): modelling of the nd(10)5f(2)→nd(9)5f(3) transitions with n = 3, 4 and 5 by ligand field tools and density functional theory.

    Science.gov (United States)

    Ramanantoanina, Harry; Kuri, Goutam; Daul, Claude; Bertsch, Johannes

    2016-07-28

    Ligand field density functional theory (LFDFT) calculations have been used to model the uranium M4,5, N4,5 and O4,5-edge X-ray absorption near edge structure (XANES) in UO2, characterized by the promotion of one electron from the core and the semi-core 3d, 4d and 5d orbitals of U(4+) to the valence 5f. The model describes the procedure to resolve non-empirically the multiplet energy levels originating from the two-open-shell system with d and f electrons and to calculate the oscillator strengths corresponding to the dipole allowed d(10)f(2)→ d(9)f(3) transitions appropriate to represent the d electron excitation process. In the first step, the energy and UO2 unit-cell volume corresponding to the minimum structures are determined using the Hubbard model (DFT+U) approach. The model of the optical properties due to the uranium nd(10)5f(2)→nd(9)5f(3) transitions, with n = 3, 4 and 5, has been tackled by means of electronic structure calculations based on the ligand field concept emulating the Slater-Condon integrals, the spin-orbit coupling constants and the parameters of the ligand field potential needed by the ligand field Hamiltonian from Density Functional Theory. A deep-rooted theoretical procedure using the LFDFT approach has been established for actinide-bearing systems that can be valuable to compute targeted results, such as spectroscopic details at the electronic scale. As a case study, uranium dioxide has been considered because it is a nuclear fuel material, and both atomic and electronic structure calculations are indispensable for a deeper understanding of irradiation driven microstructural changes occurring in this material.

  20. Magnetic structure of RPdSn (R=Tb, Ho) single crystal compounds under strong magnetic field

    International Nuclear Information System (INIS)

    Andoh, Y.; Kurisu, M.; Nakamoto, G.; Tsutaoka, T.; Kawano, S.

    2003-01-01

    Rare earth compounds RTX, where R stands for rare earth elements, T for Ni, Pd or Rh, and X for Sn or Ge, crystallize to a rhombic ε-TiNiSi structure. Only rare earth elements R contribute to magnetic properties since T and X atoms are nonmagnetic. The competition between RKKY indirect interaction and large magnetic anisotropy generates many complicated magnetic phases. At a low temperature phase, complicated magnetisms such as meta-magnetism were observed in magnetization curves with many steps. In previous experiments dealing with RPdSn where R means Tb or Ho, some characteristics of magnetic properties of these compounds were deduced from magnetization measurements and neutron diffraction without external magnetic field. In this report, the change of magnetic scattering of neutron diffraction was studied under external magnetic fields in order to reveal the mechanism of the phase transformations of the compounds. The difference between TbPdSn and HoPdSn compounds was observed in magnetic field dependence of the wave vectors of the magnetic scattering. Two independent wave vectors in magnetic scattering existed in HoPdSn compound. (Y. Kazumata)

  1. Field Ion Microscopy and Atom Probe Tomography of Metamorphic Magnetite Crystals

    Science.gov (United States)

    Kuhlman, K.; Martens, R. L.; Kelly, T. F.; Evans, N. D.; Miller, M. K.

    2001-01-01

    Magnetite has been analysed using Field Ion Microscopy (FIM) and Atom Probe Tomography (APT), highly attractive techniques for the nanoanalysis of geological materials despite the difficulties inherent in analyzing semiconducting and insulating materials. Additional information is contained in the original extended abstract.

  2. Near-field imaging of light propagation in photonic crystal waveguides: Explicit role of Bloch harmonics

    DEFF Research Database (Denmark)

    Bozhevolnyi, Sergey I.; Volkov, V.S.; Søndergaard, Thomas

    2002-01-01

    the interference between a quasihomogeneous background field and Bloch harmonics of the PCW mode, we account for spatial frequency spectra of the intensity variations and determine the propagation constant of the PCW mode at 1520 nm. The possibilities and limitations of SNOM imaging for the characterization...

  3. Influence of Magnetic Field in the Kinetics of Crystallization of Diamagnetic and Paramagnetic Inorganic Salts

    Czech Academy of Sciences Publication Activity Database

    Freitas, A. M.; Landgraf, F. J. G.; Nývlt, Jaroslav; Giulietti, M.

    1999-01-01

    Roč. 34, č. 10 (1999), s. 1239-1244 ISSN 0232-1300 Institutional research plan: CEZ:AV0Z4032918 Keywords : zinc sulfate * diamagnetism * magnetic field Subject RIV: CA - Inorganic Chemistry Impact factor: 0.576, year: 1999

  4. Orbital Configuration of the Valence Electrons, Ligand Field Symmetry, and Manganese Oxidation States of the Photosynthetic Water Oxidizing Complex: Analysis of the S(2) State Multiline EPR Signals.

    Science.gov (United States)

    Zheng, Ming; Dismukes, G. Charles

    1996-05-22

    state is caused by change in the intermanganese exchange coupling, without appreciable change in the intrinsic hyperfine tensors. The lack of good simulations of the Ca(2+)-depleted MLS suggests that Ca(2+)-depletion changes both Mn ligation and intermanganese exchange coupling. The 3Mn(IV)-1Mn(III) oxidation model is disfavored because only approximate simulations could be found for the native MLS and no agreement with the NH(3)-bound MLS was obtained. The scalar part of the hyperfine tensors for both Mn(III) and Mn(IV) ions were found to approximate (+/-5%) the values for the dimanganese(III,IV) catalase enzyme, suggesting similar overall ligand types. However, the large (30%) anisotropic part of the Mn(III) hyperfine interaction is opposite in sign to that found in all tetragonally extended six-coordinate Mn(III) ions (i.e., the usual Jahn-Teller splitting). The distribution of spin density from the high-spin d(4) electron configuration of each Mn(III) ion corresponds to a flattened (oblate) ellipsoid. This electronic distribution is favored in five-coordinate ligand fields having trigonally compressed bipyramidal geometry, but it could also arise, in principle, in strained six-coordinate ligand fields having tetragonally compressed geometry, i.e. [Mn(2)(&mgr;-O)](4+) (reverse Jahn-Teller distortion). The resulting valence electronic configurations are described as e'(2)e"(2) and (d(pi))(3)(d(x)()()2(-)(y)()()2)(1), respectively, in contrast to the (d(pi))(3)(d(z)()()2)(1) configuration common to unstrained six-coordinate tetragonally-extended Mn(III) ions, such as found in the [Mn(2)(&mgr;-O)(2)](3+) core in several synthetic dimers and catalase. Both of the former geometries predict strongly oxidizing Mn(III) ions, thereby suggesting a structural basis for the oxidative reactivity of the Mn(4) cluster in the WOC. The magnetic model needed to explain the MLS is not readily reconciled with the simplest structural and electronic models deduced from EXAFS studies of

  5. Liquidus temperature in the spinel primary phase field: A comparison between optical and crystal fraction methods

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Brian J.; Hrma, Pavel; Crum, Jarrod V.; Vienna, John D.; Schweiger, Michael J.; Rodriguez, Carmen P.; Peterson, Jacob A.

    2018-03-01

    Liquidus temperature (TL) was measured for simulated high-level waste borosilicate glasses covering a Hanford composition region, using an optical method and a crystal-fraction extrapolation method with X-ray diffraction data from isothermal heat treatments. The 38 glasses encompassed a one-component-at-a-time variation of a 16-component matrix. The TL values ranged from 1006°C to 1603°C. First-order polynomial models were fitted to data to obtain coefficients in terms of the effect of 1 mass% component addition on the TL: TL-increasing oxides Cr2O3 (264°C), “Others” (minor components, 163°C), oxides of noble metals (137°C), NiO (91°C), Al2O3 and Fe2O3 (~19–21°C); TL-decreasing oxides K2O (-26°C), Na2O (-41°C), and Li2O (-68°C); oxides of little effect MnO, P2O5, ZrO2, F, Bi2O3, SiO2, B2O3, and CaO (9 to -12°C). Also presented are temperatures (T1%) at which glasses contain 1 vol% of spinel as these values are considered relevant to the Hanford Tank Waste Treatment and Immobilization Plant. The measured and estimated values are compared and contrasted and the effect of TL and T1% on glass formulation is discussed.

  6. Porous shaped photonic crystal fiber with strong confinement field in sensing applications: Design and analysis

    Directory of Open Access Journals (Sweden)

    Sawrab Chowdhury

    2017-04-01

    Full Text Available In this article, porous core porous cladding photonic crystal fiber (P-PCF has been proposed for aqueous analytes sensing applications. Guiding properties of the proposed P-PCF has been numerically investigated by utilizing the full vectorial finite element method (FEM. The relative sensitivity and confinement loss are obtained by varying distinct geometrical parameters like the diameter of air holes, a pitch of the core and cladding region over a wider range of wavelength. The proposed P-PCF is organized with five rings air hole in the cladding and two rings air hole in a core territory which maximizes the relative sensitivity expressively and minimizes confinement loss depressively compare with the prior-PCF structures. After completing all investigations, it is also visualized that the relative sensitivity is increasing with the increment of the wavelength of communication band (O + E + S + C + L + U. Higher sensitivity is gained by using higher band for all applied liquids. Finally the investigating effects of different structural parameters of the proposed P-PCF are optimized which shows the sensitivity of 60.57%, 61.45% and 61.82%; the confinement loss of 8.71 × 10−08 dB/m, 1.41 × 10−10 dB/m and 6.51 × 10−10 dB/m for Water (n = 1.33, Ethanol (n = 1.354 and Benzene (n = 1.366 respectively at 1.33 μm wavelength. The optimized P-PCF with higher sensitivity and lower confinement loss has high impact in the area of the chemical as well as gas sensing purposes. Keywords: Porous shaped PCF, Sensitivity, Optical sensing, Liquid sensor, Confinement loss

  7. Molecular dynamics simulations of the d(CCAACGTTGG)2 decamer in crystal environment: comparison of atom-centered charge, extra-point and polarizable force fields.

    Science.gov (United States)

    Baucom, Jason; Transue, Thomas; Fuentes-Cabrera, Miguel; Krahn, Joseph; Darden, Thomas; Sagui, Celeste

    2004-03-01

    Molecular dynamics simulations of the DNA duplex d(CCAACGTTGG)2 were used to study the relationship between DNA sequence and structure. Three different force fields were used: a traditional description based on atomic point charges, a polarizable force field and an ``extra-point" force field (with additional charges on extra-nuclear sites). It is found that in crystal environment all the force fields reproduce fairly well the sequence-dependent features of the experimental structure. The polarizable force fields, however, outperforms the other two, pointing out to the need of the inclusion of polarization for accurate descriptions of DNA.

  8. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  9. Unit-cell design for two-dimensional phase-field simulation of microstructure evolution in single-crystal Ni-based superalloys during solidification

    Directory of Open Access Journals (Sweden)

    Dongjia Cao

    2017-12-01

    Full Text Available Phase-field simulation serves as an effective tool for quantitative characterization of microstructure evolution in single-crystal Ni-based superalloys during solidification nowadays. The classic unit cell is either limited to γ dendrites along crystal orientation or too ideal to cover complex morphologies for γ dendrites. An attempt to design the unit cell for two-dimensional (2-D phase-field simulations of microstructure evolution in single-crystal Ni-based superalloys during solidification was thus performed by using the MICRESS (MICRostructure Evolution Simulation Software in the framework of the multi-phase-field (MPF model, and demonstrated in a commercial TMS-113 superalloy. The coupling to CALPHAD (CALculation of PHAse Diagram thermodynamic database was realized via the TQ interface and the experimental diffusion coefficients were utilized in the simulation. Firstly, the classic unit cell with a single γ dendrite along crystal orientation was employed for the phase-field simulation in order to reproduce the microstructure features. Then, such simple unit cell was extended into the cases with two other different crystal orientations, i.e., and . Thirdly, for crystal orientations, the effect of γ dendritic orientations and unit cell sizes on microstructure and microsegregation was comprehensively studied, from which a new unit cell with multiple γ dendrites was proposed. The phase-field simulation with the newly proposed unit cell was further performed in the TMS-113 superalloy, and the microstructure features including the competitive growth of γ dendrites, microsegregation of different solutes and distribution of γ′ grains, can be nicely reproduced.

  10. Ligand identification using electron-density map correlations

    International Nuclear Information System (INIS)

    Terwilliger, Thomas C.; Adams, Paul D.; Moriarty, Nigel W.; Cohn, Judith D.

    2007-01-01

    An automated ligand-fitting procedure is applied to (F o − F c )exp(iϕ c ) difference density for 200 commonly found ligands from macromolecular structures in the Protein Data Bank to identify ligands from density maps. A procedure for the identification of ligands bound in crystal structures of macromolecules is described. Two characteristics of the density corresponding to a ligand are used in the identification procedure. One is the correlation of the ligand density with each of a set of test ligands after optimization of the fit of that ligand to the density. The other is the correlation of a fingerprint of the density with the fingerprint of model density for each possible ligand. The fingerprints consist of an ordered list of correlations of each the test ligands with the density. The two characteristics are scored using a Z-score approach in which the correlations are normalized to the mean and standard deviation of correlations found for a variety of mismatched ligand-density pairs, so that the Z scores are related to the probability of observing a particular value of the correlation by chance. The procedure was tested with a set of 200 of the most commonly found ligands in the Protein Data Bank, collectively representing 57% of all ligands in the Protein Data Bank. Using a combination of these two characteristics of ligand density, ranked lists of ligand identifications were made for representative (F o − F c )exp(iϕ c ) difference density from entries in the Protein Data Bank. In 48% of the 200 cases, the correct ligand was at the top of the ranked list of ligands. This approach may be useful in identification of unknown ligands in new macromolecular structures as well as in the identification of which ligands in a mixture have bound to a macromolecule

  11. Photonic crystal carpet: Manipulating wave fronts in the near field at 1.55 μm

    Science.gov (United States)

    Scherrer, G.; Hofman, M.; Śmigaj, W.; Kadic, M.; Chang, T.-M.; Mélique, X.; Lippens, D.; Vanbésien, O.; Cluzel, B.; de Fornel, F.; Guenneau, S.; Gralak, B.

    2013-09-01

    Ground-plane cloaks, which transform a curved mirror into a flat one, and recently reported at wavelengths ranging from the optical to the visible spectrum, bring the realm of optical illusion a step closer to reality. However, all carpet-cloaking experiments have thus far been carried out in the far field. Here, we demonstrate numerically and experimentally that a dielectric photonic crystal (PC) of an irregular shape made of a honeycomb array of air holes can scatter waves in the near field like a PC with a flat boundary at stop band frequencies. This mirage effect relies upon a specific arrangement of dielectric pillars placed at the nodes of a quasiconformal grid dressing the PC. Our carpet is experimentally shown to flatten the scattered wave fronts of a PC with a bump throughout the range of wavelengths from 1520 to 1580 nm within the stop band extending from 1280 to 1940 nm. The device has been fabricated using a single-mask advanced nanoelectronics technique on III-V semiconductors and the near field measurements have been carried out in order to image the wave fronts’ curvatures around the telecommunication wavelength 1550 nm. Interestingly, comparisons of our near-field experimental results with full-wave simulations suggest the relatively low aspect ratio of the fabricated carpet (pillars have 200 nm diameter and 2 μm height) makes it inherently three dimensional. Moreover, this carpet is constrained to normal incidence. We therefore propose an elaborated design of the carpet (with pillars of varying radii) which should work at different angles of incidence.

  12. Enhanced crystal-field splitting and orbital-selective coherence induced by strong correlations in V2O3

    Science.gov (United States)

    Poteryaev, Alexander I.; Tomczak, Jan M.; Biermann, Silke; Georges, Antoine; Lichtenstein, Alexander I.; Rubtsov, Alexey N.; Saha-Dasgupta, Tanusri; Andersen, Ole K.

    2007-08-01

    We present a study of the paramagnetic metallic and insulating phases of vanadium sesquioxide by means of the Nth order muffin-tin orbital implementation of density functional theory combined with dynamical mean-field theory. The transition is shown to be driven by a correlation-induced enhancement of the crystal-field splitting within the t2g manifold, which results in a suppression of the hybridization between the a1g and egπ bands. We discuss the changes in the effective quasiparticle band structure caused by the correlations and the corresponding self-energies. At temperatures of about 400K , we find the a1g orbital displays coherent quasiparticle behavior, while a large imaginary part of the self-energy and broad features in the spectral function indicate that the egπ orbitals are still far above their coherence temperature. The local spectral functions are in excellent agreement with recent bulk sensitive photoemission data. Finally, we also make a prediction for angle-resolved photoemission experiments by calculating momentum-resolved spectral functions.

  13. Crystal fields in Sc, Y, and the heavy-rare-earth metals Tb, Dy, Ho, Er, Tm, and Lu

    DEFF Research Database (Denmark)

    Touborg, P.

    1977-01-01

    -field parameters for all these 15 alloy systems deduced. The consistency of the parameters was confirmed by a variety of magnetic measurements, including neutron spectroscopy. Crystal-field parameters have also been derived for the ions in pure magnetic rare-earth metals and their alloys using the results......—with the inaccuracies somewhat increased—are expected to be representative also for the magnetic rare-earth metals. For rare-earth ions in the Sc host the values B40 / β=9.9±1.9 K, B60 / γ=19.8±1.5 K, and B66 / γ=(9.4±0.9)β60 / γ were deduced. B20 / α is a host-sensitive parameter which has the average values of -102.......7, -53.4, and 29.5 K for rare-earth ions in Y, Lu, and Sc, respectively. There is also evidence that this parameter varies with the solute. B20 / α for ions in the pure magnetic rare-earth metals and their alloys shows a linear variation with c / a ratio characteristic of each ion. The results indicate...

  14. Molecular structure and elastic properties of thermotropic liquid crystals: Integrated molecular dynamics—Statistical mechanical theory vs molecular field approach

    Science.gov (United States)

    Capar, M. Ilk; Nar, A.; Ferrarini, A.; Frezza, E.; Greco, C.; Zakharov, A. V.; Vakulenko, A. A.

    2013-03-01

    The connection between the molecular structure of liquid crystals and their elastic properties, which control the director deformations relevant for electro-optic applications, remains a challenging objective for theories and computations. Here, we compare two methods that have been proposed to this purpose, both characterized by a detailed molecular level description. One is an integrated molecular dynamics-statistical mechanical approach, where the bulk elastic constants of nematics are calculated from the direct correlation function (DCFs) and the single molecule orientational distribution function [D. A. McQuarrie, Statistical Mechanics (Harper & Row, New York, 1973)]. The latter is obtained from atomistic molecular dynamics trajectories, together with the radial distribution function, from which the DCF is then determined by solving the Ornstein-Zernike equation. The other approach is based on a molecular field theory, where the potential of mean torque experienced by a mesogen in the liquid crystal phase is parameterized according to its molecular surface. In this case, the calculation of elastic constants is combined with the Monte Carlo sampling of single molecule conformations. Using these different approaches, but the same description, at the level of molecular geometry and torsional potentials, we have investigated the elastic properties of the nematic phase of two typical mesogens, 4'-n-pentyloxy-4-cyanobiphenyl and 4'-n-heptyloxy-4-cyanobiphenyl. Both methods yield K3(bend) >K1 (splay) >K2 (twist), although there are some discrepancies in the average elastic constants and in their anisotropy. These are interpreted in terms of the different approximations and the different ways of accounting for the structural properties of molecules in the two approaches. In general, the results point to the role of the molecular shape, which is modulated by the conformational freedom and cannot be fully accounted for by a single descriptor such as the aspect ratio.

  15. Phase field study on crystal orientation effects in eutectoid phase transformation

    Directory of Open Access Journals (Sweden)

    Dong-qiao Zhang

    2017-11-01

    Full Text Available In this present work, a multi-phase field model was used to simulate the eutectoid transformation process, and on the basis of the nucleation model that was previously proposed by our research team, anisotropic and orientation relationship models were introduced to study the growth mechanism of the pearlite lamellae with anisotropy. It was found that the growth direction of the pearlite lamellae is related to its orientation and spacing. In the process of lamellar growth, deflection growth of pearlite will appear along with the adjustment of lamellar spacing, and the deflection angle is equal to the orientation difference between the austenite and the pearlite. Comparison between experimental and numerical results indicates a good consistency in pearlite morphology.

  16. Mixed-ligand binuclear copper(II) complex of 5 ...

    Indian Academy of Sciences (India)

    ligand binuclear copper(II) complex of 5-methylsalicylaldehyde and 2,2 -bipyridyl: Synthesis, crystal structure, DNA binding and nuclease activity. PERUMAL GURUMOORTHYa, JAYARAM RAVICHANDRANa,b and AZIZ KALILUR RAHIMANa,∗.

  17. Copper in the terrestrial environment: Verification of a laboratory-derived terrestrial biotic ligand model to predict earthworm mortality with toxicity observed in field soils

    NARCIS (Netherlands)

    Koster, Marijke; Groot, Arthur de; Vijver, Martina G; Peijnenburg, Willie J G M

    2006-01-01

    This study was set up for validation of a regression model to predict mortality in the terrestrial earthworm Aporrectodea caliginosa following exposure to copper. This model was derived from a terrestrial biotic ligand model and incorporates the protective effects of H+ and Na+ on copper toxicity.

  18. Single crystal EPR of the mixed-ligand complex of copper(II) with L-glutamic acid and 1,10-phenanthroline: a study on the narrowing of the hyperfine structure by exchange.

    Science.gov (United States)

    Neuman, Nicolás I; Franco, Vanina G; Ferroni, Felix M; Baggio, Ricardo; Passeggi, Mario C G; Rizzi, Alberto C; Brondino, Carlos D

    2012-12-20

    We report an EPR study at X- and Q-bands of polycrystalline and single crystal samples of the mixed copper(II) complex with L-glutamic acid (glu) and 1,10-phenantroline (phen), [Cu(glu)(phen)(H(2)O)](+) NO(3)(-)·2(H(2)O). The polycrystalline sample spectrum at Q-band showed well resolved g(∥ )and g(⊥) features and partially solved hyperfine structure at g(∥), typical for weakly exchange coupled systems. This is confirmed from the angular variation of the EPR spectra which shows for certain magnetic field orientations a partially solved hyperfine structure characteristic of weak exchange, whereas a single Lorentzian line corresponding to strong exchange is observed for others. Analysis and simulation of the single crystal EPR spectra were performed using the random frequency modulation model of Anderson. Numerical simulations of the angular variation of the EPR spectra showed that the narrowing of the hyperfine structure is due to an exchange-mediated mechanism in which transitions between any pair of lines are equally likely. The exchange interaction responsible for this process is mediated by hydrophobic interactions between two phen molecules and a mixed chemical path of the type CuA-O(ap)H···O-C-O(eq)-CuB, for which we evaluated an average isotropic exchange parameter |J| ≈ 25 × 10(-4) cm(-1).

  19. A non-empirical calculation of 2p core-electron excitation in compounds with 3d transition metal ions using ligand-field and density functional theory (LFDFT).

    Science.gov (United States)

    Ramanantoanina, Harry; Daul, Claude

    2017-08-09

    Methodological advents for the calculation of the multiplet energy levels arising from multiple-open-shell 2p 5 3d n+1 electron configurations, with n = 0, 1, 2,… and 9, are presented. We use the Ligand-Field Density Functional Theory (LFDFT) program, which has been recently implemented in the Amsterdam Density Functional (ADF) program package. The methodology consists of calculating the electronic structure of a central metal ion together with its ligand coordination by means of the Density Functional Theory code. Besides, the core-hole effects are treated by incorporating many body effects and corrections via the configuration interaction algorithm within the active space of Kohn-Sham orbitals with dominant 2p and 3d characters of the transition metal ions, using an effective ligand-field Hamiltonian. The Slater-Condon integrals (F 2 (3d,3d), F 4 (3d,3d), G 1 (2p,3d), G 3 (2p,3d) and F 2 (2p,3d)), spin-orbit coupling constants (ζ 2p and ζ 3d ) and parameters of the ligand-field potential (represented within the Wybourne formalism) are therefore determined giving rise to the multiplet structures of systems with 3d n and 2p 5 3d n+1 configurations. The oscillator strengths of the electric-dipole allowed 3d n → 2p 5 3d n+1 transitions are also calculated allowing the theoretical simulation of the absorption spectra of the 2p core-electron excitation. This methodology is applied to transition metal ions in the series Sc 2+ , Ti 2+ ,…, Ni 2+ and Cu 2+ but also to selective compounds, namely SrTiO 3 and MnF 2 . The comparison with available experimental data is good. Therefore, a non-empirical ligand-field treatment of the 2p 5 3d n+1 configurations is established and available in the ADF program package illustrating the spectroscopic details of the 2p core-electron excitation that can be valuable in the further understanding and interpretation of the transition metal L 2,3 -edge X-ray absorption spectra.

  20. Crystal field parameters with Wannier functions: application to Nd.sub.2./sub.Fe.sub.14./sub.B systems

    Czech Academy of Sciences Publication Activity Database

    Yoshioka, T.; Tsuchiura, H.; Novák, Pavel

    2015-01-01

    Roč. 19, Sup.3 (2015), S4-S8 ISSN 1432-8917 Institutional support: RVO:68378271 Keywords : crystal field parameters * Nd-Fe-B permanent magnet Subject RIV: BM - Solid Matter Physics ; Magnet ism Impact factor: 0.830, year: 2014